ANTI-BLUE LIGHT COMPOUND, PREPARATION METHOD AND APPLICATION THEREOF

Abstract

Disclosed is a blue light absorbing compound, its preparation method and use. The compound has high stability and is suitable for high temperature processing conditions as well as outdoor application. A method of covalently bonding a blue light absorbing compound with an ultraviolet light absorbing compound for increasing its stability is also provided. The compound is capable of absorbing or blocking ultraviolet light (UVA, UVB) and blue light to protect eyes. But long-wavelength blue light can be absorbed diminishingly, so that the transmitted light has a particularly good visual experience.

##STR00001##

Claims

1. An anti-blue light compound of formula (1), ##STR00084## R.sub.1˜R.sub.3 are a bond or/and any divalent linking groups; A˜C are unsubstituted or one or more R.sub.4 substituted benzene ring, benzo carbocyclic ring, nitrogen-containing heterocyclic ring, or benzo nitrogen-containing heterocyclic ring; R.sub.4 is each independently selected from hydrogen, halogen, hydroxyl, amino, nitro, cyano, linear or branched C.sub.1˜C.sub.18 alkyl, C.sub.1˜C.sub.18 alkenyl, phenyl, OR.sub.5, SR.sub.5, SO.sub.2R.sub.5, SO.sub.3R.sub.5, COOR.sub.5, COR.sub.5, OCOR.sub.5, C(O)NR.sub.6R.sub.7, SO.sub.2NR.sub.6R.sub.7, and NR.sub.6R.sub.7, wherein R.sub.5, R.sub.6, and R.sub.7 are independently hydrogen, or linear or branched C.sub.1˜C.sub.8; X is one or more groups, each independently selected from COOR.sub.8, CN, CONR.sub.6R.sub.7 and COR.sub.8, wherein R.sub.8 is selected from H, linear or branched C.sub.1˜C.sub.18 alkyl, C.sub.1˜C.sub.18 alkenyl, and polyethylene glycol with molecular weight 50˜1000 daltons; Z is a carbon atom, Z and R.sub.3 are connected via single, or double, or triple bond; Z and X, are connected via 1˜3 single bonds, wherein n=1˜3; [A]r ring and R.sub.1 are connected via 1 or 2 single bonds, wherein r=1˜2; C ring and R.sub.3 are connected via 1 or 2 or 3 single bonds, wherein m=1˜3.

2. The anti-blue light compound according to claim 1, wherein, R.sub.1˜R.sub.3 is a bond, or/and a chain consisting of 1-10 groups selected from the following:—O—, —S—, —C(═O)—, —COO—, —C(═S)—, —C(═NR.sub.9)—, —CH.sub.2—, —CH(R.sub.9)—, —C(R.sub.9).sub.2—, —C(R.sub.9)═, —C≡, —C(R.sub.9)═C(R.sub.9)—, —N(R.sub.9)—, —C(R.sub.9)═N—, and phenyl; R.sub.9 is H, linear or branched C.sub.1˜C.sub.8 alkyl, unsubstituted phenyl, or phenyl substituted by OH, halogen, C.sub.1˜C.sub.4 alkoxy, linear or branched C.sub.1˜C.sub.4 alkyl; Z and R.sub.3 are connected via a double bond; Z and X are connected via two single bonds, wherein n=2.

3. The anti-blue light compound according to claim 1, including at least one blue light absorbing group selected from: ##STR00085## wherein, R.sub.11˜R.sub.14 are the same or different from each other independently selected from H, linear or branched C.sub.1˜C.sub.18 alkyl or alkenyl, and unsubstituted phenyl, or OH, halogen, C.sub.1˜C.sub.4 alkoxy, linear or branched C.sub.1˜C.sub.4 alkyl substituted phenyl, and at least one ultraviolet light absorbing group selected from ##STR00086## ##STR00087##

4. The anti-blue light compound according to claim 1, wherein, A is selected from: ##STR00088## B is selected from: ##STR00089## C is selected from: ##STR00090## R.sub.4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, linear or branched C.sub.1˜C.sub.8 alkyl, C.sub.1˜C.sub.8 alkenyl, OR.sub.5, SR.sub.5, SO.sub.2R.sub.5, COOR.sub.5, COR.sub.5, C(O)NR.sub.6R.sub.7, and NR.sub.6R.sub.7, wherein R.sub.5, R.sub.6, and R.sub.7 are each independently hydrogen, or a linear or branched C.sub.1˜C.sub.8 alkyl group, p=1˜3.

