Imidazole Compounds

Abstract

To provide an imidazole compound which has good solubility to a raw material at the time of resin synthesis, and good reactivity of dimerization-cleavage reaction in the resin.SOLUTION: An imidazole compound is represented by formula (1). In formula (1), Ar1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. L1 represents -O-, -COO- or -OCO-. L2 represents a single bond or -O-. R1 represents a polyoxyalkylene group or a divalent hydrocarbon group which may have a substituent and has 1 to 50 carbon atoms, and -CH2- contained in the hydrocarbon group may be substituted with -O- and / or -CO-. Ra1 represents a (meth)acryloyl group, or an oxetanyl group which may have a substituent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an imidazole compound. [Background technology]

[0002] Hexaarylbiimidazole (HABI) is known as a photochromic compound that changes color upon exposure to light and fades upon heating. Its applications in various fields, such as color-matching materials, optical recording materials, and display materials for holograms, are being explored.

[0003] HABI is also known to generate triarylimidazolyl radicals upon irradiation with light, and is widely used as a photopolymerization initiator (see, for example, Patent Documents 1 to 3).

[0004] In recent years, attempts have been made to apply the photochromism of HABI to toner, and it has been proposed that if a copolymer crosslinked by bonds between the imidazole rings of triaryl imidazole is used as a toner binder, the glass transition point can be lowered by applying pressure, thereby achieving low-temperature fixability (see, for example, Patent Document 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-332045 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-137252 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-247958 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-128142 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors, while investigating whether the reversible dimerization-cleavage reaction of HABI can be applied to resin molded articles, found that conventionally known imidazole compounds do not have sufficient solubility in the raw materials used in resin synthesis, and that the reactivity of the dimerization-cleavage reaction in the resin is not fully satisfactory. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an imidazole compound that has good solubility in the raw materials used in resin synthesis and good reactivity of the dimerization-cleavage reaction in the resin. [Means for solving the problem]

[0007] The imidazole compound of the present invention is represented by formula (1).

[0008] [ka] [In formula (1), Ar 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar 2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar 3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. L 1 represents -O-, -COO- or -OCO-. L 2 represents a single bond or -O-. R 1 represents a polyoxyalkylene group or a divalent hydrocarbon group of 1 to 50 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced with -O- and / or -CO-. R a1 represents a (meth)acryloyl group or an oxetanyl group which may have a substituent. [Effects of the Invention]

[0009] The imidazole compound of the present invention has good solubility in raw materials during resin synthesis and good reactivity in the dimerization-cleavage reaction in the resin. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows the 1H-NMR spectrum of compound 1. [Figure 2] FIG. 2 shows the 13C-NMR spectrum of compound 1. [Figure 3] FIG. 3 shows the MALDI-MS spectrum of compound 1. [Figure 4] FIG. 4 shows the MALDI-MS spectrum of dimer 37. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, a "compound represented by formula (x)" may be simply referred to as a "compound (x)", etc. The compounds of the present invention also include tautomers and salts thereof, and the components, substituents, and functional groups exemplified below can be used alone or in combination.

[0012] The imidazole compound of the present invention is represented by formula (1). In the imidazole compound of the present invention, the reactive group is not directly bonded to the aromatic ring bonded to the 2-position of the imidazole, but is bonded via a hydrocarbon group or a bonding group, and therefore the imidazole compound has good solubility in raw materials during resin synthesis and good reactivity in the dimerization-cleavage reaction in the resin.

[0013] [ka]

[0014] [In formula (1), Ar 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar 2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. Ar 3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. L 1represents -O-, -COO- or -OCO-. L 2 represents a single bond or -O-. R 1 represents a polyoxyalkylene group or a divalent hydrocarbon group of 1 to 50 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced with -O- and / or -CO-. R a1 represents a (meth)acryloyl group or an oxetanyl group which may have a substituent.

[0015] The compounds of the present invention include their tautomers and salts, and the components and functional groups exemplified below can be used alone or in combination.

[0016] Ar 1 , Ar 2 Examples of the aromatic hydrocarbon groups represented by the formula (I) are, independently, a phenyl group, a naphthyl group, an anthracenyl group, and the like.

[0017] Ar 1 , Ar 2 The aromatic hydrocarbon group represented by the formula (I) may have a substituent. Examples of the substituent include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; aromatic hydrocarbon groups having 6 to 10 carbon atoms, such as phenyl and naphthyl; halogen atoms, such as fluorine, chlorine, bromine, and iodine; and hydroxy groups.

[0018] Ar 1 , Ar 2 The aromatic group represented by the formula (I) has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms (including the carbon atoms of the substituent, if any).

[0019] Ar 3 Examples of the aromatic hydrocarbon group represented by the formula include a phenylene group, a naphthylene group, and an anthracenediyl group.

[0020] Ar 3 The aromatic hydrocarbon group represented by the formula (I) may have a substituent. Examples of the substituent include Ar 1 , Ar 2 Examples of the substituents that may be possessed by the group include the same groups as those exemplified above.

