Novel Polycyclic Compound

Abstract

Novel polycyclic compounds, synthesis methods and applications thereof are provided. The compound comprise a plurality of carbocyclic and/or heterocyclic structures having at least one group that emits visible light or fluorescence and at least one ultraviolet and/or visible (blue) light absorbing group covalently bonded to provide stability. The compounds can be used as a light conversion agent, dye, pigment, fluorescence agent, ultraviolet light or blue light absorber, and is applied to optical film, agricultural film, optical disk (disc), optical lens, goggles, skin care, makeup, lighting, coatings, adhesives, light stabilizers, or panels.

Claims

1. A novel type of polycyclic compound, a structure of the compound is represented by formula (1) or formula (2),
A-R.sub.1—B—R.sub.2—C—R.sub.3-D   (1),
A-R.sub.1—B—R.sub.2-D-R.sub.3—C   (2), including at least one visible light or fluorescence emitting group, and at least an additional ultraviolet light absorbing group, wherein the visible light or fluorescence emitting group is R.sub.2—C—R.sup.3-D or R.sub.2-D-R.sub.3—C; the ultraviolet light absorbing group is A-R.sub.1—B; R.sub.1 to R.sub.3 are each independently a bond or/and any divalent linking group; A, B, and C are each independently a benzene ring, a benzo-carbocyclic ring, a nitrogen-containing 5˜7 membered heterocyclic ring, or a nitrogen-containing 5˜7 membered benzo-heterocyclic ring, which substituted by R.sub.4; D is a substituted 5˜7 membered heterocyclic ring or a 5˜7 membered benzo-heterocyclic ring composed of carbon, nitrogen, oxygen, and sulfur atoms, wherein, each substituent of the ring on carbon atom is selected from the group consisting of hydrogen, hydroxyl, oxo, thio, thiol, amine, imino, C.sub.1˜C.sub.8 linear or branched alkyl or alkenyl, and R.sub.4, and the substituent of the ring on nitrogen atom is selected from the group consisting of hydrogen, hydroxyl, oxo, and linear or branched C.sub.1˜C.sub.8 alkyl; R.sub.4 is one or more substituents, each independently selected from the group consisting of hydrogen, halogen, hydroxyl, amino, nitro, cyano, linear or branched C.sub.1˜C.sub.18 alkyl, alkenyl or alkoxy, unsubstituted or substituted phenyl, 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 each independently hydrogen and linear or branched C.sub.1˜C.sub.8 alkyl groups; R.sub.4 and adjacent R.sub.4, or adjacent ring, together form 3-6 atom fused carbocyclic or fused heterocyclic ring.

2. The compound according to claim 1, wherein, D is selected from the group consisting of ##STR00230## n=0˜1, p=0˜3, and X.sub.1 to X.sub.6 are each independently selected from the group consisting of C═O, C═S, C═N—R.sub.8, N, NR.sub.9, C, O, S, CR.sub.10, CR.sub.11R.sub.12, CNR.sub.11R.sub.12, and CR.sub.10NR.sub.11R.sub.12, wherein, R.sub.8˜R.sub.12 are each independently selected from the group consisting of hydrogen, linear or branched, C.sub.1˜C.sub.8 alkyl or alkenyl, and unsubstituted or phenyl substituted with one or more linear or branched C.sub.1˜C.sub.6 alkyl or halogen; R.sub.4 is a substituent, and each is independently selected from the group consisting of hydrogen, halogen, nitro, cyano, linear or branched C.sub.1˜C.sub.8 alkyl, alkenyl or alkoxy, 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 linear or branched C.sub.1˜C.sub.8 alkyl.

3. The compound according to claim 2, wherein, D is ##STR00231## n=0˜1, X.sub.1 to X.sub.6 are each independently selected from the group consisting of C═O, C═S, C═N—R.sub.8, N, NR.sub.9, C, O, S, CR.sub.10, and CR.sub.11R.sub.12, R.sub.9˜R.sub.12 are each independently hydrogen, linear or branched, and C.sub.1˜C.sub.6 alkyl or alkenyl; R.sub.4 is a substituent, and each is independently selected from the group consisting of hydrogen, halogen, nitro, cyano, linear or branched C.sub.1˜C.sub.8 alkyl, alkenyl or alkoxy, 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 linear or branched C.sub.1˜C.sub.6 alkyl; p=0˜2.

4. The compound according to claim 2, wherein, R.sub.1 to R.sub.3 are each a bond or a chain composed of 1˜10 groups selected from the following groups: —O—, —S—, —C(═O)—, —COO—, —C(═S)—, —C(═N—R.sub.13)—, —N(R.sub.13)—, —C(R.sub.14)(R.sub.15)—, —C(R.sub.16)═, —C≡, —C(R.sub.17)═C(R.sub.18)—, and -Ph-, R.sub.13˜R.sub.18 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, unsubstituted or halogen-substituted linear or branched C.sub.1˜C.sub.6 alkyl or alkenyl, and an unsubstituted phenyl or a phenyl substituted with 1 or 2 halogens or linear or branched C.sub.1˜C.sub.6 alkyl chain, Ph is an unsubstituted phenyl or a phenyl substituted with one or more halogen, hydroxyl, C.sub.1˜C.sub.6 alkoxy, or linear or branched C.sub.1˜C.sub.6 alkyl.

5. The compound according to claim 4, wherein, A is selected from: ##STR00232## B is selected from: ##STR00233## C is selected from: ##STR00234## wherein, R.sub.19˜R.sub.20 are each independently hydrogen, linear or branched C.sub.1˜C.sub.6 alkyl, or an unsubstituted phenyl or a phenyl substituted with one or more halogens or linear or branched C.sub.1˜C.sub.6 alkyl; Ph is an unsubstituted phenyl or a phenyl substituted with one or more halogens, hydroxyl, C.sub.1˜C.sub.6 alkoxy, or linear or branched C.sub.1˜C.sub.6 alkyl.

