A polycyclic compound, preparation method and membrane

Abstract

The present invention provides a polycyclic compound, a preparation method and a film. The compound of the present invention includes a plurality of carbon rings and / or heterocyclic structures, has a group that emits visible light or fluorescence, and is covalently bonded with at least one ultraviolet light and / or visible light (blue light) absorbing group to provide stability. The compound of the present invention can be used as a light conversion agent, dye, pigment, fluorescent agent, ultraviolet light or blue light absorber, and is applied to products such as optical films, agricultural films, optical discs (discs), optical lenses, goggles, skin care, makeup, lighting, coatings, adhesives, light stabilizers, or panels.

Description

Technical Field

[0001] The present invention relates to novel polycyclic compounds, preparation methods and films. The compounds of the present invention include multiple carbon rings and / or heterocyclic structures, have groups that emit visible light or fluorescence, and are covalently bonded to at least one ultraviolet light and / or blue light absorbing group to provide stability. The compounds of the present invention can be used as light conversion agents, dyes, pigments, fluorescent agents, ultraviolet light or blue light absorbers, and are applied to products such as optical films, agricultural films, optical discs, optical lenses, goggles, skin care, makeup, lighting, coatings, adhesives, light stabilizers, or panels. Background Art

[0002] Currently, organic compounds with light-emitting properties, including dyes, pigments or fluorescent substances, are widely used in agriculture, electronics industry, medicine or other fields. For example, light conversion agents or optical recording media for optical discs.

[0003] In agriculture, adding photoconverters to agricultural films can convert ultraviolet light or short-wave blue light in sunlight into light that is useful to plants. Red light is the most important light for crop growth and can promote crop yields. For example, in the early stage of cabbage heading, red light promotes the formation of leafy cabbage, but excessive blue light has an inhibitory effect (Journal of Agricultural Machinery, ISSN: 1019-0430, Vol 8 (2), 1999 Jun, p. 63-74). In addition, there have been documents that commercial organic photoconverter RL1000 (Compound A, BASF) used in agricultural films can absorb ultraviolet light to reduce pests such as aphids and emit visible light (about 635nm) that is beneficial to plants, but its stability is insufficient (CN 100500754 C).

[0004]

[0005] Generally, organic compounds are prone to degradation when used outdoors, such as organic light-converting agents, such as RL1000. Therefore, improving stability is an important indicator for improving light-converting agents.

[0006] On the other hand, known optical recording media, such as optical discs, irradiate a laser beam to an organic dye in a recording layer. In a short period of time, the laser light is converted into heat energy, causing the recording layer to be thermally deformed, such as becoming molten. Information is recorded based on the difference in reflectivity of light between the deformed portion and the non-deformed portion. Since the local high temperature caused by the laser light conversion to heat energy is as high as 250°C or above, the melting point and thermal stability of the dye become important conditions. There have been documents that disclose organic compounds (B) used in optical recording media (JP 3876970 B2). However, the melting point is low and the stability is poor.

[0007]

[0008] In addition, it is known that ultraviolet light and / or blue light irradiation is an important factor causing the degradation of organic materials, such as agricultural films or optical recording media. Isolating or adding blue light and / or ultraviolet light blocking agents can increase the shelf life of agricultural films or optical discs. Traditional blue light blocking agents can only achieve the functions of blue light blocking and long-wave ultraviolet light (UVA) blocking at the same time. If it is necessary to block blue light and long-wave and short-wave ultraviolet light (UVA+UVB) at the same time, an additional ultraviolet light absorber (UVB) must be added. This is not conducive to industrial utilization. Therefore, the development of compounds with absorption bands covering ultraviolet light (UVA+UVB) and blue light has become the goal of industrial efforts.

[0009] In summary, increasing the stability of dyes or light-converting agents used in luminescent recording media and developing compounds that absorb wavelengths covering ultraviolet light (UVA+UVB) and blue light are the goals of the industry. Summary of the invention

[0010] The development of highly stable organic dyes, light-converting agents, or compounds with absorption bands covering ultraviolet light (UVA+UVB) and blue light has always been the goal of the industry. To achieve this goal, the inventors have specially designed a polycyclic compound, a preparation method, and a film.

[0011] The design concept of the compounds of formula (1) and formula (2) of the present invention is to covalently bond the dye or light-converting substance with the substance that absorbs ultraviolet light or / and blue light. The compounds of formula (1) or formula (2) designed with this new concept greatly increase the stability of the original organic dye or light-converting agent, and also increase the stability of the protected organic material due to the wide range of blue light and ultraviolet light (UVA+UVB) protection.

[0012] This may be because the covalently bonded UV light absorbing group provides stability to the light-converting agent itself within the molecule. Furthermore, the UV light absorbing group also provides stability to the protected organic materials around the molecule, such as agricultural film. As a result of this dual effect, the usable time or stability of the agricultural film is greatly increased.

[0013] The organic light conversion agent A (RL1000, BASF) currently used in agricultural films can emit orange-red light under sunlight. However, its light stability is insufficient. When used in outdoor PE agricultural films, RL1000 can only maintain stability for two seasons.

[0014]

[0015] The inventors covalently bonded it with benzotriazole to obtain MP259 (Compound 7), which can maintain the outdoor stability of PE agricultural film for more than three seasons (Example 43).

[0016] For example, the melting point of the organic dye compound (B) used in the optical recording medium is 175°C. After being covalently bonded with benzotriazole, the melting point of A rises to 224°C (Example 42).

[0017] This is an important and unexpected improvement.

[0018]

[0019] Because the organic dye of the optical disc absorbs laser light and converts it into heat energy, it will cause local high temperature (250°C or above). After the compound (B) is covalently bonded with benzotriazole, not only the melting point and thermal stability are improved, but the ultraviolet light (UVA+UVB) absorption capacity provided by benzotriazole can also increase the storage life of the optical disc.

[0020] Preferably, the compounds of the present invention increase the stability without affecting the original luminescent properties of the organic dye or the light conversion agent.

[0021] More preferably, the structures of R1 to R3 in the compound of formula (1) or formula (2) are designed to increase or decrease the conjugation, thereby increasing or decreasing the original luminescent properties of the organic dye or light-converting agent. For example, the compound (19) of Example 11 has increased conjugation compared to the compound (18) on the one hand, and also increases the wavelength of visible light absorbed or emitted on the other hand. The application field can also be expanded from dyes to other fields, such as agricultural films. In addition, the highly stable compound (7) can be applied to agricultural films and can also be applied to the red laser (640nm) commonly used in DVD-R discs.

[0022] Furthermore, the compounds of the present invention can also be used as ultraviolet light and / or blue light absorbers. Since the compounds of the present invention have luminescent properties, they can be used as ultraviolet light absorbers and / or blue light absorbers with special colors. Traditional anti-blue light absorbers can only absorb ultraviolet light (UVA) and blue light. The compounds of the present invention have a wide range of ultraviolet light (UVA+UVB) absorption, so without the need to add an additional ultraviolet light (UVB) absorber, they can absorb ultraviolet light (UVA+UVB) and blue light at the same time, fully achieving the function of protecting the human body, polymers or other organic materials.

[0023] The compound provided by the present invention is a polycyclic compound having a structure shown in formula (1) or formula (2).

[0024] A——R1——B——R2——C——R3——D (1)

[0026] A——R1——B——R2——D——R3——C (2)

[0028] The constituent fragments A, B, C, and D of the compounds represented by formula (1) or formula (2) of the present invention are the same, and the only difference is the order of ring C and ring D. The compounds of formula (1) and formula (2) of the present invention are monotonic.

