Photochromic compound, naphthol derivative, curable composition, optical article, lens, and glasses

Abstract

The purpose of the present invention is to provide: a photochromic compound having excellent temperature dependence and fading speed; a naphthol derivative that can be used as an intermediate of the photochromic compound; a curable composition containing the photochromic compound; an optical article; according to one embodiment, a photochromic compound having a skeleton represented by formula (1) is provided. In formula (1), M is C, Si or Ge. Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted fused polyring in which an aromatic ring or an aromatic heterocyclic ring is fused to these rings. Z1 represents a group represented by formula (1a) or a group represented by formula (1b).

Description

Technical Field

[0001] This invention relates to photochromic compounds, naphthol derivatives, curable compositions, optical articles, lenses, and eyeglasses. Background Technology

[0002] Photochromic compounds are compounds that can reversibly acquire two isomers with different absorption spectra when exposed to ultraviolet light, such as sunlight or mercury lamp light. Generally, by irradiating a colorless, achromatic compound with ultraviolet light, its color changes rapidly, isomerizing into a colored, chromogenic state (a colorimetric reaction). Photochromic compounds are being researched and developed as materials for photochromic lenses.

[0003] In the application of such photochromic lenses, photochromic compounds sometimes require the following properties.

[0004] (I) The chromaticity (hereinafter referred to as initial chromaticity) in the visible light region before ultraviolet irradiation is small.

[0005] (II) The speed from the start of ultraviolet irradiation to the saturation of color development concentration (hereinafter referred to as color development concentration) is high.

[0006] (III) High speed from the start of ultraviolet irradiation to the saturation of colorimetric concentration (hereinafter also referred to as high colorimetric sensitivity).

[0007] (IV) The rate at which the irradiation of ultraviolet light ceases and the color returns to its original state (hereinafter referred to as the fading rate) is high.

[0008] (V) The reversible effects described above have high durability.

[0009] (VI) It has high solubility in the matrix material of the lens and high dispersibility in the cured product.

[0010] As photochromic compounds capable of meeting such requirements, chromene compounds having an inden(2,1-f)naphtho(1,2-b)pyran structure as the basic framework are known. For example, chromene compounds represented by formula (A) (Patent Document 1), chromene compounds represented by formula (B) (Patent Document 2), and chromene compounds represented by formula (C) (Patent Document 3) are known.

[0011]

[0012] In recent years, the performance requirements for photochromic compounds have become increasingly sophisticated. In addition to the properties described in (I) to (VI) above, high color rendering concentration is also required even at high temperatures, such as in summer. This characteristic is sometimes referred to as "low temperature dependence." Generally, by improving the thermal stability of the color-developing state, high color rendering concentration can be maintained even at high temperatures, but the fading rate decreases. Therefore, there is a trade-off between color rendering concentration and fading rate at high temperatures. A photochromic compound that can balance color rendering concentration at high temperatures and the properties described in (IV) is required.

[0013] Existing technical documents

[0014] Patent documents

[0015] Patent Document 1: International Publication No. 2001 / 19813

[0016] Patent Document 2: International Publication No. 2019 / 228604

[0017] Patent Document 3: International Publication No. 2013 / 042800

[0018] Patent Document 4: International Publication No. 2015 / 035325

[0019] Patent Document 5: International Publication No. 2018 / 235771

[0020] Patent Document 6: International Publication No. 2012 / 102410

[0021] Patent Document 7: International Publication No. 2011 / 053615

[0022] Patent Document 8: International Publication No. 2011 / 034202

[0023] Patent Document 9: International Publication No. 2019 / 013249

[0024] Patent Document 10: International Publication No. 2016 / 143910

[0025] Patent Document 11: International Publication No. 2019 / 228604

[0026] Patent Document 12: International Publication No. 2019 / 013249

[0027] Patent Document 13: International Publication No. 2016 / 143910

[0028] Non-patent literature

[0029] Non-patent literature 1: Journal of Organic Chemistry 69(10)3282-3293; 2004

[0030] Non-patent literature 2: Synthetic Communications 23(16)2241-2249(1993)

[0031] Non-patent literature 3: J.Am.Chem.Soc.132(41)14324-14326(2010)

[0032] Non-patent literature 4: Org. Lett. 16, 6492-6495 (2014) Summary of the Invention

[0033] The problem the invention aims to solve

[0034] The object of the present invention is to provide a photochromic compound with excellent temperature dependence and fading speed, a naphthol derivative that can be an intermediate of the photochromic compound, a curable composition comprising the photochromic compound, optical articles, lenses and eyeglasses.

[0035] Solution for solving the problem

[0036] This disclosure relates to photochromic compounds having a skeleton as shown in formula (1) or (1A).

[0037]

[0038] In formula (1), M is C, Si or Ge. Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[0039] Z 1 It is a group represented by formula (1a) or formula (1b) below.

[0040]

[0041] In equation (1a), R 1 For substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, or substituted or unsubstituted fused polycyclic groups with aromatic rings or aromatic heterocycles fused to these substituents. R 2 It is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a) below.

[0042] -Q1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[0043] In equation (2a), Q 1 It is an alkylene or haloalkylene.

[0044] Q 2 It is an alkylene or haloalkylene, Q 3 It is an alkyl or haloalkyl group. X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O). R 700 and R 701 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, where a is 0, or more than 1 and less than 3.

[0045] In formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings. 1 The substituted or unsubstituted methylene group. 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C = CR 602 Or CC. R 600 R 601 and R 602 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. 3 The m group is either substituted or unsubstituted. m is an integer from 1 to 4, n is an integer from 0 to 4, and m+n is an integer greater than 2.

[0046]

[0047] In equation (1A), M, ring A and ring B have the same meaning as in equation (1).

[0048] In equation (1A), Y 111 The substituted or unsubstituted methylene group. 112 For substituted or unsubstituted methylene, oxygen atom, sulfur atom, NR 600 Or SO2. R 600It has the same meaning as described in equation (1b).

[0049] In equation (1A), R 111 and R 112 Each of the following can be independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted aryloxy group, a thiol group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (2a) above.

[0050] In addition, this disclosure relates to curable compositions. The curable compositions comprise the aforementioned photochromic compounds and include at least one selected from the group consisting of radical polymerizable monomers, cationic polymerizable monomers, compounds having polymerizable reactive groups, and (thio)carbamate (urea) polymers.

[0051] Furthermore, this disclosure relates to cured products. Cured products are cured versions of the aforementioned curable compositions.

[0052] Furthermore, this disclosure relates to optical articles. These optical articles comprise cured products of the aforementioned curable composition.

[0053] In addition, this disclosure relates to lenses. The lenses contain the aforementioned photochromic compounds.

[0054] Furthermore, this disclosure relates to eyeglasses. Eyeglasses include the aforementioned lenses.

[0055] In addition, this disclosure relates to naphthol derivatives. Naphthol derivatives have a skeleton as shown in formula (6) or (6A).

[0056]

[0057] In equation (6), M, ring A, and Z 1 They are independently equivalent to the meaning in equation (1) above.

[0058]

[0059] In equation (6A), M, ring A, ring B, and Y... 111 Y 112 R 111 and R 112 They are independently equivalent to the meanings in the above formula (1A).

[0060] The effects of the invention

[0061] According to the present invention, a photochromic compound with excellent temperature dependence and fading rate is provided, a naphthol derivative which can be an intermediate of the photochromic compound, a curable composition comprising the photochromic compound, optical articles, lenses and eyeglasses. Attached Figure Description

[0062] Figure 1 This is a figure illustrating the relationship between the 23°C fading half-life and high-temperature color development of the photochromic laminates of the embodiments and comparative examples.

[0063] Figure 2 This is another example of the relationship between the 23°C fading half-life and the high-temperature color development rate of the photochromic laminates of the embodiments and comparative examples. Detailed Implementation

[0064] [Photochromic compounds]

[0065] According to an embodiment, a photochromic compound having a skeleton as shown in the following formula (1) is provided.

[0066]

[0067] In formula (1), M is C, Si, or Ge. Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic aromatic ring or aromatic heterocycle fused to these rings. Z 1 It is a group represented by formula (1a) or formula (1b) below.

[0068]

[0069] In equation (1a), R 1 It can be a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 2 It is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a) below.

[0070] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[0071] In equation (2a), Q 1 It is an alkylene or haloalkylene. Q 2 It is an alkylene or haloalkylene. Q3 It is an alkyl or haloalkyl group. X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O). R 700 and R 701 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. a is 0, or an integer greater than or equal to 1 and less than or equal to 3.

[0072]

[0073] In formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings. 1 The substituted or unsubstituted methylene group. 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C = CR 602 Or CC. R 600 R 601 and R 602 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. 3 The substituted or unsubstituted methylene group or oxygen atom. m is an integer from 1 to 4, n is an integer from 1 to 4, and m+n is an integer greater than 2.

[0074] This photochromic compound exhibits excellent temperature dependence and fading rate. The reason for this is not yet clear, but the inventors believe it to be as follows.

[0075] Substituent Z of the photochromic compound in the embodiments 1 Using formula (1a) or formula (1b) above. It is believed that formulas (1a) and (1b) above, through the structure of aryl or heteroaryl groups directly bonded to the nitrogen atom, can utilize the p orbital on the nitrogen atom in the framework and substituent Z shown in formula (1). 1 Conjugation. It is believed that the conjugation is extended in compounds with this structure compared to the unsubstituted compounds of formulas (1a) and (1b) above. This extension is thought to increase absorbance in the achromatic state, thus improving colorimetric concentration even at high temperatures. Furthermore, it is believed that durability is improved due to electron delocalization via the resonance structure.

[0076] Additionally, if the substituent Z 1 When the bonded substitution site is replaced by a substituent with high electron-donating capacity, the fading rate of the photochromic compound tends to decrease. As mentioned above, it is believed that substituent Z... 1 The presence of aryl or heteroaryl groups bonded to the nitrogen atom reduces electron-donating ability due to conjugation. Therefore, it is considered that the presence of substituent Z... 1 The fading rate of the photochromic compound was suppressed.

[0077] As can be seen from the above, when using the photochromic compound of the embodiment, a cured product with excellent temperature dependence and fading rate, and thus excellent durability, can be achieved. Therefore, such a photochromic compound is suitable for optical articles used in environments with large temperature variations, such as sunglasses.

[0078] The following is a detailed description of photochromic compounds having the framework shown in formula (1).

[0079] <m>

[0080] In equation (1), M is C, Si, or Ge. M is preferably C.

[0081] <Ring A>

[0082] In formula (1), ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[0083] Examples of aromatic hydrocarbon rings include the benzene ring and the cyclotetradecane-7-ene ring.

[0084] Examples of aromatic heterocyclic rings include furan rings, thiophene rings, and pyridine rings.

[0085] Examples of fused polycyclic rings include naphthalene rings, fluorene rings, anthracene rings, phenanthrene rings, tetraphenylene rings, pentaphenylene rings, and benzo[a]pyrene rings. Rings, including pyrene rings, triphenylene rings, perylene rings, benzofuran rings, benzothiophene rings, quinoline rings, isoquinoline rings, indole rings, pyrimidine rings, quinazoline rings, pyridazine rings, cyclophosphine rings, phthalazine rings, 1,2,3-, 1,2,4- or 1,3,5-triazine rings, carbazole rings, benzoxazole rings, isothiazazole rings, etc.

[0086] Preferably, the rings are benzene ring, naphthalene ring, fluorene ring, phenanthrene ring, pyrene ring, furan ring, thiophene ring, or pyridine ring; more preferably, benzene ring, naphthalene ring, fluorene ring, or phenanthrene ring; and most preferably, benzene ring.

[0087] <Z 1 >

[0088] In equation (1), Z 1 It is a group represented by formula (1a) or formula (1b) below. The dashed line represents a bond bonded to the carbon atom at position 7 in the skeleton shown in formula (1).

[0089]

[0090]

[0091] (R 1 )

[0092] R 1 For substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, or substituted or unsubstituted fused polycyclic compounds with aromatic rings or aromatic heterocycles fused to these substituents. Regarding the possibility of becoming R... 1 The groups that may have substituents will be described later.

[0093] The substituted or unsubstituted aryl group has, for example, 5 or more and 12 or less carbon atoms, preferably 6 or more and 10 or less. The heteroatom of the substituted or unsubstituted heteroaryl group can be at least one selected from the group consisting of oxygen, sulfur, nitrogen, and phosphorus atoms. The substituted or unsubstituted heteroaryl group has, for example, 1 or more and 3 or less heteroatoms, preferably 1 or 2. The substituted or unsubstituted heteroaryl group has, for example, 4 or more and 11 or less carbon atoms, preferably 5 or more and 9 or less.

[0094] R 1 Preferably, it is a substituted or unsubstituted phenyl, a substituted or unsubstituted 1-naphthyl, a substituted or unsubstituted 2-naphthyl, a substituted or unsubstituted thiophene, a substituted or unsubstituted furanyl, a substituted or unsubstituted pyrrolinyl, a substituted or unsubstituted pyridinyl, a substituted or unsubstituted benzothiophene, a substituted or unsubstituted benzofuranyl, or a substituted or unsubstituted benzopyrrolinyl, more preferably a substituted or unsubstituted phenyl, a substituted or unsubstituted 1-naphthyl, or a substituted or unsubstituted 2-naphthyl.

[0095] As R 1 The substituents that may be present are preferably selected from at least one of the following groups: straight-chain or branched alkyl groups having 1 or more and 6 or less carbon atoms; straight-chain or branched haloalkyl groups having 1 or more and 6 or less carbon atoms; straight-chain or branched alkoxy groups having 1 or more and 6 or less carbon atoms; and halogen atoms. The number of substituents is, for example, 1 or more and 3 or less.

[0096] (R 2 )

[0097] R 2 It is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a) below.

[0098] R 2 Preferably, it is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a) below, and more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a group represented by formula (2a) below.

[0099] The alkyl group is preferably an unsubstituted alkyl group having 1 or more and 10 or less carbon atoms, and more preferably an unsubstituted alkyl group having 1 or more and 6 or less carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl or hexyl.

[0100] The haloalkyl group is preferably a haloalkyl group having 1 to 6 carbon atoms. The number of halogen atoms is preferably 1 or more and 10 or less, more preferably 2 or more and 5 or less. As a haloalkyl group having 1 to 6 carbon atoms, it is preferably an alkyl group substituted with a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group is preferably terminally perfluoromethyl. Examples of preferred haloalkyl groups include trifluoromethyl, trifluoroethyl, trifluoropropyl, tetrafluoroethyl, chloromethyl, 2-chloroethyl, and bromomethyl.

[0101] The cycloalkyl group is preferably a cycloalkyl group with 3 to 8 carbon atoms (a cycloalkyl group forming a ring with 3 to 8 carbon atoms). Examples of cycloalkyl groups with 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. It should be noted that the cycloalkyl group may have substituents, but the number of carbon atoms in the ring (3 to 8 carbon atoms) mentioned above does not include the number of carbon atoms of the substituents.

[0102] The preferred alkoxy group is one with 1 to 6 carbon atoms. Examples of suitable alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy.

[0103] Aryl groups can be used with R 1 The same group as the one illustrated. The aryl group is preferably phenyl or naphthyl.

[0104] Heteroaryl groups can be used with R 1 The same group is shown in the example.

[0105] As R 2 The substituents that may be present are preferably selected from at least one of the following groups: straight-chain or branched alkyl groups having 1 or more and 6 or less carbon atoms; straight-chain or branched haloalkyl groups having 1 or more and 6 or less carbon atoms; straight-chain or branched alkoxy groups having 1 or more and 6 or less carbon atoms; and halogen atoms. The number of substituents is, for example, 1 or more and 3 or less.

[0106] R 2 Preferably, the alkyl group has 1 or more but less than 5 carbon atoms, the fluoroalkyl group has 1 or more but less than 5 carbon atoms, the alkoxy group has 1 or more but less than 5 carbon atoms, the alkoxyalkyl group has 2 or more but less than 6 carbon atoms, the phenyl group, or the phenyl group having a substituent. The fluoroalkyl group has 1 or more but less than 5 carbon atoms preferably has a perfluoromethyl group at the end.

[0107] From the perspective of increasing colorimetric concentration, R 2 Preferably, it is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. It is assumed that if such a structure is present, the skeleton shown in formula (1) and the substituent Z... 1 The conjugation is further extended.

[0108] (The group shown in formula (2a))

[0109] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[0110] In equation (2a), Q 1 It is an alkylene or haloalkylene.

[0111] The alkylene group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 12 or less, even more preferably 1 or more and 7 or less, and most preferably 2 or more and 6 or less. The halogen atom used as the alkylene haloside can be at least one selected from the group consisting of I, Cl, Br, and F. The halogen atom is preferably at least one of Cl and F, more preferably F. In the alkylene haloside, the terminal carbon atom is preferably bonded to the halogen atom, more preferably the terminal carbon is a perfluoromethyl group.

[0112] Q 2 It is an alkylene or haloalkylene. The preferred method for alkylene or haloalkylene is related to Q. 1 Same. Q 2 The number of carbon atoms in the alkylene or haloalkylene group can be related to Q. 1 The number of carbon atoms in alkylene or haloalkylene compounds can be the same or different.

[0113] Q 3 It can be an alkyl or haloalkyl group, and can be straight-chain or branched, preferably straight-chain.

[0114] The alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 12 or less, and most preferably 1 or more and 7 or less. The halogen atom, as the haloalkyl group, can be at least one selected from the group consisting of I, Cl, Br, and F. The halogen atom is preferably at least one of Cl and F, more preferably F.

[0115] Q 3 Preferably, it is a straight-chain alkyl group.

[0116] X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O). X 1 and X 2 Preferably O, S, or NR 700 The optimal choice is O.

[0117] R 700 and R 701 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0118] R 700 Preferably, it consists of a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The alkyl group is preferably methyl, ethyl, propyl, butyl, or pentyl. The aryl group is preferably phenyl or naphthyl.

[0119] R 701 Preferably, it consists of a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The alkyl group is preferably methyl, ethyl, propyl, butyl, or pentyl. The aryl group is preferably phenyl or naphthyl.

[0120] a is 0 or 1 or higher and 3 or lower.

[0121] Formula (2a) is preferably alkylene alkoxy, alkylene thioalkyl or alkylene oxyalkylene alkoxy.

[0122] Specific examples of equation (2a) include -CH2OCH3, -CH2SCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2SCH3, -CH2CH2CH2OCH3, -CH2CH2CH2SCH3, -CH2CH2OCH2CH2OCH3, and -CH2CH2OCH2CH2OCH2CH3.

[0123] The group represented by formula (2a) is preferably -CH2OCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2CH2OCH3, -CH2CH2OCH2CH2OCH3, or -CH2CH2OCH2CH2OCH2CH3.

[0124] If a suitable equation (1a) is exemplified, then it is as follows.

[0125]

[0126] <Equation (1b)>

[0127]

[0128] In equation (1b),

[0129] Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring to which an aromatic ring or aromatic heterocycle is fused. The meaning of suitable ring B is the same as that exemplified in ring A.

[0130] Y 1 The substituent may be substituted or unsubstituted methylene. The substituent is preferably a halogen atom, a haloalkyl group having 1 or more but 3 or fewer carbon atoms, or an alkyl group having 1 or more but 3 or fewer carbon atoms; more preferably, it is a fluorine atom or a methyl group. The number of substituents is 1 or 2.

[0131] Y 1 More preferably, it is a methylene group substituted with a methyl or fluorine atom, or an unsubstituted methylene group, and particularly preferably an unsubstituted methylene group.

[0132] Y 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C = CR 602 Or CC.

[0133] R 600 R 601 and R 602 Each of these groups is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group. As these groups, those associated with R can be used. 1 Or R 2 The same group is shown in the example.

[0134] The haloalkoxy group is preferably a haloalkoxy group having 1 to 6 carbon atoms. The number of halogen atoms is preferably 1 or more and 10 or less, more preferably 2 or more and 5 or less. As a haloalkoxy group having 1 to 6 carbon atoms, it is preferably an alkoxy group substituted with a fluorine, chlorine, or bromine atom. The haloalkoxy group preferably has a perfluoromethyl terminal. Examples of preferred haloalkoxy groups include trifluoromethoxy, pentafluoroethoxy, heptafluoropropoxy, 2,2,2-trifluoroethoxy, 3,3,3-trifluoropropoxy, and 2,2,3,3,3-pentafluoropropoxy.

[0135] Y 2 Preferably, it contains substituted or unsubstituted methylene, O, S, SO2, or NR. 600 More preferably, it is an unsubstituted methylene, O, S or SO2.

[0136] Y 3 For substituted or unsubstituted methylene, regarding the suitable Y 3 , with Y 1 The examples in the text have the same meaning.

[0137] m is an integer from 1 to 4. m is preferably 1 or 2. n is an integer from 0 to 4. n is preferably 0 or 1. m+n is an integer of 2 or more. m+n is preferably 2 or more and 4 or less, more preferably 2 or 3.

[0138] When n is 0, Y 2 It bonds with ring B.

[0139] If a suitable equation (1b) is exemplified, then it is as follows.

[0140]

[0141] <The compound shown in formula (2)>

[0142] The photochromic compound of the embodiment preferably has a naphthylpyran skeleton as shown in formula (2) below. In formula (2) below, Z 1 M and M have the same meaning as in equation (1).

[0143]

[0144] <The skeleton shown in formula (3)>

[0145] The photochromic compound used in the embodiments is preferably a compound having the framework shown in the following formula (3). In the following formula (3), Z 1 M and M have the same meaning as in equation (1).

[0146]

[0147] <R 3 and R 4 >

[0148] R 3 and R 4 Each of the following can be independently a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, a group represented by formula (X) below, or a group represented by formula (X3) above.

[0149] As substituted or unsubstituted alkyl, haloalkyl, group shown in formula (2a), substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, it can be used with R 1 Or R 2 The same group is shown in the example.

[0150] The amino group can be a primary amino group (-NH2) or a secondary or tertiary amino group in which one or two hydrogen atoms are substituted. Examples of substituents for substituted amino groups include alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms. Suitable examples of amino groups include amino, methylamino, dimethylamino, ethylamino, diethylamino, methylphenylamino, and diphenylamino.

[0151] As a heterocyclic group, a heterocyclic group having 3 to 10 atoms is preferred. The heteroatom in the heterocyclic group is preferably at least one selected from the group consisting of oxygen, nitrogen, sulfur, and phosphorus atoms. The number of heteroatoms is, for example, 1 or more and 5 or less, preferably 1 or 2. Specifically, examples include aliphatic heterocyclic groups such as morpholino, piperidinyl, pyrrolyl, piperazine, and N-methylpiperazine, or aromatic heterocyclic groups such as indole. The heterocyclic group can be 2,6-dimethylmorpholino, 2,6-dimethylpiperidinyl, and 2,2,6,6-tetramethylpiperidinyl.

[0152] The alkylthio group is preferably an alkylthio group with 1 to 6 carbon atoms. Examples of alkylthio groups with 1 to 6 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, and tert-butylthio.

[0153] The arylthio group is preferably an arylthio group with 6 to 10 carbon atoms. Examples of arylthio groups with 6 to 10 carbon atoms include phenylthio, 1-naphthio, and 2-naphthio.

[0154] The alkyl carbonyl group is preferably an alkyl carbonyl group having 2 to 7 carbon atoms. Examples of alkyl carbonyl groups having 2 to 7 carbon atoms include acetyl and ethyl carbonyl groups.

[0155] The preferred alkoxycarbonyl group is one with 2 to 7 carbon atoms. Examples of alkoxycarbonyl groups with 2 to 7 carbon atoms include methoxycarbonyl and ethoxycarbonyl.

[0156] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0157] The aralkyl group is preferably an aralkyl group with 7 to 11 carbon atoms. Examples of aralkyl groups with 7 to 11 carbon atoms include benzyl, phenylethyl, phenylpropyl, phenylbutyl, and naphthylmethyl.

[0158] The preferred arylalkoxy group is one with 7 to 11 carbon atoms. Examples of arylalkoxy groups with 7 to 11 carbon atoms include benzyloxy and naphthylmethoxy.

[0159] The aryloxy group is preferably an aryloxy group with 6 to 12 carbon atoms. Examples of aryloxy groups with 6 to 12 carbon atoms include phenoxy and naphthoxy groups.