[0021] Ar 3 The aromatic hydrocarbon group represented by the following formula (I) has 6 to 20 carbon atoms, and preferably 6 to 10 carbon atoms (including the number of carbon atoms of the substituent, if any).

[0022] L 1 Examples of the alkyl group include -O-, -COO-, and -OCO-, and -O- or -COO- are preferred. 3 is assumed to be bound to

[0023] L 2 represents a single bond or -O-.

[0024] R 1 Examples of the polyoxyalkylene group represented by the formula (I) include groups whose repeating units are combinations of alkylene groups having 2 to 5 carbon atoms, such as polyoxyethylene groups, polyoxypropylene groups, and polyoxybutylene groups, with -O-. The number of repeating units is preferably 2 to 50, more preferably 2 to 20, and even more preferably 2 to 10.

[0025] R 1 Examples of the divalent hydrocarbon group represented by the formula (I) include divalent aliphatic hydrocarbon groups having 1 to 50 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and groups having 4 to 50 carbon atoms which are a combination of two or more of the above divalent aliphatic hydrocarbon groups, divalent alicyclic hydrocarbon groups, and divalent aromatic hydrocarbon groups.

[0026] Examples of the aliphatic hydrocarbon group include saturated or unsaturated aliphatic hydrocarbon groups, and preferred are alkanediyl groups such as methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, hexadecanediyl, heptadecanediyl, octadecanediyl, nonadecanediyl, and eicosanediyl. The aliphatic hydrocarbon group may be linear or branched.

[0027] R 1 may be a group in which one or more -CH2- groups contained in the aliphatic hydrocarbon group are replaced with -O- and / or -CO-. Furthermore, two or more -CH2- groups may be replaced with -O- and / or -CO- groups to form an ester bond (-OCO-, -COO-) or a carbonate bond (-OCOO-). The number of -CH2- groups replaced with -O- and / or -CO- groups in the aliphatic hydrocarbon group may be, for example, one or more, two or more, or may be 10 or less, or 5 or less. However, it is preferable that adjacent -CH2- groups are not simultaneously replaced with -O-.

[0028] The aliphatic hydrocarbon group may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded to the alkyl group.

[0029] The aliphatic hydrocarbon group preferably has 1 to 50 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms.

[0030] Examples of the alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, and preferred are monocyclic alicyclic hydrocarbon groups such as a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group, a cyclononanediyl group, and a cyclodecanediyl group; and polycyclic alicyclic hydrocarbon groups such as a bicyclo[1.1.0]butanediyl group, a tricyclo[2.2.1.0]heptanediyl group, a bicyclo[3.2.1]octanediyl group, a bicyclo[2.2.2]octanediyl group, an adamantanediyl group, a bicyclo[4.3.2]undecanediyl group, and a tricyclo[5.3.1.1]dodecanediyl group.

[0031] The alicyclic hydrocarbon group may have, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -R a A group represented by the following formula may be bonded to the alkyl group.

[0032] The alicyclic hydrocarbon group may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded to the alkyl group.

[0033] The alicyclic hydrocarbon group preferably has 3 to 50 carbon atoms (including the number of carbon atoms of the substituent, if any) and more preferably has 5 to 20 carbon atoms and even more preferably has 3 to 10 carbon atoms.

[0034] The aromatic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include a phenylene group, a naphthylene group, an anthracenediyl group, and a fluorenediyl group.

[0035] The aromatic hydrocarbon group may have, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; -R 2 -R a A group represented by the following formula may be bonded to the alkyl group.

[0036] The aromatic hydrocarbon group may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a A group represented by the following formula may be bonded to the alkyl group.

[0037] The aromatic hydrocarbon group preferably has 6 to 50 carbon atoms (including the number of carbon atoms of the substituent, if any) and more preferably has 6 to 20 carbon atoms.

[0038] The group formed by combining two or more of the divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, and the divalent aromatic hydrocarbon group is preferably a divalent group formed by combining an aliphatic hydrocarbon group with an alicyclic hydrocarbon group, or a divalent group formed by combining an aliphatic hydrocarbon group with an aromatic hydrocarbon group.

[0039] The group formed by combining two or more of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group preferably has 4 to 50 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 4 to 10 carbon atoms.

[0040] R 1 The hydrocarbon group represented by the formula (I) may have as a substituent -R 2 -L 3 -R a2 In the group represented by 2represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms, in which -CH2- contained in the hydrocarbon group may be replaced by -O- and / or -CO-, and a hydrogen atom contained in the hydrocarbon group may be replaced by a hydroxy group. 3 represents a single bond or -O-. a2 represents a reactive group.

[0041] R 2 The polyoxyalkylene group represented by R 1 Examples of the polyoxyalkylene group include the same groups as those exemplified as the polyoxyalkylene group represented by the following formula:

[0042] R 2 The hydrocarbon group represented by the formula (including groups in which -CH2- contained in the hydrocarbon group is replaced by -O- and / or -CO-) is R 1 Examples of the hydrocarbon group represented by the formula (I) include the same groups as those exemplified above.

[0043] R 2 The substituent that the hydrocarbon group represented by the formula (I) may have includes a hydroxy group.

[0044] L 3 represents a single bond or -O-.