[0029] The compound of formula (1) or (2) of the present invention is characterized in that it comprises at least one visible light or fluorescent light emitting group and at least one additional ultraviolet light absorbing group;

[0030] Wherein, R2——C——R3——D or R2——D——R3——C is a visible light emitting group or a fluorescent emitting group;

[0031] A——R1——B is an ultraviolet light absorbing group;

[0032] R1-R3 are a bond and / or any divalent linking group; preferably, R1 is a bond or any divalent linking group, more preferably, R1 is both a bond and a divalent linking group, for example, A——R1——B is 9-hydrocarbazole or dibenzothiophene;

[0033] A, B, C are unsubstituted or R4-substituted 5-7 membered rings, preferably benzene rings, benzocarbon rings, nitrogen-containing 5-7 membered heterocycles, or benzonitrogen-containing 5-7 membered heterocycles. Nitrogen-containing heterocycles do not exclude other heteroatoms. Benzonitrogen-containing 5-7 membered heterocycles refer to benzene rings and nitrogen-containing 5-7 membered heterocycles fused together;

[0034] D is an unsubstituted or substituted 5-7 membered heterocyclic ring or benzo 5-7 membered heterocyclic ring composed of carbon, nitrogen, oxygen, or sulfur atoms, wherein the substituents of the carbon atoms of the ring are selected from one or more H, hydroxyl, oxo, thioxo, thiol, amino, imino, C1-C8 straight or branched alkyl, or R4, and the substituents of the nitrogen atoms of the ring are selected from one or more H, hydroxyl, oxo, straight or branched C1-C8 alkyl;

[0035] R4 is one or more substituents (in the structural formula of the present invention, the indefinite position substitution of R4 or other substituents refers to any position on the ring. For example, when the structural formula shows that the bond of R4 on the ring is between two atoms, it means that R4 can be bonded at any position on the ring), and each is independently selected from hydrogen, halogen, hydroxyl, amino, nitro, cyano, straight or branched C1-C 18 Alkyl, alkenyl or alkoxy, substituted or unsubstituted phenyl, SR5, SO2R5, SO3R5, COOR5, COR5, OCOR5, C(O)NR6R7, SO2NR6R7, NR6R7, wherein R5, R6, R7 are each independently selected from hydrogen, a straight chain or branched C1-C8 alkyl group, and R4 and the adjacent R4, or R4 and the adjacent ring, together represent a fused carbocyclic ring or a fused heterocyclic ring of 3-6 atoms, preferably, a fused heterocyclic ring of 3-6 atoms containing one or more C, N, O, S, preferably, the halogen is chlorine.

[0036] Preferably, R1-R3 is a bond, or a chain consisting of 1-10 groups selected from the following groups: -O-, -S-, -C(=O)-, -COO-, -C(=S)-, -C(=NR 13 )-、-N(R 13 )-、-C(R 14 )(R 15 )-、-C(R 16 )=、-C≡、-C(R 17 )=C(R 18 )-、-Ph-。 13 ~R 18 is one or more, and each is independently selected from hydrogen, halogen, hydroxyl, unsubstituted or halogen-substituted straight or branched C1-C6 alkyl (preferably C1-C4 alkyl), unsubstituted or halogen-substituted or C1-C6 alkyl (preferably C1-C4 alkyl) substituted phenyl. Ph is unsubstituted or substituted by halogen, OH group or straight or branched C1-C6 alkyl (preferably C1-C4 alkyl) substituted phenyl, preferably, halogen is chlorine.

[0037] A is selected from:

[0038]

[0039] A is substituted by one or more R4 or Ph. Wherein, p=0-3, preferably, p=0-2; R4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, straight or branched C1-C8 alkyl, alkenyl or alkoxy, SR5, SO2R5, COOR5, COR5, C(O)NR6R7, NR6R7, wherein R5, R6, R7 are independently selected from hydrogen, straight or branched C1-C8 alkyl, preferably, R5, R6, R7 are hydrogen or straight or branched C1-C4 alkyl, preferably, halogen is chlorine. Ph is unsubstituted or substituted phenyl, preferably, the substituent is phenyl substituted by halogen, hydroxyl, C1-C6 alkoxy (preferably, C1-C4 alkoxy) or C1-C6 alkyl (preferably, C1-C4 alkyl), preferably, halogen is chlorine. R 19 ~R 20 is one or more and each is independently selected from hydrogen, a linear or branched C1-C6 alkyl group (preferably a C1-C4 alkyl group), an unsubstituted or substituted phenyl group, preferably, the substituent is a halogen or a linear or branched C1-C6 alkyl group (preferably a C1-C4 alkyl group).

[0040] B is selected from:

[0041] C is selected from:

[0042] D is selected from:

[0043]

[0044] Wherein, p=0-3, preferably, p=0-2; n=0-1; X1-X6 are each independently selected from C=O, C=S, C=N-R8, N, NR9, C, O, S, CR 10 , CR 11 R 12 , CNR 11 R 12 , CR 10 NR 11 R 12 Among them, R8~R 12 is one or more, and each is independently selected from hydrogen, a straight or branched C1-C8 alkyl or alkenyl, an unsubstituted or straight or branched C1-C6 alkyl (preferably a C1-C4 alkyl) or phenyl substituted with a halogen; the D ring is unsubstituted or substituted with R4 and is connected to the outside of the ring via 1-2 double bonds or single bonds. Preferably, the D ring is connected to the outside of the ring via a double bond. Preferably, the halogen is chlorine.

[0045] More preferably, R1-R3 is a bond, or / and a chain consisting of 1-6 groups selected from the following groups: -O-, -C(=O)-, -COO-, -N(R 13 )-、-C(R 14 )(R 15 )-、-C(R 16 )=、-C(R 17 )=C(R 18 )-、-Ph-。 Among them, R 13 ~R 18 is one or more, and each is independently selected from H, unsubstituted or halogen-substituted straight or branched C1-C6 alkyl (preferably C1-C4 alkyl), unsubstituted or halogen-substituted or C1-C6 alkyl (preferably C1-C4 alkyl) substituted phenyl. Ph is unsubstituted or halogen-substituted, OH group or C1-C6 alkyl (preferably C1-C4 alkyl) substituted phenyl, preferably, halogen is chlorine.

[0046] A is selected from:

[0047]

[0048] p = 0-2;

[0049] R4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, straight or branched C1-C8 alkyl, alkenyl or alkoxy, SR5, SO2R5, COOR5, COR5, C(O)NR6R7, NR6R7, wherein R5, R6, R7 are independently selected from hydrogen, straight or branched C1-C8 alkyl. Preferably, R5, R6, R7 are hydrogen or straight or branched C1-C4 alkyl, preferably, halogen is chlorine. Ph is phenyl which is unsubstituted or substituted by R4, preferably, the substituent is phenyl substituted by hydrogen, halogen, OH group, C1-C6 alkoxy (preferably, C1-C4 alkoxy) or C1-C6 alkyl (preferably, C1-C4 alkyl), preferably, halogen is chlorine;

[0050] B is selected from:

[0051] C is selected from:

[0052] D is selected from:

[0053]

[0054] Wherein, when n=0, X1 is selected from C=O, C=S, and X2, X3, and X4 are each independently selected from C=O, C=S, C=N-R8, C-NR 11 R 12、N、NR9、C、O、S、CR 10 , CR 11 R 12 ;

[0055] When n=1, X4 and X6 are each independently selected from C=O, C=S, and X1, X2, and X3 are each independently selected from C=O, C=S, C=N-R8, N, NR9, C, O, S, CR 10 , CR 11 R 12 、C-NR 11 R 12 ; R8~R 12 is one or more, and each is independently selected from H, a linear or branched C1-C6 alkyl (preferably a C1-C4 alkyl), an unsubstituted or halogen or C1-C6 alkyl (preferably a C1-C4 alkyl) substituted phenyl. The D ring is unsubstituted or substituted by R4 and is connected to the outside of the ring via 1-2 double bonds or single bonds. Preferably, the D ring is connected to the outside of the ring via a double bond.