[0160] The alkoxyalkylthio group is preferably an alkoxyalkylthio group with 2 to 9 carbon atoms. Examples of alkoxyalkylthio groups with 2 to 9 carbon atoms include methoxymethylthio, methoxyethylthio, methoxyn-propylthio, methoxyn-butylthio, ethoxyethylthio, and n-propoxypropylthio.

[0161] The haloalkylthio group is preferably a haloalkylthio group with 1 to 6 carbon atoms. Examples of haloalkylthio groups with 1 to 6 carbon atoms include trifluoromethylthio, tetrafluoroethylthio, chloromethylthio, 2-chloroethylthio, and bromomethylthio.

[0162] The cycloalkylthio group is preferably a cycloalkylthio group with 3 to 8 carbon atoms. Examples of cycloalkylthio groups with 3 to 8 carbon atoms include cyclopropylthio, cyclobutylthio, cyclopentylthio, and cyclohexylthio. It should be noted that the cycloalkylthio group may have substituents, but the number of carbon atoms (3 to 8) does not include the number of carbon atoms of the substituents.

[0163] Silyyl groups may have substituents. There are no particular restrictions on the substituents that can be present in substituted silyl groups, and examples include alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms.

[0164] Oxymethylsilyl groups may have substituents. There are no particular limitations on the substituents that can be present in substituted oxymethylsilyl groups, and examples include alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms.

[0165] It should be noted that cycloalkyl, arylthio, arylalkyl, arylalkoxy, aryloxy, aryl, heteroaryl, and cycloalkylthio groups can be unsubstituted. Where substituents are present, preferably 1 to 8 hydrogen atoms, and particularly preferably 1 to 4 hydrogen atoms, in the group forming the ring are substituted with a substituent selected from hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, amino, substituted amino, heterocyclic group with 3 to 8 carbon atoms, cyano, nitro, and halogen atoms. Specific examples of these substituents are described later.

[0166] R 3 and R 4 It can be a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aroxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or the following formula (X3).

[0167] R 3 and R 4 Preferably, it is a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by formula (2a), or a group represented by formula (X3). If R 3 and R 4 For these groups, there is a tendency for photochromic compounds to fade faster.

[0168] R 3 and R 4 Together with M, they can form substituted or unsubstituted aliphatic rings with 3 to 20 carbon atoms, substituted or unsubstituted fused polycyclic rings with aromatic hydrocarbon rings or aromatic heterocycles fused to an aliphatic ring, substituted or unsubstituted heterocycles with 3 to 20 cyclic atoms, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to a heterocycle.

[0169] R 3 and R 4 Preferably, the ring is formed with a substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or aromatic heterocycle fused to the aliphatic ring, or a substituted or unsubstituted heterocyclic ring having 3 to 20 cyclic atoms. More preferably, it is formed together with M to form a ring selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, and spirobicyclohexane. Furthermore, the ring may have 1 to 10 alkyl groups having 1 to 5 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms as substituents, and the cycloalkyl groups having 5 to 7 carbon atoms may be fused. Specifically, the ring shown below is more preferably formed.

[0170]

[0171] R 3 and R 4 Details of the substituents that the group may have are described later. As substituents that may be present in these groups, straight-chain or branched alkyl groups having 1 or more and 6 or fewer carbon atoms are preferred.

[0172] <The group shown in formula (X3)>

[0173] L 1 -R 400 (X3)

[0174] In equation (X3),

[0175] R 400 It is a silyl group that is a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or has alkyl, alkoxy or aryl substituents.

[0176] L 1 It is the group represented by the following formula (X2).

[0177]

[0178] In equation (X2), R 30 It is a group represented by the following formula (X2a).

[0179]

[0180] In formulas (X2) and (X2a), J is a divalent group. Multiple Js can be independently directly attached, substituted or unsubstituted methylene groups, oxygen atoms, sulfur atoms, or NR groups. 301 R 301 It can be a hydrogen atom or an alkyl group. R 301 Preferably, it is an alkyl group having 1 to 20 carbon atoms. The alkyl group preferably has a silyl group, polymeric group or photochromic group having 1 to 10 carbon atoms as a substituent.

[0181] Examples of polymerizable groups include vinyl, 1-chlorovinyl, allyl, styryl, (meth)acryloyl, 2-(methacryloyloxy)ethylcarbamoyl, 2-(methacryloyloxy)ethoxycarbonyl, and crotonyl. In addition, epoxy, cyclosulfide, thiocyclobutyl, OH, SH, NH2, COOH, NCO, or NCS groups can also be listed. Preferably, the polymerizable group is selected from at least one group consisting of (meth)acryloyl, 2-(methacryloyloxy)ethylcarbamoyl, 2-(methacryloyloxy)ethoxycarbonyl, epoxy, OH, SH, NH2, and COOH groups.

[0182] A photochromic group is a group that contains a photochromic site. Examples of representative photochromic groups include naphthopyran, spirooxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene. From the perspective of exhibiting excellent photochromic properties, indene-naphthopyran is preferred, and indene[2,1-f]naphtho[1,2-b]pyran is particularly preferred.

[0183] The indo[2,1-f]naphtho[1,2-b]pyran is preferably represented by the group shown in the following formula (X4).

[0184]

[0185] In equation (X4), R 401 and R 402 It can be the same as the above R 3 and R 4 The same groups are used.

[0186] R 403 and R 404 They can be used independently as R as described above. 3 and R 4 The same groups are used.

[0187] R 405 and R 406 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 405 and R 406 It can be related to R as described later. 5 and R 6 The same groups are used.

[0188] In equation (X4), o is an integer from 0 to 4.

[0189] n is an integer from 0 to 4.

[0190] When o is 2 to 4, multiple R 403 Choose either the same or different from each other.

[0191] When n is 2 to 4, multiple R 404 Choose either the same or different from each other.

[0192] R 401 R 402 R 403 R 404 and R 405 At least one of the substituents on the aryl or heteroaryl group is associated with L 1 Bonding.

[0193] The particularly suitable group represented by formula (X2) is represented by the following formula.

[0194]

[0195] In formulas (X2) and (X2a), L represents an oxygen atom or a sulfur atom.

[0196] R 300 It is an alkylene group, or a silylene group having alkyl or aryl substituents. R 300 Preferably, it is an alkylene group having 1 to 6 carbon atoms, or a silylene group having 1 to 6 carbon atoms as a substituent.

[0197] R 302 R 303 and R 304 Each is an alkylene group, independently. R 302 Preferably, it is an alkylene group having 1 to 6 carbon atoms. 303 Preferably, it is an alkylene group having 1 to 6 carbon atoms. 304 Preferably, it is an alkylene group having 1 to 6 carbon atoms.

[0198] h, j, k, and l are each an independent integer of 0 or 1.

[0199] In equation (X2a), i is an integer from 1 to 200. When i is 2 or higher, multiple R... 30 The structures can be chosen to be the same or different. i is preferably 5 to 100, more preferably 8 to 75, and most preferably a number in the range of 10 to 70.

[0200] The dashed line indicates the relationship with R. 400 . bond.

[0201] <Group represented by formula (X)>

[0202]

[0203] In formula (X), E is an oxygen atom or NR. 101 R 101 It can be a hydrogen atom or an alkyl group. Preferably, E is NR. 101 And R 101 It is an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0204] F can be an oxygen atom or a sulfur atom. F is preferably an oxygen atom.

[0205] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. G is preferably NH.

[0206] g is 0 or 1.

[0207] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. When G is an oxygen atom or a sulfur atom, R... 201 It is a group other than a hydrogen atom. R 201 Preferably, it is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0208] The suitable group represented by formula (X) is shown below.

[0209]

[0210] (The skeleton shown in Equation (7))

[0211] A particularly suitable framework for the photochromic compound used as an embodiment is the framework shown in the following formula (7).

[0212]

[0213] In equation (7), M and Z 1 The meanings of ring A and ring A are the same as those in equation (1).

[0214] R 11 The group can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkathio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. As these groups, R can be used. 1 ~R 4 The same group is shown in the example.

[0215] R 12 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, or a substituted or unsubstituted aryloxy group. As these groups, R can be used... 1 ~R 4 The same group is shown in the example.

[0216] If the skeleton shown in equation (7) is present, then Z 1 Base and as with Z 1 R of the substituent at the substituent position adjacent to the base 11 and R 12 The stereorepulsion is small, thus enabling the skeleton shown in formula (7) to interact more effectively with the substituent Z. 1 Conjugate.

[0217] R 11 and R 12 The atom is preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted arylthio group, or a substituted or unsubstituted aryloxy group, more preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, or a substituted or unsubstituted heterocyclic group, and particularly preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, or a substituted or unsubstituted alkoxy group.

[0218] R 11 and R 12 Details regarding the substituents that the group may have are described later. 11 and R 12 The groups are preferably unsubstituted.

[0219] <Compounds shown in formula (4)>

[0220] The photochromic compound used in the embodiments is preferably a compound represented by the following formula (4).

[0221]

[0222] In equation (4), R 3 R 4 Z 1 M and M have the same meaning as in equation (3).

[0223] <R 5 and R 6 >

[0224] In equation (4), R 5 and R 6 Each group is independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. These groups can be used with R 1 The same group is shown in the example.

[0225] R 5 and R 6 Each and every one of the following is preferably independently substituted or unsubstituted: phenyl, substituted or unsubstituted 1-naphthyl, substituted or unsubstituted 2-naphthyl, substituted or unsubstituted thiophene, substituted or unsubstituted furanyl, substituted or unsubstituted pyrrolinyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzofuranyl, or substituted or unsubstituted benzopyrrolinyl. Furthermore, R is preferred. 5 and R 6 At least one of them is a substituted or unsubstituted phenyl, more preferably R 5 and R 6 All are substituted phenyl groups.

[0226] The substituents of the phenyl group are preferably groups represented by formula (2a), hydroxyl, alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, alkoxy, amino, substituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, substituted or unsubstituted arylalkyl, substituted or unsubstituted arylalkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or groups represented by formula (X3). As a substituent, it is more preferably an alkyl, haloalkyl, alkoxy, amino, substituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, alkoxyalkylthio, haloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or a group represented by formula (X3).

[0227] <R 7 and R 8 >

[0228] R 7 and R 8 Each of these groups can be independently hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, a group represented by formula (2a), a group represented by formula (X) below, or a group represented by formula (X3). As these groups, R can be used... 1 ~R 4 The same group is shown in the example.

[0229] In equation (4), b is an integer from 0 to 3.

[0230] c is an integer from 0 to 4.

[0231] When b is 2 to 3, multiple R 7 Choose either the same or different. In R where b is 2-3 and there are adjacent pairs... 7 In the case of two adjacent R 7 Choose to bond together with R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. As adjacent R 7 The combination represents the 5th and 6th positions of this chromene compound.

[0232] When c is 2 to 4, multiple R 8 Choose either the same or different. In R where c is 2–4 and there are adjacent pairs... 8 In the case of two adjacent R 8 Choose to bond together with R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. As adjacent R 8 The combination is the 9th and 10th positions, or the 10th and 11th positions, or the 11th and 12th positions of the chromene compound.

[0233] Includes R 7 Or R 8 The bonded carbon atoms can form a ring with 5 to 8 atoms. Furthermore, this ring can also have substituents, such as those selected from hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen atoms. Specific examples of these substituents will be described later.

[0234] As a suitable ring, the ring shown in the following formula (X5) can be cited.

[0235]

[0236] In formula (X5), Q and T are independently sulfur atoms, substituted or unsubstituted methylene groups, oxygen atoms, or NR atoms, respectively. 307 The group shown. R 307 It is a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, or a group represented by formula (2a).

[0237] R 305 and R 306 Each of the following is preferably hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, substituted or unsubstituted heterocyclic, cyano, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, halogen atom, substituted or unsubstituted aralkyl, substituted or unsubstituted aralkoxy, substituted or unsubstituted aryl, thiol, alkathio, alkoxyalkathio, haloalkathio, cycloalkylthio, or substituted or unsubstituted arthio.

[0238] Additionally, R 305 and R 306 The carbon atoms bonded to them can be optionally combined to form substituted or unsubstituted aliphatic rings. Examples of specific aliphatic rings include cyclopentane rings and cyclohexane rings. Furthermore, in this aliphatic ring, 1 to 8 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms, can be substituted with at least one group selected from hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, heterocyclic, cyano, nitro, and halogen atoms. Specific examples of these substituents are described later.

[0239] In the formula, m1 is an integer from 1 to 4.

[0240] <The photochromic compound shown in formula (5)>

[0241] As particularly suitable chromene compounds, compounds represented by the following formula (5) can be listed.

[0242]

[0243] In equation (5),

[0244] R 3 R 4 R 7 R 8 Z 1 b and c have the same meaning as in equation (4) independently.

[0245] <R 9 and R 10 >

[0246] R 9 and R 10 Each of the following is independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3).

[0247] d represents R 9 The number of elements is an integer from 0 to 5. When d is greater than 2, R... 9 These can be any groups that are the same or different from each other.

[0248] In R where d is 2 to 5 and there are adjacent pairs 9 In the case of two adjacent R 9 Choose to bond together with R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings.

[0249] e represents R 10 The number of elements is an integer from 0 to 5. When e is greater than 2, R... 10 These can be any groups that are the same or different from each other.

[0250] In R where e is 2 to 5 and there are adjacent values 10 In the case of two adjacent R 10 Choose to bond together with R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings.

[0251] R 9 and R 10 Two independent, adjacent cyclic groups can be combined to form a cyclic group optionally containing at least one atom selected from the group consisting of oxygen, sulfur, carbon, and nitrogen atoms. The cyclic group is not particularly limited, but preferably contains R. 9 and R 10 The bonded carbon atoms form a ring with 5 to 8 atoms. This ring may also have substituents. Examples of such substituents include hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen groups. Specific examples of these substituents are groups identical to those described above. Preferably, the ring is formed together with the ring shown in formula (X5).

[0252] <Detailed explanation of substituents, etc.>

[0253] As in the above R 1 ~R 10 Substituents that may be present on the group include hydroxyl, cyano, halogen atom, nitro, formyl, hydroxycarbonyl, thiol, group shown in formula (2a), group shown in formula (X), group shown in formula (X3), alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, heterocyclic, halogen atom, alkylthio, arylthio, alkylcarbonyl, alkoxycarbonyl, arylalkyl, arylalkoxy, aryl, heteroaryl, alkoxyalkylthio, haloalkylthio, cycloalkylthio, silyl, or oxysilyl. As these groups, R can be used... 1 ~R 4 The same group as the group detailed in the text.

[0254] <Specific examples of suitable photochromic compounds>

[0255] If a particularly suitable photochromic compound is to be specifically exemplified, the photochromic compound shown in the following formula can be cited.

[0256]

[0257] [Naphthol derivatives]

[0258] The naphthol derivative of the embodiment has the skeleton shown in formula (6) below. This naphthol derivative can be used as an intermediate for synthesizing photochromic compounds having the skeletons shown in formula (1) and formula (2) above.

[0259]

[0260] In equation (6), M and Z 1 The meanings of ring A and ring A are independently the same as those in equation (1) above.

[0261] <Naphthol derivatives shown in formula (6a)>

[0262] The naphthol derivative shown in formula (6a) can be used as an intermediate for synthesizing the photochromic compounds shown in formula (3), formula (4) and formula (5) above.

[0263]

[0264] In equation (6a), M and Z 1 Each of these has the same meaning as in equation (1) above, independently. 3 and R 4 Each has the same meaning as in equation (3) above, independently.

[0265] R 3 R 4 c and d have the same meaning as in equation (4) above.

[0266] <Specific examples of naphthol derivatives>

[0267] Specific examples of naphthol derivatives used in implementation methods include compounds represented by the following formulas.

[0268]

[0269] <Compounds having the skeleton shown in formula (1A)>

[0270] According to an embodiment, a photochromic compound having a skeleton as shown in the following formula (1A) is provided.

[0271]

[0272] In equation (1A), M, ring A and ring B have the same meaning as in equation (1).

[0273] <Y 111 >

[0274] Y 111 The substituted or unsubstituted methylene group. 111 Preferably, it is an unsubstituted methylene group.

[0275] <Y 112 >

[0276] Y 112 For substituted or unsubstituted methylene, oxygen atom, sulfur atom, NR 600 Or SO2. R 600 It has the same meaning as described in equation (1b).

[0277] Y 112 Preferably, it is an unsubstituted methylene group or a methylene group having an alkyl group among its substituents.

[0278] <R 111 and R 112 >

[0279] R 111 and R 112 Each of these groups is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, a substituted or unsubstituted aryloxy group, a thiol group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (2a) above. As these groups, R can be used. 1 ~R 8 The same group is shown in the example.

[0280] By using these groups as R 111 and R 112 Photochromic compounds tend to exhibit increased temperature dependence, fading rate, and durability.

[0281] R 111 and R 112 Details regarding the substituents that the group may have are described later. As R 111 and R 112 The substituents that the group may have are preferably selected from at least one of the following groups: straight-chain or branched alkyl groups having 1 or more and 6 or less carbon atoms; straight-chain or branched haloalkyl groups having 1 or more and 6 or less carbon atoms; straight-chain or branched alkoxy groups having 1 or more and 6 or less carbon atoms; and halogen atoms. The number of substituents is, for example, 1 or more and 3 or less.

[0282] R 111 and R 112 Each of the following is preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a substituted or unsubstituted haloalkoxy group, or a group represented by formula (2a) below.

[0283] R 111 More preferably, it is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, and even more preferably, it is a methyl or methoxy group. 12 More preferably, it is a hydrogen atom.

[0284] <Compounds having the skeleton shown in formula (2A)>

[0285] The photochromic compound of the embodiment preferably has a naphthopyran skeleton as shown in formula (2A). In formula (2A), rings B, M, and R... 111 R 112 Y 111 and Y 112 They have the same meaning as in equation (1A).

[0286]

[0287] <Compounds having the skeleton shown in formula (3A)>

[0288] The photochromic compound used in the embodiments is preferably a compound having the framework shown in the following formula (3A). In the following formula (3A), Y 111 Y 112 R 111 R 112 M and R have the same meaning as in equation (1A). 3 and R 4 They are independent of each other and have the same meaning as in equation (3).

[0289]

[0290] <Y 114 >

[0291] Y 4 It is a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (2a).

[0292] As a substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted alkylthio, substituted or unsubstituted heterocyclic, substituted or unsubstituted arylthio, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted haloalkylthio, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or a group represented by formula (2a) below, it can be used with R 111 Or R 112 The same group is shown in the example.

[0293] Y 114 Preferably, it is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a haloalkyl group, or a halogen atom; more preferably, it is a straight-chain alkyl group with 1 or more and 3 or less carbon atoms, a straight-chain alkoxy group with 1 or more and 3 or less carbon atoms, a perfluoroalkyl group with 1 or more and 3 or less carbon atoms, or a fluorine atom.

[0294] p is an integer from 0 to 4. p can be 0 or 1 to 3.

[0295] <Compound shown in formula (4A)>

[0296] The photochromic compound used in the embodiments is preferably a compound represented by the following formula (4A). In formula (4A), Y 111 Y 112 Y 114 R 3 R 4 R 111 R 112 M and p have the same meaning as in equation (3A). 5 R 6 R 8 c has the same meaning as in equation (4).

[0297]

[0298] R 113 The following groups are represented as hydrogen atoms, hydroxyl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted haloalkyl groups, substituted or unsubstituted haloalkoxy groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted amino groups, substituted or unsubstituted heterocyclic groups, cyano groups, halogen atoms, substituted or unsubstituted alkylthio groups, substituted or unsubstituted arylthio groups, nitro groups, formyl groups, hydroxycarbonyl groups, substituted or unsubstituted alkylcarbonyl groups, substituted or unsubstituted alkoxycarbonyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, thiols, substituted or unsubstituted alkoxyalkylthio groups, substituted or unsubstituted haloalkylthio groups, substituted or unsubstituted cycloalkylthio groups, substituted or unsubstituted silyl groups, substituted or unsubstituted oxysilyl groups, groups represented by formula (2a), groups represented by formula (X), or groups represented by formula (X3). 113 Hydrogen atoms are preferred.

[0299] R 111 and R 113 Together with bonded carbon atoms, they can form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0300] <The photochromic compound shown in formula (5A)>

[0301] Compounds represented by formula (5A) are particularly suitable chromene compounds. In formula (5A), Y 111 Y 112 Y 114 R 3 R 4 R 8 R 111 R 112 R 113 c and p have the same meaning independently as in equation (4A). 9 R 10 , d and e have the same meaning as in equation (5) independently.

[0302]

[0303] <Detailed explanation of substituents, etc.>

[0304] As in the above R 111 ~R 113 Y 111 ~Y 114 Substituents that may be present on the group include hydroxyl, cyano, halogen atom, nitro, formyl, hydroxycarbonyl, thiol, group shown in formula (2a), group shown in formula (X), group shown in formula (X3), alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, heterocyclic, halogen atom, alkylthio, arylthio, alkylcarbonyl, alkoxycarbonyl, aralkyl, arylalkoxy, aryl, aryl, heteroaryl, alkoxyalkylthio, haloalkylthio, cycloalkylthio, silyl, or oxysilyl. The same groups as those detailed in R3 to R12 can be used as these groups.

[0305] <Specific examples of suitable photochromic compounds>

[0306] If a particularly suitable photochromic compound is to be specifically exemplified, the photochromic compound shown in the following formula can be cited.

[0307]

[0308] [Naphthol derivatives]

[0309] The naphthol derivative of the embodiment has the skeleton shown in formula (6A). This naphthol derivative can be used as an intermediate for synthesizing photochromic compounds having the skeletons shown in formula (1A) and formula (2A) above. In formula (6A), ring A, ring B, and ring Y... 111 Y 112 R 111 R 112 M and M have the same meaning as in equation (1A) above, respectively.

[0310]

[0311] <Naphthol derivatives represented by formula (6Aa)>

[0312] The naphthol derivative shown in formula (6Aa) can be used as an intermediate in the synthesis of photochromic compounds shown in formulas (3A), (4A), and (5A) above. In formula (6Aa), Y... 111 Y 112 Y 114 R 3 R 4 R 111 R 112 R 113 c and p have the same meaning as in equations (3A), (4A) or (5A) above, respectively.

[0313]

[0314] <Specific examples of naphthol derivatives>

[0315] Specific examples of naphthol derivatives used in implementation methods include compounds represented by the following formulas.

[0316]

[0317] [Methods for manufacturing photochromic compounds]

[0318] The photochromic compounds of the embodiments can be manufactured by any synthetic method. Representative examples of methods for manufacturing photochromic compounds are described, but the method is not limited to these. It should be noted that, in the following description, unless otherwise specified, the symbols in the formulas have the meanings explained in the above formulas.

[0319] The photochromic compound can be prepared by reacting the naphthol derivative shown in formula (6a) or formula (6Aa) above with the propargyl alcohol compound shown in formula (7) below in the presence of an acid catalyst.

[0320]

[0321] The reaction ratio of the naphthol compound to the propargyl alcohol compound is preferably selected from the range of 1:10 to 10:1 (molar ratio). As an acid catalyst, for example, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina, etc., can be used. The acid catalyst is preferably used in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the total amount of naphthol compound and propargyl alcohol compound. The reaction temperature is preferably 0 to 200°C. As a solvent, aprotic organic solvents are preferably used, such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene, etc. The purification method for the product obtained by this reaction is not particularly limited. For example, silica gel column purification can be performed, followed by purification by recrystallization.

[0322] <Synthetic methods of naphthol derivatives>

[0323] Naphthol derivatives can be synthesized, for example, based on the reaction methods described in papers such as Non-Patent Literature 1, Non-Patent Literature 2, and Patent Literature 3.

[0324] The method of synthesizing the naphthol compound shown in formula (6a) is not particularly limited. For example, when M is a carbon atom, it can be synthesized as follows.

[0325] First, by reacting the benzene compound shown in formula (8) with the acyl chloride compound shown in formula (9), the benzophenone compound shown in formula (10) is obtained. It should be noted that in formula (10), Z... 1 R 7 R 8 b and c have the same meaning as in equation (4).

[0326]

[0327] It should be noted that, depending on the desired structure and substituents of the photochromic compound to be synthesized, the substituents of the acyl chloride compound and the benzene compound can be interchanged. That is, it is possible to synthesize a compound with Z... 1 R 7 Acyl chloride compounds with R 8 The reaction of benzene compounds.