6. The compound according to claim 5, wherein, A is selected from: ##STR00235## B is selected from: ##STR00236## C is selected from: ##STR00237## D is selected from: ##STR00238## when n=0, X.sub.1 is C═O or C═S, X.sub.2, X.sub.3, and X.sub.4 are each independently selected from the group consisting of C═O, C═S, C═N—R.sub.8, N, NR.sub.9, C, O, S, CR.sub.10, CR.sub.11R.sub.12, and CNR.sub.11R.sub.12; when n=1, X.sub.4 and X.sub.6 are each C═O or C═S, X.sub.1, X.sub.2, and X.sub.3 are each independently selected from the group consisting of C═O, C═S, C═N—R.sub.8, N, NR.sub.9, C, O, S, CR.sub.10, and CR.sub.11R.sub.12, R.sub.1 to R.sub.3 are a bond, or/and a chain comprising of 1-6 groups selected from the group consisting of —O—, —C(═O)—, —COO—, —N(R.sub.13)—, —C(R.sub.14)(R.sub.15)—, —C(R.sub.16)═, and —C(R.sub.17)═C(R.sub.18)—; R.sub.4 is a substituent, and each is independently selected from the group consisting of hydrogen, halogen, nitro, cyano, linear or branched C.sub.1˜C.sub.8 alkyl, alkenyl or alkoxy, COOR.sub.5, CO R.sub.5, and NR.sub.6R.sub.7; p=0˜2; R.sub.5˜R.sub.7 are each independently hydrogen or linear or branched C.sub.1˜C.sub.6 alkyl groups; R.sub.8˜R.sub.12 are each independently hydrogen, linear or branched C.sub.1˜C.sub.6 alkyl, or unsubstituted phenyl or phenyl substituted with 1 or 2 halogens or C.sub.1˜C.sub.6 alkyl; R.sub.13˜R.sub.18 are each independently hydrogen, halogen, linear or branched C.sub.1˜C.sub.6 alkyl, or unsubstituted phenyl or phenyl substituted with 1 or 2 halogens or C.sub.1˜C.sub.6 alkyl; R.sub.19 is hydrogen, linear or branched C.sub.1˜C.sub.6 alkyl, or unsubstituted phenyl or phenyl substituted with 1 or 2 halogens or C.sub.1˜C.sub.6 alkyl; Ph is unsubstituted phenyl or phenyl substituted with 1 or 2 halogens, hydroxyl, C.sub.1˜C.sub.6 alkoxy groups, or linear or branched C.sub.1˜C.sub.6 alkyl.

7. The compound according to claim 6, wherein, R.sub.2 is a bond or —(CHR.sub.21).sub.q N(R.sub.22)—, wherein R.sub.21 and R.sub.22 are each independently hydrogen, or linear or branched C.sub.1˜C.sub.6 alkyl; q=0˜6; D is selected from: ##STR00239## ##STR00240## R.sub.4 is a substituent, and each independently selected from the group consisting of hydrogen, halogen, linear or branched C.sub.1˜C.sub.8 alkyl or alkoxy, COOR.sub.5, COR.sub.5, and NR.sub.6R.sub.7, wherein R.sub.5, R.sub.4, and R.sub.7 are each independently hydrogen or linear or branched C.sub.1˜C.sub.6 alkyl; p=0˜2; R.sub.9, and R.sub.23˜R.sub.34 are each independently linear or branched C.sub.1˜C.sub.6 alkyl, or unsubstituted phenyl or phenyl substituted with 1 or 2 linear or branched C.sub.1˜C.sub.6 alkyl.

8. The compound according to claim 1, wherein, A-R.sub.1—B is selected from: ##STR00241## ##STR00242## R.sub.4 is a substituent, and each independently selected from the group consisting of hydrogen, halogen, linear or branched C.sub.1˜C.sub.8 alkyl or alkoxy, 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 linear or branched C.sub.1˜C.sub.6 alkyl; p=0˜2; R.sub.9, and R.sub.23˜R.sub.34 are each independently hydrogen, linear or branched C.sub.1˜C.sub.6 alkyl, and unsubstituted phenyl or phenyl substituted with 1 or 2 linear or branched C.sub.1˜C.sub.6 alkyl; Ph is unsubstituted phenyl or phenyl substituted with 1 or 2 halogen, hydroxyl, or linear or branched C.sub.1˜C.sub.6 alkyl groups.

9. The compound according to claim 1, wherein, R.sub.2—C—R.sub.3-D is selected from: ##STR00243## R.sub.2-D-R.sub.3—C is selected from: ##STR00244## D is selected from: ##STR00245## A-R.sub.1—B is selected from: ##STR00246## ##STR00247## wherein, the visible light emitting groups or the ultraviolet light absorbing groups are substituted by (R.sub.4)p substituent, wherein p=0˜3; R.sub.4 is a substituent, and each is independently selected from the group consisting of hydrogen, halogen, hydroxyl, amino, nitro, cyano, linear or branched C.sub.1˜C.sub.18 alkyl, alkenyl or alkoxy, unsubstituted phenyl or phenyl substituted by one or more linear or branched C.sub.1˜C.sub.6 alkyl, halogen, 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 each independently hydrogen, linear or branched C.sub.1˜C.sub.8 alkyl groups; R.sub.4 and adjacent R.sub.4, or adjacent ring, together form 3˜6 atom fused carbocyclic or fused heterocyclic ring; R.sub.40˜R.sub.49 are the same or different and are each independently hydrogen, linear or branched C.sub.1˜C.sub.8 alkyl or alkenyl, unsubstituted phenyl or phenyl substituted by linear or branched C.sub.1˜C.sub.6 alkyl or halogen; R.sub.50 is selected from hydrogen, monovalent metal, linear or branched C.sub.1˜C.sub.8 alkyl or alkenyl, unsubstituted phenyl or phenyl substituted with one or more linear or branched C.sub.1˜C.sub.6 alkyl or halogen.

10. The compound according to claim 1, wherein, the structural formula is: ##STR00248## ##STR00249## ##STR00250## ##STR00251##

11. A method for preparing the compound represented by formula (1) or formula (2) according to claim 1, comprising any one of the following reaction steps ##STR00252## wherein, A to D and R.sub.1 to R.sub.3 are defined in claim 1, D′ is a precursor of the D ring, represented by ##STR00253## D″ is a precursor of the D ring, represented by ##STR00254## Z is a leaving group, represented by halogen, or C.sub.1˜C.sub.6 alkoxy; T is the same or different, each independently represented by NH, NH.sub.2, OH, and SH; U and V are C═O, C═S, C═N—R.sub.51, or C(R.sub.52)(R.sub.53); R.sub.50˜R.sub.53 are the same or different and are independently a bond, hydrogen, or linear or branched C.sub.1˜C.sub.6 alkyl.

12. A film, which comprises one or more additives including light conversion agent, dye, pigment, fluorescence agent, ultraviolet light absorber or blue light absorber, a structure of the additive is represented by formula (1) or formula (2) of according to claim 1.

13. The compound according to claim 3, wherein, R.sub.1 to R.sub.3 are each a bond or a chain composed of 1˜10 groups selected from the following groups: —O—, —S—, —C(═O)—, —COO—, —C(═S)—, —C(═N—R.sub.13)—, —N(R.sub.13)—, —C(R.sub.14)(R.sub.15)—, —C(R.sub.16)═, —C≡, —C(R.sub.17)═C(R.sub.18)—, and -Ph-, R.sub.13˜R.sub.18 are each independently selected from the group consisting of hydrogen, halogen, hydroxyl, unsubstituted or halogen-substituted linear or branched C.sub.1˜C.sub.6 alkyl or alkenyl, and an unsubstituted phenyl or a phenyl substituted with 1 or 2 halogens or linear or branched C.sub.1˜C.sub.6 alkyl chain, Ph is an unsubstituted phenyl or a phenyl substituted with one or more halogen, hydroxyl, C.sub.1˜C.sub.6 alkoxy, or linear or branched C.sub.1˜C.sub.6 alkyl.