5. The anti-blue light compound according to claim 4, wherein, ##STR00091## is selected from: ##STR00092## ##STR00093## wherein, R.sub.4 is one or more substituents, and each is independently selected from hydrogen, halogen, nitro, cyano, straight or branched C.sub.1˜C.sub.8 alkyl, C.sub.1˜C.sub.8 alkenyl, OR.sub.5, SR.sub.5, SO.sub.2R.sub.5, COOR.sub.5, COR.sub.5, C(O)NR.sub.6R.sub.7, and NR.sub.6R.sub.7, wherein, R.sub.5, R.sub.6, and R.sub.7 are each independently hydrogen, or a linear or branched C.sub.1˜C.sub.6 alkyl group, R.sub.10 is H, linear or branched C.sub.1˜C.sub.8 alkyl, unsubstituted phenyl, or phenyl substituted by OH, halogen, C.sub.1˜C.sub.4 alkoxy, linear or branched C.sub.1˜C.sub.4 alkyl, p=1˜3.

6. The anti-blue light compound according to claim 1, wherein, A is selected from: ##STR00094## B is selected from: ##STR00095## C is ##STR00096## wherein, R.sub.1 and R.sub.3 are a bond, or/and a chain consisting of 1˜6 selected from the following groups: —O—, —N(R.sub.9)—, —C(═O)—, —COO—, —CH.sub.2—, —CH(R.sub.9)—, —C(R.sub.9).sub.2—, —C(R.sub.9)═, —C≡, —C(R.sub.9)═N—, —NH—C(═O)—C(═O)—NH—, —(R.sub.9)N—CH═N—, phenyl, wherein, R.sub.2 is a bond, —(CHR.sub.9).sub.q N(C═O)(R.sub.9)—, or —(CHR.sub.9).sub.q N(R.sub.9)—, R.sub.4 is one or more substituents, and each is independently selected from hydrogen, halogen, linear or branched C.sub.1˜C.sub.8 alkyl, C.sub.1˜C.sub.8 alkenyl, OR.sub.5, SR.sub.5, COOR.sub.5, COR.sub.5, C(O)NR.sub.6R.sub.7, and NR.sub.6R.sub.7, wherein R.sub.5, R.sub.6, and R.sub.7 are each independently hydrogen, or a linear or branched C.sub.1˜C.sub.6 alkyl group, X is 1˜2 substituents, each independently selected from COOR.sub.8, CN, CONR.sub.6R.sub.7 and COR.sub.8, wherein, R.sub.8 is selected from H, linear or branched C.sub.1˜C.sub.8 alkyl, and C.sub.1˜C.sub.8 alkenyl, R.sub.9 is H, linear or branched C.sub.1˜C.sub.6 alkyl or phenyl, Z and R.sub.3 are connected via a double bond, m=1, n=1˜2, p=1˜3, q=0˜6.

7. The anti-blue light compound according to claim 6, wherein, C is a divalent benzene ring; R.sub.2 is —CH.sub.2 N(CH.sub.2)— or —CH.sub.2 N(CH.sub.2CH.sub.3)—; n=2, and X is the same or different and each independently selected from COOR.sub.8, and CN; R.sub.8 is selected from a linear or branched C.sub.1˜C.sub.8 alkyl group and a C.sub.1˜C.sub.8 alkenyl group.

8. The anti-blue light compound according to claim 7, wherein, A is selected from benzotriazole and benzene ring, B is a divalent benzene ring, when A and B are benzene rings, A and B together form a fused ring, which is selected from the group consisting of carbazole, dibenzothiophene, and dibenzofuran.

9. The anti-blue light compound according to claim 1, the compound is ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101##

10. A method for manufacturing the anti-blue light compound according to claim 1, wherein, comprising the following step: bonding covalently the anti-blue light compound and a UV blocking compound.

11. The method according to claim 10, comprises following reaction step:
A-R.sub.1—B—R.sub.2—C—CHO+Z--[—X].sub.n.fwdarw.formula (1) compound
or
A-R.sub.1—B—CH.sub.2Cl+NHR.sub.15—C-R.sub.3---Z--[—X].sub.n].sub.m.fwdarw.formula(1)compound wherein, A˜C, R.sub.1˜R.sub.3, X, Z, m, n, and the compound of formula (1) are the same as defined in claim 1; R.sub.15 is H, a linear or branched C.sub.1˜C.sub.8 alkyl or a phenyl.

12. An UV or/and blue light blocking composition, comprising a compound of formula (1) according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0074] FIG. 1 is a UV-VIS absorption graph of the compound L-486 (10 mg/chloroform), of the present invention;

[0075] FIG. 2 is a UV-VIS absorption graph of compound L-500 (10 mg/chloroform);

[0076] FIG. 3 is a UV-VIS absorption graph of compound L-467 (10 mg/chloroform);

[0077] FIG. 4 is a UV-VIS absorption profile of the compound L-538 (10 mg/chloroform);

[0078] FIG. 5 is a TGA diagram of compound L-486;

[0079] FIG. 6 is a TGA chart of compound L-487.

DETAILED DESCRIPTION

[0080] The specific embodiments of the present invention are described below, but are not limited to these embodiments.