[0328] Furthermore, benzophenone compound (10) is subjected to the Stobbe reaction, cyclization reaction, hydrolysis reaction using a base or acid, benzyl protection, or debenzylation based on hydrolysis reaction using a base or acid to obtain a carboxylic acid with a hydroxyl group protected by a benzyl (Bn) as shown in formula (11). Next, the benzyl-protected carboxylic acid shown in formula (11) is converted into an amine by methods such as the Curtius rearrangement, Hofmann rearrangement, and Lossen rearrangement, thereby preparing a diazonium salt. The diazonium salt is converted into a halide such as a bromide or iodide by the Sandmeyer reaction, etc., to obtain a halide shown in formula (12) (where Hal represents a halogen).

[0329]

[0330] The obtained halide is reacted with magnesium, lithium, etc., to prepare an organometallic reagent. This organometallic reagent is then reacted with the following formula (13) (where R... 3 and R 4 The ketone (with the same meaning as in formula (4)) is reacted in an organic solvent at -100 to 70 °C to give the compound shown in formula (14). After debenzylation of the obtained compound (14), it is reacted under neutral to acidic conditions at 10 to 120 °C for 10 minutes to 2 hours to spirocyclize the alcohol, thereby synthesizing the naphthol derivative of formula (6a) as the target.

[0331]

[0332]

[0333] In this reaction, the reaction ratio of the organometallic reagent to the ketone shown in formula (13) can be used in a wide range, preferably from 1:10 to 10:1 (molar ratio). The reaction temperature is preferably -100 to 70°C. As a solvent, aprotic organic solvents such as diethyl ether, tetrahydrofuran, benzene, and toluene are preferred. Spirocyclization of the alcohol under neutral to acidic conditions is preferably carried out in the presence of an acid catalyst. As an acid catalyst, acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, and acidic alumina are used, for example. Such an acid catalyst is suitable to be used in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the alcohol. Spirocyclization is preferably carried out in the presence of solvents such as tetrahydrofuran, benzene, and toluene.

[0334] The above method demonstrates the use of a substituent Z. 1 This is one example of a method using raw materials, but it is also possible, for example, to use Z after synthesizing a precursor having halogen atoms. 1 Amines with -H structures and the Buchwald reaction using Pd catalysts, etc., introduce substituents Z. 1 .

[0335] Importing substituent Z 1 The reaction is not particularly limited; for example, it can be introduced after the synthesis of a photochromic compound having halogen atoms. An example is shown below.

[0336] First, replace the substituent Z with a halogen atom. 1 The compound is reacted in the same way as in the example above, using a halogen atom instead of Z. 1 The benzophenone compound is obtained by spirocyclization of the carboxylic acid compound shown in formula (15) under neutral to acidic conditions through the Stobbe reaction, cyclization reaction, hydrolysis reaction using base or acid, or reduction reaction using hydrogen or hydrazine, thereby obtaining the naphthol derivative shown in formula (16).

[0337]

[0338] As an alternative to the above methods, the compound of formula (16) can also be synthesized by intramolecular cyclization of the halogen compound of formula (15) in the presence of a palladium catalyst.

[0339] Using the obtained naphthol derivative, a photochromic compound of the following formula (17) was obtained.

[0340]

[0341] The obtained photochromic compound was reacted with R under alkaline conditions. 3 The halide reaction yields the photochromic compound precursor of the following formula (18).

[0342]

[0343] By reacting the halogen atoms of the obtained precursor with Z 1 The photochromic compound of this invention can be obtained by performing the Buchwald reaction using a Pd catalyst on an amine with a -H structure.

[0344] It should be noted that the naphthol compound shown in formula (6Aa) can be obtained by the following method. First, by reacting the benzene compound shown in formula (8A) with the acyl chloride compound shown in formula (9), the benzophenone compound shown in formula (10A) is obtained. In addition to using the benzophenone compound, the naphthol compound shown in formula (6Aa) is obtained by the same method as that used to produce the naphthol compound shown in formula (6).

[0345]

[0346]

[0347] It should be noted that, depending on the structure and substituents of the desired photochromic compound, the substituents of the acyl chloride compound and the benzene compound can be interchanged. That is, compounds with R... 111 ~R 113 Acyl chloride compounds with R 8 The reaction of benzene compounds.

[0348] <Synthetic methods for naphthol derivatives containing Si and Ge>

[0349] The following describes an example of a method for manufacturing a naphthol derivative in formula (6) where M is Si or Ge.

[0350] First, the halide shown in formula (12) is reacted with magnesium, lithium, etc., to prepare an organometallic reagent. This organometallic reagent is then reacted with the following formula (19) (where R... 3 and R 4 The monohalides (with the same meaning as in formula (4)) are reacted in an organic solvent at -100 to 70°C to give the compound shown in formula (20) below.

[0351]

[0352]

[0353] The obtained compound (20) was subjected to a reaction method described in Non-Patent Literature 3, Non-Patent Literature 4, Patent Literature 4, etc., to obtain the cyclized body shown in the following formula (21).

[0354]

[0355] By debenzylated the obtained cyclized form, the naphthol derivative of formula (6a) can be obtained. It should be noted that, except for changing Z... 1 In addition, the naphthol derivative shown in formula (6Aa) can be obtained by the same method.

[0356] Identification of Photochromic Compounds

[0357] The photochromic compound in the embodiments is, for example, a solid or a viscous liquid at room temperature and pressure. In this solid or liquid state, the photochromic compound can be separated by separation operations such as thin-layer chromatography, silica gel column chromatography, high-performance liquid chromatography, and gas chromatography. Furthermore, it has been confirmed that no byproducts such as starting materials or coloring components exist other than the photochromic compound.

[0358] By using proton nuclear magnetic resonance spectroscopy ( 1 Photochromic compounds, as determined by ¹H-NMR, exhibit peaks based on aromatic and alkene protons in the δ range of 5.0–9.0 ppm, and peaks based on alkyl and alkylene protons in the δ range of 1.0–4.0 ppm. Furthermore, by comparing the relative spectral intensities, the number of protons in each bonding group can be determined. This allows for the identification of the skeleton and substituents of the photochromic compound.

[0359] In addition, when the photochromic compound is contained in a cured product such as a resin, the photochromic compound can be separated by dissolving the resin and using the separation method described above.

[0360] <Photochromic Composition>

[0361] The photochromic compound of the embodiment can be dissolved in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the photochromic compound having the skeleton shown in formula (1) is dissolved in such a solvent, a colorless and transparent solution is obtained. It exhibits a good photochromic effect, rapidly developing color when exposed to sunlight or ultraviolet light, and reversibly and rapidly returning to its original colorless state when sunlight is blocked.

[0362] Furthermore, the photochromic compounds in the embodiments can be used in combination with photochromic compounds having other structures, depending on the intended use. For example, to obtain various hues required for photochromic lenses, they can also be used in combination with other photochromic compounds. Known compounds can be used without any limitations when combining them. Examples include indene-naphthopyran, naphthopyran, spiroxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene. Among these, indene-naphthopyran compounds are particularly preferred from the viewpoints of uniformly maintaining the hue during color development and fading, suppressing color deviation during color development that accompanies the deterioration of photochromic properties, and thus reducing initial coloration. In particular, to balance high color development concentration and rapid fading rate at high temperatures, as well as excellent durability, it is preferable to use multiple photochromic compounds to adjust the hue.

[0363] When preparing a photochromic composition containing the photochromic compound of the embodiment and other photochromic compounds, the mixing ratio of each photochromic compound can be appropriately determined according to the desired hue.

[0364] <Photochromic Curable Composition>

[0365] The curable composition of the embodiments comprises the photochromic compound of the embodiments, and comprises at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerization reactive group, and a (thio)carbamate (urea) polymer. Here, the (thio)carbamate (urea) polymer comprises at least one selected from the group consisting of carbamate polymers, thiocarbamate polymers, carbamate urea polymers, and thiocarbamate urea polymers.

[0366] The photochromic compound and photochromic composition of the embodiments are preferably combined with polymeric compounds and used in the form of a photochromic curable composition.

[0367] The photochromic curable composition depends on the color rendering intensity of the photochromic compound, the selected lens material, and the lens thickness; therefore, it cannot be generalized. It is preferable to use the photochromic compound (or photochromic composition) in an amount of 0.001 to 10 parts by weight relative to 100 parts by weight of the polymeric compound. The optimal mixing amount varies depending on the intended application. For example, the following describes the case where the photochromic curable composition is used as a thin film optical article and as a thick film optical article.

[0368] (Used as a thin-film optical article)

[0369] For example, when the photochromic curable composition is made into a thin film (a polymer film polymerized from the photochromic curable composition) with a thickness of 10 μm or more and less than 1000 μm, for example, about 100 μm, the hue can be adjusted by using 0.001 to 10 parts by mass of the photochromic compound (or photochromic composition) relative to 100 parts by mass of other polymeric monomers.

[0370] (Use as a thick-film optical material)

[0371] In the case of a thick cured material (a polymer molded body formed by polymerizing the photochromic curing composition), for example, a cured material with a thickness of 1 mm or more, the hue can be adjusted by 0.001 to 1 part by mass of the photochromic compound (or photochromic composition) of the present invention relative to 100 parts by mass of the thick cured material or other polymeric monomers that provide the thick cured material.

[0372] <Polymerizing compounds>

[0373] As described above, the photochromic compound is preferably used in combination with a polymerizable compound to form a photochromic curable composition. Examples of polymerizable compounds include urethane or urea-based polymeric compounds capable of forming urethane bonds, urea bonds, etc.; compounds having polymerizable reactive groups; free radical polymeric compounds; and epoxy polymeric compounds. These polymeric compounds are not particularly limited; for example, the polymeric compound described in Patent Document 5 may be suitably used.

[0374] Among them, the following polymeric compounds are particularly suitable for use.

[0375] <Compounds with polymerizable reactive groups>

[0376] Compounds having polymerization-reactive groups include those having isocyanate groups. Isocyanate compounds are compounds having either isocyanate or isothiocyanate groups, and may contain both. This compound is preferably used in combination with compounds containing active hydrogen, as described later. However, this is not a limitation, and the following compounds are examples of such isocyanate compounds.

[0377] (polyisocyanate)

[0378] Polyisocyanates are compounds having at least two isocyanate groups in a single molecule. Examples of polyisocyanates include aromatic polyisocyanates with aromatic rings such as m-xylene diisocyanate and 4,4'-diphenylmethane diisocyanate, as well as aliphatic polyisocyanates such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate.

[0379] (Compounds containing active hydrogen)

[0380] The compound having active hydrogen is not limited to this; compounds having hydroxyl and / or thiol groups are preferred, and polyfunctional compounds having two or more active hydrogens in one molecule are particularly preferred. Specific examples of compounds having active hydrogen include polyfunctional thiols such as pentaerythritol tetra(3-mercaptopropionate), 4-mercaptomethyl-3,6-dithiooctanedithiol; and polyfunctional alcohols such as trimethylolpropane and pentaerythritol.

[0381] (Free radical polymeric compounds)

[0382] Radical polymerizable compounds include polyfunctional and monofunctional radical polymerizable compounds. They can be used individually or in combination. Examples of radical polymerizable substituents include groups with unsaturated double bonds, namely vinyl groups (including styryl, (meth)acryloyl, allyl, etc.).

[0383] Polyfunctional radical polymerizable compounds are compounds having two or more radical polymerizable substituents within their molecules. These polyfunctional radical polymerizable compounds include first polyfunctional radical polymerizable compounds with 2 to 10 radical polymerizable substituents and second polyfunctional radical polymerizable compounds with more than 10 radical polymerizable substituents.

[0384] There are no particular limitations on the first type of polyfunctional radical polymerizable compound, but the number of radical polymerizable substituents is more preferably 2 to 6. Specific examples are described below.

[0385] (Polyfunctional (meth)acrylate compounds)

[0386] Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol diglycidyl(meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane.

[0387] (Multifunctional allyl compounds)

[0388] Diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chloramphenicol, diallyl hexahydrophthalate, diallyl carbonate, allyl diethylene glycol carbonate, and trimethylolpropane triallyl carbonate.

[0389] (Polyfunctional thio(meth)acrylate compounds)

[0390] 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl) ether, 1,4-bis(methacryloylthiomethyl)benzene.

[0391] (Vinyl compounds)

[0392] Divinylbenzene.

[0393] Examples of highly functional free radical polymerizable compounds with more than 10 free radical polymerizable substituents include silsesquioxane compounds and polyrotaxane compounds with relatively large molecular weights.

[0394] In addition, a monofunctional free radical polymerizable compound is a compound having one free radical polymerizable substituent in the molecule. However, it is not limited to this specific example, and the following compounds can be cited as examples.

[0395] (Unsaturated carboxylic acids)

[0396] Acrylic acid, methacrylic acid, maleic anhydride.

[0397] ((meth)acrylate)

[0398] Methyl methacrylate, benzyl methacrylate, phenyl methacrylate.

[0399] 2-Hydroxyethyl methacrylate, glycidyl methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyl etheroxymethacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 3-(glycidyl etheroxy-1-isopropyloxy)-2-hydroxypropyl acrylate, 3-glycidyl etheroxy-2-hydroxypropyloxy)-2-hydroxypropyl acrylate.

[0400] (Fumarate)

[0401] Diethyl fumarate, diphenyl fumarate.

[0402] (Thio(meth)acrylic acid)

[0403] Methyl thioacrylate, benzyl thioacrylate, benzyl thiomethacrylate.

[0404] (Vinyl compounds)

[0405] Styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene.

[0406] The free radical polymerizable compound can be used alone or in mixtures of several compounds. In this case, relative to a total of 100 parts by mass of the free radical polymerizable compound, it is preferable to set 80-100 parts by mass of the multifunctional free radical polymerizable compound and 0-20 parts by mass of the monofunctional free radical polymerizable compound; more preferably, it is preferable to set 90-100 parts by mass of the multifunctional free radical polymerizable compound and 0-10 parts by mass of the monofunctional free radical polymerizable compound. Furthermore, relative to a total of 100 parts by mass of the free radical polymerizable compound, it is preferable to set 80-100 parts by mass of the first multifunctional free radical polymerizable compound, 0-20 parts by mass of the second multifunctional free radical polymerizable compound, and 0-20 parts by mass of the monofunctional free radical polymerizable compound; even more preferably, it is preferable to set 85-100 parts by mass of the first multifunctional free radical polymerizable compound, 0-10 parts by mass of the second multifunctional free radical polymerizable compound, and 0-10 parts by mass of the monofunctional free radical polymerizable compound.

[0407] (Various compounding agents)

[0408] In curable compositions, various known compounding agents can be formulated without impairing the effect. These compounding agents include, for example, release agents, UV absorbers, infrared absorbers, UV stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and various other stabilizers. Additionally, solvents and leveling agents can also be formulated. Thiols such as tert-dodecyl mercaptan can be formulated as polymerization modifiers.

[0409] Among the aforementioned compounding agents, ultraviolet (UV) stabilizers are suitable from the perspective of improving the durability of photochromic sites. Known UV stabilizers include hindered amine light stabilizers, hindered phenolic antioxidants, and sulfur-based antioxidants. Particularly suitable UV stabilizers are described below.

[0410] Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87 manufactured by ADEKA CORPORATION, 2,6-di-tert-butyl-4-methylphenol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] manufactured by BASF Japan Ltd., IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565 manufactured by BASF Japan Ltd. There are no particular restrictions on the amount of such UV stabilizer used, as long as it does not impair the effect. It is usually in the range of 0.001 to 10 parts by weight, especially 0.01 to 1 part by weight, relative to 100 parts by weight of the photochromic curing composition.

[0411] In addition to UV stabilizers, UV absorbers can also be used. Known UV absorbers such as benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, and benzoate compounds can be used as UV absorbers, with cyanoacrylate compounds and benzophenone compounds being particularly preferred. The UV stabilizer is preferably used in the range of 0.001 to 5 parts by weight relative to 100 parts by weight of the photochromic curable composition containing the photochromic compound and the polymerizable compound.

[0412] <Instructions for use of photochromic curable compositions; optical articles>

[0413] Photochromic cured materials are obtained by curing photochromic curable compositions. The polymerization and curing of photochromic cured materials are carried out through free radical polymerization, ring-opening polymerization, anionic polymerization, or polycondensation using active energy rays such as ultraviolet light, alpha rays, beta rays, and gamma rays, heat, or a combination of both. In other words, appropriate polymerization methods are employed depending on the type of polymerizable compound, the type of polymerization accelerator, and the morphology of the resulting photochromic cured material.

[0414] When a curable composition containing polymerizable compounds is thermally polymerized, the temperature affects the properties of the resulting photochromic cured product.

[0415] The temperature conditions are affected by the type and amount of the thermal polymerization initiator and the type of polymerizable compound, so they cannot be generalized. Generally, it is suitable to start polymerization at a relatively low temperature and then slowly increase the temperature. The polymerization time, like the temperature, varies for various reasons, so it is preferable to predetermine the optimal time corresponding to these conditions, but it is generally preferred to select conditions in a way that completes polymerization in 2 to 48 hours. In the case of obtaining photochromic laminates, polymerization is preferably carried out at the temperature at which the polymerizable functional groups react with each other; in this case, the optimal temperature and time are determined in a manner that achieves the target molecular weight.

[0416] Furthermore, during photopolymerization of the curable composition, the polymerization conditions, particularly the UV intensity, affect the properties of the resulting photochromic cured product. These irradiation conditions vary depending on the type and amount of the photopolymerization initiator and the type of polymerizable monomer, and therefore cannot be generalized. Generally, irradiation at a wavelength of 365 nm for 0.5 to 5 minutes at a rate of 50 to 500 mW / cm² is preferred. 2 The selection criteria for UV light mode.

[0417] [Optical Items]

[0418] The photochromic compounds described in this embodiment can be widely used as photochromic materials. For example, they can be used as various storage materials, photocopying materials, photoreceptors for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holography, and other storage materials, replacing silver halide photosensitive materials. Photochromic materials can also be used as photochromic lens materials, optical filter materials, display materials, light meters, decorative materials, fabrics, threads, and other materials.

[0419] The photochromic compound described in this embodiment is particularly suitable for use in photochromic lenses. Photochromic lenses are suitable for use as lenses in eyeglasses such as sunglasses. Known methods can be used to manufacture photochromic lenses as long as they achieve uniform light-adjusting performance.

[0420] When photochromic properties are manifested by a mixing method, the above-mentioned curing composition is injected into a glass mold held by an elastomer gasket or spacer. Depending on the type of polymerizable compound and polymerization curing accelerator, a photochromic cured product can be obtained by casting polymerization under heating in an air furnace and irradiation with active energy rays such as ultraviolet light, and can be shaped into an optical material such as a lens.

[0421] In the case of developing photochromic properties through a lamination method, a coating liquid is prepared by appropriately dissolving a curable composition in an organic solvent. The coating liquid is then applied to the surface of an optical substrate such as a lens substrate by spin coating or dipping. The organic solvent is removed by drying. Subsequently, polymerization and curing are carried out by UV irradiation in an inactive gas such as nitrogen or heating, thereby forming a photochromic layer (coating method) formed by the photochromic cured product on the surface of the optical substrate.

[0422] Alternatively, by placing an optical substrate, such as a lens substrate, face-to-face with a glass mold in a manner that forms a predetermined gap, and injecting a curable composition into the gap, a photochromic layer formed by the photochromic cured material can be formed on the surface of the optical substrate (casting polymerization method) by casting polymerization based on an inner mold that is polymerized and cured by UV irradiation, heating, etc.

[0423] When a photochromic layer is formed on the surface of an optical substrate using the lamination method (coating method and casting polymerization method) as described above, the adhesion between the photochromic layer and the optical substrate can be improved by performing pre-treatment on the surface of the optical substrate using chemical treatment based on alkaline solutions, acidic solutions, corona discharge, plasma discharge, or physical treatment based on grinding. Alternatively, a transparent adhesive resin layer can be pre-formed on the surface of the optical substrate.

[0424] Furthermore, in the case of exhibiting photochromic properties through an adhesive method, a photochromic sheet is produced by sheet forming of a curable composition, and then sandwiched between two transparent sheets (optical sheets) and subjected to the aforementioned polymerization and curing, thereby obtaining a photochromic laminate with a photochromic layer as the adhesive layer.

[0425] In this case, a coating method using a coating liquid prepared by dissolving the curable composition in an organic solvent can also be used in the fabrication of the photochromic film. Alternatively, an adhesive layer can be provided between the photochromic film and the optical film.

[0426] The photochromic laminate produced in this way is installed in a mold, and then an optical substrate such as a lens is injection molded with a thermoplastic resin (e.g., polycarbonate), thereby obtaining an optical substrate such as a lens with a specified shape that is endowed with photochromic properties.

[0427] In addition, the photochromic laminate can also be bonded to the surface of an optical substrate using an adhesive or similar agent, thereby obtaining a photochromic lens.

[0428] It should be noted that, in the case of manufacturing photochromic laminates as described above, especially in terms of high adhesion to optical substrates, urethane or urea-based polymeric compounds, particularly urethane-based polymeric compounds, are preferably used as polymeric compounds to form polyurethane.

[0429] The above-mentioned curable composition exhibits excellent photochromic properties with high color development concentration at high temperatures.

[0430] In addition, the photochromic layer and photochromic cured product formed by the curable composition can be dyed with dyes such as disperse dyes, made with silane coupling agents, hard coatings with hard coating agents mainly composed of sols such as silicon, zirconium, antimony, aluminum, tin, and tungsten, formed by vapor deposition of thin films based on metal oxides such as SiO2, TiO2, and ZrO2, and post-processing such as anti-reflective treatment and antistatic treatment using thin films coated with organic polymers.

[0431] Example

[0432] The invention will be described in more detail through the following examples. These examples are for illustrative purposes only, and the spirit and scope of the invention are not limited to these examples.

[0433] (Example 1)

[0434] First process

[0435] Referring to the method described in Patent Document 6, 28.9 g (62.4 mmol) of the compound of formula (22) synthesized from 3-bromo-4-methoxybenzophenone, 550 mL of toluene, 9.36 g (87.4 mmol) of N-methylaniline, and 24.0 g (249.6 mmol) of sodium tert-butoxide were added, and the mixture was stirred under reduced pressure to remove dissolved oxygen. Then, 30.57 g (0.6 mmol) of Pd2(dba) and 1.19 g (2.5 mmol) of X-phos were added to the reaction solution, and the mixture was heated to 80 degrees Celsius.

[0436]

[0437] Continue heating until the raw material disappears. After the reaction is complete, cool to room temperature and filter. Add 500 mL of tetrahydrofuran and 10% hydrochloric acid to the filtrate, neutralize, and separate. Concentrate the obtained organic layer and then purify it by re-slurrying with 100 mL of methanol to obtain the carboxylic acid compound shown in formula (23) in 90% yield.

[0438]

[0439] Second process

[0440] In addition to using the carboxylic acid compound obtained in the first step, the iodine compound shown in the following formula (24) was obtained in a yield of 82% by referring to the method of Patent Document 6.

[0441]

[0442] Third process

[0443] 26.3 g (46.1 mmol) of the compound of formula (24) obtained in the second step was added to 400 mL of toluene, and azeotropic dehydration was performed until the water content in the toluene was below 100 ppm. After azeotropic dehydration, the mixture was slowly cooled to -20 °C, and 35 mL of n-BuLi (1.6 mol / L hexane solution) was slowly added dropwise while maintaining the temperature at -15 to -20 °C. After confirming that the raw material had been consumed, 3.5 g of dehydrated acetone was added dropwise. After the addition, the temperature was slowly raised to room temperature. After the temperature was raised, 200 mL of water was added, and the mixture was separated. The water washing was repeated until the pH of the aqueous layer reached 7-8. The solvent of the obtained organic layer was removed, and the mixture was purified by silica gel-based chromatography, thereby obtaining the compound of formula (25) in 83% yield.

[0444]

[0445] Fourth process

[0446] 28.4 g (150.0 mmol) of p-toluenesulfonic acid monohydrate was added to 750 mL of toluene, and azeotropic dehydration was carried out until the water content in the toluene was below 300 ppm. Then, a toluene solution prepared by dissolving 19.3 g (38.3 mmol) of the aforementioned formula (25) in 100 mL of toluene was slowly added while maintaining the temperature at 85-100 °C, and the solution was refluxed after the addition was completed. After confirming that the raw material was consumed, the solution was cooled to room temperature, 500 mL of water was added, and the solution was separated. This operation was repeated 3 times, the solvent of the resulting organic layer was removed, and the solution was purified by silica gel-based chromatography, thereby obtaining the naphthol derivative shown in the following formula (26) in 74% yield.