[0056] More preferably, R2 is a bond or -(CHR 21 ) q N(R 22 )-, where R 21 , R 22 Each is independently selected from hydrogen, a straight or branched C1-C8 alkyl group (preferably a C1-C4 alkyl group), an unsubstituted phenyl group or a phenyl group substituted by a C1-C6 alkyl group (preferably a C1-C4 alkyl group), wherein q=0-18, preferably, q=0-8, more preferably, q=0-4, particularly preferably, q=0-2, and most preferably, q=1;

[0057] D is selected from the following rings:

[0058]

[0059]

[0060] Wherein, R4 is one or more substituents, and each is independently selected from hydrogen, halogen, linear or branched C1-C8 alkyl, alkenyl or alkoxy (preferably C1-C6 or C1-C4 alkyl, alkenyl or alkoxy), SR5, SO2R5, COOR5, COR5, C(O)NR6R7, NR6R7, wherein R5, R6, R7 are each independently selected from hydrogen, linear or branched C1-C6 alkyl (preferably C1-C4 alkyl), preferably, halogen is chlorine; p=0-2; preferably, p=0-1, particularly preferably, p=0; R9, R 23 ~R 34The present invention is selected from hydrogen, linear or branched C1-C6 alkyl (preferably C1-C4 alkyl), unsubstituted phenyl or phenyl substituted by C1-C6 alkyl (preferably C1-C4 alkyl).

[0061] Particularly preferably, A——R1——B is selected from the following groups:

[0062]

[0063]

[0064] R4 is one or more substituents, and each is independently selected from hydrogen, halogen, hydroxyl, amino, nitro, cyano, straight chain or branched C1-C 18 alkyl, alkenyl or alkoxy, substituted or unsubstituted phenyl, SR5, SO2R5, SO3R5, COOR5, COR5, OCOR5, C(O)NR6R7, SO2NR6R7, NR6R7, wherein R5, R6, R7 are each independently selected from hydrogen, a straight or branched C1-C8 alkyl (preferably a C1-C4 alkyl), and R4 and the adjacent R4, or R4 and the adjacent ring, together represent a fused carbocyclic ring or a fused heterocyclic ring of 3-6 atoms, preferably a fused heterocyclic ring of 3-6 atoms containing C, N, O, S, preferably, the halogen is chlorine; p=0-2, preferably, p=0-1, more preferably, p=0.

[0065] R 19 , R 35 ~R 39 is one or more and each is independently selected from H, a linear or branched C1-C6 alkyl group (preferably a C1-C4 alkyl group), an unsubstituted or halogen or C1-C6 alkyl group (preferably a C1-C4 alkyl) substituted phenyl group; Ph is an unsubstituted or halogen, OH group or a C1-C6 alkyl group (preferably a C1-C4 alkyl) substituted phenyl group, preferably, the halogen is chlorine.

[0066] Very preferably, the compound of formula (1) or formula (2) comprises at least one visible light or fluorescent light emitting group and at least one covalently linked ultraviolet light absorbing group, wherein the visible light or fluorescent light emitting group is R2——C——R3——D or R2——D——R3——C, selected from:

[0067]

[0068]

[0069] D is selected from:

[0070]

[0071]

[0072] Wherein, the ultraviolet light absorbing group is A——R1——B, selected from:

[0073] Benzotriazole:

[0074] Triazine:

[0075] Carbazole:

[0076] Oxanilide:

[0077] Benzoxazinone:

[0078] Quinazolinone:

[0079] Dibenzoylmethane:

[0080] Phenylformamidine:

[0081] Azomethine:

[0082] Quinazoline:

[0083] Benzoic acid:

[0084] Benzophenone:

[0085] Dibenzothiophene:

[0086] Dibenzofuran:

[0087] Diphenyl sulfide:

[0088] Oxydibenzene:

[0089] The above visible light (fluorescence) emitting groups or ultraviolet light absorbing groups are all (R4) p R4 is one or more substituents, and each is independently selected from hydrogen, halogen, hydroxyl, amino, nitro, cyano, straight or branched C1-C 18 alkyl, alkenyl or alkoxy, substituted or unsubstituted phenyl, SR5, SO2R5, SO3R5, COOR5, COR5, OCOR5, C(O)NR6R7, SO2NR6R7, NR6R7, wherein R5, R6, R7 are each independently selected from hydrogen, a linear or branched C1-C8 alkyl (preferably a C1-C4 alkyl), and R4 and the adjacent R4, or R4 and the adjacent ring, together represent a fused carbocyclic ring or a fused heterocyclic ring of 3-6 atoms, preferably, a fused heterocyclic ring of 3-6 atoms containing one or more C, N, O, S; R 40 ~R 49 are the same or different and are independently selected from hydrogen, straight or branched C1-C8 alkyl or alkenyl (preferably C1-C4 alkyl or alkenyl), unsubstituted or substituted by straight or branched C1-C6 alkyl (preferably C1-C4 alkyl) or halogen phenyl; R 50 Selected from hydrogen, monovalent metal, linear or branched C1-C8 alkyl or alkenyl (preferably C1-C4 alkyl), unsubstituted or linear or branched C1-C6 alkyl (preferably C1-C4 alkyl) or phenyl substituted with halogen. Preferably, halogen is chlorine. Preferably, monovalent metal is lithium or sodium.

[0090] Most preferably, the compound of formula (1) or formula (2) is as follows:

[0091]

[0092]

[0093]

[0094]

[0095] The method for preparing the compound of formula (1) or formula (2) is characterized by comprising one of the following reaction steps.

[0096] The preparation of the compound of formula (1) comprises one of the following reaction steps:

[0097]

[0098] Wherein, the preparation of the compound of formula (2) comprises one of the following reaction steps:

[0099]

[0100] Wherein, A to D rings, R1 to R3, are as defined above;

[0101] D' is a precursor of the D ring, selected from D' is a precursor of the D ring, selected from

[0102] D" is the precursor of D ring,

[0103] Z is a leaving group, including but not limited to halogen, C1-C 10 Sulfonate group, C1~C 10 Preferably, Z is selected from halogen, p-toluenesulfonate (OTs), methanesulfonate (OMs), C1-C4 alkoxy. Preferably, halogen is chlorine.

[0104] U, V are selected from C=O, C=S, C=NR 51 , C(R 52 )(R 53 );R 50 ~R 53 The alkyl groups are the same or different and are independently selected from a bond, hydrogen, a straight chain or a branched C1-C8 alkyl group. Preferably, the alkyl group is a straight chain or a branched C1-C4 alkyl group.

[0105] T is the same or different and is independently selected from NH, NH2, OH, and SH.

[0106] The specific preparation method 1 of the compound (1) of the present invention includes the preparation methods of Examples 1-11, 15-22, and 33. The preparation method of the compound of Example 1-4 is as follows:

[0107]

[0108] The specific preparation method 2 of the compound (1) of the present invention includes the preparation methods of Examples 12-14, 23-32. The preparation method of Example 13 is as follows:

[0109]

[0110] The specific preparation method 1 of the compound (2) of the present invention includes the preparation method of Example 34. The preparation method is as follows:

[0111]

[0112] The specific preparation method 2 of the compound (2) of the present invention includes the preparation method of Example 35. The preparation method is as follows:

[0113]

[0114] The specific preparation method 3 of the compound (2) of the present invention includes the preparation method of Example 36. The preparation method is as follows:

[0115]

[0116] The specific preparation method 4 of the compound (2) of the present invention includes the preparation method of Example 37, and the preparation method is as follows:

[0117]

[0118] The specific preparation method 5 of the compound (2) of the present invention includes Example 38. The preparation method is as follows:

[0119]

[0120] The specific preparation method 6 of the compound (2) of the present invention includes the preparation method of Example 39. The preparation method is as follows:

[0121]

[0122]

[0123] The specific preparation method of the traditional benzotriazole compound is usually synthesized by using 2-nitroaniline and various substituted phenols as starting materials. The first step is to form an azo compound, and the second step is a reduction reaction to form a benzotriazole compound (US3773751), such as Example 6. The preparation method is as follows:

[0124]

[0125] The compounds of the present invention can be applied to thin films. For example, they can be used as light-converting agents in agricultural films. They can also be used in UV-proof films or blue-light-proof films to protect the eyes or other tissues. The compounds of the present invention can be applied to general thin films or organic materials to protect the thin films or organic materials themselves. For another example, the compounds of the present invention can be applied to the recording layer of optical recording media. The compounds of the present invention can also be used in combination with other compounds according to different needs. These applications can be implemented using common industrial methods.