Example 1, Preparation of 2-(2-hydroxy-3-(chloromethyl)-5-methyl)benzotriazole (Compound 32)

[0081] ##STR00035##

[0082] Add 350 g of 2-(2-hydroxy-5-methyl)benzotriazole (UV-P), 55 g of paraformaldehyde, 2000 g of acetic acid and 300 g of 35% hydrochloric acid in a 5000 ml reaction flask, and heat it to 60° C., then keep it warm. After reacting for 10 hours, samples were taken to monitor the reaction. After completion, it was cooled, washed with water, and dried to obtain 409 g of white powder (Compound 32) with a yield may over 90%, C14 H12 ClN3 O. Melting point: 163-164° C.

Example 2, Preparation of 2-(2-hydroxy-3-(N,N-dimethylaniline)-5-methyl) benzotriazole (Compound 33)

[0083] ##STR00036##

[0084] Put 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 (32) in a reaction flask. The temperature was raised to 90-100° C., reacted for 5 hours, and samples were taken to monitor the reaction. Cool down to 30° C., wash with water and recover the toluene. Add 180 g of methanol and stir it, filter and dry to obtain 42 g of solid (compound 33). The yield is about 80%, C21H20N4O. Melting point: 98-100° C.

Example 3, Preparation of 2-(2-hydroxy-3-(4-methanyl-N,N-dimethylaminophenyl)-5-methyl)benzotriazole (Compound 34)

[0085] ##STR00037##

[0086] 35 g of compound (33) and 8.7 g of DMF were added in a reaction flask, and 18.4 g of phosphorus oxychloride was added dropwise at room temperature. The temperature was raised to 90° C. for 2 hours, and samples were taken to monitor the reaction. The reaction material was slowly added to 300 g of water below 30° C. for hydrolysis. After the addition, the pH is adjusted to 8 with 30% caustic alkali liquids, and the solid was filtered out. Dissolved with 150 g of toluene, washed twice with water at 50° C., and cooled to 15° C. to precipitate 31.8 g of solid (Compound 34), with a yield of about 80%, C21H19N4O2. Melting point: 111˜113° C.

Example 4, Preparation of (4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl) amino) benzylidene) dimethyl malonate (Compound 4, L-486)

[0087] ##STR00038##

[0088] Add 60 g of 2-(2-hydroxy-3-(4-methanyl-N,N-dimethyl-aminobenzene)-5-methyl)benzotriazole (compound 34), 21 g of dimethyl malonate ester, and 150 g of toluene in a reaction flask, and heating up. Then add 10 g of ammonium acetate and 20 g of acetic acid. First, react at 95° C. for 2 hours, then reflux to dehydrate (about 112° C.) for 6 hours. Monitor the reaction, and cool to 30° C. The solid was filtered, washed twice with water, and dried to obtain a yellow solid (compound 4), C.sub.27H.sub.26N.sub.4O.sub.5. Melting point: 191° C.-193° C.

Example 5, Preparation of (4-((3-(2H-benzo[d][1,2,3] triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino) benzylidene) dimethyl malonate (Compound 5, L-500)

[0089] ##STR00039##

[0090] According to the method of Example 1-4, but use N-ethylaniline to replace N-methylaniline, to obtain 2-(2-hydroxy-3-(4-methanyl-N-ethyl-anilino)-5-Methyl) benzotriazole (Compound 35), C.sub.22H.sub.22N.sub.4O.sub.2. Melting point: 156-157° C. According to the method of Examples 1-4, dimethyl malonate was added to react to obtain compound (5), C.sub.28H.sub.28N.sub.4O.sub.5. Melting point: 173° C.-178° C.

Example 6, Preparation of 3-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl) amino) phenyl) Ethyl-2-cyanoacrylate (Compound 6, L-467)

[0091] ##STR00040##

[0092] Add 60 g of 2-(2-hydroxy-3-(4-methanyl-N,N-dimethylamino-benzene)-5-methyl) benzotriazole (Compound 34), 2-cyanoacetic acid ethyl acetate 18 g, toluene 150 g, in a reaction flask. Add 10 g of ammonium acetate and 20 g of acetic acid. First react at 95° C. for 2 hours, then reflux to dehydrate for 6 hours, and take samples to monitor the reaction. Cool to 30° C., filter out the solid, and the solid was washed and dried to obtain a solid (compound 6), C.sub.27H.sub.25N.sub.5O.sub.3. Melting point: 177-179° C.

Example 7, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl) amino) benzylidene) diisopropyl malonate (Compound 7, L-542)

[0093] ##STR00041##

[0094] According to the method of Examples 1-4, but add diisopropyl malonate to replace methyl malonate. The reaction yields compound (7), C.sub.31H.sub.34N.sub.4O.sub.5. Melting point: 80° C.-87° C.