[0447]

[0448] Fifth process

[0449] Dissolve 1.98 g (5.0 mol) of the naphthol derivative of formula (26) and 1.60 g (6.0 mmol) of propargyl alcohol of formula (27) in 40 mL of toluene, then add 0.12 g (0.5 mmol) of p-toluenesulfonic acid pyridinium salt, and stir at 85 °C for 1 hour.

[0450]

[0451] After the naphthol derivative of the raw material was consumed, the mixture was cooled to room temperature, 40 mL of water was added, and the mixture was separated. The solvent of the obtained organic layer was removed, and the mixture was purified by silica gel-based chromatography, thereby obtaining the photochromic compound shown in the following formula (28) in 83% yield.

[0452]

[0453] The elemental analysis values ​​of the photochromic compound shown in formula (28) are C: 81.86%, H: 6.04%, and N: 2.14%, which are similar to C. 44 H 49 The calculated values ​​of NO4, namely C: 81.83%, H: 6.09%, and N: 2.17%, are in good agreement.

[0454] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 9H peak based on methyl groups in the vicinity of δ0.5–3.0 ppm, a 9H peak based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0455] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0456] (Example 2)

[0457] In the first step of Example 1, diphenylamine was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol derivative shown in formula (29) below, and then the photochromic compound shown in formula (30) below was obtained in 75% yield.

[0458]

[0459] The elemental analysis values ​​of the photochromic compound shown in formula (30) are C: 83.17%, H: 5.86%, and N: 1.96%, which are similar to C. 49 H 41 The calculated values ​​of NO4, namely C: 83.14%, H: 5.84%, and N: 1.98%, are in good agreement.

[0460] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 6H peak based on methyl groups in the vicinity of δ0.5–3.0 ppm, a 9H peak based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 26H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0461] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0462] (Example 3)

[0463] In the third step of Example 1, 4-heptanone was used instead of acetone, and the reaction was carried out in the same manner to synthesize the naphthol derivative shown in formula (31) below, and then the photochromic compound shown in formula (32) below was obtained in 80% yield.

[0464]

[0465] The elemental analysis values ​​of the photochromic compound shown in formula (32) are C: 82.11%, H: 6.78%, and N: 1.99%, which are similar to C. 48 H 47 The calculated values ​​for NO4, namely C: 82.14%, H: 6.75%, and N: 2.00%, were in good agreement. Furthermore, proton NMR spectroscopy revealed a 17H peak based on methyl and propyl groups near δ 0.5–3.0 ppm, a 9H peak based on methoxy groups near δ 3.0–5.0 ppm, and a 21H peak based on aromatic and alkene protons near δ 5.0–9.0 ppm.

[0466] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0467] (Example 4)

[0468] In Example 3, N-methyl-(4-fluorophenyl)amine was used instead of N-methylaniline, and the reaction was carried out in the same manner to synthesize the naphthol derivative shown in formula (33) below, and then the photochromic compound shown in formula (34) below was obtained in 79% yield.

[0469]

[0470] The elemental analysis values ​​of the photochromic compound shown in formula (34) are C: 79.58%, H: 5.79%, and N: 2.14%, which are similar to C. 44 H 38 The calculated values ​​for FNO4, namely C: 79.62%, H: 5.77%, and N: 2.11%, were in good agreement. Furthermore, proton NMR spectroscopy revealed a 9H peak based on methyl groups near δ 0.5–3.0 ppm, a 9H peak based on methoxy groups near δ 3.0–5.0 ppm, and a 20H peak based on aromatic and alkene protons near δ 5.0–9.0 ppm.

[0471] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0472] (Example 5)

[0473] First process

[0474] Referring to the method described in Patent Document 6, 95.4 g (500 mmol) of p-toluenesulfonic acid monohydrate and 1000 mL of toluene were added to 35.7 g (100 mmol) of carboxylic acid of formula (35) synthesized from 3-bromo-4-methylbenzophenone, and the reaction was carried out while undergoing azeotropic dehydration. After confirming that the raw materials were consumed, the mixture was cooled to room temperature, and the resulting solid was filtered to obtain the carbonyl compound of formula (36) in 90% yield.

[0475]

[0476] Second process

[0477] Referring to the method described in Patent Document 7, the carbonyl compound represented by the aforementioned formula (36) was reacted to obtain the naphthol compound represented by the following formula (37) in a yield of 87%.

[0478]

[0479] Third process

[0480] 25.5 g (78.3 mmol) of the naphthol compound shown in formula (37) and 12.4 g (97.6 mmol) of benzyl chloride were dissolved in 250 ml of DMF. 19.4 g (140.6 mmol) of potassium carbonate was added to the solution, and the mixture was stirred at 80 °C. After the starting material was consumed, the mixture was cooled to room temperature and washed with water until neutral. The solvent was removed from the resulting organic layer, and the solution was purified by silica gel-based chromatography to give the benzyl compound shown in formula (38) in 97% yield.

[0481]

[0482] Fourth process

[0483] Add 4.2 g (10.0 mmol) of the benzyl compound of formula (38), 8.4 g (50.0 mmol) of 1-bromo-4-methoxybutane, and 60 mL of THF, and chill. While maintaining the temperature at 0–5°C, add 3.4 g (30.0 mmol) of tBuOK in four portions. After the starting material is consumed, neutralize with 10% hydrochloric acid, add 30 mL of toluene, and separate the layers. After removing the solvent from the resulting organic layer, purify by silica gel-based chromatography to obtain the benzyl compound of formula (39) in 83% yield.

[0484]

[0485] Fifth process

[0486] The reaction was carried out in the same manner as the first step of Example 1 to obtain the benzyl body shown in formula (40). 40 mL of THF and 1.0 g of 5% Pd / C (50% water content) were added to the obtained benzyl body, and the mixture was stirred under hydrogen pressure for 12 hours. After the reaction was complete, the mixture was filtered to remove THF from the filtrate, and then purified by silica gel-based chromatography to obtain the naphthol derivative shown in formula (41) in 88% yield.

[0487]

[0488]

[0489] Sixth process

[0490] In the fifth step of Example 1, the naphthol derivative of the aforementioned formula (41) was used instead of the naphthol derivative of the aforementioned formula (26), and the propargyl alcohol of the following formula (42) was used instead of the propargyl alcohol of the aforementioned formula (27). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (43) in a yield of 76%.

[0491]

[0492]

[0493] The elemental analysis values ​​of the photochromic compound shown in formula (43) are C: 82.43%, H: 7.27%, and N: 1.84%, which are similar to C. 52 H 55 The calculated values ​​for NO4, namely C: 82.40%, H: 7.31%, and N: 1.85%, were in good agreement. Furthermore, proton NMR spectroscopy measurements revealed peaks based on methyl and butylene protons in the vicinity of δ 0.5–3.0 ppm, peaks based on methoxy and butyleneoxy protons in the vicinity of δ 3.0–5.0 ppm, and peaks based on aromatic and olefinic protons in the vicinity of δ 5.0–9.0 ppm.

[0494] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0495] (Example 6)

[0496] First process

[0497] In the first step of Example 1, N-(2-methoxy)ethylaniline was used instead of N-methylaniline, and the reaction was carried out in the same manner otherwise, to obtain the iodine compound shown in the following formula (44) in 70% yield.

[0498]

[0499] Second process

[0500] In the third step of Example 1, cyclooctanone was used instead of acetone, and the reaction was carried out in the same manner otherwise, to obtain the naphthol derivative shown in the following formula (45) in a yield of 43%.

[0501]

[0502] Third process

[0503] In the fifth step of Example 1, the naphthol derivative of the following formula (45) was used instead of the naphthol derivative of the aforementioned formula (26), and the propargyl alcohol of the aforementioned formula (46) was used instead of the propargyl alcohol of the aforementioned formula (27). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (47) in a yield of 71%.

[0504]

[0505] The elemental analysis values ​​of the photochromic compound shown in formula (47) are C: 81.19%, H: 7.34%, and N: 1.69%, which are similar to C. 52 H 59 The calculated values ​​of NO5, namely C: 81.15%, H: 7.31%, and N: 1.72%, are in good agreement.

[0506] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 26H peak based on ethylene, cyclooxygenide, and propoxy in the vicinity of δ0.5–3.0 ppm, a 12H peak based on methoxy, ethyleneoxy, and propoxy in the vicinity of δ3.0–5.0 ppm, and a 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0507] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0508] (Example 7)

[0509] First process

[0510] In the first step of Example 3, diphenylamine was used instead of N-methylamine, and the reaction was carried out in the same manner to synthesize the naphthol derivative shown in formula (48) below, and propargyl alcohol shown in formula (49) below was used, and the reaction was carried out in the same manner to obtain the photochromic compound shown in formula (50) below in 77% yield.

[0511]

[0512] The elemental analysis values ​​of the photochromic compound shown in formula (50) are C: 82.09%, H: 6.68%, and N: 3.39%, which are similar to C. 56 H 54 The calculated values ​​of N2O4, namely C: 82.12%, H: 6.65%, and N: 3.42%, are in good agreement.

[0513] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on propyl and morpholino groups of 18H in the vicinity of δ0.5–3.0 ppm, peaks based on methoxy and morpholino groups of 10H in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons of 26H in the vicinity of δ5.0–9.0 ppm.

[0514] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0515] (Example 8)

[0516] First process

[0517] In the first step of Example 5, 3-bromo-4-methoxy-4'-methylbenzophenone was used instead of 3-bromo-4-methylbenzophenone, and the reaction was carried out in the same manner otherwise, to obtain the benzyl compound shown in the following formula (51) in 83% yield.

[0518]

[0519] Second process

[0520] In the fifth step of Example 5, 1,2,3,4-tetrahydroquinoline was used instead of N-methylaniline, and the reaction was carried out in the same manner to obtain the benzyl compound shown in the following formula (52).

[0521]

[0522] Third process

[0523] In the fourth step of Example 5, 4-bromo-1,1,1-trifluorobutane was used instead of 1-bromo-4-methoxybutane, and the reaction was carried out in the same manner to synthesize the naphthol derivative shown in the following formula (53).

[0524]

[0525] Fourth process

[0526] In the first step of Example 7, the naphthol derivative of the aforementioned formula (53) was used instead of the naphthol derivative of the aforementioned formula (48), and the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (54) in a yield of 73%.

[0527]

[0528] The elemental analysis values ​​of the photochromic compound shown in formula (54) are C: 72.06%, H: 5.82%, N: 3.04%, which are similar to C. 56 H 54 The calculated values ​​for F6N2O4, namely C: 72.09%, H: 5.83%, and N: 3.00%, are in good agreement. Furthermore, proton NMR spectroscopy measurements revealed peaks around δ0.5–3.0 ppm for 25H based on methyl, trifluoropropyl, morpholino, and tetrahydroquinoline rings; around δ3.0–5.0 ppm for 10H based on methoxy and morpholino groups; and around δ5.0–9.0 ppm for 19H based on aromatic and alkene protons.

[0529] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0530] (Example 9)

[0531] First process

[0532] In the first step of Example 6, N-methyl-4-(trifluoromethyl)aniline was used, and the reaction was carried out in the same manner otherwise, to obtain the iodine compound shown in the following formula (55) in 75% yield.

[0533]

[0534] Second process

[0535] In the second step of Example 6, 4,4-diethylcyclohexanone was used instead of cyclooctanone, and the reaction was carried out in the same manner otherwise, to obtain the naphthol derivative shown in the following formula (56) in 83% yield.

[0536]

[0537] Third process

[0538] In the sixth step of Example 5, the naphthol derivative of the aforementioned formula (56) was used instead of the naphthol derivative of the aforementioned formula (41), and the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (57) in a yield of 76%.

[0539]

[0540] The elemental analysis values ​​of the photochromic compound shown in formula (57) are C: 78.70%, H: 6.33%, and N: 1.75%, which are similar to C. 52 H 50 The calculated values ​​of F3NO3, namely C: 78.66%, H: 6.35%, and N: 1.76%, are in good agreement.

[0541] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on 24H of methyl and diethylcyclohexyl groups in the vicinity of δ0.5–3.0 ppm, a peak based on 6H of methoxy groups in the vicinity of δ3.0–5.0 ppm, and a peak based on 20H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0542] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0543] (Example 10)

[0544] First process

[0545] In the first step of Example 3, 3,4-dihydro-2H-1,4-benzoxazine was used instead of N-methylaniline, and the reaction was carried out in the same manner to synthesize the naphthol derivative shown in formula (58) below, and then the photochromic compound shown in formula (59) below was obtained in 83% yield.

[0546]

[0547] The elemental analysis values ​​of the photochromic compound shown in formula (59) are C: 80.66%, H: 6.49%, and N: 1.90%, which are similar to C. 49 H 47 The calculated values ​​of NO5, namely C: 80.63%, H: 6.49%, and N: 1.92%, are in good agreement.

[0548] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on the 16H of the propyl, benzoxazolin ring in the vicinity of δ0.5–3.0 ppm, a peak based on the 11H of the methoxy, benzoxazolin ring in the vicinity of δ3.0–5.0 ppm, and a peak based on the 20H of the aromatic proton and alkene proton in the vicinity of δ5.0–9.0 ppm.

[0549] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0550] (Example 11)

[0551] First process

[0552] In Example 5, 3-bromo-4-methoxybenzophenone was used instead of 3-bromo-4-methylbenzophenone, and the reaction was carried out in the same manner to obtain the benzyl matrix shown in the following formula (60) in 79% yield.

[0553]

[0554] Second process

[0555] In the first step of Example 1, bis(4-trifluoromethylphenyl)amine was used instead of N-methylaniline, and the reaction was carried out in the same manner otherwise, to obtain the naphthol derivative shown in the following formula (61) in 86% yield.

[0556]

[0557] Third process

[0558] In the fifth step of Example 1, the naphthol derivative of the aforementioned formula (61) was used instead of the naphthol derivative of the aforementioned formula (26), and the propargyl alcohol of the aforementioned formula (62) was used instead of the propargyl alcohol of the aforementioned formula (27). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (63) in a yield of 82%.

[0559]

[0560]

[0561] The elemental analysis values ​​of the photochromic compound shown in formula (63) are C: 72.06%, H: 5.87%, and N: 1.41%, which are similar to C. 61 H 59 The calculated values ​​of F6NO6, namely C: 72.10%, H: 5.85%, and N: 1.38%, are in good agreement.

[0562] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 17H of butylene and propyl groups in the vicinity of δ0.5–3.0 ppm, peaks based on 18H of methoxy, butyleneoxy, and propyleneoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks based on 24H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0563] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0564] (Example 12)

[0565] First process

[0566] In the first step of Example 1, bis(4-fluorophenyl)amine was used instead of N-methylaniline, and the reaction was carried out in the same manner otherwise, to obtain the iodine compound shown in the following formula (64) in 76% yield.

[0567]

[0568] Second process

[0569] In the third step of Example 1, dibutyl ketone was used instead of acetone, and the reaction was carried out in the same manner to obtain the naphthol derivative shown in the following formula (65) in 80% yield.

[0570]

[0571] Third process

[0572] The reaction was carried out in the same manner as the fifth step of Example 1, except that the naphthol derivative of the aforementioned formula (65) was used instead of the naphthol derivative of the aforementioned formula (26), and the photochromic compound shown in the following formula (66) was obtained in a yield of 87%.

[0573]

[0574] The elemental analysis values ​​of the photochromic compound shown in formula (66) are C: 79.76%, H: 6.21%, and N: 1.70%, which are similar to C. 55 H 51 The calculated values ​​of F2NO4, namely C: 79.78%, H: 6.21%, and N: 1.69%, are in good agreement.

[0575] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on 18H of butyl in the vicinity of δ0.5–3.0 ppm, a peak based on 9H of methoxy in the vicinity of δ3.0–5.0 ppm, and a peak based on 24H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0576] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0577] (Example 13)

[0578] First process

[0579] In Example 7, (4-methylphenyl)phenylamine was used instead of diphenylamine, and the reaction was carried out in the same manner to obtain the naphthol derivative shown in the following formula (67) in 87% yield.

[0580]

[0581] Second process

[0582] The reaction was carried out in the same manner as the fifth step of Example 1, except that the naphthol derivative of the aforementioned formula (67) was used instead of the naphthol derivative of the aforementioned formula (26), and the photochromic compound shown in the following formula (68) was obtained in a yield of 89%.

[0583]

[0584] The elemental analysis values ​​of the photochromic compound shown in formula (68) are C: 83.39%, H: 6.64%, and N: 1.81%, which are similar to C. 54 H 51 The calculated values ​​of NO4, namely C: 83.37%, H: 6.61%, and N: 1.80%, are in good agreement.

[0585] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 17H peak based on methyl and propyl groups in the vicinity of δ0.5–3.0 ppm, a 9H peak based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 25H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0586] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0587] (Example 14)

[0588] First process

[0589] In the first step of Example 11, 1-iodo-4-(methoxymethoxy)butane was used instead of 1-bromo-4-methoxybutane, and the reaction was carried out in the same manner to obtain the benzyl body shown in the following formula (69). Then, in the second step of Example 11, bis(4-methylphenyl)amine was used instead of bis(4-trifluoromethylphenyl)amine, and the reaction was carried out in the same manner to obtain the naphthol derivative shown in the following formula (70) in 80% yield.

[0590]

[0591]

[0592] Second process

[0593] The reaction was carried out in the same manner as the third step of Example 6, except that the naphthol derivative of the aforementioned formula (70) was used instead of the naphthol derivative of the aforementioned formula (45), to obtain the photochromic compound shown in the following formula (71) in 80% yield.

[0594]

[0595] The elemental analysis values ​​of the photochromic compound shown in formula (71) are C: 78.39%, H: 7.41%, and N: 1.39%, which are similar to C. 66 H 73 The calculated values ​​of NO8, namely C: 78.36%, H: 7.39%, and N: 1.41%, are in good agreement.

[0596] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 28H of butylene oxide, propoxy, and methyl in the vicinity of δ0.5–3.0 ppm, peaks based on 21H of methoxy, propoxy, and butylene oxide in the vicinity of δ3.0–5.0 ppm, and peaks based on 24H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0597] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0598] (Example 15)

[0599] First process

[0600] In the first step of Example 1, (4-methylphenyl)(4-methoxyphenyl)amine was used instead of N-methylaniline, and the reaction was carried out in the same manner otherwise to obtain the iodine compound shown in formula (72) below. The obtained iodine compound was reacted with 3,3,5,5-tetramethylcyclohexanone, and the reaction was carried out in the same manner as in the third step of Example 1, to obtain the naphthol derivative shown in formula (73) below in 87% yield.

[0601]

[0602]

[0603] Second process

[0604] In the fifth step of Example 1, the naphthol derivative of the aforementioned formula (73) was used instead of the naphthol derivative of the aforementioned formula (26), and the propargyl alcohol of the following formula (74) was used instead of the propargyl alcohol of the aforementioned formula (27). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (75) in a yield of 82%.

[0605]

[0606]

[0607] The elemental analysis values ​​of the photochromic compound shown in formula (75) are C: 82.44%, H: 7.34%, and N: 1.52%, which are similar to C. 63 H 67 The calculated values ​​of NO5, namely C: 82.41%, H: 7.35%, and N: 1.53%, are in good agreement.

[0608] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl, 3,3,5,5-tetramethylcyclohexyl, and hexoxy groups in the vicinity of δ0.5–3.0 ppm, peaks based on methoxy and hexoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0609] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0610] (Example 16)

[0611] First process

[0612] In the first step of Example 11, N-butyl(4-fluorophenyl)amine was used instead of bis(4-trifluoromethylphenyl)amine, and the reaction was carried out in the same manner to obtain the naphthol derivative shown in the following formula (76) in 76% yield.

[0613]

[0614] Second process

[0615] The reaction was carried out in the same manner as the fifth step of Example 1, except that the naphthol derivative of the aforementioned formula (76) was used instead of the naphthol derivative of the aforementioned formula (26), and the photochromic compound shown in the following formula (77) was obtained in a yield of 84%.

[0616]

[0617] The elemental analysis values ​​of the photochromic compound shown in formula (77) are C: 77.75%, H: 7.08%, and N: 1.68%, which are similar to C. 55 H 60 The calculated values ​​of FNO6, namely C: 77.71%, H: 7.11%, and N: 1.65%, are in good agreement.

[0618] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 21H based on butyl and butylene oxide in the vicinity of δ0.5–3.0 ppm, a peak of 19H based on methoxy and butylene oxide in the vicinity of δ3.0–5.0 ppm, and a peak of 20H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0619] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0620] (Example 17)

[0621] First process

[0622] In the first step of Example 5, 3-bromo-4-methyl-4'-methylbenzophenone was used instead of 3-bromo-4-methylbenzophenone, and the reaction was carried out in the same manner otherwise, to obtain the naphthol derivative shown in the following formula (78) in 76% yield.

[0623]

[0624] Second process

[0625] In the second step of Example 11, the naphthol derivative of the aforementioned formula (78) was used instead of the naphthol derivative of the aforementioned formula (61), and the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (79) in a yield of 79%.

[0626]

[0627] The elemental analysis values ​​of the photochromic compound shown in formula (79) are C: 80.94%, H: 7.52%, and N: 1.73%, which are similar to C. 55 H 61 The calculated values ​​for NO5, namely C: 80.95%, H: 7.53%, and N: 1.72%, were in good agreement. Furthermore, proton NMR spectroscopy revealed peaks of 26H based on methyl, butylene oxide, and propoxy groups near δ 0.5–3.0 ppm, peaks of 15H based on methoxy, butylene oxide, and propoxy groups near δ 3.0–5.0 ppm, and peaks of 20H based on aromatic and olefinic protons near δ 5.0–9.0 ppm.

[0628] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0629] (Example 18)

[0630] In the second step of Example 8, N-methylaniline was used instead of 1,2,3,4-tetrahydroquinoline, and in the third step, iodopropane was used instead of 4-bromo-1,1,1-trifluorobutane. Otherwise, the reaction was carried out in the same manner to obtain the naphthol derivative shown in the following formula (80) in 81% yield.

[0631]

[0632] Second process

[0633] The reaction was carried out in the same manner as the fifth step of Example 1, except that the naphthol derivative of the aforementioned formula (80) was used instead of the naphthol derivative of the aforementioned formula (26), and the photochromic compound shown in the following formula (81) was obtained in a yield of 73%.

[0634]

[0635] The elemental analysis values ​​of the photochromic compound shown in formula (81) are C: 82.23%, H: 6.89%, and N: 1.96%, which are similar to C. 49 H 49 The calculated values ​​of NO4, namely C: 82.21%, H: 6.90%, and N: 1.96%, are in good agreement.

[0636] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl and propyl 20H in the vicinity of δ0.5–3.0 ppm, peaks based on methoxy 9H in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0637] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0638] (Example 19)

[0639] First process

[0640] In the first step of Example 1, 3,4-dihydro-2H-1,4-benzoxazine was used instead of N-methylaniline, and the reaction was carried out in the same manner to synthesize the naphthol derivative shown in formula (82) below, and then the photochromic compound shown in formula (83) below was obtained in 78% yield.

[0641]

[0642] The elemental analysis values ​​of the photochromic compound shown in formula (83) are C: 80.24%, H: 5.80%, and N: 2.10%, which are similar to C. 45 H 39 The calculated values ​​of NO5, namely C: 80.21%, H: 5.83%, and N: 2.08%, are in good agreement.

[0643] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed an 8H peak based on methyl and benzoxazoline rings in the vicinity of δ0.5–3.0 ppm, an 11H peak based on methoxy and benzoxazoline rings in the vicinity of δ3.0–5.0 ppm, and a 20H peak based on aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[0644] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0645] (Example 20)

[0646] First process

[0647] In the first step of Example 16, N-methyl-(4-methylphenyl)amine was used instead of N-butyl(4-fluorophenyl)amine, and the reaction was carried out in the same manner otherwise, to obtain the naphthol derivative shown in the following formula (84) in 79% yield.

[0648]

[0649] Second process

[0650] The reaction was carried out in the same manner as the third step of Example 6, except that the naphthol derivative of the aforementioned formula (84) was used instead of the naphthol derivative of the aforementioned formula (45), and the photochromic compound shown in the following formula (85) was obtained in a yield of 84%.

[0651]

[0652] The elemental analysis values ​​of the photochromic compound shown in formula (85) are C: 79.61%, H: 7.58%, and N: 1.61%, which are similar to C. 57 H 65 The calculated values ​​of NO6, namely C: 79.59%, H: 7.62%, and N: 1.63%, are in good agreement.