[0126] Agricultural film is usually made of resin raw materials such as polyvinyl chloride, ethylene or low-density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA), metallocene linear polyethylene (MLLDPE), etc., and after adding additives, it is made through blow molding and calendering processes. The specific manufacturing method, for example, takes 1kg of low-density polyethylene as the base material, 200g of metallocene linear polyethylene, 5g of light-converting agent, 8g of antioxidant, 5g of ultraviolet absorber, 9g of glyceride, mixes well, and then blows it into shape by conventional blow molding through a film blowing unit. A transparent film with a thickness of 0.03 to 2.0mm. The amount of light-converting agent added depends on the type of crops and the thickness of the agricultural film, usually ranging from but not limited to 0.001% to 20%, preferably, 0.2% to 5%.

[0127] In the manufacture of anti-ultraviolet film or anti-blue light film, or agricultural film, the light-converting or anti-blue light composition can also be coated on the base layer or release layer and used after hardening. Or a transfer coating process is adopted, first coated on the release film, and then transferred to the base layer. The film upper and lower layers are each bonded with a layer of release film, which is OCA optical adhesive (Optically Clear Adhesive). The coating method is a conventional technique, including traditional brush coating, spray coating, curtain coating, roller coating, slit coating, air knife coating, doctor blade coating, and metering rod coating. The drying method includes natural drying, microwave drying, ultraviolet drying, infrared drying, and hot air drying. The base layer includes one or more mixtures of polyester, glass, polyethylene, polypropylene, polycarbonate, polyamide, polyacrylate, polymethacrylate, polyvinyl acetate, and polyvinyl chloride. The release film includes silicone-oxygen compound type and non-silicone-oxygen compound material. A light conversion or blue light protection composition comprises the light conversion agent of the present invention, an ultraviolet light protection agent or a blue light protection agent, a polymer, a solvent, and / or an auxiliary agent, and / or an initiator, and / or a monomer.

[0128] The compound of the present invention is used for the recording layer of an optical recording medium. The organic dye recording layer can be coated on a substrate by a spin coating method. The substrate can be made of polycarbonate (PC) or polyacrylamide. The thickness of the recording layer is usually several nanometers to tens of nanometers. After coating, a reflective layer is formed on the recording layer by a sputtering method. Then, an adhesive layer is spin coated, and a cover plate is adhered to the reflective layer through the adhesive layer to form an optical disc. BRIEF DESCRIPTION OF THE DRAWINGS

[0129] Figure 1 UV-VIS absorption diagram of compound (7) of the present invention (10 mg / tetrahydrofuran);

[0130] Figure 2 TGA (thermogravimetric analyzer) chart of compound (7) of the present invention;

[0131] Figure 3UV-VIS absorption diagram of the compound (18) of the present invention (10 mg / tetrahydrofuran);

[0132] Figure 4 The appearance of the agricultural film made of the light conversion agent of the present invention. DETAILED DESCRIPTION

[0133] Specific embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

[0134] A——R1——B——R2——C——R3——D (1)

[0136] Table 1 is a compound of formula (1)

[0137]

[0138]

[0139]

[0140]

[0141] A——R1——B——R2——D——R3——C (2)

[0143] Table 2 is the compound of formula (2)

[0144]

[0145]

[0146] Example 1

[0147] Preparation of 2-(2-hydroxy-3-(chloromethyl)-5-methyl)benzotriazole (Compound 3)

[0148]

[0149] Add 350g of 2-(2-hydroxy-5-methyl)benzotriazole (UV-P, compound 3), 55g of paraformaldehyde, 2000g of acetic acid, and 300g of 35% hydrochloric acid to a 5000ml reaction bottle, heat to 60℃ and keep warm for 10 hours, take samples to monitor the reaction. Cool down, wash with water, and dry to obtain a white powder (chloromethyl UV-P, compound 4), with a yield of 96%. 14 H 12 ClN3O, melting point: 163-164℃.

[0150] Example 2

[0151] Preparation of 2-(2-hydroxy-3-(N,N-dimethylaniline)-5-methyl)benzotriazole (Compound 5)

[0152]

[0153] Add 180 ml of toluene, 17 g of potassium carbonate, 13.9 g of N-methylaniline, 0.2 g of phase catalyst, and 33.3 g of compound (4), heat to 90-100 °C and react for 5 hours, take samples to monitor the reaction. Cool to 30 °C, wash with water and recover toluene. Add 180 g of methanol and stir, filter and dry to obtain a solid (compound 5). Purity 98.3%, yield 84%. 21 H 20 N4O, melting point: 98-100℃.

[0154] Example 3

[0155] Preparation of 2-(2-hydroxy-3-(4-formyl-N,N-dimethylaminobenzene)-5-methyl)benzotriazole (Compound 6)

[0156]

[0157] Add 35g of compound (5) and 8.7g of DMF, and add 18.4g of phosphorus oxychloride dropwise at 20-25°C for about 2 hours. Heat to 90°C for 2 hours, and take samples to monitor the reaction (Vilsmeier-Haack formylation). Slowly add the reaction material to 300g of water below 30°C for hydrolysis, and then neutralize with 30% liquid alkali after addition, adjust the pH to 8, and filter out the solid. Dissolve with toluene, wash with water, cool to 15°C, solid precipitates, and dry to obtain 31.8g of yellow solid (compound 6). 21 H 19 N4O2, melting point: 111-113℃.

[0158] Example 4

[0159] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)pyrimidine-2,4-,6(1H,3H,5H)trione (Compound 7)

[0160]

[0161] 50 g of compound (6) and 17.1 g of barbituric acid were dissolved in toluene, 5 g of ammonium acetate and 10 g of acetic acid were added, and the mixture was kept at 80-90°C for 1 hour. The mixture was then heated to reflux for 8 hours, and samples were taken to monitor the reaction. After the reaction was completed, the mixture was cooled, the solid was filtered out, and the mixture was washed with toluene and then with dichloroethane, filtered, washed with water, and dried to obtain a solid compound (7). Yield: about 80%. 26 H 22 N6O4, melting point: 262-270℃.

[0162] Example 5

[0163] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)benzylidene)pyrimidine-2,4-,6(1H,3H,5H)trione (Compound 8).

[0164]

[0165] According to the method of Example 1-4, but using N-ethylaniline instead of N-methylaniline, compound (8) was obtained. 27 H 24 N6O4, melting point: 263-267℃.

[0166] Example 6

[0167] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-(2-methylhept-2-yl)benzyl)(ethyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 9).

[0168]

[0169] The raw material 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (Compound 10) comes from Eutec co. (Eusorb329, melting point: 102-106°C), or can be prepared in the following manner. 13.8 grams of o-nitroaniline is added to 25 ml of 37% hydrochloric acid and stirred, diluted with 40 ml of water and cooled to -15°C. 7.5 g of sodium nitrite (dissolved in water) is added, and the temperature is maintained at 0-5°C to obtain the diazonium salt. 5.2 g of 4-tert-Octylphenol, 20 ml of petroleum ether, 5 ml of water and 2.5 g of calcium hydroxide are mixed, and a sample is taken to monitor the reaction. After the reaction is completed, 20 g of ice is added and the temperature is raised to 0°C. The aforementioned diazonium salt is added and stirred for 2 hours. Concentrated hydrochloric acid was added to neutralize and dried to obtain 2-((2-nitrophenyl)diazenyl)-4-(2,4,4-trimethylpentan-2-yl)phenol (Compound 11). 20 H 25 N3O3, melting point: 114-115°C. Take 35.7g of compound (11) and dissolve it in 100ml of petroleum ether, add 17.2g of zinc and 100ml of water. Add 41.6g of NaOH solution (25%) at 50°C within 4 hours and leave it for 1 hour. Add 100ml of concentrated hydrochloric acid and leave it for 2 hours. Take samples to monitor the reaction, wash the organic layer with water, and remove the solvent to obtain compound (10). 20 H 25 N3O, melting point: 102-106℃.

[0170]

[0171] According to the method of Example 1-5, but using 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (Eusorb 329, compound 10) instead of UV-P (compound 3) as the starting material, compound (9) was obtained. 34 H 38 N6O4,m / z:594.3[M] + .