14. The compound according to claim 5, wherein, A-R.sub.1—B is selected from: ##STR00255## ##STR00256## R.sub.4 is a substituent, and each independently selected from the group consisting of hydrogen, halogen, linear or branched C.sub.1˜C.sub.8 alkyl or alkoxy, 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 linear or branched C.sub.1˜C.sub.6 alkyl; p=0˜2; R.sub.9, and R.sub.23˜R.sub.34 are each independently hydrogen, linear or branched C.sub.1˜C.sub.6 alkyl, and unsubstituted phenyl or phenyl substituted with 1 or 2 linear or branched C.sub.1˜C.sub.6 alkyl; Ph is unsubstituted phenyl or phenyl substituted with 1 or 2 halogen, hydroxyl, or linear or branched C.sub.1˜C.sub.6 alkyl groups.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0074] FIG. 1, UV-VIS absorption compound (7) of the present invention (10 mg/tetrahydrofuran);

[0075] FIG. 2, TGA (thermogravimetric analyzer) diagram of the compound (7) of the present invention:

[0076] FIG. 3, UV-VIS absorption of compound (18) of the present invention (10 mg/tetrahydrofuran);

[0077] FIG. 4 The appearance of the agricultural film made of the light conversion agent of the present invention.

DETAILED DESCRIPTION

[0078] Specific embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

A-R.sub.1—B—R.sub.2—C—R.sub.3-D   (1)

TABLE-US-00001 TABLE 1 the compounds of formula (1) Ex A-R.sub.1-B R2 C R3 D R4 4 [00039] CH2NCH3 [00040] —CH═ [00041] H, CH3, OH 5 [00042] CH2NC2H5 [00043] —CH═ [00044] H, CH3, OH 6 [00045] CH2NC2H5 [00046] —CH═ [00047] H, CH, OH, C(CH3)2CH2C(CH3)3 7 [00048] CH2NC2H5 [00049] —CH═ [00050] H, CH3, OH, Cl 8 [00051] CH2NC2H5 [00052] —CH═ [00053] H, CH3, OH, OCH3 9 [00054] CH2NC2H5 [00055] —CH═ [00056] H, CH3,OH, COO(CH2)5CH3 10 [00057] CH2NC2H5 [00058] —CH═ [00059] H, CH3, OH 11 [00060] CH2NC2H5 [00061] —HC═CH—CH═ [00062] H, CH3, OH 13 [00063] CH2NCH3 [00064] —CH═ [00065] H, CH3, OH 14 [00066] CH2NCH3 [00067] [00068] [00069] H, CH3, OH 15 [00070] CH2 [00071] —CH═ [00072] H, CH3, OH 16 [00073] CH2NCH3 [00074] —CH═ [00075] H, CH3, OH 17 [00076] CH2NCH3 [00077] —CH═ [00078] H, CH3, OH 18 [00079] CH2NCH3 [00080] —CH═ [00081] H, CH3, OH 19 [00082] CH2NCH3 [00083] —CH═ [00084] H, CH3, OH 20 [00085] CH2NCH3 [00086] —CH═ [00087] H, CH3, OH 21 [00088] CH2NCH3 [00089] —CH═ [00090] H, CH3, OH 22 [00091] CH2NCH3 [00092] —CH═ [00093] H, CH3, OH 23 [00094] CH2CH2CONCH3 [00095] —CH═ [00096] H, CH3, OH, C(CH3)3, Ph 24 [00097] CH2NCH3 [00098] —CH═ [00099] H, CH3, OH, Ph 25 [00100] CH2NCH3 [00101] —CH═ [00102] H, OH, OC8H17 26 [00103] CH2NCH3 [00104] —CH═ [00105] H 27 [00106] CH2NCH3 [00107] —CH═ [00108] H, OH 28 [00109] CH2NCH3 [00110] —CH═ [00111] H, CH3, COOC2H5 29 [00112] CH2NCH3 [00113] —CH═ [00114] H, C2H5, OC2H5 30 [00115] CH2NCH3 [00116] —CH═ [00117] H 31 [00118] CONCH3 [00119] —CH═ [00120] H 32 [00121] CH2NCH3 [00122] —CH═ [00123] H 33 [00124] CH2NCH3 [00125] —CH═ [00126] C(CH3)3, H, OH

A-R.sub.1—B—R.sub.2-D-R.sub.3—C   (2)

TABLE-US-00002 TABLE 2 compounds of formula (2) exam- ple A-R.sub.1-B R2 D R3 C R4 34 [00127] CH2 [00128] —CH═ [00129] N(CH3)2 35 [00130] CH2 [00131] —CH═ [00132] N(CH3)2, CH3, C(CH3)3 36 [00133] CH2 [00134] A bond [00135] H, N(CH3)2, CH3, 36 [00136] CH═ [00137] A bond [00138] H, N(CH3)2, CH3, 37 [00139] A bond [00140] A bond [00141] H, N(CH3)2, C2H5, 38 [00142] CHCl [00143] [00144] H, N(C2H5)2, C2H5, 38 [00145] CH═ [00146] [00147] H, N(C2H5)2, C2H5, 39 [00148] CHCH3 [00149] —CH═ [00150] H, N(CH3)2 40 [00151] CH2CH2COO [00152] —C═N— [00153] H, OH, N(CH3)2, C(CH3)3

Example 1

2-(2-hydroxy-3-(chloromethyl)-5-methyl)benzotriazole (Compound 3)

[0079] ##STR00154##

[0080] Add 350 g of 2-(2-hydroxy-5-methyl)benzotriazole (UV-P, compound 3), 55 g of paraformaldehyde, 2000 g of acetic acid, and 300 g of 35% hydrochloric acid to a 5000 ml reaction flask, and heat to 60° C. The reaction was kept for 10 hours, and samples were taken to monitor the reaction. By cooling, washing with water, and drying, the white powder (chloromethyl UV-P, compound 4) was obtained with a yield of 96%. C.sub.14H.sub.12ClN.sub.3O, mp: 163˜164° C.

Example 2

2-(2-hydroxy-3-(N,N-dimethylaniline)-5-methyl)benzotriazole (Compound 5)

[0081] ##STR00155##

[0082] 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) were put together. The temperature was raised to 90˜100° C. for 5 hours, and samples were taken to monitor the reaction. Cool down to 30° C. and wash with water. Add 180 g of methanol, stir, filter, and dry to obtain a solid (compound 5). The purity is 98.3%, and the yield is 84%. C.sub.21H.sub.20N.sub.4O, mp: 98˜100° C.