[0653] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 28H based on methyl, butyloxy, and propoxy in the vicinity of δ0.5–3.0 ppm, a peak of 17H based on methoxy and butyloxy in the vicinity of δ3.0–5.0 ppm, and a peak of 20H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0654] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0655] (Example 21)

[0656] First process

[0657] In the first step of Example 3, propargyl alcohol of formula (27) was used instead of propargyl alcohol of formula (86) below, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of formula (87) below in a yield of 82%.

[0658]

[0659] The elemental analysis values ​​of the photochromic compound shown in formula (87) are C: 84.47%, H: 6.50%, N: 3.33%, which are similar to C. 59 H 54 The calculated values ​​of N2O3, namely C: 84.45%, H: 6.49%, and N: 3.34%, are in good agreement.

[0660] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on methyl and propyl 17H in the vicinity of δ0.5–3.0 ppm, a peak based on methoxy 6H in the vicinity of δ3.0–5.0 ppm, and a peak based on aromatic protons and olefin protons 31H in the vicinity of δ5.0–9.0 ppm.

[0661] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0662] (Example 22)

[0663] First process

[0664] In the first step of Example 7, propargyl alcohol of formula (49) was used instead of propargyl alcohol of formula (88) and the reaction was carried out in the same manner to obtain the photochromic compound of formula (89) in a yield of 86%.

[0665]

[0666] The elemental analysis values ​​of the photochromic compound shown in formula (89) are C: 86.08%, H: 6.61%, and N: 3.41%, which are similar to C. 59 H 54 The calculated values ​​of N2O2, namely C: 86.10%, H: 6.61%, and N: 3.40%, are in good agreement.

[0667] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on methyl and propyl 20H in the vicinity of δ0.5–3.0 ppm, a peak based on methoxy 3H in the vicinity of δ3.0–5.0 ppm, and a peak based on aromatic protons and olefin protons 31H in the vicinity of δ5.0–9.0 ppm.

[0668] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0669] (Analysis results of naphthol derivatives)

[0670] Table 1 summarizes the analytical results of the naphthol derivatives used in Examples 1-20.

[0671] [Table 1]

[0672] Table 1

[0673]

[0674] (Physical property evaluation of photochromic plastic lenses produced by coating method)

[0675] (Example 23)

[0676] (Preparation of curable compositions)

[0677] First, the photochromic compound, photopolymerization initiator, and polymerizable compound obtained in Example 1 above are mixed to obtain a curable composition.

[0678] As a polymerizable compound, a polymerizable compound is used that is formulated by combining the following free radical polymerizable monomers.

[0679] Polyethylene glycol dimethacrylate (average molecular weight 736): 42 parts by weight

[0680] Polyethylene glycol dimethacrylate (average molecular weight 536): 12 parts by weight

[0681] Trimethylolpropane trimethacrylate: 38 parts by weight

[0682] γ-Methacryloxypropyltrimethoxysilane: 2 parts by weight

[0683] Glycidyl methacrylate: 1 part by weight

[0684] It should be noted that when the total amount of free radical polymerizable monomers in the curable composition is set to 100g, the photochromic compound is added in a manner that results in 0.25mmol.

[0685] The following additives are used as additives.

[0686] Phenylenol bis(2,4,6-trimethylbenzoyl)phosphine oxide (photopolymerization initiator: Omnirad 819): 0.3 parts by weight

[0687] Ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (stabilizer, Irganox 245): 1 part by weight

[0688] bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate: 3 parts by weight

[0689] Dow-Toray Corporation Leveling agent (L7001): 0.1 parts by weight

[0690] It should be noted that the above additives are the mixing ratio when the total amount of free radical polymerizable monomers is set to 100 parts by mass.

[0691] (Manufacturing of optical items)

[0692] Using this curable composition, polymerization is carried out as follows to obtain a photochromic laminate based on a lamination method.

[0693] First, a thiocarbamate-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as the optical substrate. It should be noted that the thiocarbamate-based plastic lens was first subjected to alkaline etching at 50°C for 5 minutes using a 10% sodium hydroxide aqueous solution, and then thoroughly cleaned with distilled water.

[0694] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) was applied to the surface of the aforementioned plastic lens at a speed of 70 rpm for 15 seconds, followed by a 10-second application at 1000 rpm. Then, approximately 2 g of the aforementioned photochromic curable composition was spin-coated at a speed of 60 rpm for 40 seconds, followed by a 10-20 second application at 600 rpm, to achieve a photochromic coating thickness of 40 μm.

[0695] A lens with a photochromic curable composition (photochromic coating) coated on its surface was used in a nitrogen atmosphere with an output power of 200mW / cm. 2 The coating is cured by irradiating it with a metal halide lamp for 90 seconds. Then, it is further heated at 110°C for 1 hour to produce a photochromic laminate with a photochromic layer.

[0696] (Examples 24-44)

[0697] Photochromic laminates were fabricated using the photochromic compounds obtained in Examples 2-22, following the same method as in Example 23.

[0698] (Comparative Examples 1-8)

[0699] Using the photochromic compounds shown in formulas (A) to (H) below, each photochromic laminate was obtained in the same manner as in Example 23.

[0700]

[0701]

[0702]

[0703] (Synthesis of compound E)

[0704] In Example 11, iodomethane was used instead of 1-bromo-4-methoxybutane, and the reaction was carried out in the same manner to give the benzyl matrix shown in the following formula (90) in 86% yield.

[0705]

[0706] The reaction was carried out in the same manner except that the benzyl body of the aforementioned formula (90) was used instead of the benzyl body of the aforementioned formula (60), piperidine was used instead of bis(4-trifluoromethylphenyl)amine, and the aforementioned formula (27) was used instead of the compound of the aforementioned formula (62), to synthesize compound (E).

[0707] (Synthesis of compound F)

[0708] In the synthesis of compound E, 1,2,3,4-tetrahydroisoquinoline was used instead of piperidine, and the reaction was carried out in the same manner to synthesize compound (F).

[0709] (Synthesis of compound G)

[0710] In the synthesis of compound E, hexamethyleneimine was used instead of piperidine, and the reaction was carried out in the same manner to synthesize compound (G).

[0711] (Synthesis of compound H)

[0712] In the synthesis of compound E, bis(2-methoxyethyl)amine was used instead of piperidine, and the reaction was carried out in the same manner to synthesize compound (G).

[0713] <Evaluation Methods>

[0714] The obtained photochromic laminate was evaluated using the method shown below.

[0715] (1) Photochromic properties

[0716] [1] Maximum absorption wavelength (λmax):

[0717] The maximum absorption wavelength after color development was determined using a spectrophotometer (MCPD3000 instantaneous multichannel photodetector) manufactured by OTSUKA ELECTRONICS CO.,LTD, and used as an indicator of hue during color development.

[0718] [2] Colorimetric concentration at 23℃ (A) 23 ):

[0719] The difference between the absorbance {ε(240)} after 240 seconds of light irradiation at 23°C at the maximum absorption wavelength and the absorbance ε(0) before irradiation is used as an indicator of colorimetric concentration. It can be said that the higher this value, the better the photochromic property.

[0720] [3] Colorimetric concentration at 35℃ (A) 35 ):

[0721] The difference between the absorbance {ε(240)} at the first and second absorption wavelengths after 240 seconds of light irradiation at 35°C and the absorbance ε(0) before irradiation is used as an indicator of colorimetric concentration. It can be said that the higher this value, the better the photochromic properties.

[0722] [4] High temperature colorimetric rate (A 35 / A 23 ×100):

[0723] 35℃ colorimetric concentration (A) 35 ) / 23℃ colorimetric concentration (A) 23 (%)×100(%). If this value is high, it can be said that the difference in colorimetric concentration between high and low temperatures is small, and the temperature dependence is low.

[0724] [5] Fading half-life at 23℃ [τ1 / 2(sec.)]:

[0725] The time required for the absorbance of the sample at its maximum absorption wavelength to decrease to half of {ε(240)-ε(0)} after 240 seconds of light irradiation at 23°C and then stopping the light irradiation is used as an indicator of the fading rate. The shorter this time, the faster the fading rate.

[0726] [6] Survival rate (A) 90 / A0×100):

[0727] The obtained photochromic plastic lenses were subjected to 90 hours of accelerated degradation using a Suga Test Instruments Co., Ltd. X25 xenon weathering apparatus. Then, the colorimetric concentration was evaluated before and after the test, measuring the colorimetric concentration before the test (A0) and the colorimetric concentration after the test (A...). 90 ), and the ratio (A) 90 / A0) is used as the retention rate, which serves as an indicator of color development durability. The higher the retention rate, the higher the color development durability.

[0728] The results of Examples 23 to 33 are summarized in Table 2, the results of Examples 34 to 44 are summarized in Table 3, and the results of Comparative Examples 1 to 8 are summarized in Table 4.

[0729] [Table 2]

[0730] Table 2

[0731]

[0732] [Table 3]

[0733] Table 3

[0734] [Table 4]

[0735] Table 4

[0736]

[0737] Figure 1 This is a figure illustrating the relationship between the 23°C fading half-life and high-temperature color development of the photochromic laminates of the embodiments and comparative examples. Figure 1 Data from Examples 23 (using the photochromic compound of Example 1), 24 (using the photochromic compound of Example 2), 26 (using the photochromic compound of Example 4), 41 (using the photochromic compound of Example 19), and Comparative Examples 1-8. Figure 1 In the comparison examples, from left to right, they are Comparative Example 4, Comparative Example 3, Comparative Example 2, Comparative Example 1, Comparative Example 6, Comparative Example 5, Comparative Example 8, and Comparative Example 7.

[0738] (Example 45)

[0739] First process

[0740] The benzophenone compound of formula (91) synthesized by reacting 3-bromoanisole with 4'-(1,1-dimethylethyl)[1,1'-biphenyl]-4-carbonyl chloride according to the method described in Patent Document 6 was used in place of 3-bromo-4-methylbenzophenone in the first step of Example 5, and iodoethane was used in place of 1-bromo-4-methoxybutane in the fourth step of Example 5. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound of formula (92) in 79% yield.

[0741]

[0742] Second process

[0743] In the fifth step of Example 1, the naphthol compound of formula (92) was used instead of the naphthol compound of formula (26), and the propargyl alcohol of formula (93) was used instead of the propargyl alcohol of formula (27). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (94) in a yield of 69%.

[0744]

[0745]

[0746] The elemental analysis values ​​of the photochromic compound shown in formula (94) are C: 83.57%, H: 7.22%, and N: 1.63%, which are similar to C. 59 H 61 The calculated values ​​of NO4, namely C: 83.55%, H: 7.25%, and N: 1.65%, are in good agreement.

[0747] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks of 29H based on tert-butyl, butoxy, ethyl, and methyl groups in the vicinity of δ0.5–3.0 ppm, peaks of 8H based on methoxy and butoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks of 24H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0748] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0749] (Example 46)

[0750] First process

[0751] In the first step of Example 5, benzophenone as shown in formula (95) was used instead of 3-bromo-4-methylbenzophenone, and iodobutane was used instead of 1-bromo-4-methoxybutane. Otherwise, the reaction was carried out in the same manner to obtain the benzyl compound as shown in formula (96) in 93% yield.

[0752]

[0753] Second process

[0754] 13.3 g (23.0 mmol) of the benzyl compound of formula (96) was dissolved in 230 mL of THF and cooled to -78 °C. 15.8 mL of n-BuLi (1.6 mol / L hexane solution) was slowly added dropwise while maintaining the temperature below -70 °C. After confirming that the starting material was consumed, 4.5 g (30.3 mmol) of tert-butyldimethylchlorosilane dissolved in 18 mL of THF was slowly added dropwise while maintaining the temperature below -70 °C. After the addition, the temperature was slowly raised to room temperature. After the reaction was complete, 200 mL of water and 200 mL of toluene were added, and the mixture was separated. After removing the solvent from the resulting organic layer, the mixture was purified by silica gel-based chromatography to obtain the benzyl compound of formula (97) in 54% yield.

[0755]

[0756] Third process

[0757] In the first step of Example 1, the compound of the aforementioned formula (97) was used instead of the compound of the aforementioned formula (22), and N-ethylaniline was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound of the following formula (98) in a yield of 47%.

[0758]

[0759] Fourth process

[0760] In the third step of Example 11, the naphthol compound of the aforementioned formula (98) was used instead of the naphthol compound of the aforementioned formula (61), and the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (99) in a yield of 73%.

[0761]

[0762] The elemental analysis values ​​of the photochromic compound shown in formula (99) are C: 79.96%, H: 8.05%, and N: 1.60%, which are similar to C. 59 H 71 The calculated values ​​of NO4Si, namely C: 79.96%, H: 8.07%, and N: 1.58%, are in good agreement.

[0763] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 43H based on tert-butyl, butyl, ethyl, methyl, and propoxy in the vicinity of δ0.5–3.0 ppm, a peak of 8H based on methoxy and propoxy in the vicinity of δ3.0–5.0 ppm, and a peak of 20H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0764] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0765] (Example 47)

[0766] First process

[0767] In the first step of Example 5, 3-bromo-4-methyl-4'-methoxybenzophenone was used instead of 3-bromo-4-methylbenzophenone, and the reaction was carried out in the same manner otherwise, to obtain the benzyl compound shown in the following formula (100) in 86% yield.

[0768]

[0769] Second process

[0770] In the second step of Example 8, 3,4-dihydro-2H-1,4-benzoxazine was used instead of 1,2,3,4-tetrahydroquinoline, and in the third step of Example 8, 1-fluoro-4-iodobutane was used instead of 4-bromo-1,1,1-trifluorobutane. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound shown in the following formula (101) in 68% yield.

[0771]

[0772] Third process

[0773] In the sixth step of Example 7, the naphthol compound of the aforementioned formula (48) was used instead of the naphthol compound of the aforementioned formula (101), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (102) in a yield of 69%.

[0774]

[0775] The elemental analysis values ​​of the photochromic compound shown in formula (102) are C: 76.52%, H: 6.51%, and N: 3.23%, which are similar to C. 55 H 56 The calculated values ​​of F2N2O5, namely C: 76.54%, H: 6.54%, and N: 3.25%, are in good agreement.

[0776] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 25H of methyl, fluorobutyl, morpholino, and benzoxazolino rings in the vicinity of δ0.5–3.0 ppm, peaks based on 12H of methoxy, morpholino, and benzoxazolino rings in the vicinity of δ3.0–5.0 ppm, and peaks based on 19H of aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[0777] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0778] (Example 48)

[0779] First process

[0780] In the first step of Example 46, 1-bromo-2-methoxyethane was used instead of iodobutane, and the reaction was carried out in the same manner to obtain the benzyl compound shown in the following formula (103).

[0781]

[0782] Second process

[0783] 5.8 g (10.0 mmol) of the carboxylic acid compound shown in formula (103) was mixed with 2.1 g (10.9 mmol) of p-trifluoromethylphenylboronic acid, 4.5 g (21.7 mmol) of sodium carbonate, 20.5 mL of water, 30.5 mL of 1,2-dimethoxyethane, and 2.2 mL of ethanol, and stirred while bubbling with nitrogen. Bubbling with nitrogen continued for approximately 20 minutes, then 28.5 mg (0.02 mmol) of Pd(PPh3)4 was added, and the mixture was reacted at 75 °C for 2 hours. After the reaction, the mixture was cooled to room temperature, 130 mL of THF was added, and the mixture was cooled to 0-5 °C. Concentrated hydrochloric acid was added until the pH reached 1, and the mixture was separated. The solvent was removed by washing twice with 100 mL of water. The mixture was then purified by re-slurrying with 100 mL of methanol to obtain the benzyl compound shown in formula (104) in 87% yield.

[0784]

[0785] Third process

[0786] In the third step of Example 46, the compound of the aforementioned formula (97) was used instead of the compound of the aforementioned formula (104), and 7-methyl-3,4-dihydro-2H-1,4-benzoxazine was used instead of N-ethylaniline. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound of the following formula (105) in 59% yield.

[0787]

[0788] Fourth process

[0789] In the third step of Example 6, the naphthol compound of the aforementioned formula (45) was used instead of the naphthol compound of the aforementioned formula (105), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (106) in a yield of 72%.

[0790]

[0791] The elemental analysis values ​​of the photochromic compound shown in formula (106) are C: 75.03%, H: 6.18%, and N: 1.42%, which are similar to C. 61 H 60 The calculated values ​​of F3NO7, namely C: 75.06%, H: 6.20%, and N: 1.43%, are in good agreement.

[0792] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 19H of methyl, propoxy, ethyl methoxy, and benzoxazoline rings in the vicinity of δ0.5–3.0 ppm, peaks based on 19H of methoxy, propoxy, ethyl methoxy, and benzoxazoline rings in the vicinity of δ3.0–5.0 ppm, and peaks based on 22H of aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[0793] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0794] (Example 49)

[0795] First process

[0796] In the first step of Example 1, 7-fluoro-3,4-dihydro-2H-1,4-benzoxazine was used instead of N-methylaniline, and in the third step, 4,4-diethylcyclohexanone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound shown in the following formula (107) in 72% yield.

[0797]

[0798] Second process

[0799] In the fifth step of Example 1, the naphthol compound of formula (107) was used instead of the naphthol compound of formula (26), and the propargyl alcohol of formula (27) was used instead of the propargyl alcohol of formula (108). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (109) in a yield of 65%.

[0800]

[0801] Third process

[0802] Referring to the method described in Patent Document 9, a compound of formula (110) synthesized from polytetramethylene glycol with a number average molecular weight of 1000 is reacted with a photochromic compound of formula (109) to obtain a photochromic compound of formula (111) in a yield of 73%.

[0803]

[0804]

[0805] The proton nuclear magnetic resonance spectrum of the photochromic compound shown in the aforementioned formula (111) was measured. The results showed a peak of 56H based on the ethyl, succinic acid, morpholino, and benzoxazolin rings in the vicinity of δ0.5 to 3.0 ppm, a peak of about 118H based on the methoxy, ethyleneoxy, polyethylene glycol chain, morpholino, and benzoxazolin rings in the vicinity of δ3.0 to 5.0 ppm, and a peak of 38H based on the protons of aromatic protons and olefins in the vicinity of δ5.0 to 9.0 ppm.

[0806] (Example 50)

[0807] First process

[0808] The 3-bromo-4-methoxy-4'-phenylbenzophenone obtained by reacting 3-bromoanisole with 4-phenylbenzoyl chloride according to the method described in Patent Document 6 was used instead of 3-bromo-4-methoxybenzophenone in the first step of Example 1, bis(4-trifluoromethylphenyl)amine was used instead of N-methylaniline, and spiro[5,5]undecane-3-one was used instead of acetone in the third step. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound shown in the following formula (112) in a yield of 67%.

[0809]

[0810] Second process

[0811] In the fifth step of Example 1, the naphthol compound of formula (112) was used instead of the naphthol compound of formula (26), and the propargyl alcohol of formula (27) was used instead of the propargyl alcohol of formula (113) to obtain the photochromic compound of formula (114) in a yield of 68%.

[0812]

[0813] Third process

[0814] In the third step of Example 49, polypropylene glycol monobutyl ether with a number average molecular weight of 1000 was used instead of polyethylene glycol with a number average molecular weight of 1000, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (115) in a yield of 73%.

[0815]

[0816] The proton nuclear magnetic resonance spectrum of the photochromic compound shown in the aforementioned formula (115) was measured. The results showed a peak of about 77H based on the spiro[5,5]undecane ring, succinic acid site, polypropylene glycol chain, and butoxy group near δ0.5 to 3.0 ppm, a peak of about 60H based on the methoxy group, ethyleneoxy group, polypropylene glycol chain, and butoxy group near δ3.0 to 5.0 ppm, and a peak of 28H based on the aromatic proton and olefin proton near δ5.0 to 9.0 ppm.

[0817] (Example 51)

[0818] First process

[0819] In the first step of Example 46, 4-trifluoromethoxybenzoyl chloride was used instead of 4'-(1,1-dimethylethyl)[1,1'-biphenyl]-4-carbonyl chloride, and N-butylaniline was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound shown in the following formula (116) in 70% yield.

[0820]

[0821] Second process

[0822] In the third step of Example 11, the naphthol compound of the aforementioned formula (116) was used instead of the naphthol compound of the aforementioned formula (61), and the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (117) in a yield of 73%.

[0823]

[0824] The elemental analysis values ​​of the photochromic compound shown in formula (117) are C: 75.41%, H: 6.30%, and N: 1.68%, which are similar to C. 52 H 52 The calculated values ​​of F3NO5, namely C: 75.43%, H: 6.33%, and N: 1.69%, are in good agreement.

[0825] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 24H of ethyl, butyl, and propoxy groups in the vicinity of δ0.5–3.0 ppm, peaks based on 8H of methoxy and propoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks based on 20H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0826] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0827] (Example 52)

[0828] First process

[0829] In the first step of Example 51, 4-phenoxybenzoyl chloride was used instead of 4-trifluoromethoxybenzoyl chloride, (4-methylphenyl)phenylamine was used instead of N-butylaniline, and iodohexane was used instead of iodoethane. The reaction was carried out in the same manner otherwise, and the naphthol compound shown in the following formula (118) was obtained in a yield of 64%.

[0830]

[0831] Second process

[0832] In the second step of Example 45, the naphthol compound of the aforementioned formula (118) was used instead of the naphthol compound of the aforementioned formula (92), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (119) in a yield of 71%.

[0833]

[0834] The elemental analysis values ​​of the photochromic compound shown in formula (119) are C: 83.19%, H: 7.39%, and N: 1.43%, which are similar to C. 69 H 73 The calculated values ​​of NO5, namely C: 83.18%, H: 7.39%, and N: 1.41%, are in good agreement.

[0835] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks of 36H based on methyl, hexyl, and butoxy groups in the vicinity of δ0.5–3.0 ppm, peaks of 8H based on methoxy and butoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks of 29H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0836] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0837] (Example 53)

[0838] First process

[0839] In the first step of Example 48, 2-[2-(2-methoxyethoxy)ethoxy]ethyl p-toluenesulfonate was used instead of 1-bromo-2-methoxyethane; in the second step, p-isopropoxyphenylboronic acid was used instead of p-trifluoromethylphenylboronic acid; and in the third step, N-methyl-4-(trifluoromethyl)aniline was used instead of 7-methyl-3,4-dihydro-2H-1,4-benzoxazine. The reaction was carried out in the same manner otherwise, to obtain the naphthol compound shown in formula (120) in 54% yield.

[0840]

[0841] Second process

[0842] In the fifth step of Example 1, the naphthol compound of the aforementioned formula (120) was used instead of the naphthol compound of the aforementioned formula (26), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (121) in a yield of 76%.

[0843]

[0844] The elemental analysis values ​​of the photochromic compound shown in formula (121) are C: 71.25%, H: 6.49%, and N: 1.24%, which are similar to C. 66 H 72 F3NO 11 The calculated values ​​of C: 71.27%, H: 6.52%, and N: 1.26% are in good agreement.

[0845] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on methyl, isopropoxy, and 2-[2-(2-methoxyethoxy)ethoxy]ethyl 13H in the vicinity of δ0.5–3.0 ppm, a peak based on methoxy, isopropoxy, and 2-[2-(2-methoxyethoxy)ethoxy]ethyl 36H in the vicinity of δ3.0–5.0 ppm, and a peak based on aromatic protons and olefin protons 23H in the vicinity of δ5.0–9.0 ppm.

[0846] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0847] (Example 54)

[0848] First process

[0849] In the first step of Example 1, 3-bromo-4-methoxy-4'-methoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone, N-butyl-4-(trifluoromethyl)aniline was used instead of N-methylaniline, and cyclododecane was used instead of acetone. The reaction was carried out in the same manner otherwise, and the naphthol compound shown in the following formula (122) was obtained in a yield of 48%.

[0850]

[0851] Second process

[0852] In the sixth step of Example 5, the naphthol compound of the aforementioned formula (41) was used instead of the naphthol compound of the aforementioned formula (122), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (123) in a yield of 71%.

[0853]

[0854] The elemental analysis values ​​of the photochromic compound shown in formula (123) are C: 77.90%, H: 6.97%, and N: 1.56%, which are similar to C. 58 H 62 The calculated values ​​of F3NO4, namely C: 77.91%, H: 6.99%, and N: 1.57%, are in good agreement.