[0172] Example 7

[0173] Preparation of 5-(4-((3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxybenzyl)(ethyl)amino)benzylidene)pyrimidine-2,4-,6(1H,3H,5H)trione (Compound 12).

[0174]

[0175] According to the method of Example 6, 4-chloro-2-nitroaniline was used as the starting material instead of o-nitroaniline to obtain 2-(2'-hydroxy-phenyl)-5-chloro-benzotriazole (Compound 13). 12 H8ClN3O, melting point: 139-140°C. According to the method of Example 1-5, but using 2-(2'-hydroxy-phenyl)-5-chloro-benzotriazole (Compound 13) instead of UV-P (Compound 3) as the starting material, Compound (12) was obtained. 26 H 21 ClN6O4,m / z:516.1[M] + .

[0176] Example 8

[0177] Preparation of 5-(4-((3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxybenzyl)(ethyl)amino)benzylidene)pyrimidine-2,4-,6(1H,3H,5H)trione (Compound 14).

[0178]

[0179] According to the method of Example 6, 4-methoxy-2-nitroaniline was used as the starting material instead of o-nitroaniline to obtain 2-(2'-hydroxy-phenyl)-5-chloro-benzotriazole (Compound 15). 14 H 13 N3O2, melting point: 126-127°C. According to the method of Example 1-5, but using 2-(2'-hydroxy-phenyl)-5-methoxy-benzotriazole (Compound 15) instead of UV-P (Compound 3) as the starting material, Compound (14) was obtained. 28 H 26 N6O5,m / z:526.2[M] + .

[0180] Example 9

[0181] Preparation of methyl 3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-((ethyl(4-((2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)methyl)phenyl)amino)methyl)-4-hydroxybenzoate (Compound 16).

[0182]

[0183] According to the method of Example 6, 4-hydroxybenzoic acid was used to replace 4-tert-octylphenol to obtain 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxybenzoic acid. After adding thionyl chloride and heating to reflux for 2 hours, the thionyl chloride was evaporated to dryness, and n-hexanol was added to reflux, and the reaction was monitored by sampling. 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxybenzoic acid hexyl ester (Compound 17) was obtained. 19 H 21 N3O3, melting point: 83-84℃.

[0184]

[0185] According to the method of Example 1-5, but using 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxybenzoic acid hexyl ester (Compound 17) instead of UV-P (Compound 3) as the starting material, Compound (16) was obtained. 33 H 34 N6O6,m / z:610.3[M] + .

[0186] Example 10

[0187] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)benzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (Compound 18)

[0188]

[0189] 20g of compound (6) and 8.2g of Meldrum's acid were added to toluene, and 4.1g of ammonium acetate and 10g of acetic acid were added. The mixture was refluxed and dehydrated for 4 hours, and samples were taken to monitor the reaction. After the reaction was completed, the solid was filtered out, dissolved in dichloroethane at elevated temperature, washed with water, distilled off the dichloroethane, and recrystallized by adding toluene to obtain compound (18). 29 H 28 N4O5, melting point: 220-224℃.

[0190] Embodiment 11

[0191] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)benzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (Compound 19)

[0192]

[0193] 12 g of compound (6) was added to 200 ml of a solution of 1% sodium hydroxide and 15% ethanol. 5 g of a 30% aqueous solution of acetaldehyde was added dropwise. The mixture was reacted overnight, 15 g of NaCl was added and stirred, and the pH was adjusted to neutral with dilute hydrochloric acid. Then, 3-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)phenyl)acrolein (20) was obtained after extraction with ethyl acetate and drying.

[0194]

[0195] According to the method of Example 10, compound (20) was added with Michaelis acid, ammonium acetate and acetic acid to react to obtain compound (19). 31 H 30 N4O5,m / z:538.2[M] + .

[0196] Example 12

[0197] Preparation of 5-(4-(methylamino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 21)

[0198]

[0199] Dissolve 20g of barbituric acid and 13.6g of 4-methylaminobenzaldehyde in dichloromethane. Add molecular sieves to remove water and install a calcium chloride tube to prevent water. Add 1ml of piperidine and 0.6ml of acetic acid, heat and reflux, and react for 2 hours. During the reaction, add fresh molecular sieves and take samples to monitor the reaction. After the reaction is completed, remove the solvent, wash with acid, and dry to obtain compound (21). 12 H 11 N3O3,m / z:245.1[M] + .

[0200] Embodiment 13

[0201] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)pyrimidine-2,4-,6(1H,3H,5H)trione (Compound 7)

[0202]

[0203] According to the method of Example 2, compound (7) was obtained by replacing N-methylaniline with compound (21). The chemical shift 4.6 in H1-NMR of the starting compound (4) disappeared (-C H2 Cl), and the chemical shift is 5.0 newborn (compound 7, - CH2N), indicating that the reaction is complete. The melting point range is the same as that of compound (7) prepared by the method of Example 4.

[0204] Embodiment 14

[0205] Preparation of ethyl 3-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)phenyl)-2-cyano-3-phenylacrylate (Compound 22)

[0206]

[0207] According to the method of Example 2, but using 4-methylaminobenzophenone (Compound 23) instead of N-methylaniline, Compound (24) was obtained.

[0208]

[0209] According to the method of Example 4, Compound (24) was used instead of Compound (6) and the mixture was separated by column chromatography to obtain Compound (22). 32 H 26 N6O4,m / z:558.2[M] + .

[0210] Embodiment 15

[0211] Preparation of 5-((1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-1H-indol-3-yl)methylene)pyrimidine-2,4,6-(1H,3H,5H)-trione (Compound 25)

[0212]

[0213] According to the method of Example 3, 3-indolecarboxaldehyde was used to replace N-methylaniline, and the mixture was separated by column chromatography to obtain compound (26). According to the method of Example 4, compound (26) was used to replace compound (6), and the mixture was separated by column chromatography to obtain compound (25). 27 H 20 N6O4. m / z:492.2[M] + .

[0214] 3-Indolecarboxaldehyde is an industrial raw material and can be prepared in the following way (Vilsmeier reaction): 16g of POCl3 is added dropwise to 30g of DMF in an ice bath within 30 minutes. 11g of DMF solution of indole compound is slowly added, and the mixture is heated to 35°C and stirred for 1 hour. 50g of crushed ice is added to the obtained paste and stirred, and 0.1M NaOH is slowly added under stirring. After washing with water, 3-Indolecarboxaldehyde is obtained by recrystallization with ethanol, and C9H7NO is obtained. Melting point: 196-197°C.

[0215] Example 16

[0216] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)-4-thiothiazol-2-one (Compound 27)

[0217]

[0218] According to the method of Example 4, the barbituric acid compound was replaced by 4-thiothiazol-2-one (CAS RN. 4303-29-1) to obtain compound (27). 25 H 21 N5O4,m / z:455.2[M] + .

[0219] Embodiment 17

[0220] Preparation of 5-((6-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)naphthalen-2-yl)methylene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 28)

[0221]

[0222] According to the method of Example 15, 6-(methylamino)-2-naphthaldehyde was used to replace 3-indolecarboxaldehyde to obtain compound (28). 30 H 24 N6O4,m / z:532.2[M] + .

[0223] Embodiment 18

[0224] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)oxazolidine-2,4-dione (Compound 29)

[0225]

[0226] According to the method of Example 4, the barbituric acid compound was replaced by oxazolidine-2,4-dione (CAS RN. 2346-26-1) to obtain compound (29). 25 H 21 N5O4,m / z:455.2[M] + .

[0227] Embodiment 19

[0228] Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)cyclopent-4-ene-1,3-dione (Compound 30)

[0229]

[0230] According to the method of Example 4, the barbituric acid compound was replaced by a 4-cyclopentene-1,3-dione compound to obtain compound (30). 26 H 19 N4O3,m / z:435.2[M] +

[0231] Embodiment 20

[0232] Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)-1H-indene-1,3(2H)-dione (Compound 31)

[0233]

[0234] According to the method of Example 4, the barbituric acid compound was replaced by the compound 1H-indene-1,3(2H)-dione to obtain compound (31). 31 H 24 N4O3,m / z:500.2[M] + .