Example 8, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-ethylbenzyl) (ethyl group) amino) benzylidene) diisopropyl malonate (Compound 8, L-556)

[0095] ##STR00042##

[0096] According to the method of Example 7, but add N-ethylaniline to replace N-methylaniline, Compound (8, L-556), C.sub.32H.sub.36N.sub.4O.sub.5 was obtained. Melting point: 87° C.-90° C.

Example 9, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3] triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl)amino) benzylidene) dipropionic acid-1-en-2-yl ester (Compound 9, L-538)

[0097] ##STR00043##

[0098] According to the method of Example 7, but add diisopropyl malonate instead of diisopropyl malonate. The compound (9), C.sub.31H.sub.30N.sub.4O.sub.5, was obtained. Melting point: 132-141° C.

Example 10, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl)amino)benzylidene)di(bis(2-ethylhexyl)malonate (Compound 10, L-682)

[0099] ##STR00044##

[0100] 24 g of compound (34) was dissolved in toluene and heated to reflux at 110° C. in a condensing trap. To the toluene solution, 13 g 2-ethylhexanol and 1.5 g p-toluenesulfonic acid were added. Samples were taken to monitor the reaction. After the reaction completion, the product was purified by column chromatography to obtain compound (10), C.sub.61H.sub.94N.sub.4O.sub.5.

Example 11, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3] triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl) amino) benzylidene) bis(octadecyl)malonate (Compound 11)

[0101] ##STR00045##

[0102] According to Example 10, but add stearyl alcohol instead of 2-ethylhexanol. Samples were taken to monitor the reaction. After the reaction completion, the product was purified by column chromatography to obtain compound (11), C.sub.61H.sub.94N.sub.4O.sub.5.

Example 12, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3] triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl) amino) benzylidene) malonate polyether ester (Compound 12)

[0103] ##STR00046##

[0104] According to the method of Example 10, but add methoxypolyethylene glycol to replace 2-ethylhexanol. The reaction was monitored by HPLC. After the reaction completion, the product was purified by GPC (colloid permeation chromatography) to obtain the compound of formula (12).

Example 13, Preparation of 2-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-(2,4,4-Trimethylpentan-2-yl)benzyl)(ethyl)amino)benzylidene)dimethylmalonate (Compound 13)

[0105] According to the method of Examples 1-4, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (Tinuvin 329) was used instead of UV-P as the starting material. The compound (13), C.sub.34H.sub.38N.sub.6O.sub.4, was obtained.

##STR00047##

[0106] Tinuvin 329 was obtained from Eutec co. (Eusorb UV 329), or as described in preparation method 4. The preparation: 13.8 g of o-nitroaniline was added to 25 ml of 37% hydrochloric acid and stirred, diluted with 40 ml of water and cooled to −15° C. Add 7.5 g of sodium nitrite (dissolved in water) and keep the temperature at 0˜5° C. to obtain diazonium salt (Diazonium). Mix 5.2 g of 4-tert-Octylphenol, 20 ml of petroleum ether, 5 ml of water and 2.5 g of calcium hydroxide, and take samples to monitor the reaction. Add 20 g of ice to 0° C. Add the aforementioned diazonium salt and stir for 2 hours. Add concentrated hydrochloric acid to neutralize and dry to obtain 2-((2-nitrophenyl)diazenyl)-4-(2,4,4-trimethylpent-2-yl)phenol (compound 36), C.sub.20H.sub.25N.sub.3O.sub.3. Melting point: 114-115° C.

##STR00048##

[0107] Take 35.7 g of compound (36) and dissolve in 100 ml of petroleum ether, add 17.2 g of zinc and 100 ml of water. At 50° C., 41.6 g of NaOH solution (25%) was added within 4 hours and left for 1 hour. 100 ml of concentrated hydrochloric acid was added and left for 2 hours, Samples were taken to monitor the reaction. The organic layer was washed with water, and the solvent was removed to obtain Tinuvin 329 compound. C.sub.20H.sub.25N.sub.3O, Melting point: 102-106° C.

Example 14, Preparation of 2-(4-((3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxybenzyl) (ethyl) amino) benzylidene) dimethyl malonate (Compound 14)

[0108] ##STR00049##

[0109] According to the method of Example 13, but use 4-chloro-2-nitroaniline, instead of o-nitroaniline, as the starting material to obtain 2-(2′-hydroxy-phenyl)-5-chloro-benzotriazole (compound 37), C12H8ClN3O. Melting point: 139-140° C. According to the method of Example 1-4, but use 2-(2′-hydroxy-phenyl)-5-chloro-benzotriazole (compound 37) instead of (UV-P) as the starting material, compound (14) was obtained, C.sub.27H.sub.25ClN.sub.4O.sub.5.