Example 3

2-(2-hydroxy-3-(4-formyl-N,N-dimethylaminobenzene)-5-methyl) benzotriazole (Compound 6)

[0083] ##STR00156##

[0084] Mix 35 g of compound (5), 8.7 g of DMF, and add 18.4 g of phosphorus oxychloride dropwise at 20˜25° C. for about 2 hours. The temperature was raised to 90° C. to react for 2 hours, and samples were taken to monitor the reaction (Vilsmeier-Haack formylation). The product was slowly added to 300 g of water below 30° C. for hydrolysis, After the addition, it was neutralized with 30% liquid caustic so as to adjust the pH to 8, and the solid is filtered. Dissolve the solid with toluene, and washed with water, then cooled to 15° C. The solid was separated, and dried to obtain 31.8 g of yellow solids (compound 6). C.sub.21H.sub.19N.sub.4O.sub.2, mp: 111˜113° C.

Example 4

5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl) (methyl)amino)ylidenebenzyl)pyrimidine-2,4,6 (11H,3H,5H) trione (Compound 7)

[0085] ##STR00157##

[0086] 50 g of compound (6) and 17.1 g of barbituric acid were dissolved in toluene, and 5 g of ammonium acetate and 10 g of acetic acid were added and kept at 80˜90° C. for 1 hour. Then the temperature was raised to reflux for 8 hours, and the reaction was monitored by sampling. After the reaction was completed, the temperature was lowered, and the solid was filtered, then washed with toluene, and dichloroethane. Then it was filtered, washed with water, and dried to obtain compound (7). Yield: about 80%. C.sub.26H.sub.22N.sub.6O.sub.4, mp: 262˜270° C.

Example 5

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

[0087] ##STR00158##

[0088] According to the method of examples 1˜4, but using N-ethylaniline instead of N-methylaniline, compound (8) was obtained. C.sub.27H.sub.24N.sub.6O.sub.4, mp: 263˜267° C.

Example 6

5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)benzyl)(ethyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione

[0089] ##STR00159##

[0090] 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (compound 10) is obtained from Eutec co. (Eusorb 329, melting point: 102˜106° C.), or can be prepared as described below. 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 the 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 took samples to monitor the reaction. After the reaction was completed, 20 g of ice was added and the temperature was raised to 0° C. Add the aforementioned diazonium salt and stir for 2 hours. It was neutralized by adding concentrated hydrochloric acid and dried to obtain 2-((2-nitrophenyl)diazenyl)-4-(2,4,4-trimethylpent-2-yl)phenol (Compound 11). C.sub.20H.sub.25N.sub.3O.sub.3, mp: 114˜115° C.

[0091] Dissolve 35.7 g of compound (11) in 100 ml of petroleum ether, add 17.2 g of zinc and 100 ml of water. 41.6 g of NaOH solution (25%) was added within 4 hours at 50° C. 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 compound (10). C.sub.20H.sub.25N.sub.3O, mp: 102˜106° C.

##STR00160##

[0092] 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 a starting material, compound (9) was obtained. C.sub.34H.sub.38N.sub.6O.sub.4, m/z: 594.3[M].sup.+.

Example 7

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

[0093] ##STR00161##

[0094] According to the method of example 6, but using 4-chloro-2-nitroaniline instead of o-nitroaniline as the starting material, 2-(2′-hydroxy-phenyl)-5-chloro-benzotriazole (compound 13) was obtained, C.sub.12H.sub.8ClN.sub.3O, mp: 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, the compound (12) was obtained. C.sub.26H.sub.21ClN.sub.6O.sub.4, m/z: 516.1[M].sup.+.

Example 8

5-(4-(ethyl(2-hydroxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)-5-methylbenzyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione

[0095] ##STR00162##

[0096] According to the method of example 6, but using 4-methoxy-2-nitroaniline instead of o-nitroaniline as the starting material, 2-(2′-hydroxy-phenyl)-5-chloro-benzotriazole (compound 15) was obtained. C.sub.14H.sub.13N.sub.3O.sub.2, mp: 126˜27° 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. C.sub.28H.sub.26N.sub.6O.sub.5, m/z: 526.2[M].sup.+.

Example 9

3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-((ethyl(4-((2,4,6-trioxotetrahydropyrimidine-5 (2H)-ylidene)methyl)phenyl)amino)methyl)-4-hydroxybenzoic Acid Methyl Ester (Compound 16)

[0097] ##STR00163##

[0098] According to the method of example 6, but using 4-hydroxybenzoic acid to replace 4-p-tert-octylphenol, and 3-(2H-benzo[d] [1,2,3]triazol-2-yl)-4 was obtained. Thionyl chloride was added, and the temperature was raised to reflux for 2 hours. The thionyl chloride was evaporated 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. C.sub.19H.sub.21N.sub.3O.sub.2, mp: 83˜84° C.

##STR00164##

[0099] 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) to obtain compound (16). C.sub.33H.sub.34N.sub.6O.sub.6, m/z: 610.3[M].sup.+.

Example 10

5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)ylidenebenzyl)-2,2-Dimethyl-1,3-dioxane-4,6-dione (Compound 18)

[0100] ##STR00165##

[0101] 20 g of compound (6) and 8.2 g of Meldrum's acid were dissolved in toluene, and 4.1 g of ammonium acetate and 10 g of acetic acid were added. Reflux and dehydrate for 4 hours, samples were taken to monitor the reaction. After the reaction was completed, the solid was filtered, and dissolved with dichloroethane at elevated temperature, and then washed with water. Dichloroethane is distilled out, and toluene is added for recrystallization to obtain compound (18). C.sub.29H.sub.28N.sub.4O.sub.5, mp: 220˜224° C.

Example 11

5-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(ethyl)amino)ylidenebenzyl)-2,2-Dimethyl-1,3-dioxane-4,6-dione (Compound 19)

[0102] ##STR00166##

[0103] 12 g of compound (6) was added to 200 ml of a solution of 1% sodium hydroxide and 15% ethanol, and 5 g of 30% acetaldehyde aqueous solution was added dropwise. After an overnight reacting, 15 g of NaCl was added and stirred, and the pH was adjusted to neutral with dilute hydrochloric acid. Then it was extracted with ethyl acetate and dried to obtain 3-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methyl Benzyl) (ethyl) amino) phenyl) acrolein (20).

##STR00167##

[0104] According to the method of example 10, the compound (20) was added to Mildren's acid, ammonium acetate and acetic acid to obtain the compound (19). C.sub.31H.sub.30N.sub.4O.sub.5, m/z: 538.2[M].sup.+.