[0235] Embodiment 21

[0236] Preparation of 5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)-3,5-dihydro-4H-imidazol-4-one (Compound 32)

[0237]

[0238] According to the method of Example 4, the barbituric acid compound was replaced by 1,4-dihydroimidazol-5-one (CAS RN. 1968-28-1) to obtain compound (32). 25 H 22 N6O2,m / z:438.2[M] + .

[0239] Embodiment 22

[0240] Preparation of 4-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzylidene)oxazol-5-(4H)-one (Compound 33)

[0241]

[0242] According to the method of embodiment 4, the barbituric acid compound was replaced by compound 4H-5-oxo-oxazole (CAS RN. 497-24-5) to obtain compound (33). 25 H 21 N5O3,m / z:439.2[M] + .

[0243] Embodiment 23

[0244] Preparation of 3-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)-N-(4-((2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)methyl)phenyl)propanamide (Compound 34)

[0245]

[0246] 5.2 g of methyl 3-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propanoate (Compound 35) was dissolved in toluene and heated to reflux in a flask equipped with a condenser and water separator. Compound (21) was added to the toluene solution and samples were taken to monitor the reaction. After the reaction was completed, vacuum distillation was performed. After chromatographic separation, compound (34) was obtained, C 44 H 44 N6O5. m / z:736.3[M] + .

[0247]

[0248] Preparation method of compound (35) (according to CN201710949552.0): Briefly, 16 g of 2-chloro-4,6-di(2′,4′dimethyl-phenyl)-1,3,5-triazine (compound 36) and 15 g of methyl (3-tert-butyl-4-hydroxyphenyl) propionate (compound 37) were dissolved in 150 ml of chlorobenzene, 10 g of anhydrous aluminum chloride was added, and heated and stirred to dissolve. The temperature was raised to 90°C, and samples were taken to monitor the reaction.

[0249] After the reaction was completed, the mixture was distilled under reduced pressure and separated by chromatography to obtain compound (35).

[0250]

[0251] Embodiment 24

[0252] Preparation of 5-(4-((3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(tert-butyl)-4-hydroxybenzyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 38)

[0253]

[0254] The same method as in Example 13 was used, but 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-6-(tert-butyl)-4-(chloromethyl)phenol (Compound 39) was used instead of Compound (4). The product was separated by chromatography to obtain Compound (38). 39 H 36 N6O4. m / z:652.3[M] + .

[0255]

[0256] The preparation method of compound (39) is as described in Example 23 for the preparation of compound (35), except that 4-(chloromethyl)-2-methylphenol is used instead of methyl (3-(tert-butyl)-4-hydroxyphenyl)propionate (37).

[0257] Embodiment 25

[0258] Preparation of 5-(4-((5-benzoyl-4-hydroxy-2-(octyloxy)benzyl)(methyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 40)

[0259]

[0260] The method of Example 13 was used, but (5-(chloromethyl)-2-hydroxy-4-(octyloxy)phenyl)(phenyl)methanone (Compound 41) was used instead of Compound (4). After chromatographic separation, Compound (40) was obtained. 34 H 37 N3O6. m / z:583.3[M] + .

[0261]

[0262] Preparation of compound (41): Compound (41) was prepared by the same method as in Example 1, except that (2-hydroxy-4-(octyloxy)phenyl)(phenyl)methanone (Eutec co., Eusorb UV-531) was used instead of UV-P (compound 3) to obtain compound (41).

[0263] Embodiment 26

[0264] Preparation of 5-(4-(methyl(4-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)benzyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)trione (Compound 42)

[0265]

[0266] The method of Example 13 was used, but 2-(chloromethyl)-4H-benzo[d][1,3]oxazin-4-one (Compound 43) was used instead of Compound (4). After chromatographic separation, Compound (42) was obtained. 27 H 20 N4O5. m / z:480.1[M] + .

[0267]

[0268] Preparation of compound (43): 14 g of 2-aminobenzoic acid (compound 44) ​​and 11 g of triethylamine were added to 100 ml of dichloroethane, and 19 g of 4-chloromethylbenzoyl chloride (compound 45) was added dropwise and stirred to obtain (compound 43). Preparation of compound (45): 4-(Hydroxymethyl)benzoic acid (46) was chlorinated in dichloromethane with thionyl chloride under reflux to obtain compound (45), melting point: 28°C.

[0269]

[0270] Embodiment 27

[0271] Preparation of 5-(4-((4-(((2,4-dihydroxy-quinolin-3-yl)methylene)amino)benzyl)(methyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 47)

[0272]

[0273] The same method as in Example 13 was used, but 3-(((4-(chloromethyl)phenyl)imino)methyl)quinoline-2,4-diol (Compound 48) was used instead of Compound (4) to obtain Compound (47). 29 H 23 N5O5. m / z:521.2[M] + .

[0274]

[0275] The preparation method of 3-(((4-(chloromethyl)phenyl)imino)methyl)quinoline-2,4-diol (48) was as described in Example 1, except that 3-((phenylimino)methyl)quinoline-2,4-diol (UA-3701, melting point 194°C) was used instead of UV-P (compound 3).

[0276] Embodiment 28

[0277] Preparation of ethyl 4-(((methyl(4-((methyl(4-((2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)methyl)phenyl)amino)methyl)phenyl)amino)methylene)amino)benzoate (Compound 49)

[0278]

[0279] The same method as in Example 13 was used, except that ethyl 4-((((4-(chloromethyl)phenyl)(methyl)amino)methylene)amino)benzoate (Compound 50) was used instead of Compound (4) and purified to obtain Compound (49). 30 H 29 N5O5. m / z:539.2[M] + .

[0280]

[0281] Compound (50) was prepared as in Example 1 except that ethyl 4-(((methyl(phenyl)amino)methylene)amino)benzoate (UV-1, melting point 137°C) was used instead of UV-P (compound 3).

[0282] Embodiment 29

[0283] Preparation of N1-(2-ethoxy-4-((methyl(4-((2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)methyl)phenyl)amino)methyl)phenyl)-N2-(2-ethylphenyl)oxalamide (Compound 51)

[0284]

[0285] The same method as in Example 13 was used, but N1-(4-(chloromethyl)-2-ethoxyphenyl)-N2-(2-ethylphenyl)oxalamide (Compound 52) was used instead of Compound (4) to obtain Compound (51). 31 H 31 N5O6. m / z:569.2[M] + .

[0286]

[0287] The preparation method of N 1-(4-(chloromethyl)-2-ethoxyphenyl)-N 2-(2-ethylphenyl)oxalamide (Compound 52) was as described in Example 1, except that N-(2-ethoxyphenyl)-N'-(4-ethylphenyl)-oxalamide (Eutec co., UV-312, melting point 120°C) was used instead of UV-P (Compound 3).

[0288] Embodiment 30

[0289] Preparation of 5-(4-(((9H-carbazol-3-yl)methyl)(methyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 53)

[0290]

[0291] The same method as in Example 13 was used, but 3-(chloromethyl)-9H-carbazole (compound 54) was used instead of compound (4) to obtain compound (53). 25 H 20 N4O3. m / z:424.2[M] + .

[0292]

[0293] The preparation method of 3-(chloromethyl)-9H-carbazole (Compound 44) ​​is as in Example 1, except that 9H-carbazole is used instead of UV-P (Compound 3).

[0294] Embodiment 31

[0295] Preparation of 5-(4-(((9H-carbazol-1-yl)methyl)(methyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 55)

[0296]

[0297] The same method as in Example 13 was used, but 9H-carbazole-3-carboxylic acid methyl ester (Compound 56) was used instead of Compound (4) to obtain Compound (55). 25 H 18 N4O4. m / z:438.1[M] + .

[0298]

[0299] Preparation of 9H-carbazole-1-carboxylic acid methyl ester: 9H-carbazole-1-carboxylic acid (AKOS BC-1282) was refluxed in excess methanol with concentrated sulfuric acid as a catalyst to obtain compound (56).