[0045] R a1 , R a2 Examples of the reactive group represented by the formula (I) include groups capable of forming a polymer main chain by polycondensation reaction, specifically groups containing an ethylenic double bond such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group; and groups containing a cyclic ether such as an oxetanyl group. The group containing a cyclic ether may have an aliphatic hydrocarbon group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, or a propyl group, as a substituent. Among these, R a1 , R a2 The reactive group represented by the formula (I) is preferably a vinyl group, a (meth)acryloyl group, or an oxetanyl group which may have a substituent.

[0046] Examples of the compound (1) include compounds represented by the following formulas (1-1) to (1-68): wherein n represents an integer of 2 to 10.

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] The outline of the method for producing the compound (1) is shown, for example, in the following scheme. That is, the compound (1) of the present invention can be produced by the following method: Route 1: Compound (a-1) is reacted with compound (b) to obtain compound (c) (Step 1), and compound (d) is reacted with compound (e) to produce compound (c) (Step 2). Route 2: It can also be produced by reacting compound (a-2) with compound (d) and compound (e) (step 3), and then reacting compound (g-1) or compound (g-2) (step 4), Route 3: Compound (a-1) can also be produced by reacting compound (h) with compound (a-1) to obtain compound (i) (step 5), hydrolyzing the ester bond of compound (i) to obtain compound (j) (step 6), reacting compound (d) with compound (e) to obtain compound (k) (step 7), and then further reacting with compound (l).

[0053] [ka]

[0054] [In the above scheme, Ar 1 , Ar 2 , Ar 3 , L 1 , L 2 , R 1 , R a1 is synonymous with the above. A 1 represents a heterocyclic group containing an oxygen atom. R 3 represents a polyoxyalkylene group or a hydrocarbon group having 1 to 47 carbon atoms, and -CH2- contained in the hydrocarbon group may be replaced with -O- and / or -CO-. R 4 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X 1 , X 2 each independently represents a halogen atom.

[0055] A 1 The heterocyclic group containing an oxygen atom represented by the formula (I) may be monocyclic or polycyclic, and in the case of a polycyclic group, a plurality of monocyclic heterocyclic groups may be bonded together by a covalent bond, or may be a bridged ring. 1 Examples of the heterocyclic group containing an oxygen atom represented by the formula (I) include cyclic ether groups such as an oxiranyl group and an oxetanyl group; and epoxycycloalkyl groups such as an epoxycyclohexyl group and an epoxycyclopentyl group.

[0056] R 3 The oxyalkylene group represented by R 1 The number of repeating units of the oxyalkylene is preferably 2 to 49, more preferably 2 to 19, and even more preferably 2 to 9.

[0057] R 3The hydrocarbon group represented by R 1 Among the groups described above as hydrocarbon groups represented by the formula R, groups having 1 to 47 carbon atoms can be mentioned. 3 The aliphatic hydrocarbon group represented by the formula (I) may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded to the ring. 3 The aliphatic hydrocarbon group represented by the formula (I) preferably has 1 to 47 carbon atoms, more preferably 1 to 17 carbon atoms, and even more preferably 1 to 7 carbon atoms.

[0058] R 3 The alicyclic hydrocarbon group represented by the formula (I) may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded to the ring. 3 The alicyclic hydrocarbon group represented by the following formula (I) preferably has 3 to 47 carbon atoms, more preferably 3 to 17 carbon atoms, and even more preferably 3 to 7 carbon atoms.

[0059] R 3 The aromatic hydrocarbon group represented by the formula (I) may contain, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; 2 -L 3 -R a2 A group represented by the following formula may be bonded to the ring. 3 The aromatic hydrocarbon group represented by the formula (I) preferably has 6 to 47 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0060] R 3 The group in which two or more of the aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group represented by the formula (I) are combined preferably has 4 to 47 carbon atoms, more preferably 4 to 17 carbon atoms, and even more preferably 4 to 7 carbon atoms.

[0061] R 4Examples of the aliphatic hydrocarbon group represented by R include a methyl group, an ethyl group, a butyl group, and a pentyl group. 4 The aliphatic hydrocarbon group represented by the formula (I) preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0062] X 1 , X 2 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.

[0063] Each step will be described below.

[0064] Regarding steps 1 and 5 In steps 1 and 5, compound (a-2) is reacted with compound (b) or compound (h) to obtain compound (c) or compound (i).

[0065] During the reaction, a tertiary organic phosphorus compound such as triphenylphosphine and an azodicarboxylate ester such as diethyl azodicarboxylate or diisopropyl azodicarboxylate are present as catalysts.

[0066] As the reaction solvent, an ether solvent such as tetrahydrofuran can be used.

[0067] Regarding steps 2, 3, and 7 In steps 2, 3, and 7, compound (a-2), compound (c), or compound (j) is reacted with compound (d) and compound (e) to form an imidazole ring, thereby obtaining compound (f), compound (1), or compound (k), respectively.

[0068] The reaction is carried out in the presence of a catalyst such as 1,4-diazabicyclo[2.2.2]octane.

[0069] As the reaction solvent, in steps 2 and 7, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, or butanol can be used, and in step 3, glacial acetic acid or the like can be used.