[0855] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 34H of methyl, butyl, and cyclodecane rings in the vicinity of δ0.5–3.0 ppm, peaks based on 9H of methoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks based on 19H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0856] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0857] (Example 55)

[0858] First process

[0859] In the second step of Example 8, N-methylaniline was used instead of 1,2,3,4-tetrahydroquinoline, and in the third step, 1-bromo-3-methylthiopropane was used instead of 4-bromo-1,1,1-trifluorobutane. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound shown in the following formula (124) in 56% yield.

[0860]

[0861] Second process

[0862] In the second step of Example 49, the naphthol compound of the aforementioned formula (124) was used instead of the naphthol compound of the aforementioned formula (109), and in the third step, the compound shown in the following formula (125) was used instead of the compound shown in the aforementioned formula (110). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (126) in a yield of 65%.

[0863]

[0864]

[0865] The proton nuclear magnetic resonance spectrum of the photochromic compound represented by the aforementioned formula (126) was measured. The results showed a peak of about 99H based on methyl, 3-mercaptomethylpropyl, morpholino, succinic acid site, polypropylene glycol chain, and butoxy group in the vicinity of δ0.5 to 3.0 ppm, a peak of about 129H based on methoxy, ethyleneoxy, polypropylene glycol chain, polyethylene glycol chain, and butoxy group in the vicinity of δ3.0 to 5.0 ppm, and a peak of 20H based on aromatic proton and olefin proton in the vicinity of δ5.0 to 9.0 ppm.

[0866] (Example 56)

[0867] First process

[0868] In the first step of Example 46, iodooctane was used instead of iodobutane; in the second step, triphenylchlorosilane was used instead of tert-butyldimethylchlorosilane; and in the third step, diphenylamine was used instead of N-ethylaniline. The reaction was carried out in the same manner otherwise, to obtain the naphthol compound shown in the following formula (127) in a yield of 40%.

[0869]

[0870] Second process

[0871] In the third step of Example 6, the naphthol compound of the aforementioned formula (127) was used instead of the naphthol compound of the aforementioned formula (45), and the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (128) in a yield of 63%.

[0872]

[0873] The elemental analysis values ​​of the photochromic compound shown in formula (128) are C: 83.76%, H: 7.54%, and N: 1.16%, which are similar to C. 85 H 91 The calculated values ​​of NO4Si, namely C: 83.77%, H: 7.53%, and N: 1.15%, are in good agreement.

[0874] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 44H peak based on octyl and propoxy groups near δ0.5–3.0 ppm, a 7H peak based on methoxy and propoxy groups near δ3.0–5.0 ppm, and a 40H peak based on aromatic protons and olefin protons near δ5.0–9.0 ppm.

[0875] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0876] (Example 57)

[0877] First process

[0878] In the first step of Example 46, 1-bromo-3-methoxypropane was used instead of iodobutane, and the reaction was carried out in the same manner to obtain the benzyl compound shown in the following formula (129) in 86% yield.

[0879]

[0880] Second process

[0881] Referring to the conditions described in Patent Document 3, the benzyl compound of the aforementioned formula (129) was reacted with 2,6-dimethylbenzyl mercaptan to obtain the benzyl compound of the following formula (130) in 89% yield.

[0882]

[0883] Third process

[0884] In the third step of Example 46, the compound of the aforementioned formula (97) was used instead of the compound of the aforementioned formula (130), and N-(2-methoxyethyl)-(4-trifluoromethyl)aniline was used instead of N-ethylaniline. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound of the following formula (131) in a yield of 69%.

[0885]

[0886] Fourth process

[0887] In the fifth step of Example 1, the naphthol compound of the aforementioned formula (131) was used instead of the naphthol compound of the aforementioned formula (26), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (132) in a yield of 71%.

[0888]

[0889] The elemental analysis values ​​of the photochromic compound shown in formula (132) are C: 72.50%, H: 6.18%, N: 1.41%, S: 3.16%, which are similar to C. 61 H 62 The calculated values ​​of F3NO7S, namely C: 72.52%, H: 6.19%, N: 1.39%, and S: 3.17%, are in good agreement.

[0890] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 16H of 3-methoxypropyl, 2-methoxyethyl, and methyl groups in the vicinity of δ0.5–3.0 ppm, peaks based on 24H of methoxy, 3-methoxypropyl, and 2-methoxyethyl groups in the vicinity of δ3.0–5.0 ppm, and peaks based on 22H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0891] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0892] Table 5 summarizes the analytical results of the naphthol derivatives used in Examples 45–57.

[0893] [Table 5]

[0894] Table 5

[0895]

[0896] (Examples 58-70)

[0897] Photochromic laminates were prepared using the photochromic compounds obtained in Examples 45-57, following the same method as in Example 23. The evaluation results are summarized in Table 6.

[0898] [Table 6]

[0899] Table 6

[0900]

[0901] <Property Evaluation of Photochromic Layers Fabricated Using Adhesive Method>

[0902] (Example 71)

[0903] The adhesive sheet is fabricated using the following method. The adhesive sheet consists of a first optical sheet, a first adhesive layer, a photochromic layer, a second adhesive layer, and a second optical sheet, stacked sequentially. A 400 μm thick polycarbonate sheet is used as both the first and second optical sheets.

[0904] (Preparation of the composition for forming a photochromic layer)

[0905] In a 2L four-necked flask equipped with a stirring blade, cooling pipe, thermometer, and nitrogen inlet pipe, 315 parts by mass of polycarbonate diol with a number average molecular weight of 1000, 100 parts by mass of isophorone diisocyanate, and 72 parts by mass of toluene were added. The mixture was reacted at 100°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer with isocyanate groups at the ends. After the urethane prepolymer reaction was complete, the reaction solution was cooled to approximately 0°C and dissolved in 205 parts by mass of tert-butanol and 382 parts by mass of diethyl ketone, and the solution temperature was maintained at 0°C. Then, a mixed solution of 21.3 parts by mass of bis(4-aminocyclohexyl)methane and 20 parts by mass of diethyl ketone as a chain extender was added dropwise over 30 minutes, and the reaction was carried out at 0°C for 1 hour. Then, 8.1 parts by mass of 1,2,2,6,6-pentamethyl-4-aminopiperidine were added dropwise, and the mixture was reacted at 0°C for 1 hour to obtain a diethyl ketone solution of terminal non-reactive carbamate urea resin.

[0906] 100 parts by weight of the obtained terminal non-reactive urethane resin solution, 6.3 parts by weight of the photochromic compound of Example 1 (formula (28) above), a mixture of isomers of 4,4'-methylenebis(cyclohexyl isocyanate) (polyisocyanate compound), 0.4 parts by weight of ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] as an antioxidant, and 0.06 parts by weight of DOW CORNING TORAY L-7001 as a surfactant were added and stirred and mixed at room temperature to obtain a composition for forming a photochromic layer.

[0907] In addition, a photochromic compound was added at a rate of 0.25 mmol relative to 100 parts by weight of the terminal non-reactive urethane resin.

[0908] (Preparation of the adhesive layer composition)

[0909] A 5L separable flask (4-necked) equipped with a stirring blade, cooling pipe, thermometer, and nitrogen inlet pipe was prepared. 400 parts by mass of polycarbonate diol (number average molecular weight 1000), 175 parts by mass of isophorone diisocyanate, and 120 parts by mass of toluene were added to the flask. The mixture was reacted at 110°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer with isocyanate groups at the ends. After the urethane prepolymer reaction was complete, the reaction solution was cooled to approximately 20°C and dissolved in 2500 parts by mass of propylene glycol-monomethyl ether, maintaining the temperature at 20°C. Next, 60 parts by mass of isophorone diamine, acting as a chain extender, were added dropwise, and the reaction was carried out at 20°C for 1 hour. Then, 3 parts by mass of n-butylamine were further added dropwise, and the reaction was carried out at 20°C for 1 hour, thereby obtaining a propylene glycol-monomethyl ether solution of a terminally non-reactive urethane urea resin.

[0910] Add 0.2 parts by mass of DOW CORNING TORAY L-7001 as a surfactant to 500 parts by mass of the obtained terminal non-reactive urethane resin solution, and stir and mix at room temperature to obtain a composition for adhesive layer.

[0911] (Manufacturing of adhesive sheets)

[0912] Using a coating machine (manufactured by TESTER SANGYO CO,.LTD.), the adhesive layer composition was coated onto one main surface of the first optical film at a coating speed of 0.5 m / min, and dried at a drying temperature of 110°C for 3 minutes, thereby obtaining a first optical film with a first coating film thickness of 5 μm. Using the same method, the adhesive layer composition was coated onto one main surface of the second optical film to obtain a second optical film with a second coating film.

[0913] Next, using a coating machine (manufactured by TESTER SANGYO CO,.LTD.), the photochromic layer forming composition was coated onto a 50 μm thick OPP film (stretched polypropylene film) at a coating speed of 0.3 m / min, and dried at a drying temperature of 100°C for 5 minutes. This yielded a third coating. Then, the third coating was bonded to the first optical sheet in contact with the first coating. The OPP film was peeled off from the structure, and the second optical sheet and the third coating were bonded together with the exposed main surface of the third coating in contact with the second coating. The resulting laminate was then left to stand at 40°C under vacuum for 24 hours, followed by heat treatment at 110°C for 60 minutes, then humidified at 60°C and 100% RH for 24 hours, and finally left to stand at 40°C under vacuum for 24 hours to obtain an adhesive sheet. The obtained adhesive sheet was evaluated in the same manner as in Example 23. The results are shown in Table 7.

[0914] (Examples 71-84, Comparative Examples 9-13)

[0915] Adhesive sheets were prepared using the photochromic compounds shown in Tables 7 and 8, in the same manner as in Example 70.

[0916] The results of Examples 70-73 and Comparative Examples 9-13 are summarized in Table 7, and the results of Examples 74-84 are summarized in Table 8.

[0917] [Table 7]

[0918] Table 7

[0919] [Table 8]

[0920] Table 8

[0921]

[0922] <Physical Property Evaluation of Photochromic Cured Products Produced by Mixing Method>

[0923] (Example 85)

[0924] (Preparation of curable compositions)

[0925] First, the photochromic compound, additive, and polymerizable compound obtained in Example 1 are mixed to obtain a curable composition.

[0926] As a polymerizable compound, a polymerizable compound prepared by combining and mixing the following polymerizable monomers is used.

[0927] 1,3-Bis(isocyanate methyl)cyclohexane: 36.7 parts by weight

[0928] Pentaerythritol tetra(3-mercaptopropionate): 39.4 parts by weight

[0929] Polyoxyethylene polyoxypropylene lauryl ether (manufactured by AOKIOIL INDUSTRIAL Co., Ltd., WANDERSURF140): 17.4 parts by weight

[0930] 1-Decanethiol: 2.8 parts by weight

[0931] RX-1 prepared using the method described in Patent Document 10: 3.8 parts by mass

[0932] It should be noted that when the total amount of polymerizable monomers in the curable composition is set to 100g, the photochromic compound is added in a manner that results in 0.106mmol.

[0933] The following additives are used as additives.

[0934] Dimethyltin dichloride: 0.05 parts by weight

[0935] Irganox 245: 0.1 parts by weight

[0936] 2-Ethylhexyl 4-methoxycinnamic acid: 0.6 parts by weight

[0937] (Manufacturing of solidified products)

[0938] After thorough degassing, the prepared curable composition was injected into a glass mold with a 1 mm gap, and polymerization was carried out by casting. Polymerization was performed in an air furnace, gradually increasing the temperature from 27°C to 120°C over 18 hours. After polymerization, the cured material was removed from the glass mold, yielding a 1 mm thick photochromic cured product. The obtained photochromic cured product was evaluated in the same manner as in Example 23. The results are shown in Table 9.

[0939] (Examples 86-94, Comparative Example 14)

[0940] Photochromic cured products were prepared using the photochromic compounds shown in Table 9, following the same method as in Example 85. The results are summarized in Table 9.

[0941] [Table 9]

[0942] Table 9

[0943]

[0944] (Example 95)

[0945] First process

[0946] Referring to the method described in Patent Document 6, 20.8 g (45.0 mmol) of the compound of formula (22A) synthesized from 3-bromo-4-methoxybenzophenone, 550 mL of toluene, 7.51 g (63.0 mmol) of indoline, and 17.3 g (179.7 mmol) of sodium tert-butoxide were added, and the mixture was stirred under reduced pressure to remove dissolved oxygen. Then, 0.41 g (0.4 mmol) of Pd2(dba)3 and 0.86 g (1.8 mmol) of X-phos were added to the reaction solution, and the mixture was heated to 80 degrees Celsius.

[0947]

[0948] Continue heating until the starting material disappears. After the reaction is complete and cooled to room temperature, add 700 mL of tetrahydrofuran and 10% hydrochloric acid. After neutralization, separate the layers. Concentrate the obtained organic layer and then re-slurry it with 200 mL of methanol for purification. The carboxylic acid compound shown in formula (23A) is obtained in 93% yield.

[0949]

[0950] Second process

[0951] In addition to using the carboxylic acid compound (23A) obtained in the first step, the iodine compound shown in the following formula (24A) was obtained in a yield of 75% by referring to the method of Patent Document 6.

[0952]

[0953] Third process

[0954] 18.3 g (31.3 mmol) of the compound of formula (24A) obtained in the second step was added to 400 mL of toluene, and azeotropic dehydration was performed until the water content in the toluene was below 100 ppm. After azeotropic dehydration, the mixture was slowly cooled to -20 °C, and 24 mL of n-BuLi (1.6 mol / L hexane solution) was slowly added dropwise while maintaining the temperature at -15 to -20 °C. After confirming that the starting material had been consumed, 3.5 g of dehydrated acetone was added dropwise. After the addition, the temperature was slowly raised to room temperature. After warming, 200 mL of water was added, and the mixture was separated. The water washing was repeated until the pH of the aqueous layer reached 7-8. The solvent of the obtained organic layer was removed, and the mixture was purified by silica gel-based chromatography to obtain the compound of formula (25A) in 85% yield.

[0955]

[0956] Fourth process

[0957] 19.8 g (104.18 mmol) of p-toluenesulfonic acid monohydrate was added to 620 mL of toluene, and azeotropic dehydration was carried out until the water content in the toluene was below 300 ppm. Then, a toluene solution obtained by dissolving 13.7 g (38.326.6 mmol) of the aforementioned formula (25A) in 100 mL of toluene was slowly added while maintaining the temperature at 85-100 °C, and the solution was refluxed after each addition. After confirming that the raw material was consumed, the solution was cooled to room temperature, 500 mL of water was added, and the mixture was separated. This operation was repeated 3 times, and the solvent of the resulting organic layer was removed. The solution was purified by silica gel-based chromatography, thereby giving the naphthol compound shown in formula (26A) in 74% yield.

[0958]

[0959] Fifth process

[0960] 2.04 g (5.0 mol) of the naphthol compound of formula (26A) and 1.60 g (6.0 mmol) of propargyl alcohol of formula (27A) were dissolved in 40 mL of toluene, and then 0.12 g (0.5 mmol) of p-toluenesulfonic acid pyridinium salt was added. The mixture was stirred at 85 °C for 1 hour. After the naphthol derivative of the raw material was consumed, the mixture was cooled to room temperature, 40 mL of water was added, and the mixture was separated.

[0961]

[0962] The solvent was removed from the obtained organic layer, and the mixture was purified by silica gel-based chromatography to obtain the photochromic compound shown in formula (28A) in 78% yield.

[0963]

[0964] The elemental analysis values ​​of the photochromic compound shown in formula (28A) are C: 82.16%, H: 6.01%, and N: 2.14%, which are similar to C. 45 H 39 The calculated values ​​of NO4, namely C: 82.17%, H: 5.98%, and N: 2.13%, are in good agreement.

[0965] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 6H peak based on methyl groups in the vicinity of δ0.5–3.0 ppm, a 13H peak based on indoline rings and methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 20H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0966] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0967] (Example 96)

[0968] First process

[0969] In the first step of Example 1, 3-bromo-4-methylbenzophenone was used instead of 3-bromo-4-methoxybenzophenone, and in the third step, 4-heptanone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (29A).

[0970]

[0971] Second process

[0972] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (29A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (30A). Otherwise, the same procedure was carried out to obtain the photochromic compound of the following formula (31A) in a yield of 71%.

[0973]

[0974] The elemental analysis values ​​of the photochromic compound shown in formula (31A) are C: 84.35%, H: 7.09%, and N: 1.96%, which are similar to C. 51 H 51 The calculated values ​​of NO3, namely C: 84.38%, H: 7.08%, and N: 1.93%, are in good agreement.

[0975] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 22H of methyl, propyl, and propoxy groups in the vicinity of δ0.5–3.0 ppm, peaks based on 9H of indoline ring, methoxy, and propoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks based on 20H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0976] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0977] (Example 97)

[0978] First process

[0979] Referring to the method described in Patent Document 3, benzophenone of the following formula (32A) was synthesized by reacting 4'-methyl(1,1'-biphenyl)-4-carbonyl chloride with 2-bromoanisole. Except for this, the reaction was carried out in the same manner as the first step of Example 1. In the third step, cyclooctanone was used instead of acetone to synthesize the spirocyclic compound of the following formula (33A).

[0980]

[0981] Second process

[0982] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (33A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (34A). Otherwise, the same procedure was carried out to obtain the photochromic compound of the following formula (35A) in a yield of 78%.

[0983]

[0984] The elemental analysis values ​​of the photochromic compound shown in formula (35A) are C: 84.04%, H: 7.01%, and N: 1.63%, which are similar to C. 61 H 61 The calculated values ​​of NO4, namely C: 84.01%, H: 7.05%, and N: 1.61%, are in good agreement.

[0985] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 27H of methyl, propoxy, and cyclooctane rings in the vicinity of δ0.5–3.0 ppm, peaks based on 11H of indoline, methoxy, and propoxy rings in the vicinity of δ3.0–5.0 ppm, and peaks based on 23H of aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[0986] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0987] (Example 98)

[0988] First process

[0989] In the first step of Example 95, 3-methylindoline was used instead of indoline, and the reaction was carried out in the same manner otherwise to obtain the iodine compound shown in the following formula (36A).

[0990]

[0991] Second process

[0992] 25.8 g (43.1 mmol) of the iodine compound of formula (36A) above, 1.0 g (4.3 mmol) of palladium acetate, 42.3 g (431.0 mmol) of potassium acetate, 38.8 g (387.9 mmol) of potassium bicarbonate, 74.9 g (431.0 mmol) of dibromomethane, 260 mL of N,N-dimethylformamide (DMF), 86 mL of N,N-dimethylacetamide (DMAc), 4.2 mL of IPA, and 43 mL of water were added, and the mixture was heated to 80 °C. After confirming the consumption of the iodine body, the mixture was cooled to room temperature and separated using 100 mL of water and 300 mL of ethyl acetate. The solvent of the resulting organic layer was removed, and the mixture was purified by silica gel-based chromatography to give the compound of formula (37A) below in 54% yield.

[0993]

[0994] Third process

[0995] Add 11.2 g (23.2 mmol) of the compound shown in formula (37A), 7.8 g (69.6 mmol) of potassium tert-butoxide (tBuOK), and 400 mL of THF, and cool to 0-5 °C. Add 17.8 g (116 mmol) of 1-bromo-3-methoxypropane dropwise over 15 minutes. After the addition is complete, stir at room temperature. After confirming the consumption of the starting material, cool the mixture, add 80 mL of 2% hydrochloric acid and 500 mL of toluene, and separate the layers. Add 200 mL of water to the organic layer and wash with water. Repeat the water washing until the pH of the aqueous layer reaches 6-7. After removing the solvent from the obtained organic layer, add 500 mL of THF and 0.3 g of 5% Pd / C (50% aqueous), and conduct a pressurized reaction with hydrogen at 0.05-0.1 MPa. After confirming the consumption of raw materials, Pd / C was filtered out, the solvent of the obtained organic layer was removed, and the mixture was purified by silica gel-based chromatography, thereby obtaining the naphthol compound shown in the following formula (38A) in 71% yield.

[0996]

[0997] Fourth process

[0998] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (38A) was used instead of the naphthol compound of the aforementioned formula (26A), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (39A) in a yield of 69%.

[0999]

[1000] The elemental analysis values ​​of the photochromic compound shown in formula (39A) are C: 79.29%, H: 6.76%, and N: 1.80%, which are similar to C. 52 H 53 The calculated values ​​of NO6, namely C: 79.26%, H: 6.78%, and N: 1.78%, are in good agreement.

[1001] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed an 11H peak based on methyl and methoxypropyl groups in the vicinity of δ0.5–3.0 ppm, a 22H peak based on indoline ring, methoxy, and methoxypropyl groups in the vicinity of δ3.0–5.0 ppm, and a 20H peak based on aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[1002] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1003] (Example 99)

[1004] First process

[1005] In Example 95, 3-bromo-4-methyl-4'-methylbenzophenone was used instead of 3-bromo-4-methoxybenzophenone, and diethyl ketone was used instead of acetone. The reaction was carried out in the same manner otherwise, to obtain the naphthol compound shown in the following formula (40A) in 76% yield.

[1006]

[1007] Second process

[1008] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (40A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (41A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (42A) in a yield of 74%.

[1009]

[1010]

[1011] The elemental analysis values ​​of the photochromic compound shown in formula (42A) are C: 86.30%, H: 6.79%, and N: 2.13%, which are similar to C. 48 H 45 The calculated values ​​for NO2, namely C: 86.32%, H: 6.79%, and N: 2.10%, are in good agreement.

[1012] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl and ethyl 19H in the vicinity of δ0.5–3.0 ppm, peaks based on indoline ring and methoxy 7H in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[1013] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1014] (Example 100)

[1015] In Example 98, 3-bromo-4-methyl-4'-methoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone, and 1-bromo-3-trifluoromethylpropane was used instead of 1-bromo-3-methoxypropane. The reaction was carried out in the same manner otherwise, to obtain the naphthol compound shown in the following formula (43A) in 67% yield.

[1016]

[1017] Second process

[1018] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (43A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (44A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (45A) in a yield of 67%.

[1019]

[1020] The elemental analysis values ​​of the photochromic compound shown in formula (45A) are C: 71.80%, H: 5.67%, and N: 3.08%, which are similar to C. 55 H 52 The calculated values ​​of F6N2O4, namely C: 71.88%, H: 5.70%, and N: 3.05%, are in good agreement.

[1021] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl, 4-trifluoropropyl, and morpholino groups in the vicinity of δ0.5–3.0 ppm, peaks based on indoline ring, methoxy, and morpholino groups in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[1022] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1023] (Example 101)

[1024] First process

[1025] In the first step of Example 97, 4'-trifluoromethyl(1,1'-biphenyl)-4-carbonyl chloride was used instead of 4'-methyl(1,1'-biphenyl)-4-carbonyl chloride, 5-methoxyindoline was used instead of indoline, and 3,3,5,5-tetramethylcyclohexanone was used instead of cyclooctanone. The reaction was carried out in the same manner to obtain the naphthol compound shown in formula (46A) in 69% yield.

[1026]

[1027] Second process

[1028] In the fifth step of Example 95, the naphthol compound of formula (46A) was used instead of the naphthol compound of formula (26A), and the propargyl alcohol of formula (47) was used instead of the propargyl alcohol of formula (27A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (48A) in a yield of 52%.

[1029]

[1030]

[1031] The elemental analysis values ​​of the photochromic compound shown in formula (48A) are C: 78.68%, H: 7.20%, and N: 1.32%, which are similar to C. 70 H 76 The calculated values ​​of F3NO5, namely C: 78.70%, H: 7.17%, and N: 1.31%, are in good agreement.

[1032] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 40H based on the 3,3,5,5-tetramethylcyclohexane ring and hexoxy group near δ0.5–3.0 ppm, a peak of 14H based on the indoline ring, methoxy group, and hexoxy group near δ3.0–5.0 ppm, and a peak of 22H based on aromatic protons and alkene protons near δ5.0–9.0 ppm.

[1033] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1034] (Example 102)

[1035] First process

[1036] In the first step of Example 98, 5-fluoroindoline was used instead of indoline, and 2-[2-(2-methoxyethoxy)ethoxy]ethyl p-toluenesulfonate was used instead of 1-bromo-4-methoxypropane. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound shown in the following formula (49A) in 60% yield.

[1037]

[1038] Second process

[1039] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (49A) was used instead of the naphthol compound of the aforementioned formula (26A), and the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (50A) in a yield of 62%.