[0300] Embodiment 32

[0301] Preparation of 5-(4-((dibenzo[b,d]thiophen-2-ylmethyl)(methyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 57)

[0302]

[0303] The same method as in Example 13 was used, but 2-(chloromethyl)dibenzo[b,d]thiophene (Compound 58) was used instead of Compound (4) to obtain Compound (57). 25 H 19 N3O3S. m / z:441.1[M] + .

[0304]

[0305] The preparation method of 2-(Chloromethyl)dibenzo[b,d]thiophene (Compound 58) was as described in Example 1, except that dibenzo[b,d]thiophene was used instead of UV-P (Compound 3).

[0306] Embodiment 33

[0307] Preparation of reaction mixture (59) of 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Eutec co., Eusorb UV-120) and 5-(4-(methylamino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 21)

[0308] The method is the same as in Example 2, but 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Eutecco., Eusorb UV-120, melting point 149°C) is used instead of UV-P (Compound 3). After washing with water and drying, it is directly reacted with (Compound 21) in dichloromethane and refluxed to obtain a product (59) mixture.

[0309] Embodiment 34

[0310] Preparation of 1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-5-(4-(dimethylamino)benzylidene)pyrimidine-2,4-,6(1H,3H,5H)trione (Compound 60)

[0311]

[0312] Dissolve 15 g of 4-(dimethylamino)benzaldehyde, 13.2 g of dimethyl malonate, and 15 ml of pyridine in toluene and heat to reflux. Take a sample to monitor the reaction, remove the solvent, and obtain dimethyl 2-(4-(dimethylamino)benzylidene)malonate (Compound 61) after chromatography. 14 H 17 NO4, melting point 86 -88℃.

[0313]

[0314] Take 26.3g of dimethyl 2-(4-(dimethylamino)benzylidene)malonate compound (Compound 61) and 4.6g of diaminomethane and reflux in ethanol for 3 hours. Evaporate the solvent to obtain a closed-loop compound. Mix 14.6g of the closed-loop compound, 21g of chromium trioxide, and 100ml of water. Add 45ml of concentrated sulfuric acid. After the concentrated sulfuric acid is added, add chromium trioxide (21g / 50ml water) and heat to reflux, and take samples to monitor the reaction. After cooling to room temperature, pour the reaction mixture into an equal volume of water and cool to 10°C in an ice bath. Separate the precipitate and wash with water. Disperse the precipitate in 30 ml of water and add 50ml of saturated sodium carbonate solution and stir. Filter to obtain compound (60). C 27 H 24 N6O4,MS:m / z=496.2[M] + .

[0315] Embodiment 35

[0316] Preparation of 1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-5-(4-(dimethylamino)benzylidene)-3-methylimidazolidine-2,4-dione (Compound 62)

[0317]

[0318] As in Example 2, 27.5 g of compound (4) was added to 10 g of glycine methyl ester to react to obtain (3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)glycine methyl ester (Compound 63).

[0319]

[0320] Take 16.3 g of compound (63) and 5.1 g of 2-isocyanato-2-methylpropane, heat and reflux in dichloroethane overnight, remove unreacted 2-isocyanato-2-methylpropane and dichloroethane by reduced pressure distillation, and separate by chromatography to obtain 1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-3-(tert-butyl)imidazolidine-2,4-dione (compound 64).

[0321]

[0322] As in Example 4, 4 g of compound (65) and 1.5 g of 4-(dimethylamino)benzaldehyde were reacted to obtain 1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-3-(tert-butyl)imidazolidine-2,4-dione (Compound 62). 30 H 32 N6O3,m / z:524.3[M] + .

[0323]

[0324] Embodiment 36

[0325] Preparation of 5-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-2-(4-(diethylamino)phenyl)-2-methyl-1,3-dioxane-4,6-dione (Compound 67) and 5-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzylidene)-2-(4-(diethylamino)phenyl)-2-methyl-1,3-dioxane-4,6-dione (Compound 90)

[0326]

[0327]

[0328] Take 5.2g of malonic acid (68) and dissolve it in 6ml of acetic anhydride. Add 0.15ml of concentrated sulfuric acid while cooling and stirring with ice water. Heat in a water bath to dissolve, add 4-(diethylamino)acetophenone (69), stir at room temperature overnight, wash with water, and extract with ethyl acetate to obtain 2-(4-(diethylamino)phenyl)-2-methyl-1,3-dioxane-4,6-dione (Compound 70).

[0329]

[0330] 2.75 g of compound (4) was added to 2.34 g of compound (70), and the mixture was refluxed in an ethanol solution of sodium ethoxide overnight. The solvent was removed and the mixture was neutralized with HCl, and then separated by chromatography to obtain compound (67). 29 H 30 N4O5,m / z:514.2[M] + .

[0331]

[0332] The same method as in Example 3 was used, but Compound (3) was used instead of Compound (5) to obtain 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzaldehyde (Compound 89). The same method as in Example 4 was used, but Compound (70) was used instead of barbituric acid, and Compound (89) was used instead of Compound (6) to obtain 5-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzylidene)-2-(4-(diethylamino)phenyl)-2-methyl-1,3-dioxane-4,6-dione (Compound 90). 29 H 28 N4O5,m / z:512.2[M] + .

[0333]

[0334] Embodiment 37

[0335] Preparation of 5-(9H-carbazol-3-yl)-3-(4-(dimethylamino)phenyl)oxazolidine-2,4-dione (Compound 71)

[0336]

[0337] Under an ice-water bath, 34 g of 9H carbazole was dissolved in 400 ml of dry dichloromethane, 30 g of anhydrous AlCl3 was slowly added and stirring continued for 10 minutes, and then 31 g of 2-chloro-2-oxoacetic acid methyl ester (Compound 72) was slowly added dropwise. After the addition was complete, stirring was continued at room temperature. After the reaction was completed, sampling was monitored, and the reactant was poured into a hydrochloric acid-ice-water bath, extracted with dichloromethane, and dried to obtain 2-(9H-carbazole-3-yl)-2-oxoacetic acid methyl ester (Compound 73).

[0338]

[0339] 18 g of compound (73) was added to 150 mL of anhydrous ethanol and stirred at room temperature. 2.6 g of sodium borohydride was added and the reaction mixture was stirred at room temperature for 50 minutes. After the reaction was completed, sampling was performed for monitoring and the reactants were poured into a hydrochloric acid-ice water bath. The mixture was extracted with ethyl acetate and dried to obtain methyl 2-(9H-carbazole-3-yl)-2-oxoacetate (compound 74).

[0340]

[0341] Take 2.5g of compound (74) and dissolve it in 20ml of dichloromethane. Add 1.5ml of triethylamine and stir. Add 1.6g of 4-isocyanato-N,N-dimethylaniline (75) in dichloromethane (10%) dropwise. After the addition is complete, reflux in dichloromethane and monitor the reaction. After the reaction is completed, neutralize with HCl. Wash with water, remove the solvent, and separate by chromatography to obtain compound (71). 23 H 19 N3O3,m / z:385.1[M] + .

[0342]

[0343] Embodiment 38

[0344] Preparation of 5-((9H-carbazole-3-yl)chloromethyl)-3-(4-(dimethylamino)phenyl)oxazolidine-2,4-dione (Compound 76) and 5-((9H-carbazole-3-yl)methylene)-3-(4-(dimethylamino)phenyl)oxazolidine-2,4-dione (Compound 88)

[0345]

[0346]

[0347] As in Example 3, 9H-carbazole was used instead of compound (5) to obtain 9H-carbazole-3-carboxaldehyde (Compound 77) with a melting point of 158°C.

[0348]

[0349] At 4°C, 5 g of 9H-carbazole-3-carboxaldehyde (compound 77) and 2.5 ml of methyl 2,2-dichloroacetate in anhydrous ether (30 ml) were added in batches under argon, and stirred at low temperature for 1 hour, and then heated to reflux. Sampling was monitored. After the reaction was completed, water was added and the organic layer was separated. After drying, concentration and chromatography, methyl 3-(9H-carbazole-3-yl)-3-chloro-2-oxopropanoate (79) was obtained.

[0350] The same method as in Example 37 was used, except that compound (79) was used instead of compound (73) to give methyl 3-(9H-carbazol-3-yl)-3-chloro-2-hydroxypropanoate (80).