Example 12

5-(4-(methylamino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 21)

[0105] ##STR00168##

[0106] 20 g of barbituric acid and 13.6 g of 4-methylaminobenzaldehyde were dissolved in dichloromethane. Add molecular sieve to remove water and install calcium chloride pipe for waterproof. 1 ml of piperidine and 0.6 ml of acetic acid were added, and heated to reflux for 2 hours. During the reaction, fresh molecular sieve was added, and samples were taken to monitor the reaction. After the completion of the reaction, the solvent was removed, and the compound (21) was obtained after pickling and drying. C.sub.12H.sub.11N.sub.3O.sub.3, m/z: 245.1[M].sup.+.

Example 13

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

[0107] ##STR00169##

[0108] According to the method of example 2, but replace N-methylaniline with compound (21), and compound (7) was obtained. In the H1-NMR of the starting compound (4), the chemical shift of 4.6 disappeared (—CH.sub.2Cl), and the chemical shift of 5.0 was appeared (compound 7, —CH.sub.2N), indicating that the reaction was completed. The melting point range is the same as that of compound (7) prepared by the method of example 4.

Example 14

3-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)benzene Yl)-2-cyano-3-phenyl Acrylate (Compound 22)

[0109] ##STR00170##

[0110] According to the method of example 2, but using 4-methylaminobenzophenone (compound 23) instead of compound N-methylaniline, compound (24) was obtained.

##STR00171##

[0111] According to the method of example 4, compound (24) was used to replace compound (6). Column chromatography was used for isolation to obtain compound (22). C.sub.32H.sub.26N.sub.6O.sub.4, m/z: 558.2 [M].sup.+.

Example 15

5-((1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-1H-indole-3-yl)methylene)pyrimidine-2,4,6-(1H,3H,5H)-trione (compound 25)

[0112] ##STR00172##

[0113] According to the method of example 2, 3-indolecarboxaldehyde was used, instead of N-methylaniline, and column chromatography was used to obtain compound (26). According to the method of example 3 and 4, compound (25) was used, instead of compound (6), and separated by column chromatography to obtain compound (25), C.sub.27H.sub.20N.sub.6O.sub.4. m/z: 492.2[M].sup.+. 3-indole formaldehyde is common used for industry and can be prepared in the following way (Vilsmeier reaction): 16 g of POCl3 and 30 g of DMF were mixed under ice bath in 30 minutes, and 11 g of indole compound solution (DMF) was slowly added. The temperature was raised to 35° C. and stirred for 1 hour. Add 50 g of crushed ice to the obtained paste and stir, and add 0.1M NaOH slowly while stirring. After washing with water, recrystallize it with ethanol to obtain 3-indole formaldehyde. C.sub.9H.sub.7NO, mp: 196˜197° C.

Example 16

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

[0114] ##STR00173##

[0115] According to the method of example 4, the compound 4-thiothiazol-2-one (CAS RN. 4303-29-1) was used to replace the barbituric acid compound to obtain compound (27). C.sub.25H.sub.21N.sub.5O.sub.4, m/z: 455.2 [M].sup.+.

Example 17

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

[0116] ##STR00174##

[0117] According to the method of example 15, 6-(methylamino)-2-naphthaldehyde was used, instead of 3-indole formaldehyde, to obtain compound (28). C.sub.30H.sub.24N.sub.6O.sub.4, m/z: 532.2 [M].sup.+.

Example 18

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

[0118] ##STR00175##

[0119] According to the method of example 4, the compound oxazolidine-2,4-dione (CAS RN. 2346-26-1) was used to replace the barbituric acid compound to obtain compound (29). C.sub.25H.sub.21N.sub.5O.sub.4, m/z: 455.2[M].sup.+.

Example 19

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

[0120] ##STR00176##

[0121] According to the method of example 4, 4-cyclopentene-1,3-dione compound was used to replace the barbituric acid compound to obtain compound (30). C.sub.26H.sub.19N.sub.4O.sub.3, m/z: 435.2[M].sup.+.

Example 20

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

[0122] ##STR00177##

[0123] According to the method of example 4, compound 1H-indene-1,3(2H)-dione was used to replace the barbituric acid compound to obtain compound (31). C.sub.31H.sub.24N.sub.4O.sub.3, m/z: 500.2[M].sup.+.

Example 21

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

[0124] ##STR00178##

[0125] According to the method of example 4, but using compound 1,4-dihydroimidazol-5-one (CAS RN. 1968-28-1), instead of the barbituric acid compound, and compound (32) was obtained. C.sub.25H.sub.22N.sub.6O.sub.2, m/z: 438.2[M].sup.+.

Example 22

4-(4-((3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)(methyl)amino)ylidenebenzyl)oxazole-5-(4H)-one (Compound 33)

[0126] ##STR00179##

[0127] According to the method of example 4, but using compound 4H-5-oxo-oxazole (CAS RN. 497-24-5) instead of the barbituric acid compound, and compound (33) was obtained. C.sub.25H.sub.21NO.sub.3, m/z: 439.2[M].sup.+.

Example 23

3-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)-N-(4-((2,4,6-trioxotetrahydropyrimidine-5(2H)-ylidene)methyl)phenyl)propionamide (Compound 34)

[0128] ##STR00180##

[0129] 5.2 g of 3-(3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(tert-butyl)-4-hydroxybenzene Hydroxy) methyl propionate (compound 35) was dissolved in toluene, and heated to reflux in a flask equipped with a condensation trap. Compound (21) was added to the toluene solution, and samples were taken to monitor the reaction. After the reaction was completed, vacuum distillation. After chromatographic separation, compound (34) was obtained, C.sub.44H.sub.4N.sub.6O.sub.5. m/z: 736.3 [M].sup.+.

##STR00181##

[0130] Preparation method compound (35) (according to CN201710949552.0): Briefly, 16 g of 2-chloro-4,6-bis(2′,4′ dimethyl-phenyl)-1,3,5-triazine (Compound 36) and 15 g of (3-tert-butyl-4-hydroxyphenyl) methyl propionate (Compound 37) are dissolved in 150 ml of chlorobenzene, and add 10 g of anhydrous aluminum trichloride. Heat and stir the mixture to dissolve. The temperature was then raised to 90° C., and samples were taken to monitor the reaction. After the completion of the reaction, the product was distilled under reduced pressure and then separated by chromatography to obtain compound (35).

##STR00182##

Example 24

5-(4-((3-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(tert-butyl)-4-Hydroxybenzyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 38)

[0131] ##STR00183##

[0132] According to the method of example 13, but using 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-6-(tert-butyl)-4-(chloromethyl)phenol (compound 39) to replace compound (4), and the product is separated by chromatography to obtain compound (38). C.sub.39H.sub.36N.sub.6O.sub.4, m/z: 652.3 [M].sup.+.