[1040]

[1041] The elemental analysis values ​​of the photochromic compound shown in formula (50A) are C: 72.80%, H: 6.67%, and N: 1.50%, which are similar to C. 57 H 62 FNO 10 The calculated values ​​of C: 72.82%, H: 6.65%, and N: 1.49% are in good agreement.

[1042] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on the 4H of 2-[2-(2-methoxyethoxy)ethoxy]ethyl in the vicinity of δ0.5–3.0 ppm, a peak based on the indoline ring, methoxy, and 2-[2-(2-methoxyethoxy)ethoxy]ethyl in the vicinity of δ3.0–5.0 ppm, and a peak based on the 19H of aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[1043] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1044] (Example 103)

[1045] First process

[1046] In the first step of Example 95, 5-methylindoline was used instead of indoline, and the reaction was carried out in the same manner to synthesize the naphthol compound shown in formula (51A). The obtained naphthol compound was reacted with propargyl alcohol of formula (27A) to obtain the photochromic compound shown in formula (52A) in 72% yield.

[1047]

[1048] The elemental analysis values ​​of the photochromic compound shown in formula (52A) are C: 82.21%, H: 6.17%, and N: 2.08%, which are similar to C. 46 H 41 The calculated values ​​of NO4, namely C: 82.24%, H: 6.15%, and N: 2.08%, are in good agreement.

[1049] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 9H peak based on methyl groups in the vicinity of δ0.5–3.0 ppm, a 13H peak based on indoline rings and methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 19H peak based on aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[1050] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1051] (Example 104)

[1052] First process

[1053] In Example 95, 5-trifluoromethylindoline was used instead of indoline, and 4-heptanone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in formula (53A) in 69% yield.

[1054]

[1055] Second process

[1056] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (53A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (34A) was used instead of the propargyl alcohol of the aforementioned formula (27A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (54A) in a yield of 68%.

[1057]

[1058] The elemental analysis values ​​of the photochromic compound shown in formula (54A) are C: 77.43%, H: 6.52%, and N: 1.65%, which are similar to C. 54 H 54 The calculated values ​​of F3NO4, namely C: 77.40%, H: 6.50%, and N: 1.67%, are in good agreement.

[1059] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 9H peak based on methyl groups in the vicinity of δ0.5–3.0 ppm, a 13H peak based on indoline rings and methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 19H peak based on aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[1060] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1061] (Example 105)

[1062] First process

[1063] In the third step of Example 95, spiro[5,5]undecane-3-one was used instead of acetone, and the reaction was carried out in the same manner to obtain the naphthol compound shown in the following formula (55A) in 54% yield.

[1064]

[1065] Second process

[1066] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (55A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (56A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (57A) in a yield of 61%.

[1067]

[1068]

[1069] The elemental analysis values ​​of the photochromic compound shown in formula (57A) are C: 85.11%, H: 6.46%, and N: 3.13%, which are similar to C. 64 H 58 The calculated values ​​of N2O3, namely C: 85.11%, H: 6.47%, and N: 3.10%, are consistent with each other well.

[1070] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 18H based on the spiro[5,5]undecane ring in the vicinity of δ0.5 to 3.0 ppm, a peak of 10H based on the indoline ring and methoxy group in the vicinity of δ3.0 to 5.0 ppm, and a peak of 30H based on the protons of aromatic protons and alkenes in the vicinity of δ5.0 to 9.0 ppm.

[1071] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1072] (Example 106)

[1073] First process

[1074] In the first step of Example 97, 4-phenylbenzoyl chloride was used instead of 4'-methyl(1,1'-biphenyl)-4-carbonyl chloride, and 4,4-diethylcyclohexanone was used instead of cyclooctanone. Otherwise, the reaction was carried out in the same manner to obtain the naphthol compound shown in the following formula (58A) in 69% yield.

[1075]

[1076] Second process

[1077] In the fifth step of Example 95, the naphthol compound of formula (58A) was used instead of the naphthol compound of formula (26A), and the propargyl alcohol of formula (59A) was used instead of the propargyl alcohol of formula (27A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (60A) in a yield of 68%.

[1078]

[1079] The elemental analysis values ​​of the photochromic compound shown in formula (60A) are C: 86.42%, H: 6.78%, and N: 3.63%, which are similar to C. 64 H 60 The calculated values ​​of N2O2, namely C: 86.45%, H: 6.80%, and N: 3.60%, are in good agreement.

[1080] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on the diethylcyclohexane ring and the 21H of the methyl group near δ0.5–3.0 ppm, a peak based on the indoline ring, the methyl group and the methoxy group near δ3.0–5.0 ppm, and a peak based on the aromatic proton and the proton of the alkene near δ5.0–9.0 ppm.

[1081] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1082] (Analysis results of naphthol derivatives)

[1083] Table 10 summarizes the analytical results of the naphthol derivatives used in Examples 95–106.

[1084] [Table 10]

[1085] Table 10

[1086]

[1087] (Physical property evaluation of photochromic plastic lenses produced by coating method)

[1088] (Examples 107-118, Comparative Example 15)

[1089] Photochromic laminates were prepared using the photochromic compounds obtained from Examples 95-106 and of formula (I) below, following the same method as in Example 23. It should be noted that compound (I) was synthesized according to the method described in International Publication No. 2011 / 034202.

[1090]

[1091] <Evaluation Methods>

[1092] The photochromic laminate obtained was evaluated using the same method as in Example 23. The results of Examples 107, 115, Comparative Examples 1, 4, 5, 7, 8 and 15 are summarized in Table 11, and the results of Examples 108-114, 116-118 are summarized in Table 12.

[1093] [Table 11]

[1094] Table 11

[1095]

[1096] Figure 2 This is another example of a graph showing the relationship between the 23°C fading half-life and high-temperature color development of the photochromic laminates of the embodiments and comparative examples. Figure 2 Based on data from Examples 107, 115, Comparative Examples 1, Comparative Examples 4-8, and Comparative Example 15. The comparative examples, from left to right, are Comparative Example 4, Comparative Example 15, Comparative Example 1, Comparative Example 5, Comparative Example 8, and Comparative Example 7.

[1097] [Table 12]

[1098] Table 12

[1099]

[1100] Example 119

[1101] First process

[1102] Referring to the method described in Patent Document 3, benzophenone of the following formula (61A), synthesized by reacting 4-trifluoromethylbenzoyl chloride with 2-bromotoluene, was used. Except for this, the reaction was carried out in the same manner as the first step of Example 95. In the third step, dibutyl ketone was used instead of acetone to synthesize the spirocyclic compound of the following formula (62A).

[1103]

[1104] Second process

[1105] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (62A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (63A). Otherwise, the same procedure was carried out to obtain the photochromic compound of the following formula (64A) in a yield of 71%.

[1106]

[1107]

[1108] The elemental analysis values ​​of the photochromic compound shown in formula (64A) are C: 78.75%, H: 6.51%, and N: 1.72%, which are similar to C. 53 H 52 The calculated values ​​of F3NO3, namely C: 78.78%, H: 6.49%, and N: 1.73%, are in good agreement.

[1109] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl and butyl 24H in the vicinity of δ0.5–3.0 ppm, peaks based on indoline ring and methoxy 10H in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons 18H in the vicinity of δ5.0–9.0 ppm.

[1110] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1111] Example 120

[1112] First process

[1113] In the first step of Example 98, indoline was used instead of 3-methylindoline, and in the third step, 3-bromo-1,1,1-trifluoropropane was used instead of 1-bromo-3-methoxypropane to synthesize the naphthol compound shown in formula (65A).

[1114]

[1115] Second process

[1116] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (65A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (66A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (67A) in a yield of 63%.

[1117]

[1118] The elemental analysis values ​​of the photochromic compound shown in formula (67A) are C: 70.46%, H: 5.07%, and N: 1.63%, which are similar to C. 50 H 43 The calculated values ​​of F6NO5, namely C: 70.50%, H: 5.09%, and N: 1.64%, are in good agreement.

[1119] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed an 8H peak based on 3-trifluoroethyl in the vicinity of δ0.5–3.0 ppm, a 16H peak based on indoline ring and methoxy group in the vicinity of δ3.0–5.0 ppm, and a 19H peak based on aromatic proton and alkene proton in the vicinity of δ5.0–9.0 ppm.

[1120] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1121] Example 121

[1122] First process

[1123] In the first step of Example 97, 4-phenoxybenzoyl chloride was used instead of 4'-methyl(1,1'-biphenyl)-4-carbonyl chloride, and methyl propyl ketone was used instead of cyclooctanone. Otherwise, the reaction was carried out in the same manner to synthesize the spirocyclic compound shown in the following formula (68A).

[1124]

[1125] Second process

[1126] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (68A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (69A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (70A) in a yield of 69%.

[1127]

[1128]

[1129] The elemental analysis values ​​of the photochromic compound shown in formula (70A) are C: 82.12%, H: 6.01%, and N: 1.75%, which are similar to C. 54 H 47 The calculated values ​​of NO5, namely C: 82.10%, H: 6.00%, and N: 1.77%, are in good agreement.

[1130] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl, propyl, and dihydrobenzofuranyl groups in the vicinity of δ0.5–3.0 ppm, peaks based on indoline ring, methoxy, and dihydrobenzofuranyl groups in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[1131] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1132] Example 122

[1133] First process

[1134] In the first step of Example 97, 4-trifluoromethoxybenzoyl chloride was used instead of 4'-methyl(1,1'-biphenyl)-4-carbonyl chloride, and 4,4-diethylcyclohexanone was used instead of cyclooctanone. Otherwise, the reaction was carried out in the same manner to synthesize the spirocyclic compound shown in the following formula (71A).

[1135]

[1136] Second process

[1137] In the fifth step of Example 95, the naphthol compound of formula (71A) was used instead of the naphthol compound of formula (26A), and the propargyl alcohol of formula (72A) was used instead of the propargyl alcohol of formula (27A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (73A) in a yield of 57%.

[1138]

[1139] Third process

[1140] 4.4 g (5.0 mmol) of the photochromic compound of formula (73A) and 0.75 g (11.0 mmol) of imidazole were dissolved in 50 mL of dimethylformamide. The internal temperature was cooled to below 5°C, and while maintaining the internal temperature below 5°C, a 10 mL solution of 2.3 g (5.5 mmol) of [tris(trimethylsiloxy)silylethyl]dimethylchlorosilane was slowly added dropwise. After the addition, the temperature was slowly raised to room temperature and stirred for 12 hours. After the reaction was complete, 50 mL of water and 100 mL of toluene were added, and the mixture was separated. The solvent of the resulting organic layer was removed, and the mixture was purified by silica gel-based chromatography to obtain the photochromic compound of formula (74A) in 89% yield.

[1141]

[1142] The elemental analysis values ​​of the photochromic compound shown in formula (74A) are C: 64.64%, H: 7.19%, and N: 1.10%, which are similar to C. 68 H 90 The calculated values ​​of F3NO9Si5, namely C: 64.67%, H: 7.18%, and N: 1.11%, are in good agreement.

[1143] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 57H peak based on methyl, 4,4-diethylcyclohexylcyclo, propoxy, and [tris(trimethylsiloxy)silylethyl]silyl groups in the vicinity of δ0.5–3.0 ppm, a 14H peak based on indoline ring, methoxy, and propoxy groups in the vicinity of δ3.0–5.0 ppm, and a 19H peak based on aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[1144] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1145] Example 123

[1146] First process

[1147] In the first step of Example 119, 3-bromo-4-methylbenzoyl chloride was used instead of 4-trifluoromethylbenzoyl chloride, and 2,3,4-trifluoro-1,1'-biphenyl was used instead of 2-bromotoluene to synthesize benzophenone as shown in formula (75A) in 83% yield.

[1148]

[1149] Second process

[1150] In the first step of Example 98, benzophenone of the aforementioned formula (75A) was used instead of 3-bromo-4-methoxybenzophenone, and indoline was used instead of 3-methylindoline. In the third step, 1-bromo-4-methoxybutane was used instead of 1-bromo-3-methoxypropane. The reaction was carried out in the same manner otherwise to synthesize the naphthol compound shown in the following formula (76A).

[1151]

[1152] Third process

[1153] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (76A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (77A). Otherwise, the same procedure was carried out to obtain the photochromic compound of the following formula (78A) in a yield of 71%.

[1154]

[1155]

[1156] The elemental analysis values ​​of the photochromic compound shown in formula (78A) are C: 76.13%, H: 6.17%, and N: 1.44%, which are similar to C. 61 H 59 The calculated values ​​of F4NO5, namely C: 76.15%, H: 6.18%, and N: 1.46%, are in good agreement.

[1157] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 20H of methyl, 4-methoxybutyl, and propoxy in the vicinity of δ0.5–3.0 ppm, peaks based on 19H of indoline ring, methoxy, and propyloxy in the vicinity of δ3.0–5.0 ppm, and peaks based on 20H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[1158] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1159] Example 124

[1160] First process

[1161] In the third step of Example 95, cyclooctanone was used instead of acetone, and the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (79A).

[1162]

[1163] Second process

[1164] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (79A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (72A) was used instead of the propargyl alcohol of the aforementioned formula (27A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (80A) in a yield of 67%.

[1165]

[1166] Third process

[1167] Referring to the method described in Patent Document 9 (International Publication No. 2019 / 013249), a compound of formula (81A) synthesized from polytetramethylene glycol with a number average molecular weight of 1000 is reacted with a photochromic compound of formula (80A) to obtain a photochromic compound of formula (82A) in a yield of 67%.

[1168]

[1169]

[1170] The proton nuclear magnetic resonance spectrum of the photochromic compound represented by the aforementioned formula (82A) was measured. The results showed a peak of about 96H based on the cyclooctane ring, propoxy group, succinic acid group, and polytetramethylene glycol chain in the vicinity of δ0.5 to 3.0 ppm, a peak of about 84H based on the indoline ring, methoxy group, propoxy group, and polytetramethylene glycol chain in the vicinity of δ3.0 to 5.0 ppm, and a peak of 40H based on the protons of aromatic protons and olefins in the vicinity of δ5.0 to 9.0 ppm.

[1171] Example 125

[1172] First process

[1173] In the first step of Example 98, (3-bromo-4-methoxyphenyl)[4'-(trifluoromethyl)[1,1'-biphenyl]-4-yl] methyl ketone was used instead of 3-bromo-4-methoxybenzophenone, and indoline was used instead of 3-methylindoline. In the third step, 1-bromo-2-methoxyethane was used instead of 1-bromo-3-methoxypropane. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in formula (83A).

[1174]

[1175] Second process

[1176] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (83A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (27A) was used instead of the propargyl alcohol of the aforementioned formula (84A). Otherwise, the same procedure was carried out to obtain the photochromic compound of the following formula (85A) in a yield of 75%.

[1177]

[1178] The elemental analysis values ​​of the photochromic compound shown in formula (85A) are C: 77.21%, H: 6.02%, and N: 1.53%, which are similar to C. 58 H 54 The calculated values ​​of F3NO5, namely C: 77.23%, H: 6.03%, and N: 1.55%, are in good agreement.

[1179] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed an 11H peak based on 2-methoxyethyl and propyl in the vicinity of δ0.5–3.0 ppm, a 20H peak based on indoline ring, methoxy, and 2-methoxyethyl in the vicinity of δ3.0–5.0 ppm, and a 23H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[1180] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1181] Example 126

[1182] First process

[1183] In the first step of Example 119, benzophenone of the following formula (86A) was synthesized in 85% yield by using 3-bromo-4-methoxybenzoyl chloride instead of 4-trifluoromethylbenzoyl chloride and 4-(1-methylethoxy)-1,1'-biphenyl instead of 2-bromotoluene.

[1184]

[1185] Second process

[1186] In the first step of Example 98, benzophenone of the aforementioned formula (86A) was used instead of 3-bromo-4-methoxybenzophenone, and indoline was used instead of 3-methylindoline. In the third step, 1-bromo-4-fluorobutane was used instead of 1-bromo-3-methoxypropane. The reaction was carried out in the same manner otherwise to synthesize the naphthol compound shown in the following formula (87A).

[1187]

[1188] Third process

[1189] In the fifth step of Example 95, the naphthol compound of the aforementioned formula (87A) was used instead of the naphthol compound of the aforementioned formula (26A), and the propargyl alcohol of the aforementioned formula (72A) was used instead of the propargyl alcohol of the aforementioned formula (27A). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (88A) in a yield of 62%.

[1190]

[1191] Fourth process

[1192] In the third step of Example 124, sebacate chloride was used instead of the compound of the aforementioned formula (81A), and the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (89A) in a yield of 69%.

[1193]

[1194] The elemental analysis values ​​of the photochromic compound shown in formula (89A) are C: 77.44%, H: 6.78%, and N: 1.34%, which are similar to C. 134 H 140 F4N2O 14 The calculated values ​​of C: 77.43%, H: 6.79%, and N: 1.35% are in good agreement.

[1195] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on 64H of 4-fluorobutyl, isopropoxy, propoxy, and sebacate groups in the vicinity of δ0.5–3.0 ppm, a peak based on 30H of indoline ring, methoxy, isopropoxy, and propoxy groups in the vicinity of δ3.0–5.0 ppm, and a peak based on 46H of aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[1196] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[1197] Table 13 summarizes the analytical results of the naphthol derivatives used in Examples 119–126.

[1198] [Table 13]

[1199] Table 13

[1200]

[1201] (Examples 127-134)

[1202] Photochromic laminates were prepared using the photochromic compounds obtained in Examples 119-126, following the same method as in Example 23. It should be noted that, regarding the photochromic compounds in Examples 124 and 126, when the total amount of free radical polymerizable monomers was set to 100 g in the curable composition, the photochromic compound was added at a rate of 0.125 mmol. The evaluation results are summarized in Table 14.

[1203] [Table 14]

[1204] Table 14

[1205]

[1206] <Property Evaluation of Photochromic Layers Fabricated Using Adhesive Method>

[1207] (Example 135)

[1208] The adhesive sheet is fabricated using the following method. The adhesive sheet consists of a first optical sheet, a first adhesive layer, a photochromic layer, a second adhesive layer, and a second optical sheet, stacked sequentially. A 400 μm thick polycarbonate sheet is used as both the first and second optical sheets.

[1209] (Preparation of the composition for forming a photochromic layer)

[1210] In a 2L four-necked flask equipped with a stirring blade, cooling pipe, thermometer, and nitrogen inlet pipe, 315 parts by mass of polycarbonate diol with a number average molecular weight of 1000, 100 parts by mass of isophorone diisocyanate, and 72 parts by mass of toluene were added. The mixture was reacted at 100°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer with isocyanate groups at the ends. After the urethane prepolymer reaction was complete, the reaction solution was cooled to approximately 0°C and dissolved in 205 parts by mass of tert-butanol and 382 parts by mass of diethyl ketone, and the solution temperature was maintained at 0°C. Then, a mixed solution of 21.3 parts by mass of bis(4-aminocyclohexyl)methane and 20 parts by mass of diethyl ketone as a chain extender was added dropwise over 30 minutes, and the reaction was carried out at 0°C for 1 hour. Then, 8.1 parts by mass of 1,2,2,6,6-pentamethyl-4-aminopiperidine were added dropwise, and the mixture was reacted at 0°C for 1 hour to obtain a diethyl ketone solution of terminal non-reactive carbamate urea resin.

[1211] 100 parts by weight of the obtained terminal non-reactive urethane urea resin solution, 6.3 parts by weight of the photochromic compound of Example 95 (formula (28A) above), a mixture of isomers of 4,4'-methylenebis(cyclohexyl isocyanate) (polyisocyanate compound), 0.4 parts by weight of ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] as an antioxidant, and 0.06 parts by weight of DOW CORNING TORAY L-7001 as a surfactant were added and stirred and mixed at room temperature to obtain a composition for forming a photochromic layer.

[1212] In addition, a photochromic compound was added at a rate of 0.25 mmol relative to 100 parts by weight of the terminal non-reactive urethane resin.

[1213] (Preparation of the adhesive layer composition)

[1214] A 5L separable flask (4-necked) equipped with a stirring blade, cooling pipe, thermometer, and nitrogen inlet pipe was prepared. 400 parts by mass of polycarbonate diol (number average molecular weight 1000), 175 parts by mass of isophorone diisocyanate, and 120 parts by mass of toluene were added to the flask. The mixture was reacted at 110°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer with isocyanate groups at the ends. After the urethane prepolymer reaction was complete, the reaction solution was cooled to approximately 20°C and dissolved in 2500 parts by mass of propylene glycol-monomethyl ether, maintaining the temperature at 20°C. Next, 60 parts by mass of isophorone diamine, acting as a chain extender, were added dropwise, and the reaction was carried out at 20°C for 1 hour. Then, 3 parts by mass of n-butylamine were further added dropwise, and the reaction was carried out at 20°C for 1 hour, thereby obtaining a propylene glycol-monomethyl ether solution of a terminally non-reactive urethane urea resin.

[1215] Add 0.2 parts by mass of DOW CORNING TORAY L-7001 as a surfactant to 500 parts by mass of the obtained terminal non-reactive urethane resin solution, and stir and mix at room temperature to obtain a composition for adhesive layer.

[1216] (Manufacturing of adhesive sheets)

[1217] Using a coating machine (manufactured by TESTER SANGYO CO,.LTD.), the adhesive layer composition was coated onto one main surface of the first optical film at a coating speed of 0.5 m / min, and dried at a drying temperature of 110°C for 3 minutes, thereby obtaining a first optical film with a first coating film thickness of 5 μm. Using the same method, the adhesive layer composition was coated onto one main surface of the second optical film to obtain a second optical film with a second coating film.

[1218] Next, using a coating machine (manufactured by TESTER SANGYO CO,.LTD.), the photochromic layer forming composition was coated onto a 50 μm thick OPP film (stretched polypropylene film) at a coating speed of 0.3 m / min, and dried at a drying temperature of 100°C for 5 minutes. This yielded a third coating. Then, the third coating was bonded to the first optical sheet in contact with the first coating. The OPP film was peeled off from the structure, and the second optical sheet and the third coating were bonded together with the exposed main surface of the third coating in contact with the second coating. The resulting laminate was then left to stand at 40°C under vacuum for 24 hours, followed by heat treatment at 110°C for 60 minutes, then humidified at 60°C and 100% RH for 24 hours, and finally left to stand at 40°C under vacuum for 24 hours to obtain an adhesive sheet. The obtained adhesive sheet was evaluated in the same manner as in Example 23. The results are shown in Table 7.

[1219] (Examples 136-146, Comparative Example 16)

[1220] Adhesive sheets were prepared using the photochromic compounds shown in Tables 15 and 16, following the same method as in Example 135. The results of Examples 135, 136, Comparative Examples 9, 10, 12, and 16 are summarized in Table 15, and the results of Examples 137–146 are summarized in Table 16.

[1221] [Table 15]

[1222] Table 15

[1223]

[1224] [Table 16]

[1225] Table 16

[1226]

[1227] <Physical Property Evaluation of Photochromic Cured Products Produced by Mixing Method>

[1228] (Example 147)

[1229] (Preparation of curable compositions)

[1230] First, the photochromic compound, additive, and polymerizable compound obtained in Example 95 are mixed to obtain a curable composition.

[1231] As a polymerizable compound, a polymerizable compound prepared by combining and mixing the following polymerizable monomers is used.

[1232] 1,3-Bis(isocyanate methyl)cyclohexane: 36.7 parts by weight

[1233] Pentaerythritol tetra(3-mercaptopropionate): 39.4 parts by weight

[1234] Polyoxyethylene polyoxypropylene lauryl ether (manufactured by AOKIOIL INDUSTRIAL Co., Ltd., WANDERSURF140): 17.4 parts by weight

[1235] 1-Decanethiol: 2.8 parts by weight

[1236] RX-1 prepared using the method described in Patent Document 10: 3.8 parts by mass

[1237] It should be noted that when the total amount of polymerizable monomers in the curable composition is set to 100g, the photochromic compound is added in a manner that results in 0.106mmol.

[1238] The following additives are used as additives.

[1239] Dimethyltin dichloride: 0.05 parts by weight

[1240] Irganox 245: 0.1 parts by weight

[1241] 2-Ethylhexyl 4-methoxycinnamic acid: 0.6 parts by weight

[1242] (Manufacturing of solidified products)

[1243] After thorough degassing, the prepared curable composition was injected into a glass mold with a 1 mm gap, and polymerization was carried out by casting. Polymerization was performed in an air furnace, gradually increasing the temperature from 27°C to 120°C over 18 hours. After polymerization, the cured material was removed from the glass mold, yielding a 1 mm thick photochromic cured product. The obtained photochromic cured product was evaluated in the same manner as in Example 23. The results are shown in Table 17.

