Pyridine and pyrimidine substituted triazine UV absorbers

Abstract

A compound of formula ##STR00001##
wherein V, W, X and Y represent N or CH, at least one of V, W, X and Y being N and at least two of V, W, X and Y being CH; R.sub.1, R.sub.2 and R.sub.3 are each independently of the other hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, nitro, cyano, trifluoromethyl, halogen or hydroxy; and the compound provides good lightfastness properties to textile fibre materials, in particular PES fibre materials.

Claims

1. A compound of formula ##STR00009## wherein V, X and Y represent N or CH, one or two of V, X and Y being N and the remainder of V, X and Y being CH; W is CH; and R.sub.1, R.sub.2 and R.sub.3 are each independently of the other hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, nitro, cyano, trifluoromethyl, halogen or hydroxy; with the proviso that the compounds of formulae ##STR00010## are excluded.

2. The compound of formula (1) according to claim 1, wherein X is N; and V and Y are CH.

3. The compound of formula (1) according to claim 1, wherein Y is N; and V and X are CH.

4. The compound of formula (1) according to claim 1, wherein V is N; and W and Y are CH.

5. The compound of formula (1) according to claim 1, wherein R.sub.1 is hydrogen, methyl or methoxy.

6. The compound of formula (1) according to claim 1, wherein R.sub.1 is hydrogen or methoxy.

7. The compound of formula (1) according to claim 1, wherein R.sub.2 is hydrogen, methyl, methoxy, nitro, cyano, trifluoromethyl, halogen or hydroxy.

8. The compound of formula (1) according to claim 1, wherein R.sub.2 is hydrogen or methoxy.

9. The compound of formula (1) according to claim 1, wherein R.sub.3 is hydrogen, methyl, methoxy, nitro, cyano, trifluoromethyl, halogen or hydroxy.

10. The compound of formula (1) according to claim 1, wherein R.sub.3 is hydrogen or methoxy.

11. The compound of formula (1) according to claim 1, wherein the C.sub.1-C.sub.8 alkyl is methyl and the C.sub.1-C.sub.8 alkoxy is methoxy.

12. A photochemically stabilized textile fiber material comprising undyed, dyed or printed textile fiber material and at least one compound of formula ##STR00011## wherein V, X and Y represent N or CH, one or two of V, X and Y being N and the remainder of V, X and Y being CH; W is CH; and R.sub.1, R.sub.2 and R.sub.3 are each independently of the other hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, nitro, cyano, trifluoromethyl, halogen or hydroxy; with the proviso that the compounds of formulae ##STR00012## are excluded.

13. The photochemically stabilized textile fiber material of claim 12 wherein R.sub.1, R.sub.2 and R.sub.3 are each independently hydrogen or methoxy.

14. The photochemically stabilized textile fiber material of claim 12 wherein the undyed, dyed or printed textile fiber material comprises polyester fibers.

15. The photochemically stabilized textile fiber material of claim 12 comprising from 0.01% to 15.0% by weight of the compound of formula (1).

16. A process for the photochemical stabilization of textile fiber material, comprising treating an undyed, dyed or printed textile fiber material with a liquor comprising at least one compound of formula ##STR00013## wherein V, X and Y represent N or CH, one or two of V, X and Y being N and the remainder of V, X and Y being CH; W is CH; and R.sub.1, R.sub.2 and R.sub.3 are each independently of the other hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, nitro, cyano, trifluoromethyl, halogen or hydroxy; with the proviso that the compounds of formulae ##STR00014## are excluded.

17. The process of claim 16 wherein R.sub.1, R.sub.2 and R.sub.3 are each independently hydrogen or methoxy.

18. The process of claim 16 wherein the undyed, dyed or printed textile fibre material comprises polyester fibres.

19. A process for the preparation of a compound of formula (1), comprising (I) preparing 2-aryl-4H-1,3-benzoxazin-4-one (4) by acid-catalysed ring closure reaction of salicylamide derivative (2) with carboxylic acid (3) ##STR00015## and (II) reacting the 2-aryl-4H-1,3-benzoxazin-4-one (4) with amidine (5) to provide the compound of formula (1) ##STR00016## wherein V, X and Y represent N or CH, one or two of V, X and Y being N and the remainder of V, X and Y being CH; W is CH; and R.sub.1, R.sub.2 and R.sub.3 are each independently of the other hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, nitro, cyano, trifluoromethyl, halogen or hydroxy; with the proviso that the compounds of formulae ##STR00017## are excluded.

20. The process of claim 19 wherein R.sub.1, R.sub.2 and R.sub.3 are each independently hydrogen or methoxy.

Description

I. SYNTHESIS EXAMPLES

Example 1.1

(1) Synthesis of the Compound

(2) ##STR00006##

(3) A mixture of salicylic acid (20.9 g), salicylamide (21.0 g), N,N-dimethylformamide (0.5 ml) and xylene (70 ml) is heated to 110 C., and then thionyl chloride (36.0 g) is added dropwise. The reaction mixture is stirred for 5 hours at 126 C. After completion of reaction, the reaction mixture is gradually cooled down at 10 C. and then stirred for 1 hour. The precipitate is filtered and washed with methanol and dried under vacuum to yield 2-(2-hydroxyphenyl)-4H-1,3-benzoxazin-4-one (19.1 g).