[0351]

[0352] The same method as in Example 37 was used to replace compound (74) with compound (80) to obtain methyl 3-(9H-carbazol-3-yl)-3-chloro-2-hydroxypropionate (76). 24 H 20 ClN3O3,m / z:433.1[M] + .

[0353]

[0354] 4.3 g of compound (76) was dissolved in pyridine and heated to 80°C. 1.5 ml of DBU (1,8-diazabicycloundec-7-ene) was added to react. After the reaction was completed (sampling monitoring), it was distilled under reduced pressure. After chromatographic separation, compound (88) was obtained. 24 H 19 N3O3,m / z:397.1[M] + .

[0355]

[0356] Embodiment 39

[0357] Preparation of 2-(1-(9H-carbazol-3-yl)ethyl)-5-(4-(dimethylamino)benzylidene)-1,3-dioxane-4,6-dione (Compound 81)

[0358]

[0359] Under an ice-water bath, 34 g of 9H-carbazole was dissolved in dichloromethane, and then 30 g of anhydrous AlCl3 was slowly added and stirred for 10 minutes, and then 20 ml of acetyl chloride was slowly added dropwise. After the addition was completed, stirring was continued at room temperature. After the reaction was completed, the reaction solution was slowly poured into a hydrochloric acid-ice-water bath, extracted with dichloromethane, concentrated, and separated by chromatography to obtain the main product 3-acetylcarbazole (82), with a melting point of 167°C.

[0360]

[0361] Heat 5.2 g of malonic acid, 15.3 g of acetic anhydride, and 0.2 ml of concentrated sulfuric acid in a water bath. Cool to room temperature, add 8.4 g of 3-acetylcarbazole (82) dropwise, react for 1 hour, and then place in a refrigerator overnight. After washing with water, extract with ethyl acetate, and separate by chromatography to obtain 2-(1-(9H-carbazole-3-yl)ethyl)-1,3-dioxane-4,6-dione (83).

[0362]

[0363] The same method as in Example 35 was used, but compound (83) was used instead of compound (65) to obtain compound (81). 27 H 24 N2O4,m / z:440.2[M] + .

[0364]

[0365] Embodiment 40

[0366] Preparation of 5-(((4-(dimethylamino)phenyl)imino)methyl)quinolin-7-yl 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)tert-butyl)-4-hydroxyphenyl)propanoate (Compound 84)

[0367]

[0368] 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propanoic acid methyl ester (Eutec co., BZTME, compound 85) was hydrolyzed with KOH / MeOH and neutralized with acid. It was extracted with dichloromethane to obtain 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propanoic acid (86). After sufficient drying, an excess of dichlorothionyl was added and the mixture was heated under reflux for reaction. After the reaction was completed (sampling confirmation), the unreacted dichlorothionyl was removed to obtain the compound 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propanoyl chloride, which was set aside.

[0369]

[0370] 1.75 g of 8-hydroxyquinoline-5-carboxaldehyde (NSC 122131, compound 87) was weighed and dissolved in 20 ml of dichloromethane, and 2 g of triethylamine was added and stirred. 3.6 g of the above-mentioned 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionyl chloride compound (86) in dichloromethane solution (20 ml) was added dropwise. Stir overnight at room temperature. The product was poured into ice water, extracted with dichloromethane, and then washed with 1% dilute hydrochloric acid and brine. After drying, the compound 5-formylquinolin-8-yl 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionate (91) was obtained.

[0371] Weigh 5 g of compound (91) and 1.4 g of p-(dimethylamino)aniline, dissolve in 40 ml of anhydrous ethanol, remove water, and heat under reflux for 4 hours. Take samples for monitoring. After the reaction is completed, remove the solvent to obtain compound (84). 37 H 36 N6O3,m / z:612.3[M] + .

[0372]

[0373] Embodiment 41

[0374] Used for improving the performance of optical recording media: Compound (B) is covalently bonded to obtain compound (18), as shown in the following formula.

[0375]

[0376] The melting point of compound (B) is 175°C. After being covalently bonded with a benzotriazole compound, the melting point is raised to 224°C (compound 18). This is an important improvement for organic dyes (B) used in optical recording media because compound (18) is less likely to decompose under the high temperature (250°C or above) generated locally when the laser irradiates the optical disc.

[0377] Attached Figure 3 This indicates that the absorption range of compound (18) for ultraviolet light covers UVA, UVB and blue light. This indicates that the dye of compound (18) can provide a wider range of ultraviolet light (UVA+UVB) protection for optical discs. Therefore, in terms of optical disc preservation, compound (18) is more advantageous than compound (B).

[0378] Table 3 Comparison of properties of compound (B) and compound (18) of the present invention

[0379] Compound (B) Example 10 of the present invention Compound (18) Thermal properties Melting point 175℃ Melting point 224℃ Light absorption range UVA + Visible Light UVA+UVB+Visible Light

[0380] Embodiment 42

[0381] Advantages of being used as ultraviolet light or blue light absorbers: When the compounds of the present invention are used as ultraviolet light and / or blue light absorbers, they have both ultraviolet light (UVA+UVB) and blue light absorption functions. Compared with the commercially available anti-blue light agent Eusorb UV-1990 (Eutec co.) (Table 4), it is shown that the commercially available Eusorb UV-1990 has very weak absorption of UVB (wavelength 280nm). The example compounds of the present invention have a better coverage and absorbance of ultraviolet light than the currently commercially available anti-blue light agent Eusorb UV-1990.

[0382] Table 4. Comparison of the title compound of the present invention example and the commercially available Eusorb UV-1990 blue light blocking agent

[0383]

[0384] Embodiment 43

[0385] Stability and weatherability of the light-converting agent: The thermal stability of the example compounds was measured using a thermogravimetric analyzer (TGA). The greater the weight loss, the worse the stability. Figure 2 The results show that the TGA results show that when the temperature rises to 220°C, the weight loss of compound (7) in Example 4 is less than 1%. When the temperature rises to 312°C, the weight loss is only about 5%. This shows that compound (7) has a very high thermal stability.

[0386] Attached Figure 4 This is a photo of a PE agricultural film made from compound (7) of Example 4 of the present invention under a fluorescent light (the agricultural film is placed on a gray opaque background to show the color). The agricultural film is transparent and appears orange-red.

[0387] Table 5 shows the comparison of weather resistance of agricultural film compounds before and after improvement. RL1000 (BASF) can only maintain stability for two seasons when used as outdoor agricultural film, while the compound (7) of the present invention can maintain stability for more than three seasons.

[0388]

[0389] Table 5. Comparison of weather resistance of agricultural film compounds before and after improvement

[0390] RL1000 Compound of the present invention (7) Weather resistance 2 seasons 3 Seasons Visible light emission range Orange-red (about 600-700nm) Orange-red (about 600-700nm)

[0391] The present invention has been disclosed above with preferred embodiments, but they are not intended to limit the present invention. Any technical solutions obtained by adopting equivalent replacement or equivalent transformation solutions fall within the protection scope of the present invention.

Claims

1. A polycyclic compound comprising a compound represented by formula (1): A-R1-B-R2-C-R3-D, (1) in, A-R1-B is R2 is -(CHR 21 ) q N(R 22 )-,R 21 , R 22 Each is independently selected from hydrogen, a linear or branched C1-C8 alkyl group, q=1; C is a benzene ring; R3 is -C(R16)=, R16 are each independently selected from hydrogen, straight chain or branched C1-C6 alkyl; D is R9 is H, and the double bond in the D ring is the double bond of R3; Wherein, p=0-2, and R4 is independently selected from hydrogen, chlorine, hydroxyl, straight-chain or branched C1-C8 alkyl, and C1-C4 alkoxy.

2. The polycyclic compound according to claim 1, characterized in that The compound represented by formula (1) is selected from:

3. A film comprising a light conversion agent, an ultraviolet light and / or a blue light absorber, characterized in that the light conversion agent, the ultraviolet light and / or the blue light absorber are selected from the polycyclic compounds of any one of claims 1 to 2.

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