[1244] (Examples 148-155, Comparative Examples 14 and 17)

[1245] Photochromic cured products were prepared using the photochromic compounds shown in Table 17, following the same method as in Example 147. The results are summarized in Table 17.

[1246] [Table 17]

[1247] Table 17

[1248]

[1249] The preferred embodiments of the present invention are described below. [1]

[1251] A photochromic compound having the framework shown in formula (1):

[1252]

[1253] In the aforementioned formula (1),

[1254] M is C, Si, or Ge.

[1255] Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1256] Z 1 It is a group represented by formula (1a) or formula (1b) below.

[1257]

[1258] In the aforementioned equation (1a),

[1259] R 1 The substituted or unsubstituted aryl group, the substituted or unsubstituted heteroaryl group, or the substituted or unsubstituted fused polycyclic aromatic rings fused with aromatic rings or aromatic heterocyclic rings on these substituents,

[1260] R 2 It is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a) below.

[1261] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[1262] In the aforementioned equation (2a),

[1263] Q 1 It is an alkylene or haloalkylene.

[1264] Q 2 It is an alkylene or haloalkylene.

[1265] Q 3 It is an alkyl or haloalkyl group.

[1266] X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O),

[1267] R 700 and R 701 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1268] a is an integer that is 0, or greater than 1 and less than 3.

[1269]

[1270] In equation (1b),

[1271] Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1272] Y 1 For substituted or unsubstituted methylene,

[1273] Y 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C = CR 602 Or CC,

[1274] R 600 R 601 and R 602 Each of the following can be independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1275] Y 3 For substituted or unsubstituted methylene,

[1276] m is an integer from 1 to 4, n is an integer from 0 to 4, and m+n is an integer greater than 2. [2]

[1278] The photochromic compound according to [1] has the skeleton shown in the following formula (2):

[1279]

[1280] In the aforementioned equation (2), Z 1 M and M have the same meaning as in the aforementioned equation (1). [3]

[1282] The photochromic compound according to [1] or [2] has the skeleton shown in the following formula (3):

[1283]

[1284] In the aforementioned equation (3), Z 1 M and M have the same meaning as in the aforementioned equation (1),

[1285] R 3 and R 4 Each of the following can be independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the aforementioned formula (2a), a substituted or unsubstituted cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aroxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3).

[1286] L 1 -R 400 (X3)

[1287] In the aforementioned formula (X3),

[1288] R 400 It is a silyl group that is a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or has alkyl, alkoxy, or aryl substituents.

[1289] L 1 The group represented by the following formula (X2)

[1290]

[1291] In the aforementioned equation (X2), R 30 The group is represented by the following formula (X2a).

[1292]

[1293] In the aforementioned equations (X2) and (X2a),

[1294] J is a divalent group, which can be independently a directly attached, substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR group. 301 R 301 It is a hydrogen atom or an alkyl group.

[1295] L represents an oxygen atom or a sulfur atom.

[1296] R 300 It is an alkylene group, or a silylene group having alkyl or aryl substituents.

[1297] R 302 R 303 and R 304 Each is independently an alkylene group.

[1298] h, j, k, and l are each an independent integer of 0 or 1.

[1299] i is an integer from 1 to 200. When i is 2 or higher, multiple R 30 The structures can be either the same or different, and the dashed line indicates the same as R. 400 The bond,

[1300] R 3 and R 4 Choose any one of the following to form a substituted or unsubstituted aliphatic ring with 3 to 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring with an aromatic hydrocarbon ring or an aromatic heterocycle fused to the aforementioned aliphatic ring, a substituted or unsubstituted heterocycle with 3 to 20 cyclic atoms, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or an aromatic heterocycle fused to the aforementioned heterocycle. [4]

[1302] The photochromic compound described in [4] is represented by the following formula (3):

[1303]

[1304] In the aforementioned equation (4), R 3 R 4 Z 1 M and M have the same meaning as in the aforementioned equation (3),

[1305] R 5 and R 6 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1306] R 7 and R 8 Each of the following groups can be independently hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a) above, the group represented by formula (X) below, or the group represented by formula (X3) above.

[1307] b is an integer from 0 to 3, and c is an integer from 0 to 4.

[1308] When b is 2 to 3, multiple R 7 Choose either the same or different.

[1309] When c is 2 to 4, multiple R 8 Choose either the same or different.

[1310] In R where b is 2-3 and there are adjacent values 7 In the case of two adjacent R 7 Choose to bond together with these R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings.

[1311] In R where c is 2 to 4 and there are adjacent values 8 In the case of two adjacent R 8 Choose to bond together with these R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings.

[1312]

[1313] In formula (X),

[1314] E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group.

[1315] F represents an oxygen atom or a sulfur atom.

[1316] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[1317] g is 0 or 1.

[1318] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[1319] When G is an oxygen atom or a sulfur atom, R 201 It is a group other than a hydrogen atom. [5]

[1321] The photochromic compound described in [4] is represented by the following formula (5):

[1322]

[1323] In the aforementioned equation (5),

[1324] R 3 R 4 R 7 R 8 Z 1 b and c have the same meaning independently as in the aforementioned equation (4).

[1325] R 9 and R 10 Each of the following can be independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, or a group represented by formula (X3) above.

[1326] d is an integer from 0 to 5.

[1327] When d is 2 to 5, multiple R 9 The groups can be chosen to be the same or different from each other.

[1328] In the case of adjacent R 9 In the case of two adjacent R 9 Choose to bond together with these R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings.

[1329] e is an integer from 0 to 5.

[1330] When e is 2 to 5, multiple R 10 The groups can be chosen to be the same or different from each other.

[1331] In the case of adjacent R 10 In the case of two adjacent R 10 Choose to bond together with these R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings. [6]

[1333] The photochromic compound according to any one of [1] to [5] has the skeleton shown in the following formula (7):

[1334]

[1335] In the aforementioned equation (7), M and Z 1 The meanings of ring A and ring A are the same as those in equation (1) above.

[1336] R 11 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkithhiol group, a substituted or unsubstituted arylthiol group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, or a substituted or unsubstituted aryloxy group.

[1337] R 12 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, or a substituted or unsubstituted aryloxy group. [7]

[1339] According to any one of [1] to [6], the photochromic compound, wherein Z 1 Having the group shown in formula (1a), R 1 The phenyl group can be substituted or unsubstituted. [8]

[1341] The photochromic compound according to any one of [1] to [7], wherein Z 1 Having the group shown in formula (1a) above, R 2 It is an alkyl group with 1 or more but less than 5 carbon atoms, or a phenyl group with or without substitution. [9]

[1343] According to any one of [1] to [6], the photochromic compound, wherein Z 1 It has the group shown in the following formula (1b), where ring B is a substituted or unsubstituted phenyl group.

[10]

[1345] The photochromic compound according to any one of [1] to [6] and [9], wherein Z 1 It has a group as shown in the following formula (1b), where m and n are 1.

[11]

[1347] A curable composition comprising any one of the photochromic compounds described in [1] to

[10] , and comprising at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerizable reactive group, and a (thio)carbamate (urea) polymer.

[12]

[1349] A cured product, which is a cured product of the curable composition described in

[11] .

[13]

[1351] An optical article comprising the cured material described in

[12] .

[14]

[1353] A lens comprising any one of the photochromic compounds described in [1] to

[10] .

[15]

[1355] A pair of eyeglasses comprising the lens described in

[15] .

[16]

[1357] A naphthol derivative having the skeleton shown in formula (6) below:

[1358]

[1359] In the aforementioned equation (6),

[1360] M is C, Si, or Ge.

[1361] Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1362] Z 1 It is a group represented by formula (1a) or formula (1b) below.

[1363]

[1364] In the aforementioned equation (1a),

[1365] R 1 For substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups,

[1366] R 2 It is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a) below.

[1367] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[1368] In the aforementioned equation (2a),

[1369] Q 1 It is an alkylene or haloalkylene.

[1370] Q 2 It is an alkylene or haloalkylene.

[1371] Q 3 It is an alkyl or haloalkyl group.

[1372] X 1 and X 2 Independently defined as O, S, NR 700 R 701 PR 702 R 703 Or P(=O)R 704 ,

[1373] R 700 R 701 R 702 R 703 and R 704 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1374] a is an integer that is 0, or greater than 1 and less than 3.

[1375]

[1376] In the aforementioned equation (1b),

[1377] Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1378] Y 1 For substituted or unsubstituted methylene,

[1379] Y 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C = CR 602 Or CC,

[1380] R 600 R 601 and R 602 Each of the following can be independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1381] Y 3 For substituted or unsubstituted methylene,

[1382] m is an integer from 1 to 4, n is an integer from 0 to 4, and m+n is an integer greater than 2.

[1383] [1A]

[1384] A photochromic compound having the framework shown in formula (1A):

[1385]

[1386] In the aforementioned formula (1A),

[1387] M is C, Si, or Ge.

[1388] Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1389] Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1390] Y 111 For substituted or unsubstituted methylene,

[1391] Y 112 For substituted or unsubstituted methylene, oxygen atom, sulfur atom, NR 600 Or SO2,

[1392] R 600 It can be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1393] R 111 and R 112 Each of the following groups is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, a substituted or unsubstituted aryloxy group, a thiol group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (2a) below.

[1394] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[1395] In the aforementioned equation (2a),

[1396] Q 1 It is an alkylene or haloalkylene.

[1397] Q 2 It is an alkylene or haloalkylene.

[1398] Q 3 It is an alkyl or haloalkyl group.

[1399] X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O),

[1400] R 700 and R 701 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1401] a is 0, or 1 or more but less than 3.

[1402] [2A]

[1403] The photochromic compound according to [1A] has the skeleton shown in the following formula (2A):

[1404]

[1405] In the aforementioned equation (2), rings B and Y 111 Y 112 R 111 R 112 M and M have the same meaning as in the aforementioned equation (1A).

[1406] [3A]

[1407] The photochromic compound according to [1A] or [2A] has a skeleton as shown in the following formula (3A):

[1408]

[1409] In the aforementioned equation (3), Y 111 Y 112 R 111 R 112 M and M have the same meaning as in the aforementioned equation (1A).

[1410] R 3 and R 4 Each of the following can be independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a group represented by the aforementioned formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aroxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3).

[1411] L 1 -R 400 (X3)

[1412] In the aforementioned formula (X3),

[1413] R 400 It is a silyl group that is a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or has alkyl, alkoxy, or aryl substituents.

[1414] L 1 The group represented by the following formula (X2)

[1415]

[1416] In the aforementioned equation (X2), R 30 The group is represented by the following formula (X2a).

[1417]

[1418] In the aforementioned equations (X2) and (X2a),

[1419] J is a divalent group, which can be independently a directly attached, substituted, or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR group. 301 R 301 It is a hydrogen atom or an alkyl group.

[1420] L represents an oxygen atom or a sulfur atom.

[1421] R 300 It is an alkylene group, or a silylene group having alkyl or aryl substituents.

[1422] R 302 R 303 and R 304 Each is independently an alkylene group.

[1423] h, j, k, and l are each an independent integer of 0 or 1.

[1424] i is an integer from 1 to 200. When i is 2 or higher, multiple R 30 They can be the same or different; the dashed line indicates the same as R. 400 The bond,

[1425] R 3 and R 4 Choose any combination of the following to form a substituted or unsubstituted aliphatic ring with 3 to 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring with an aromatic hydrocarbon ring or aromatic heterocycle fused to the aforementioned aliphatic ring, a substituted or unsubstituted heterocyclic ring with 3 to 20 cyclic atoms, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to the aforementioned heterocyclic ring.

[1426] Y 114 The group can be hydroxyl, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, substituted or unsubstituted haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or any group represented by formula (2a) above.

[1427] p is an integer from 0 to 4.

[1428] [4A]

[1429] The photochromic compound described in [3A] is represented by the following formula (4A):

[1430]

[1431] In the aforementioned equation (4A), Y 111 Y 112 Y 114 R 3 R 4 R 111 R 112 M and M have the same meaning as in the aforementioned equation (3A).

[1432] R 5 and R 6 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1433] R 8 and R 113 Each of the following is independently a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted haloalkyl group, substituted or unsubstituted haloalkoxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aralkyl, substituted or unsubstituted aralkoxy, substituted or unsubstituted aroxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, substituted or unsubstituted haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a) above, the group represented by formula (X) below, or the group represented by formula (X3) above.

[1434] c is an integer from 1 to 4.

[1435] When c is 2 to 4, multiple R 8 Choose either the same or different.

[1436] R 11 and R 13 They can be combined with bonded carbon atoms to form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[1437] In R where c is 2 to 4 and there are adjacent values 8 In the case of two adjacent R 8 Choose to bond together with these R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings.

[1438]

[1439] In formula (X),

[1440] E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group.

[1441] F represents an oxygen atom or a sulfur atom.

[1442] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[1443] g is 0 or 1.

[1444] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[1445] When G is an oxygen atom or a sulfur atom, R 201 It is a group other than a hydrogen atom.

[1446] [5A]

[1447] The photochromic compound according to [4A] is represented by the following formula (5A):

[1448]

[1449] In the aforementioned formula (5A),

[1450] Y 111 Y 112 Y 114 R 3 R 4 R 111 R 112 R 113 c and p have the same meaning as in the aforementioned equation (4).

[1451] R 9 and R 10 Each of the following can be independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms, a nitro group, a substituted or unsubstituted alkoxyalkylthio group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group shown in (2a) above, or a group shown in (X3) above.

[1452] d is an integer from 0 to 5.

[1453] When d is 2 to 5, multiple R 9 The groups can be chosen to be the same or different from each other.

[1454] In the case of adjacent R 9 In the case of two adjacent R 9 Choose to bond together with these R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings.

[1455] e is an integer from 0 to 5.

[1456] When e is 2 to 5, multiple R 10 The groups can be chosen to be the same or different from each other.

[1457] In the case of adjacent R 10 In the case of two adjacent R 10 Choose to bond together with these R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic aromatic rings or aromatic heterocycles fused to these rings.

[1458] [6A]

[1459] The photochromic compound according to any one of [1A] to [5A], wherein R 111 and R 112 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted arylthio group, or a substituted or unsubstituted aryloxy group.

[1460] [7A]

[1461] A curable composition comprising any one of [1A] to [6A], and comprising at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerizable reactive group, and a (thio)carbamate (urea) polymer.

[1462] [8A]

[1463] A cured product, which is a cured product of the curable composition described in [7A].

[1464] [9A]

[1465] An optical article comprising the cured material described in [8A].

[1466] [10A]

[1467] A lens comprising any one of [1A] to [6A] photochromic compounds.

[1468] [11A]

[1469] A pair of eyeglasses comprising the lens described in [10A].

[1470] [12A]

[1471] A naphthol derivative having the skeleton shown in formula (6A):

[1472]

[1473] In the aforementioned formula (6A),

[1474] M is C, Si, or Ge.

[1475] Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1476] Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1477] Y 111 For substituted or unsubstituted methylene,

[1478] Y 112 For substituted or unsubstituted methylene, oxygen atom, sulfur atom, NR 600 Or SO2,

[1479] R 600 It can be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1480] R 111 and R 112 Each of the following groups is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, a substituted or unsubstituted aryloxy group, a thiol group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (2a) below.

[1481] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[1482] In the aforementioned equation (2a),

[1483] Q 1 It is an alkylene or haloalkylene.

[1484] Q 2 It is an alkylene or haloalkylene.

[1485] Q 3 It is an alkyl or haloalkyl group.

[1486] X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O),

[1487] R 700 and R 701 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[1488] a is 0, or 1 or more but less than 3.< / m>

Claims

1. A photochromic compound having a framework as shown in formula (1) or (1A): In the above formula (1), M is C, Si, or Ge. Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings. Z 1 It is a group represented by formula (1a) or formula (1b) below. In the aforementioned formula (1a), R 1 The substituted or unsubstituted aryl group, the substituted or unsubstituted heteroaryl group, or the substituted or unsubstituted fused polycyclic aromatic rings fused with aromatic rings or aromatic heterocyclic rings on these substituents, R 2 It is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a) below. -Q 1 -(X 1 Q 2 )a-X 2 Q 3 (2a) In the aforementioned formula (2a), Q 1 It is an alkylene or haloalkylene. Q 2 It is an alkylene or haloalkylene. Q 3 It is an alkyl or haloalkyl group. X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O), R 700 and R 701 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. a is an integer that is 0, or greater than 1 and less than 3. In equation (1b), Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings. Y 1 For substituted or unsubstituted methylene, Y 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C = CR 602 Or CC, R 600 R 601 and R 602 Each of the following can be independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Y 3 For substituted or unsubstituted methylene, m is an integer from 1 to 4, n is an integer from 0 to 4, and m+n is an integer greater than 2. In the aforementioned formula (1A), M, ring A, and ring B are each independently equivalent to the meanings in equation (1). Y 111 For substituted or unsubstituted methylene, Y 112 For substituted or unsubstituted methylene, oxygen atom, sulfur atom, NR 600 Or SO2, R 600 The meaning is the same as in equation (1b). R 111 and R 112 Each of the following can be independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, a substituted or unsubstituted aryloxy group, a thiol group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (2a).

2. The photochromic compound according to claim 1, having a skeleton as shown in formula (2) or (2A): In equation (2), Z 1 M and M have the same meaning as in equation (1). In equation (2A), rings B, M, and R 111 R 112 Y 111 and Y 112 They have the same meaning as in equation (1A).

3. The photochromic compound according to claim 1 or 2, having a skeleton as shown in formula (3) or (3A): In equation (3), Z 1 M and M have the same meaning as in equation (1). R 3 and R 4 Each of the following can be independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aroxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (X3) below. L 1 -R 400 (X3) In the aforementioned formula (X3), R 400 It is a silyl group that is a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or has alkyl, alkoxy, or aryl substituents. L 1 The group represented by the following formula (X2) In the formula (X2), R 30 The group is represented by the following formula (X2a). In equations (X2) and (X2a), J is a divalent group, which can be independently a directly attached, substituted, or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR group. 301 R 301 It is a hydrogen atom or an alkyl group. L represents an oxygen atom or a sulfur atom. R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents. R 302 R 303 and R 304 Each is independently an alkylene group. h, j, k, and l are each an independent integer of 0 or 1. i is an integer from 1 to 200. When i is 2 or higher, multiple R 30 Choose either the same or different; the dashed line indicates the same as R. 400 The bond, In the aforementioned formula (3A), R 3 and R 4 Each of these has the same meaning as in equation (3). R 3 and R 4 The following can be selected together with M to form a substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or an aromatic heterocycle fused to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 cyclic atoms, or a substituted or unsubstituted fused polycyclic ring having an aromatic ring or an aromatic heterocycle fused to the heterocycle. In the aforementioned formula (3A), Y 111 Y 112 R 111 R 112 M and M have the same meaning as in equation (1A). Y 114 The group can be hydroxyl, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, substituted or unsubstituted haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or a group represented by formula (2a). p is an integer from 0 to 4.

4. The photochromic compound according to claim 3, wherein, R 3 and R 4 Each of the following is independently a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkoxy group, substituted or unsubstituted aroxy group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, or a group represented by formula (X3).

5. The photochromic compound according to claim 3, which is represented by the following formula (4) or (4A), In equation (4), R 3 R 4 Z 1 M and M have the same meaning as in equation (3). R 5 and R 6 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 7 and R 8 Each of the following groups can be independently hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), the group represented by formula (X) below, or the group represented by formula (X3). b is an integer from 0 to 3, and c is an integer from 0 to 4. When b is 2 to 3, multiple R 7 Choose either the same or different. When c is 2 to 4, multiple R 8 Choose either the same or different. In R where b is 2-3 and there are adjacent values 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. In R where c is 2 to 4 and there are adjacent values 8 In the case of two adjacent R 8 Optional and bonded to R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. In the formula (X), E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group. F represents an oxygen atom or a sulfur atom. G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. g is 0 or 1. R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. When G is an oxygen atom or a sulfur atom, R 201 Groups other than hydrogen atoms In the aforementioned formula (4A), Y 111 Y 112 Y 114 R 3 R 4 R 111 R 112 M and p have the same meaning as in equation (3A). R 5 R 6 R 8 c has the same meaning as in equation (4). R 113 The following groups are included: hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted haloalkyl group, substituted or unsubstituted haloalkoxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, substituted or unsubstituted haloalkoxythio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a), group represented by formula (X), or group represented by formula (X3). R 111 and R 113 Optional and bonded to R 111 and R 113 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

6. The photochromic compound according to claim 5, which is represented by the following formula (5) or (5A), In the above formula (5), R 3 R 4 R 7 R 8 Z 1 b and c have the same meaning independently as in equation (4). R 9 and R 10 Each of the following groups is independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3). d is an integer from 0 to 5. When d is 2 to 5, multiple R 9 The groups can be chosen to be the same or different from each other. In the case of adjacent R 9 In the case of two adjacent R 9 Optional and bonded to R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. e is an integer from 0 to 5. When e is 2 to 5, multiple R 10 The groups can be chosen to be the same or different from each other. In the case of adjacent R 10 In the case of two adjacent R 10 Optional and bonded to R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. In the aforementioned formula (5A), Y 111 Y 112 Y 114 R 3 R 4 R 8 R 111 R 112 R 113 c and p have the same meaning independently as in equation (4A). R 9 R 10 , d and e have the same meaning as in equation (5) independently.

7. The photochromic compound according to claim 1, having the skeleton shown in formula (7): In equation (7), M and Z 1 The meanings of ring A and ring A are the same as those in equation (1). R 11 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkithhiol group, a substituted or unsubstituted arylthiol group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, or a substituted or unsubstituted aryloxy group. R 12 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, or a substituted or unsubstituted aryloxy group.

8. The photochromic compound according to claim 1, wherein, Z 1 Having the group shown in formula (1a), R 1 The phenyl group can be substituted or unsubstituted.

9. The photochromic compound according to claim 1, wherein, Z 1 Having the group shown in formula (1a), R 2 It is an alkyl group with 1 or more but less than 5 carbon atoms, or a phenyl group with or without substitution.

10. The photochromic compound according to claim 1, wherein, Z 1 It has the group shown in formula (1b), where ring B is a substituted or unsubstituted phenyl group.

11. The photochromic compound according to claim 1, wherein, Z 1 It has the group shown in formula (1b), where m and n are 1.

12. A curable composition comprising the photochromic compound of claim 1, and comprising at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerizable reactive group, and a (thio)carbamate (urea) polymer.

13. A cured product, which is a cured product of the curable composition of claim 12.

14. An optical article comprising the cured material of claim 13.

15. A lens comprising the photochromic compound of claim 1.

16. A pair of eyeglasses comprising the lens of claim 15.

17. A naphthol derivative having a skeleton as shown in formula (6) or (6A): In the aforementioned formula (6), M is C, Si, or Ge. Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings. Z 1 It is a group represented by formula (1a) or formula (1b) below. In the aforementioned formula (1a), R 1 For substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups, R 2 It is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a) below. -Q 1 -(X 1 Q 2 )a-X 2 Q 3 (2a) In the aforementioned formula (2a), Q 1 It is an alkylene or haloalkylene. Q 2 It is an alkylene or haloalkylene. Q 3 It is an alkyl or haloalkyl group. X 1 and X 2 Independently defined as O, S, NR 700 R 701 PR 702 R 703 Or P(=O)R 704 , R 700 R 701 R 702 R 703 and R 704 Each of the following is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. a is an integer that is 0, or greater than 1 and less than 3. In the aforementioned formula (1b), Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings. Y 1 For substituted or unsubstituted methylene, Y 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C = CR 602 Or CC, R 600 R 601 and R 602 Each of the following can be independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Y 3 For substituted or unsubstituted methylene, m is an integer from 1 to 4, n is an integer from 0 to 4, and m+n is an integer greater than 2. In the aforementioned formula (6A), M, ring A, and ring B are each independently equivalent to the meanings in equation (6). Y 111 For substituted or unsubstituted methylene, Y 112 For substituted or unsubstituted methylene, oxygen atom, sulfur atom, NR 600 Or SO2, R 600 The meaning is the same as in equation (1b). R 111 and R 112 Each of the following can be independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, a hydroxyl group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkoxy group, a substituted or unsubstituted aryloxy group, a thiol group, a substituted or unsubstituted haloalkylthio group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (2a).

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