Example 15, Preparation of 2-(4-(ethyl(2-hydroxy-3-(5-methoxy-2H-benzo[d] [1,2,3]triazol-2-yl)benzyl) Amino) benzylidene) dimethyl malonate (Compound 15)

[0110] ##STR00050##

[0111] According to the method of Example 14, but use 4-methoxy-2-nitroaniline instead of 4-chloro-2-nitroaniline as the starting material to obtain 2-(2-hydroxy-phenyl)-5-methoxy-benzotriazole (Compound 38), C.sub.14H.sub.13N.sub.3O.sub.2. Melting point: 126-127° C.

[0112] According to the method of Example 1-4, but use 2-(2-hydroxy-phenyl)-5-methoxy-benzotriazole (compound 38) instead of (UV-P) as the starting material to obtain compound (15), C.sub.29H.sub.30N.sub.4O.sub.6.

Example 16, Preparation of 3-(2H-benzo[d][1,2,3] triazol-2-yl)-5-((ethyl(4-((2,4,6-trioxo tetrahydro-pyrimidine-5(2H)-ylidene)methyl)phenyl)amino)methyl)-4-hydroxybenzoic acid methyl ester (Compound 16)

[0113] ##STR00051##

[0114] According to the method of Example 13, but replace 4-p-tert-octylphenol with 4-hydroxybenzoic acid, 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-Hydroxybenzoic acid. Then add sulphurous chloride, heat to reflux for 2 hours, evaporate the sulphurous chloride, add n-hexanol and reflux for 1 hour. Take samples to monitor the reaction. 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxybenzoic acid hexyl ester was obtained (Compound 39), C.sub.19H.sub.21N.sub.3O.sub.3. Melting point: 83-84° C. According to the method of Examples 1-4, but use compound (39) instead of UV-P as the starting material, and compound (16), C.sub.34H.sub.38N.sub.4O.sub.7 was obtained.

Example 17, Preparation of 2-((1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-3a, 7α Dihydro-1H-indol-3-yl) methylene) dimethyl malonate (Compound 17)

[0115] ##STR00052##

[0116] According to the method of Examples 1-4, 3-indolecarboxaldehyde (Compound 40) was used instead of N-methylaniline. Compound (41) was obtained. According to the method of Example 4, compound (41) was used instead of compound (34) and separated by column chromatography to obtain compound (17), C.sub.28H.sub.26N.sub.4O.sub.5, m/z: 498.2[M].sup.+.

[0117] 3-indole formaldehyde is can be bought or prepared in the following way (Vilsmeier reaction): In an ice bath, drop 16 g POCl3 into 30 g DMF within 30 minutes. 11 g indole compound was slowly added to the DMF solution and the temperature was raised to 35° C. The reaction was stirred for 1 hour. Add 50 g of crushed ice and stir to the obtained paste, and add 0.1M NaOH slowly while stirring. After washing with water, it was recrystallized with ethanol to obtain compound (40), C.sub.9H.sub.7NO. Melting point: 196˜197° C.

Example 18, Preparation of 3-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl (amino) phenyl)-2-cyano-3-phenylethyl acrylate (Compound 18)

[0118] ##STR00053##

[0119] According to the method of Example 2, but use 4-methylaminobenzophenone instead of N-methylaniline, and compound (42) was obtained. According to the method of Example 4, but replace the compound (34) with the compound (42), and the mixture was separated by column chromatography to obtain compound (18), C.sub.33H.sub.29N.sub.5O.sub.3. m/z: 543.2 [M].sup.+.

Example 19, Preparation of 2,2′-((2-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl (ethyl) amino)-1,4-phenylene)bis(methanelidene))tetraethyl dimalonic acid (Compound 19)

[0120] ##STR00054##

[0121] According to the method of Example 2, but use dimethyl 5-(ethylamino)isophthalate (compound 43, melting point 118° C.) instead of N-methylaniline. The product was separated by column chromatography to obtain ((3-(2H-Benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl) (ethyl)amino)dimethyl isophthalate (Compound 44).

##STR00055##

[0122] 24 g of compound (44) was dissolved in 100 ml of toluene. At −78° C., under an argon atmosphere, 120 ml of a 1M toluene solution of diisobutylaluminum hydride (DIBAL-H) was added dropwise to the compound (44) solution. After adding DIBAH, continue stirring for 2 hours. Add methanol, then keep it at room temperature. Add 1M HCl, stir for 5 minutes, and extract it with ethyl acetate. After washing with saturated NaCl aqueous solution and drying with MgSO4, filtrate it and remove the solvent under reduced pressure, Compound (45) was obtained. According to the method of Example 4, but replace the compound (34) with compound (45). The product was separated by column chromatography to obtain the compound (19), C.sub.38H.sub.42N.sub.4O.sub.9. m/z: 698.3 [M].sup.+.