[0070] About step 4 In step 4, compound (f) is reacted with compound (g-1) or compound (g-2) to react the carboxy group of compound (f) with the hydroxyl group of compound (g-1), or the carboxy group of compound (f) with the cyclic ether of compound (g-2), thereby obtaining compound (1).

[0071] The reaction is carried out in the presence of a catalyst. When reacting with compound (g-1), a tertiary organic phosphorus compound such as triphenylphosphine and an azodicarboxylate ester such as diethyl azodicarboxylate or diisopropyl azodicarboxylate are used as catalysts. As the reaction solvent, an amide solvent such as dimethylformamide or dimethylacetamide can be used.

[0072] When reacting with compound (g-2), a catalyst such as tetrabutylammonium chloride can be used, and an amide solvent such as dimethylformamide can be used as the reaction solvent.

[0073] About step 6 In step 6, compound (j) can be obtained by hydrolyzing the ester bond of compound (i).

[0074] The reaction may be carried out in the presence of an alkali catalyst such as potassium hydroxide, etc. As the reaction solvent, an alcohol solvent such as ethanol can be used.

[0075] About step 8 In step 8, compound (k) is reacted with compound (l) to obtain compound (1).

[0076] In the reaction, an amine catalyst such as triethanolamine can be used, and an ether solvent such as tetrahydrofuran can be used as the reaction solvent.

[0077] The imidazole compound of the present invention has good solubility in raw materials during resin synthesis and good reactivity in the dimerization-cleavage reaction in the resin, and is useful as an agent for imparting photochromic properties to a resin, a radical polymerization initiator, a photochromic dye, etc. [Example]

[0078] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and can be practiced with appropriate modifications within the scope of the above and below-described aims, and all such modifications are within the technical scope of the present invention.

[0079] Synthesis Example 1: Synthesis of Compound A

[0080] [ka]

[0081] A 100 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 14.17 g (98.26 mmol) of 4-hydroxybutyl acrylate (4HBA [trade name], manufactured by Osaka Organic Chemical Industry Co., Ltd.), 140 g of tetrahydrofuran (THF), 25.77 g (98.26 mmol) of triphenylphosphine (Ph3P), and 10.00 g (81.89 mmol) of 4-hydroxybenzaldehyde, and the contents were stirred. A pale yellow, transparent solution was obtained. Subsequently, in an ice bath, 19.87 g (98.26 mmol) of diisopropyl azodicarboxylate (DIAD) diluted in 20 g of tetrahydrofuran was added dropwise over 30 minutes. The orange, transparent reaction solution was stirred at room temperature for 10 hours. Hexane was added to the reaction solution to precipitate and remove by-products such as triphenylphosphine. The solution was then extracted with chloroform, washed with water and saturated brine, and dried over magnesium sulfate. The solvent was removed by distillation using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=80:20) to obtain 13.62 g of the target compound A in a yield of 67.0%.

[0082] Example 1: Synthesis of Compound 1

[0083] [ka]

[0084] A 100 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 4.87 g (19.62 mmol) of compound A, 15 g of methanol (MeOH), 0.00154 g (0.137 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO), 4.948 g (23.54 mmol) of benzil, 3.629 g (47.08 mmol) of ammonium acetate (NH4OAc), 1500 ppm of methoquinone, and 500 ppm of BHT. The mixture was stirred at 65°C for 24 hours with nitrogen gas blown in from above and air bubbling through the solution. The solution gradually became a reddish-brown color, and after several hours, a yellow solid precipitated on the wall. After cooling to near room temperature, the mixture was extracted with ethyl acetate, washed with water and saturated brine, and then dried over magnesium sulfate. The solvent was removed by distillation using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=80:20) to obtain 3.31 g of target compound 1 in a yield of 38.5%.

[0085] [Method for identifying structure] The structure of the product (lophine compound) was identified under the following conditions: 1 H-NMR, 13 C-NMR and MALDI-MS were used. 1 The H-NMR spectrum is shown in Figure 1. 13 The C-NMR spectrum is shown in FIG. 2, and the MALDI-MS spectrum is shown in FIG.

[0086] 1 H-NMR was measured using a JEOL RESONANCE "JNM-ECM400S" under the following conditions.

[0087] Magnetic field strength: 400MHz Accumulation count: 16 times Solvent: deuterated chloroform Sample concentration: 2mg / 0.5ml

[0088] 13 C-NMR was measured using a JEOL RESONANCE "JNM-ECM400S" under the following conditions.

[0089] Magnetic field strength: 100MHz Accumulation count: 1000 times Solvent: deuterated chloroform Sample concentration: 2mg / 0.5ml

[0090] MALDI-MS was performed using an "AXIMA-QIT" manufactured by Shimadzu Corporation / KRATOS under the following conditions. Device name:AXIMA-QIT Manufacturer: Shimadzu Corporation

[0091] Measurement range: m / z = 50.00 to 2000.00 Rate of change: 25.6mA / min Final current value: 40mA Cathode voltage: -10kV Measurement mode m / z ~300: extraLow 300~750:Low 750~:Mid

[0092] Synthesis Example 2: Synthesis of Compound B

[0093] [ka]

[0094] The same procedure as in Synthesis Example 1 was carried out except that hydroxyethyl acrylate (HEA [trade name], manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 12.11 g of Compound B represented by the above structural formula was obtained in a yield of 67.15%.