##STR00184##

[0133] According to the preparation method of compound (35) in example 23, but 4-(chloromethyl)-2-methylphenol is used instead of (3-(tert-butyl)-4-hydroxyphenyl) methyl propionate (compound 37).

Example 25

5-(4-((5-Benzoyl-4-hydroxy-2-(octyloxy)benzyl)(methyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-triketone (Compound 40)

[0134] ##STR00185##

[0135] According to the method of example 13, but use (5-(chloromethyl)-2-hydroxy-4-(octyloxy)phenyl)(phenyl)methanone (compound 41) instead of compound (4). After chromatographic separation, compound (40) was obtained. C.sub.34H.sub.37N.sub.3O.sub.6o m/z: 583.3[M].sup.+.

##STR00186##

[0136] According to the method of example 1, but using (2-hydroxy-4-(octyloxy) phenyl)(phenyl)methanone (Eutec co., Eusorb UV-531) instead of UV-P (compound 3), the compound (41). was obtained.

Example 26

5-(4-(Methyl(4-(4-oxo-4H-benzo[d][1,3]azin-2-yl)benzyl)amino)benzylidene)pyrimidine-2,4,6(1H, 3H, 5H) triketone (Compound 42)

[0137] ##STR00187##

[0138] According to the method of example 13, but use 2-(chloromethyl)-4H-benzo[d][1,3]oxazin-4-one (Compound 43) instead of compound (4). After chromatographic separation, compound (42) was obtained, C.sub.27H.sub.20N.sub.4O.sub.5, m/z: 480.1[M].sup.+.

##STR00188##

[0139] Preparation method of compound (43): Add 14 g of 2-aminobenzoic acid (compound 44) and 11 g of triethylamine to 100 ml of dichloroethane. Drop 19 g of 4-chloromethylbenzoyl chloride (compound 45) and stir and compound (43) was obtained. Preparation method of compound (45): 4-(hydroxymethyl)benzoic acid (46) was refluxed and chlorinated with thionyl chloride in dichloromethane to obtain compound (45), mp: 28° C.

##STR00189##

Example 27

5-(4-((4-(((2,4-Dihydroxy-quinolin-3-yl)methylene)amino)benzyl)(methyl)amino)benzylidene)pyrimidine-2,4,6(1H,3H,5H)-triketone (Compound 47)

[0140] ##STR00190##

[0141] According to the method of example 13, but using 3-(((4-(chloromethyl)phenyl)imino)methyl)quinoline-2,4-diol (compound 48), instead of compound (4), the compound (47) was obtained. C.sub.29H.sub.23N.sub.5O.sub.5, m/z: 521.2 [M].sup.+.

##STR00191##

[0142] According to the method of example 1, but use 3-((benzene Subimino)methyl)quinoline-2,4-diol (UA-3701, melting point 194° C.) instead of UV-P (compound 3).

Example 28

4-(((methyl(4-((methyl(4-((2,4,6-trioxotetrahydropyrimidine-5(2H)-ylidene)methyl)phenyl)amino)methyl) phenyl) amino) methylene) amino) ethyl Benzoate (Compound 49)

[0143] ##STR00192##

[0144] According to the method of example 13, but use 4-((((4-(chloromethyl)phenyl)(methyl)amino)methylene)amino)ethyl benzoate (compound 50), instead of (compound 4). After purification, compound (49) was obtained. C.sub.30H.sub.29N.sub.5O.sub.5, m/z: 539.2 [M].sup.+.

##STR00193##

[0145] Preparation method of compound (50): According to the method of example 1, but use 4-(((methyl(phenyl)amino)methylene)amino) ethyl benzoate (UV-1, melting point 137° C.) instead of UV-P (Compound 3).

Example 29

N1-(2-ethoxy-3-((methyl(4-((2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)methyl)phenyl)amino)methyl)phenyl)-N2-(2-ethylphenyl)oxalamide (Compound 51)

[0146] ##STR00194##

[0147] According to the method of example 13, but using N 1-(4-(chloromethyl)-2-ethoxyphenyl)-N 2-(2-ethylphenyl)oxamide (compound 52), instead of compound (4), compound (51) was obtained, C.sub.31H.sub.31N.sub.5O.sub.6. m/z: 569.2 [M].sup.+.

##STR00195##

[0148] Preparation method of N 1-(4-(chloromethyl)-2-ethoxyphenyl)-N 2-(2-ethylphenyl)oxamide (compound 52): According to example 1, but use N-(2-ethoxyphenyl)-N′-(4-ethylphenyl)-oxalamide (Eutec co., UV-312, mp: 120° C.) instead of UV-P (compound 3).

Example 30

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

[0149] ##STR00196##

[0150] According to the method of example 13, but using 3-(chloromethyl)-9H-carbazole (compound 54), instead of compound (4), compound (53) was obtained, C.sub.25H.sub.20N.sub.4O.sub.3 m/z: 424.2[M].sup.+.

##STR00197##

[0151] Preparation method of 3-(chloromethyl)-9H-carbazole (compound 44): According to the method of example 1, but use 9H-carbazole instead of UV-P (compound 3).

Example 31

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

[0152] ##STR00198##

[0153] According to the method of example 13, but using 9H-carbazole-3-carboxylic acid methyl ester (compound 56), instead of compound (4), compound (55) was obtained, C.sub.25H.sub.18N.sub.4O.sub.4, m/z: 438.1 [M].sup.+.

##STR00199##

[0154] Preparation method of 9H-carbazole-1-carboxylic acid methyl ester (compound 56): 9H-carbazole-1-carboxylic acid (AKOS BC-1282), was refluxed in excess methanol using concentrated sulfuric acid as a catalyst, compound (56) was to obtained.

Example 32

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

[0155] ##STR00200##

[0156] Method of 9H-carbazole-1-carboxylic acid methyl ester preparation: 9H-carbazole-1-carboxylic acid (AKOS BC-1282), using concentrated sulfuric acid as a catalyst, refluxed in excess methanol to obtain compound (56), C.sub.25H.sub.19N.sub.3O.sub.3S. m/z: 441.1 [M].sup.+.

##STR00201##

[0157] Preparation method of 2-(chloromethyl)dibenzo[b,d]thiophene (compound 58): According to the method of Example 1, but using dibenzo[b,d]thiophene instead of UV-P (Compound 3).

Example 33

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 Base) pyrimidine-2,4,6(1H,3H,5H)-trione (Compound 21)

[0158] According to the method of example 1 to 4, but using 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (Eutec co., Eusorb UV-120, melting point 149° C.) instead UV-P (compound 3). UV-120 and compound (21) were refluxed in dichloromethane. The product was washed with water and dried to obtain a mixture of product (59).