##STR00056##

Example 20, Preparation of 3-(4-(3-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)-N-methyl-propanamido) phenyl)-2-cyanoacrylate (Compound 20)

[0123] ##STR00057##

[0124] Take 5.2 g of 3-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(tert-butyl)-4-Hydroxyphenyl) methyl propionate (compound 46), dissolve in toluene, and heat to reflux at 110° C. in a flask equipped with a condensation trap. To the toluene solution, was added 3.7 g of ethyl 2-cyano-3-(4-(methylamino)phenyl) acrylate (Compound 47). Use HPLC to monitor the reaction. After the reaction was completed, vacuum it and separate with column chromatography. Compound (20) was obtained, C.sub.45H.sub.47N.sub.5O.sub.4, m/z: 721.4 [M].sup.+.

##STR00058##

[0125] Preparation method of Compound (46), according to CN201710949552.0. Briefly, 16 g of 2-chloro-4,6-bis(2′,4′-phenyl)-1,3,5-triazine (Compound 48) and 15 g of methyl 3-(3-(tert-butyl)-4-hydroxyphenyl)propionate (Compound 49) were dissolved in 150 mL of chlorobenzene, and 10 g of anhydrous aluminum trichloride was added. Heat and stir to dissolve it. The temperature was raised to 90° C., and the reaction was monitored by HPLC. After the completion of the reaction, it was distilled under reduced pressure and subjected to silica gel column chromatography to obtain compound (46). preparation method of 2-cyano-3-(4-(methylamino)phenyl) ethyl acrylate (compound 47): 20 g of dimethyl malonate and 13.6 g of 4-methylaminobenzene formaldehyde were dissolved in dichloromethane. Add molecular sieve to remove water and install calcium chloride pipe for waterproof. Add 1 ml piperidine and 0.6 ml acetic acid, and heat the reaction at reflux temperature for 2 hours. During the reaction, add fresh molecular sieve. After the completion of the reaction, remove solvent, wash and dry to obtain compound (47).

Example 21, Preparation of 2-(4-((3-(4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazin-2-yl)-5-(methyl)-4-hydroxybenzyl) (methyl)amino)benzylidene)dimethylmalonate (Compound 21)

[0126] ##STR00059##

[0127] According to the method of Example 2, but use 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-6-(methyl)-4-(Chloromethyl)phenol (Compound 50) instead of Compound (32), and use dimethyl 2-(4-(methylamino)benzylidene) malonate (Compound 51) instead of N-methylaniline. After separation by column chromatography, compound (21) was obtained. C.sub.40H.sub.40N.sub.4O.sub.5, m/z: 656.3[M].sup.+.

##STR00060##

[0128] The preparation method of compound 50 is the same as in Example 20, but 4-(chloromethyl)-2-methylphenol is used instead of 3-(3-(tert-butyl)-4-hydroxyphenyl)propionate (49). The preparation method of dimethyl 2-(4-(methylamino) benzylidene)malonate (Compound 51) is the same as in Example 20, but dimethyl malonate is used instead of ethyl 2-cyanoacetate.

Example 22, preparation of 2-(4-((2,4-di-tert-butyl-3-hydroxy-6-((2,4-di-tert-butylphenoxy)carbonyl)benzyl)(methyl)amino)benzylidene)malonate dimethyl and 2-(4-((3,5-di-tert-butyl-2-((3,5-di-tert-butyl-4-hydroxybenzyl) Mixture of ((methyl)amino)benzylidene) dimethyl malonate ((methyl)oxy)benzyl)(22)

[0129] ##STR00061##

[0130] According to the method of Example 21, but use the mixture (52) of 3,5-di-tert-butyl-2-(chloromethyl)-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl and 2,4-di-tert-butyl benzyl-6-(chloromethyl)phenyl 3,5-di-tert-butyl-4-hydroxybenzoate to replace 2-(4,6-bis(2,4-dimethyl) (Phenyl)-1,3,5-triazin-2-yl)-6-(methyl)-4-(chloromethyl)phenol (Compound 50) to obtain a mixture (22).

[0131] Preparation of mixture of 3,5-di-tert-butyl-2-(chloromethyl)-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester and 2,4-di-tert-butyl-6-(chloromethyl)) phenyl 3,5-di-tert-butyl-4-hydroxy-benzoate: as in Example 2, but use 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-Hydroxybenzoate (Eutec co., Eusorb UV-120) instead of UV-P.

Example 23, preparation of (4-((5-benzyl-4-hydroxy-2-(octyloxy)benzyl)(methyl)amino)benzylidene) dimethyl malonate (Compound 23)

[0132] ##STR00062##

[0133] According to the method of Example 21, but use 5-(chloromethyl)-2-hydroxy-4-(octyloxy)phenyl)(phenyl)methanone (compound 53) instead of (compound 50) to obtain compound (23), C.sub.35H.sub.41NO.sub.7, m/z: 587.3 [M].sup.+.

##STR00063##

[0134] The preparation method of 5-(chloromethyl)-2-hydroxy-4-(octyloxy)phenyl)(phenyl)methanone (Compound 53): as in Example 2, but use 2,4-di-tert butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Eutec co., Eusorb UV-120) instead of UV-P.