[0095] Example 2: Synthesis of Compound 2

[0096] [ka]

[0097] The same procedure as in Example 1 was carried out except that compound B was used instead of compound A, and 3.92 g of target compound 2 represented by the above structural formula was obtained in a yield of 42.1%.

[0098] Synthesis Example 3: Synthesis of Compound C

[0099] [ka]

[0100] The same procedure as in Synthesis Example 1 was carried out except that 2-hydroxyethyl methacrylate (HEMA [trade name], manufactured by Nippon Shokubai Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 13.83 g of Compound C represented by the above structural formula was obtained in a yield of 72.1%.

[0101] Example 3: Synthesis of Compound 3

[0102] [ka]

[0103] The same procedure as in Example 1 was carried out except that compound C was used instead of compound A, and 4.02 g of target compound 3 represented by the above structural formula was obtained in a yield of 44.4%.

[0104] Synthesis Example 4: Synthesis of Compound D

[0105] [ka]

[0106] The same procedure as in Synthesis Example 1 was carried out except that 2-hydroxypropyl acrylate (HPA [trade name], manufactured by Nippon Shokubai Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 11.11 g of Compound D represented by the above structural formula was obtained in a yield of 57.9%.

[0107] Example 4: Synthesis of Compound 4

[0108] [ka]

[0109] The same procedure as in Example 1 was carried out except that compound D was used instead of compound A, and 2.90 g of target compound 4 represented by the above structural formula was obtained in a yield of 32.0%.

[0110] Synthesis Example 5: Synthesis of Compound E

[0111] [ka]

[0112] The same procedure as in Synthesis Example 1 was carried out except that 2-hydroxybutyl acrylate (Light Acrylate HOB-A [trade name], manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 11.36 g of compound E represented by the above structural formula was obtained in a yield of 55.9%.

[0113] Example 5: Synthesis of Compound 5

[0114] [ka]

[0115] The same procedure as in Example 1 was carried out except that compound E was used instead of compound A, and 1.99 g of target compound 5 represented by the above structural formula was obtained in a yield of 22.5%.

[0116] Synthesis Example 6: Synthesis of Compound F

[0117] [ka]

[0118] The same procedure as in Synthesis Example 1 was carried out except that diethylene glycol monoacrylate was used instead of 4-hydroxybutyl acrylate, to obtain 15.57 g of compound F represented by the above structural formula in a yield of 72.0%.

[0119] Example 6: Synthesis of Compound 6

[0120] [ka]

[0121] The same procedure as in Example 1 was carried out except that compound F was used instead of compound A, and 2.67 g of target compound 6 represented by the above structural formula was obtained in a yield of 31.0%.

[0122] Synthesis Example 7: Synthesis of Compound G

[0123] [ka]

[0124] The same procedure as in Synthesis Example 1 was carried out except that polypropylene glycol monoacrylate (Blemmer AP-400 [trade name], manufactured by NOF Corporation) was used instead of 4-hydroxybutyl acrylate, and 30.29 g of compound G represented by the above structural formula was obtained in a yield of 70.5%.

[0125] Example 7: Synthesis of Compound 7

[0126] [ka]

[0127] The same procedure as in Example 1 was carried out except that compound G was used instead of compound A, and 2.86 g of target compound 7 represented by the above structural formula was obtained in a yield of 28.6%.

[0128] Synthesis Example 8: Synthesis of Compound H

[0129] [ka]

[0130] The same procedure as in Synthesis Example 1 was carried out except that pentaerythritol triacrylate was used instead of 4-hydroxybutyl acrylate, to obtain 14.20 g of compound H represented by the above structural formula in a yield of 43.1%.

[0131] Example 8: Synthesis of Compound 8

[0132] [ka]

[0133] The same procedure as in Example 1 was carried out except that compound H was used instead of compound A, and 1.444 g of target compound 8 represented by the above structural formula was obtained in a yield of 9.81%.

[0134] Synthesis Example 9: Synthesis of Compound I

[0135] [ka]

[0136] The same procedure as in Synthesis Example 1 was carried out except that glycerin dimethacrylate (701 [trade name], manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 14.18 g of Compound I represented by the above structural formula was obtained in a yield of 52.1%.

[0137] Example 9

[0138] [ka]

[0139] The same procedure as in Example 1 was carried out except that Compound I was used instead of Compound A, and 2.14 g of the target compound 9 represented by the above structural formula was obtained in a yield of 13.6%.

[0140] Synthesis Example 10: Synthesis of Compound J

[0141] [ka]

[0142] A 500 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 17.85 g (118.91 mmol) of terephthalaldehydic acid, 285 g of glacial acetic acid, 0.0934 g (0.832 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO), 25.00 g (118.91 mmol) of benzyl ether, and 27.50 g (356.75 mmol) of ammonium acetate, and the mixture was stirred at 105° C. for 6 hours. After cooling to near room temperature, the mixture was added to ice water, and the resulting solid was filtered and washed with chloroform to obtain 38.45 g of the target compound J in a 95.0% yield.