Example 34

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)

[0159] ##STR00202##

[0160] 15 g of 4-(dimethylamino)benzaldehyde, 13.2 g of dimethyl malonate, and 15 ml of pyridine were dissolved in toluene and heated to reflux. Take samples to monitor the reaction, remove the solvent, and obtain dimethyl 2-(4-(dimethylamino)benzylidene)malonate (Compound 61) after chromatography. C.sub.14H.sub.17NO.sub.4, mp: 86-88° C.

##STR00203##

[0161] 26.3 g of dimethyl 2-(4-(dimethylamino)benzylidene)malonate (Compound 61) and 4.6 g of diaminomethane were refluxed in ethanol for 3 hours. Evaporate the solvent to obtain a closed ring compound. Mix 14.6 g of the closed ring compound, 21 g of chromium trioxide, and 100 ml of water. Drop 45 ml of concentrated sulfuric acid. After dropping, add chromium trioxide (21 g/50 ml water) dropwise, and heat to reflux, take samples to monitor the reaction. After cooling to room temperature, the reaction mixture was poured into an equal volume of water and cooled to 10° C. in an ice bath. The precipitate was separated and washed with water. Disperse the precipitate in 30 ml of water, add 50 ml of saturated sodium carbonate solution and stir. Compound (60) was obtained by filtration. C.sub.27H.sub.24N.sub.6O.sub.4, MS: m/z=496.2 [M].sup.+.

Example 35

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)

[0162] ##STR00204##

[0163] According to the method of example 2, take 27.5 g of compound (4) and add 10 g of glycine methyl ester to react to obtain (3-(2H-benzo[d] [1,2,3]triazol-2-yl)-2-hydroxyl-5-methylbenzyl)glycine methyl ester (Compound 63).

##STR00205##

[0164] 16.3 g of compound (63) and 5.1 g of 2-isocyanato-2-methylpropane were heated to reflux overnight in dichloroethane, and the unreacted 2-isocyanato-2-methylpropane was removed by distillation under reduced pressure. After 2-isocyanato-2-methylpropane and dichloroethane are separated by chromatography, 1-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzyl)-3-(tert-butyl)imidazolidine-2,4-dione (compound 64).

##STR00206##

[0165] According to the method of 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). C.sub.30H.sub.32N.sub.6O.sub.3, m/z: 524.3[M].sup.+.

##STR00207##

Example 36

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) 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-diketone (Compound 90)

[0166] ##STR00208##

[0167] Dissolve 5.2 g of malonic acid (68) in 6 ml of acetic anhydride, add 0.15 ml of concentrated sulfuric acid with stirring in ice water. Heat the mixture to dissolve in a water bath. Add 4-(diethylamino) acetophenone (69) at room temperature and stir overnight. The product was washed with water and extracted with ethyl acetate to obtain 2-(4-(diethylamino) phenyl)-2-methyl-1,3-dioxane-4,6-dione (Compound 70).

##STR00209##

[0168] 2.34 g of compound (70) and 2.75 g of compound (4) were mixed to react under reflux in ethanol solution of sodium ethoxide overnight. After removing the solvent and neutralizing with HCl, the product is separated by chromatography to obtain compound (67). C.sub.29H.sub.30N.sub.4O.sub.5, m/z: 514.2 [M].sup.+.

##STR00210##

[0169] According to the method of example 3, but using compound (3) instead of compound (5), and 3-(2H-benzo[d] [1,2,3]triazol-2-yl)-2-hydroxy-5-methylbenzaldehyde (compound 89) was obtained. According to the method of example 4, but use compound (70) instead of barbituric acid and use compound (89) instead of compound (6). 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-diketone (compound 90) was obtained. C.sub.29H.sub.28N.sub.4O.sub.5, m/z: 512.2[M].sup.+.

##STR00211##

Example 37

5-(9H-carbazol-3-yl)-3-(4-(dimethylamino)phenyl)oxazolidine-2,4-dione (Compound 71)

[0170] ##STR00212##

[0171] Under the ice-water bath, dissolve 34 g 9H carbazole in 400 ml dry dichloromethane, slowly add 30 g anhydrous AlCl.sub.3 and continue stirring for 10 minutes, then slowly add 31 g of 2-chloro-2-oxoacetic acid methyl esters (compound 72) and continue stirring at room temperature. Take samples for monitoring, while the reaction was completed, pour the reactant into a hydrochloric acid in ice-water bath, extract with dichloromethane, and dry to obtain methyl 2-(9H-carbazol-3-yl)-2-oxoacetate (compound 73)

##STR00213##

[0172] 18 g of compound (73) and 150 mL of absolute ethanol were mixed and stir at room temperature. 2.6 g of sodium borohydride was added, and the reaction mixture was stirred at room temperature for 50 minutes and taken samples for monitoring. After the reaction is completed, pour the product into a hydrochloric acid in ice-water bath and extracted with ethyl acetate and dried to obtain methyl 2-(9H-carbazol-3-yl)-2-oxoacetate (Compound 74).

##STR00214##

[0173] 2.5 g of compound (74) was dissolved in 20 ml of dichloromethane, and 1.5 ml of triethylamine was added and stirred. 1.6 g of 4-isocyanato-N,N-dimethylaniline (75) in dichloromethane solution (10.sup.0% c) was added dropwise. After the addition, reflux it in dichloromethane and monitor the reaction. After the reaction was completed, neutralize it with HCl. After washing with water and evacuating the solvent, it was separated by chromatography to obtain compound (71). C.sub.23H.sub.19N.sub.3O.sub.3, m/z: 385.1 [M].sup.+.

##STR00215##

Example 38

5-((9H-carbazol-3-yl)chloromethyl)-3-(4-(dimethylamino)phenyl)oxazolidine-2,4-dione (Compound 76), 5-((9H-carbazol-3-yl)methylene)-3-(4-(dimethylamino)phenyl)oxazolidine-2,4-dione (Compound 88)

[0174] ##STR00216##

[0175] According to the method of example 3, using H-carbazole instead of compound (5), 9H-carbazole-3-carbaldehyde (compound 77) was obtained with a melting point of 158° C.

##STR00217##

[0176] At 4° C., 5 g of 9H-carbazole-3-carbaldehyde (compound 77) and 2.5 ml of 2,2-dichloroacetic acid methyl ester were mixed in 30 ml of hydrous ether solution. Add 1.95 g of sodium methoxide under argon and keep stirring at low temperature for 1 hour, and then heated to reflux. Samples were taken to monitor. After the reaction was completed, water was added and the organic layer was separated. After drying, and chromatographic separation, methyl 3-(9H-carbazol-3-yl)-3-chloro-2-oxopropionate (79) was obtained.