Example 24, Preparation of 2-(4-(4-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)benzyl)amino)benzylidene) dimethyl malonate (Compound 24)

[0135] ##STR00064##

[0136] According to the method of Example 21, but use 2-(4-(chloromethyl)phenyl)-4H-benzo[d][1,3]oxazin-4-one (compound 54) instead of 2-(4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-6-(methyl)-4-(chloromethyl)phenol (compound 50), to obtain 2-(4-(4-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)benzyl)amino)benzylidene)dimethylmalonate (compound 24), C.sub.28H.sub.24N.sub.2O.sub.6, m/z: 484.2[M].sup.+.

##STR00065##

[0137] The preparation method of 2-(4-(chloromethyl)phenyl)-4H-benzo[d][1,3]oxazin-4-one (compound 54): 14 g of 2-aminobenzoic acid (compound 55) and 11g of triethylamine were added to 100 ml of dichloroethane, and 19 g of 4-chloromethylbenzyl chloride (Compound 56) was dropped and stirred to obtain Compound (54).

[0138] The preparation method of compound (56): 4-(hydroxymethyl)benzoic acid (57) was chlorinated in dichloromethane and refluxed with thionyl chloride to obtain compound (56), melting point: 28° C.

##STR00066##

Example 25, preparation of 2-(4-(Methyl((4-oxo-2-(4-(4-oxo-4H-benzo[d] [1,3]oxazin-2-yl)phenyl)-4H-Benzo[d][1,3] oxazine-6-yl)methyl)amino)benzylidene)dimethylmalonate (Compound 25)

[0139] ##STR00067##

[0140] In 200 ml of toluene, add 40 g of 2-amino-5-(((4-(3-methoxy-2-(methoxycarbonyl)-3-oxoprop-1-en-1-yl) phenyl) (methyl) amino) methyl) benzoic acid (compound 59), 11 g of triethylamine, and 29 g of 4-(4-oxo-4H-benzo[d][1,3]oxazine-2-yl) benzoyl chloride (compound 58) with stirring. And the product was separated by column chromatography to obtain compound (25), C.sub.36H.sub.27N.sub.3O.sub.8, m/z: 629.2[M].sup.+.

##STR00068##

[0141] The preparation method of compound (58): as in Example 24, but use methyl 4-(chlorocarbonyl)benzoate (60) instead of compound (56) to obtain compound (58).

##STR00069##

[0142] The preparation method of compound (59): as in Example 21, but use methyl 4-(chlorocarbonyl)benzoate (compound 61) instead of compound (54) to obtain compound (59).

##STR00070##

Example 26, preparation of 2-(4-(((2,4-dihydroxy-quinolin-3-yl) methylene)amino)benzyl) (methyl)amino) benzylidene)propane dimethyl acid (Compound 26, L-3701)

[0143] ##STR00071##

[0144] According to Example 21, use 3-(((4-(chloromethyl) phenyl)imino)methyl)quinoline-2,4-diol (compound 62) instead of compound (51) to obtain compound (26), C.sub.30H.sub.27N.sub.3O.sub.6, m/z: 525.2 [M].sup.+.

##STR00072##

[0145] The preparation method of 3-(((4-(chloromethyl)phenyl) imino)methyl)quinoline-2,4-diol (62): as in Example 2, but use 3-((Phenylimino)methyl)quinoline-2,4-diol (UA-3701, melting point 194° C.) instead of UV-P.

Example 27, Preparation of 2-(4-((4-(N′-(4-(ethoxy-carbonyl)phenyl)-N-methyliminomethamido)benzyl)(methyl)amino)benzylidene)dimethyl malonate (Compound 27, UV-1)

[0146] ##STR00073##

[0147] According to Example 21, but use 4-((((4-(chloromethyl) phenyl)(methyl)amino)methylene)amino) ethyl benzoate (Compound 62) instead of compound (54), to obtain compound (27), C.sub.31H.sub.33N.sub.3O.sub.6, m/z: 543.24 [M].sup.+.

##STR00074##

[0148] The preparation method of Compound (62): as in Example 2 method, but use 4-(((phenyl)(methyl)amino)methylene)amino) ethyl benzoate (Eutec co., UV-1, melting point 137° C.) instead of UV-P.

Example 28, preparation of 2-(4-((3-ethoxy-4-(2-((2-ethylphenyl)amino)-2-oxoacetamido)benzyl)(methyl)amino)benzylidene)dimethyl malonate (Compound 28)

[0149] ##STR00075##

[0150] According to Example 21, but use 4-((((4-(chloromethyl) phenyl)(methyl)amino)methylene)amino)ethyl benzoate (compound 63) instead of compound (54), Compound (28), C.sub.32H.sub.35N.sub.3O.sub.7, was obtained. m/z: 573.3 [M].sup.+.