[0143] Example 10

[0144] [ka]

[0145] A 200 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 15.00 g (44.07 mmol) of compound J, 90 g of dimethylformamide (DMF), 0.3184 g (1.146 mmol) of tetrabutylammonium chloride (TBACl), 6.62 g (44.07 mmol) of glycidyl methacrylate (GMA), 1500 ppm of methoquinone, and 500 ppm of BHT. Nitrogen gas was blown from above, and air was bubbled through the liquid, followed by stirring at 85 °C for 40 hours. After cooling to near room temperature, the mixture was extracted with ethyl acetate, washed with water and saturated brine, and then dried over magnesium sulfate. The solvent was removed by evaporation, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=90:10). After cooling to near room temperature, the liquid was added to ice water, and the resulting solid was filtered and washed with chloroform to obtain 12.5 g of the target compound 10 in a yield of 58.8%.

[0146] Example 11: Synthesis of Compound 11

[0147] [ka]

[0148] The same procedure as in Example 10 was carried out except that Cyclomer M-100 (manufactured by Daicel Chemical Industries, Ltd.) was used instead of GMA, and 11.52 g of the target compound 11 represented by the structural formula above was obtained in a yield of 48.7%.

[0149] Example 12: Synthesis of Compound 12

[0150] [ka]

[0151] A 100 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 5.00 g (14.689 mmol) of compound J, 2.54 g (17.63 mmol) of 4HBA, 4.62 g (17.63 mmol) of triphenylphosphine, and 15.66 g of DMF, and the mixture was stirred. A pale yellow, transparent solution was obtained. Subsequently, in an ice bath, 3.56 g (17.63 mmol) of diisopropyl azodicarboxylate diluted in 3.56 g of DMF was added dropwise over 30 minutes. The orange, transparent reaction solution was stirred at room temperature for 10 hours. The reaction solution was dried, and chloroform and hexane were added to precipitate and remove by-products such as triphenylphosphine. The mixture was then extracted with chloroform, washed with water and saturated brine, and dried over magnesium sulfate. The solvent was removed by distillation using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=80:20) to obtain 5.24 g of the target compound 12 in a yield of 76.44%.

[0152] Example 13: Synthesis of Compound 13

[0153] [ka]

[0154] The same procedure as in Example 12 was carried out except that HEA was used instead of 4HBA, and 5.16 g of the target compound 13 represented by the above structural formula was obtained in a yield of 80.12%.

[0155] Example 14: Synthesis of Compound 14

[0156] [ka]

[0157] The same procedure as in Example 12 was carried out except that HEMA was used instead of 4HBA, to obtain 5.38 g of the target compound 14 represented by the above structural formula in a yield of 81.01%.

[0158] Example 15: Synthesis of Compound 15

[0159] [ka]

[0160] The same procedure as in Example 12 was carried out except that HPA was used instead of 4HBA, to obtain 4.38 g of the target compound 15 represented by the above structural formula in a yield of 65.97%.

[0161] Example 16: Synthesis of Compound 16

[0162] [ka]

[0163] The same procedure as in Example 12 was carried out except that Light Ester HOP (Kyoeisha Chemical) was used instead of 4HBA, to obtain 3.95 g of the target compound 16 represented by the above structural formula in a yield of 57.65%.

[0164] Example 17: Synthesis of Compound 17

[0165] [ka]

[0166] The same procedure as in Example 12 was carried out except that light ester HOBA (Kyoeisha Chemical) was used instead of 4HBA, to obtain 3.86 g of the target compound 17 represented by the above structural formula in a yield of 56.32%.

[0167] Example 18: Synthesis of Compound 18

[0168] [ka]

[0169] The same procedure as in Example 12 was carried out except that light ester HOBA (Kyoeisha Chemical) was used instead of 4HBA, to obtain 3.91 g of the target compound 18 represented by the above structural formula in a yield of 55.42%.

[0170] Example 19: Synthesis of Compound 19

[0171] [ka]

[0172] The same procedure as in Example 12 was carried out except that Blenmer AE-90U (NOF Corp.) was used instead of 4HBA, to obtain 6.99 g of the target compound 19 represented by the above structural formula in a yield of 72.19%.

[0173] Example 20: Synthesis of Compound 20

[0174] [ka]

[0175] The same procedure as in Example 12 was carried out except that Blenmer PE-90 (NOF Corp.) was used instead of 4HBA, and 5.26 g of the target compound 20 represented by the above structural formula was obtained in a yield of 53.21%.

[0176] Example 21: Synthesis of Compound 21

[0177] [ka]

[0178] The same procedure as in Example 12 was carried out except that Blenmer AP-200 (NOF Corp.) was used instead of 4HBA, to obtain 7.46 g of the target compound 21 represented by the above structural formula in a yield of 68.32%.

[0179] Example 22: Synthesis of Compound 22

[0180] [ka]

[0181] The same procedure as in Example 12 was carried out except that Blenmer PP-500 (NOF Corp.) was used instead of 4HBA, to obtain 4.68 g of the target compound 22 represented by the above structural formula in a yield of 42.10%.