[0177] According to the method of example 37, using compound (79) instead of compound (73), methyl 3-(9H-carbazol-3-yl)-3-chloro-2-hydroxypropionate (80) was obtained.

##STR00218##

[0178] According to the method of example 37, using compound (80) instead of compound (74), methyl 3-(9H-carbazol-3-yl)-3-chloro-2-hydroxypropionate (76) was obtained. C.sub.24H.sub.20ClN.sub.3O.sub.3, m/z: 433.1 [M].sup.+.

##STR00219##

[0179] 4.3 g of compound (76) was dissolved in pyridine and heated to 80° C. Add 1.5 ml of DBU (1,8-diazabicycloundec-7-ene) to react. After the completion of the reaction (sampling monitoring), distillation was performed under reduced pressure. After chromatographic separation, compound (88) is obtained. C.sub.24H.sub.19N.sub.3O.sub.3, m/z: 397.1 [M].sup.+.

##STR00220##

Example 39

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

[0180] ##STR00221##

[0181] In an ice-water bath, dissolve 34 g of 9H-carbazole in dichloromethane, then slowly add 30 g of anhydrous AlCl.sub.3 and continue stirring for 10 minutes, and then slowly add 20 ml of acetyl chloride dropwise. After the addition was complete, continue stirring at room temperature. After the reaction is completed, the reaction solution was slowly poured into a hydrochloric acid in 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.

##STR00222##

[0182] 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. After cooling to room temperature, 8.4 g of 3-acetylcarbazole (82) was added dropwise and kept for 1 hour, then placed in a refrigerator overnight. After washing with water, it was extracted with ethyl acetate and separated by chromatography to obtain 2-(1-(9H-carbazol-3-yl)ethyl)-1,3-dioxane-4,6-dione (83).

##STR00223##

[0183] According to the method of example 35, but using compound (83) instead of compound (65), compound (81) was obtained. C.sub.27H.sub.24N.sub.2O.sub.4, m/z: 440.2 [M].sup.+.

##STR00224##

Example 40

5-(((4-(Dimethylamino)phenyl)imino)methyl)quinolin-7-yl-3-(3-(2H-benzo[d][1,2,3]triazole-2-yl)tert-butyl)-4-hydroxyphenyl) propionate (Compound 84)

[0184] ##STR00225##

[0185] Methyl 3-(3-(2H-benzo[d] [1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionate (Eutec co., BZTME, compound 85), hydrolyzed in KOH/MeOH, and then neutralized by adding acid. Extract with dichloromethane to obtain 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propane diacid (86). After fully drying, add excess thionyl chloride, heat to reflux. After the reaction was completed (sampling for confirmation), evaporate the unreacted thionyl chloride to obtain the compound 3-(3-(2H-benzo[d][1,2,3]Triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionyl chloride for further use.

##STR00226##

[0186] 1.75 g of 8-hydroxyquinoline-5-carbaldehyde (NSC 122131, compound 87) was dissolved in 20 ml of dichloromethane, and 2 g of triethylamine was added and stirred. Drop 3.6 g of the aforementioned 3-(3-(2H-benzo[d] [1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl) propionyl chloride dichloromethane solution (20 ml) of compound (86). Stir overnight at room temperature. The product was poured into ice water, extracted with dichloromethane, and 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).

[0187] 5 g of compound (91) and 1.4 g of p-(dimethylamino)aniline were dissolved in 40 ml of absolute ethanol and heated to reflux for 4 hours. Sample was taken to monitor. After the reaction was completed, the solvent was removed to obtain compound (84). C.sub.37H.sub.36N.sub.6O.sub.3, m/z: 612.3[M].sup.+.

##STR00227##

Example 41

[0188] The improvement of the performance on optical recording media: after covalent bonding, compound (18) was synthesized from compound (B) as shown in the figure below.

##STR00228##

[0189] The melting point of compound (B) is 175° C. After covalent bonding with benzotriazole compounds, the melting point raises to 224° C. (compound 18). This is an important improvement for organic dyes (B) used in optical recording media. This is because compound (18) is less likely to decompose under the high temperature (250° C., or above) generated locally by laser irradiating the disc.

[0190] FIG. 3 illustrates the UV absorption range of compound (18), covering UVA, UVB and blue light. This indicates that the dye of compound (18) can provide a wide range of ultraviolet light (UVA+UVB) protection for optical discs. Therefore, compared with compound (B), compound (18) is more advantageous in the storage of optical discs.

TABLE-US-00003 TABLE 3 Comparison of compound (B) and compound (18) compound (18) of the compound (B) present invention Heat properties Mp 175° C. Mp 224° C. Absorption UVA + visible light UVA + UVB + visible light range

Example 42

[0191] Advantages of being used in ultraviolet light or blue light absorbers: when the compound of the present invention is used in ultraviolet light and/or blue light absorbers, it has both ultraviolet light (UVA+UVB) and blue light absorption functions. Compared with the commercial anti-blue light agent, Eusorb UV-1990 (Eutec co.), (Table 4) it shows that the commercial product Eusorb UV-1990 has weak absorption of UVB (wavelength 280 nm). The example compound of the present invention has better coverage and absorption of ultraviolet light than the currently commercially available anti-blue light agent Eusorb UV-1990.

TABLE-US-00004 TABLE 4 Comparison of the title compounds of the examples and the commercially available Eusorb UV-1990 anti-blue light agent Abs UVB(about 280 nm) Blue light(about 390 nm) Title compounds of >0.2  >0.9 examples 4-40 Commercial available <0.05 >0.8 anti-blue light agent Eusorb UV-1990

Example 43

[0192] Stability and weather resistance of the light conversion agent: Thermogravimetric analyzer (TGA) was used to measure the thermal stability of the example compounds. The greater the weight loss, the worse the stability is. FIG. 2 shows the results of TGA: when the temperature is increased to 220° C., the weight loss of compound (7) of example 4 is less than 1%. Rising to 312° C., the weight loss is only about 5%. This shows that compound (7) has very high thermal stability.

[0193] FIG. 4 is a photograph of the PE agricultural film made of compound (7) of example 4 of the present invention under a fluorescent lamp (to show the color, the agricultural film is placed on a gray opaque background). The agricultural film is transparent and orange-red. Table 5 shows the comparison of the weather resistance before and after the modification of RL1000. The RL1000 product (BASF) can only maintain the stability of two seasons when used in outdoor agricultural film, while the compound (7) of the present invention is more than three seasons.

##STR00229##

TABLE-US-00005 TABLE 5 Comparison of weather resistance RL1000 compound(7) weather resistance two seasons three seasons Emission about 600-700 nm about 600-700 nm

[0194] The present invention has been disclosed in preferred embodiments above, but it is not intended to limit the present invention. All technical solutions obtained by equivalent substitutions or equivalent changes fall within the protection scope of the present invention.