##STR00076##

[0151] The preparation method of 4-((((4-(chloromethyl)phenyl)(methyl) amino) methylene) amino) ethyl benzoate (compound 63): as in Example 2, but replace UV-P with 4-(((methyl(phenyl) amino)methylene)amino)ethyl benzoate (Eutec co., UV-312, melting point 120° C.).

Example 29, Preparation of 2-(4-(((9H-carbazole-3-yl)methyl)(methyl)amino)benzylidene)malonate (Compound 29)

[0152] ##STR00077##

[0153] According to Example 21, but use 3-(chloromethyl)-9H-carbazole (Compound 64), instead of Compound (54). Compound (29), C.sub.26H.sub.24N.sub.2O.sub.4, was obtained. m/z: 428.2 [M].sup.+.

##STR00078##

[0154] The preparation method of 3-(chloromethyl)-9H-carbazole (compound 64): as in Example 2, but use 9H-carbazole instead of UV-P.

Example 30, Preparation of 2-cyano-3-(4-(N-methyl-9H-carbazole-1-carboxamido)phenyl) ethyl acrylate (Compound 30)

[0155] ##STR00079##

[0156] According to the method of Example 20, but use 9H-carbazole-1-carboxylic acid methyl ester (Compound 65) instead of Compound (54). Compound (30), C.sub.26H.sub.21N.sub.3O.sub.3, was obtained. m/z: 423.2[M].sup.+.

##STR00080##

[0157] The preparation method of 9H-carbazole-1-carboxylic acid methyl ester: Using concentrated sulfuric acid as a catalyst, 9H-carbazole-1-carboxylic acid was in excess methanol with reflux to obtain compound (65).

Example 31, Preparation of dimethyl 2-(4-((dibenzo[b,d] thiophen-2-yl-methyl)(methyl)amino)benzylidene) malonate (Compound 31)

[0158] ##STR00081##

[0159] According to the method of Example 21, but use 2-(chloromethyl)dibenzo[b,d]thiophene (compound 66) instead of compound (54). Compound (31) was obtained. C.sub.26H.sub.23NO.sub.4S, m/z: 445.1 [M].sup.+.

##STR00082##

[0160] The preparation method of 2-(Chloromethyl)dibenzo[b,d]thiophene: as in Example 2, but use dibenzo[b,d]thiophene instead of UV-P.

Example 32 Thermal Stability Analysis

[0161] UV or blue light blocking agents usually need to be processed at high temperatures or/and used outdoors. However, most ultraviolet or blue light blocking agents cannot maintain high stability at high temperatures. Here, we used the commercially available ultraviolet blocking compound, UV-P, or/and the blue light blocking compound, blue-1, as controls, and compared the thermal stability (thermogravimetric analyzer, TGA) with the current example compounds. The greater the weight loss, the worse the stability is.

##STR00083##

[0162] For UV-P, the weight loss caused by heat is 5% at 190° C. For blue-1, the weight loss caused by heat is 5% at 178.3° C. These agents cannot be used in high temperature processing of plastics. Surprisingly, the TGA of FIG. 5 shows that the compound of Example 4 (L-486) of the present invention has a thermal weight loss of less than 1% when the temperature is raised to 300° C. The TGA in FIG. 6 shows that when the temperature of the compound of Example 6 (L-467) reaches 300° C., the thermal weight loss is less than 1%. These compounds of the present invention can be used in polycarbonate (PC) processing. For the example compounds of the present invention, the temperature for 5% weight loss is above 200° C. They can be used for most plastic processing.

TABLE-US-00001 TABLE 1 Thermal stability Compounds of Compound Compound ex. 4, ex. 6 UV-P blue-1 (FIG. 5, 6) Decomposition 190° C. 178.3° C. above 330° C. temperature (5%)

Example 33. Absorption Analysis for Blue Light

[0163] UVA (about 320-400 nm) can penetrate glass, is the main indoor ultraviolet light band. UVB (about 290-320 nm) is the main ultraviolet light band that causes photobiological effects of solar radiation on the skin. In many applications, simultaneous absorption of UVA, UVB and blue light is expected. UVA (about 320-400 nm). For example, FIGS. 1-4 are the UV-VIS absorption graphs of 10 mg/L in chloroform. It is the typical UV-VIS absorption pattern of the compound of the present invention. FIGS. 1-4 show that compounds of example simultaneously absorb ultraviolet light and blue light. And the absorption of long-wavelength blue light gradually decreases (indicating that the transmitted blue light has better color visual effects).

TABLE-US-00002 TABLE 2 Absorption analysis for blue light Compounds of Compounds example Compound of example 4-5, 7-11, blue-1 6, 12, 18 13-17, 19-31 UVA + UVA + UVB + UVA + UVB + blue light blue light blue light Evaluation of + +++ +++ absorption range Absorption (max.) about 380 nm about 420 nm about 380 nm Evaluation of color +++ +++ +++ visual effect Evaluation of — +++ +++ thermal stability