[0182] Example 23: Synthesis of Compound 23

[0183] [ka]

[0184] The same procedure as in Example 12 was carried out except that Sartomer SR-495 (Sartomer) was used instead of 4HBA, to obtain 1.50 g of the target compound 23 represented by the above structural formula in a yield of 44.87%.

[0185] Example 24: Synthesis of Compound 24

[0186] [ka]

[0187] The same procedure as in Example 12 was carried out except that Aronix M-305 (Toagosei) was used instead of 4HBA, to obtain 1.39 g of the target compound 24 represented by the above structural formula in a yield of 38.98%.

[0188] Example 25

[0189] [ka]

[0190] The same procedure as in Example 12 was carried out except that NK Ester 701A (Shin-Nakamura Chemical) was used instead of 4HBA, to obtain 1.62 g of the target compound 25 represented by the above structural formula in a yield of 50.19%.

[0191] Synthesis Example 11: Synthesis of Compound K

[0192] [ka]

[0193] The same procedure as in Synthesis Example 1 was carried out except that 4-hydroxybutyl vinyl ether (HBVE) (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 13.08 g of compound K represented by the above structural formula was obtained in a yield of 72.5%.

[0194] Example 26: Synthesis of Compound 26

[0195] [ka]

[0196] The same procedure as in Example 1 was carried out except that compound K was used instead of compound A, and 2.81 g of target compound 26 represented by the above structural formula was obtained in a yield of 30.2%.

[0197] Synthesis Example 12: Synthesis of Compound L

[0198] [ka]

[0199] The same procedure as in Synthesis Example 1 was carried out except that 2-hydroxyethyl vinyl ether (HEVE) (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 11.47 g of compound L represented by the above structural formula was obtained in a yield of 72.9%.

[0200] Example 27: Synthesis of Compound 27

[0201] [ka]

[0202] The same procedure as in Example 1 was carried out except that compound L was used instead of compound A, and 2.96 g of target compound 27 represented by the above structural formula was obtained in a yield of 29.8%.

[0203] Synthesis Example 13: Synthesis of Compound M

[0204] [ka]

[0205] The same procedure as in Synthesis Example 1 was carried out except that 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (Aron Oxetane OXT-101 (OXA) [trade name], manufactured by Toagosei Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 12.64 g of compound M represented by the above structural formula was obtained in a yield of 70.1%.

[0206] Example 28: Synthesis of Compound 28

[0207] [ka]

[0208] The same procedure as in Example 1 was carried out except that Compound M was used instead of Compound A, and 11.85 g of the target compound 28 represented by the above structural formula was obtained in a yield of 63.6%.

[0209] Synthesis Example 14: Synthesis of Compound N

[0210] [ka]

[0211] The same procedure as in Synthesis Example 1 was carried out except that 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane (ETERNACOLL (registered trademark) HBOX [product name], manufactured by Ube Industries, Ltd.) was used instead of 4-hydroxybutyl acrylate, and 9.56 g of compound N represented by the above structural formula was obtained in a yield of 79.9%.

[0212] Example 29: Synthesis of Compound 29

[0213] [ka]

[0214] The same procedure as in Example 1 was carried out except that compound N was used instead of compound A, and 5.55 g of target compound 29 represented by the above structural formula was obtained in a yield of 67.3%.

[0215] Example 30: Synthesis of Compound 30

[0216] [ka]

[0217] The same procedure as in Example 12 was carried out except that 4-hydroxybutyl vinyl ether (HBVE) (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 4HBA, and 5.01 g of the target compound 30 represented by the above structural formula was obtained in a yield of 77.7%.

[0218] Example 31: Synthesis of Compound 31

[0219] [ka]

[0220] The same procedure as in Example 12 was carried out except that 2-hydroxyethyl vinyl ether (HEVE) (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 4HBA, and 4.55 g of the target compound 31 represented by the above structural formula was obtained in a yield of 75.4%.

[0221] Example 32: Synthesis of Compound 32

[0222] [ka]

[0223] The same procedure as in Example 12 was carried out except that 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (Aron Oxetane OXT-101 (OXA) [trade name], manufactured by Toagosei Co., Ltd.) was used instead of 4HBA, to obtain 4.59 g of the target compound 32 represented by the above structural formula in a yield of 71.29%.

[0224] Example 33: Synthesis of Compound 32

[0225] [ka]

[0226] The same procedure as in Example 12 was carried out except that 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane (ETERNACOLL (registered trademark) HBOX [trade name], manufactured by Ube Industries, Ltd.) was used instead of 4HBA, and 5.24 g of the target compound 33 represented by the above structural formula was obtained in a yield of 69.85%.

[0227] Synthesis Example 15

[0228] [ka]

[0229] A 500 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 7.00 g (57.32 mmol) of 4-hydroxybenzaldehyde, 150 g of DMF, and 9.00 g (65.12 mmol) of potassium carbonate, and stirred at 90°C. Next, 7.90 g (49.38 mmol) of 4-chlorobutyl acetate was added dropwise over 30 minutes. After the addition, the mixture was reacted at 90°C for 4 hours, cooled to room temperature, transferred to a 2 L beaker, and 250 g of water was added. Extraction was performed with diethyl ether, washed with 100 g of 10% aqueous potassium hydroxide solution, washed with saturated saline, and then dried over magnesium sulfate. The solvent was removed using an evaporator, yielding 9.03 g of the target compound O in a 66.7% yield.

[0230] 4.00 g (16.93 mmol) of compound O was placed in a 200 ml recovery flask, 100 g of ethanol (EtOH) and 3.00 g (53.47 mmol) of potassium hydroxide were added, and the mixture was heated to reflux for 4 hours. After the reaction was complete, the mixture was cooled to room temperature, neutralized with 10% hydrochloric acid, extracted with diethyl ether, washed with saturated brine, and then dried over magnesium sulfate. The solvent was removed using an evaporator, and the resulting viscous liquid was purified by column chromatography (eluent: n-hexane:ethyl acetate = 60:40) to obtain 2.11 g of the desired compound P in a 64.2% yield.

[0231] Synthesis Example 16: Synthesis of Compound Q

[0232] [ka]

[0233] The same procedure as in Example 1 was carried out except that compound P was used instead of compound A, and 2.93 g of the target compound Q represented by the above structural formula was obtained in a yield of 70.1%.

[0234] Example 34: Synthesis of Compound 34

[0235] [ka]

[0236] A 100 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 2.00 g (5.20 mmol) of Q, 40 g of anhydrous THF, and 1.00 g (9.88 mmol) of triethylamine (TEA) and stirred. In an ice bath, 1.10 g (10.52 mmol) of acryloyl chloride was slowly added via syringe. After the addition was complete, the mixture was allowed to react at room temperature for 16 hours. After the reaction was complete, the mixture was extracted with chloroform, washed with saturated brine, and then dried over magnesium sulfate. The solvent was removed using an evaporator, and the resulting viscous liquid was purified by column chromatography (developing solvent: chloroform: ethyl acetate = 90:10) to obtain 1.76 g of the target compound 34 in a 74.7% yield.

[0237] Synthesis Example 16: Synthesis of Compound R

[0238] [ka]

[0239] The same procedure as in Synthesis Example 1 was carried out except that ethylene glycol monoallyl ether was used instead of 4-hydroxybutyl acrylate, to obtain 11.94 g of compound R represented by the above structural formula in a yield of 70.7%.

[0240] Example 15: Synthesis of Compound 35

[0241] [ka]

[0242] The same procedure as in Example 1 was carried out except that Compound R was used instead of Compound A, and 2.29 g of the target compound 35 represented by the above structural formula was obtained in a yield of 25.4%.

[0243] Example 36: Synthesis of Compound 36

[0244] [ka]

[0245] The same procedure as in Example 12 was carried out except that ethylene glycol monoallyl ether was used instead of 4HBA, to obtain 4.54 g of the target compound 36 represented by the above structural formula in a yield of 72.8%.

[0246] Example 37: Preparation of dimers

[0247] [ka]

[0248] A 200 mL three-neck flask equipped with a stirrer and thermometer was charged with 0.50 g (1.14 mmol) of compound 1, 10 g of ethyl acetate, 30 g of normal hexane, and 30 g of ion-exchanged water, and the mixture was stirred. Next, 1.00 g (17.82 mmol) of potassium hydroxide was added in an ice bath. 0.400 g (1.21 mmol) of potassium ferricyanide was added in small portions. Immediately after the addition, the solution was orange, then quickly turned blue. The mixture was stirred vigorously at room temperature, and the reaction was terminated when the solution changed from a clear blue to a clear yellow solution.

[0249] The mixture was transferred to a separatory funnel and washed until the water in the funnel was no longer colored. The solvent was dried up to obtain 0.9376 g of the desired dimer 37 in a yield of 94.00%.

[0250] The product was subjected to MALDI-MS measurement, and it was confirmed that dimer 37 of compound 1 was obtained. The MALDI-MS spectrum of dimer 37 is shown in FIG.

[0251] The same procedure was carried out for substances 2 to 36 to obtain dimers 38 to 72. [Industrial Applicability]

[0252] The imidazole compound of the present invention has good solubility in raw materials during resin synthesis and good reactivity in the dimerization-cleavage reaction in the resin, and is useful as an agent for imparting photochromic properties to a resin, a radical polymerization initiator, a photochromic dye, etc.

Claims

1. An imidazole compound represented by formula (1): Imidazole compounds represented by the following formulas (1-1) to (1-44) and (1-61) to (1-68). 【Chemistry 1】 [In formula (1), Ar1 represents a phenyl group having 6 to 10 carbon atoms. Ar2 represents a phenyl group having 6 to 10 carbon atoms. Ar3 represents a divalent phenylene group having 6 to 10 carbon atoms. L1 represents —O— or —COO—. L2 represents a single bond or --O--. R1 represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O- and / or -CO-. Ra1 represents a (meth)acryloyl group or an oxetanyl group which may have a substituent. 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】

2. A dimer of the imidazole compound according to claim 1.

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