(4) 30% sodium methylate in methanol (13.0 g) is added to the mixture of methanol (140 ml) and 4-pyridinecarboxamidine hydrochloride (7.5 g) which is prepared according to the patent of U.S. Pat. No. 6,004,965 at room temperature. Then, 2-(2-hydroxyphenyl)-4H-1,3-benzoxazin-4-one (12.1 g) is added at 35 C. The reaction mixture is stirred for 4 hours at 50 C. After cooling of the reaction mixture to room temperature, the precipitate is collected by suction filtration, washed with methanol and water and dried at 60 C. under vacuum to yield 2,4-bis(2-hydroxyphenyl)-6-(4-pyridinyl)-1,3,5-triazine (8.9 g). Melting point: 258-260 C.

(5) .sub.max=280 nm/352 nm.

Example 1.2

(6) Synthesis of the Compound

(7) ##STR00007##

(8) A mixture of salicylic acid (132 g), salicylamide (126 g), N,N-dimethylformamide (3 ml) and xylene (240 ml) is heated to 110 C., and then thionyl chloride (216 g) is added dropwise. The reaction mixture is stirred for 5 hours at 126 C. After completion of reaction, the reaction mixture is gradually cooled down at 10 C. and then stirred for 1 hour. The precipitate is filtered and washed with methanol and dried under vacuum to yield 2-(2-hydroxyphenyl)-4H-10-1,3-benzoxazin-4-one (143 g).

(9) 30% sodium methylate in methanol (9.0 g) is added to the mixture of methanol (140 ml) and 2-pyrimidinecarboxamidine hydrochloride (7.9 g) which is prepared according to the patent of WO 2011/024056 A2 at room temperature. Then, 2-(2-hydroxyphenyl)-4H-1,3-benzoxazin-4-one (12.6 g) is added at 35 C. The reaction mixture is stirred for 4 hours at 50 C. After cooling of the reaction mixture to room temperature, the precipitate is collected by suction filtration, washed with methanol and water and dried at 60 C. under vacuum to yield 2,4-bis(2-hydroxyphenyl)-6-(2-pyrimidinyl)-1,3,5-triazine (11.8 g). Melting point: 321-325 C. (decomposed).

(10) .sub.max=280 nm/354 nm.

Examples 1.3-1.16

(11) Analogously to the procedure described in Example 1.1, the compounds listed in Table 1 are prepared.

(12) ##STR00008##

(13) TABLE-US-00001 TABLE 1 Compound R.sub.1 R.sub.2 R.sub.3 V W X Y (105) H H H N CH CH CH (106) H CH.sub.3 H N CH CH CH (107) H OCH.sub.3 H N CH CH CH (108) H Cl H N CH CH CH (109) H Br H N CH CH CH (110) H H H CH CH CH N (111) H OH H CH CH CH N (112) H CH.sub.3 H CH CH CH N (113) H OCH.sub.3 H CH CH CH N (114) H Cl H CH CH CH N (115) H Br H CH CH CH N (116) H H H CH CH N CH (117) H CH.sub.3 H CH CH N CH (118) H OCH.sub.3 H CH CH N CH (119) H Cl H CH CH N CH (120) H Br H CH CH N CH (121) H H H CH N N CH (122) H CH.sub.3 H CH N N CH (123) H OCH.sub.3 H CH N N CH (124) H Cl H CH N N CH (125) H Br H CH N N CH (126) H H CH.sub.3 N CH CH CH (127) H H OCH.sub.3 N CH CH CH (128) H H CN N CH CH CH (129) H H CF.sub.3 N CH CH CH (130) H H Cl N CH CH CH (131) H H Br N CH CH CH (132) H H CH.sub.3 CH CH CH N (133) H H OCH.sub.3 CH CH CH N (134) H H CN CH CH CH N (135) H H CF.sub.3 CH CH CH N (136) H H Cl CH CH CH N (137) H H Br CH CH CH N (138) H H CH.sub.3 CH CH N CH (139) H H OCH.sub.3 CH CH N CH (140) H H CN CH CH N CH (141) H H CF.sub.3 CH CH N CH (142) H H Cl CH CH N CH (143) H H Br CH CH N CH (144) H H CH.sub.3 CH N N CH (145) H H OCH.sub.3 CH N N CH (146) H H CN CH N N CH (147) H H CF.sub.3 CH N N CH (148) H H Cl CH N N CH (149) H H Br CH N N CH (150) H OH CH.sub.3 N CH CH CH (151) H OH OCH.sub.3 N CH CH CH (152) H OH CF.sub.3 N CH CH CH (153) H OH Cl N CH CH CH (154) H OH Br N CH CH CH (155) H OH CH.sub.3 CH CH CH N (156) H OH OCH.sub.3 CH CH CH N (157) H OH CF.sub.3 CH CH CH N (158) H OH Cl CH CH CH N (159) H OH Br CH CH CH N (160) H OH CH.sub.3 CH CH N CH (161) H OH OCH.sub.3 CH CH N CH (162) H OH CF.sub.3 CH CH N CH (163) H OH Cl CH CH N CH (164) H OH Br CH CH N CH (165) H OH CH.sub.3 CH N N CH (166) H OH OCH.sub.3 CH N N CH (167) H OH CF.sub.3 CH N N CH (168) H OH Cl CH N N CH (169) H OH Br CH N N CH (170) CH3 H H N CH CH CH (171) CH3 H CH.sub.3 N CH CH CH (172) CH3 H OCH.sub.3 N CH CH CH (173) CH3 H CN N CH CH CH (174) CH3 H CF.sub.3 N CH CH CH (175) CH3 H Cl N CH CH CH (176) CH3 H Br N CH CH CH (177) CH3 H H CH CH CH N (178) CH3 H CH.sub.3 CH CH CH N (179) CH3 H OCH.sub.3 CH CH CH N (180) CH3 H CN CH CH CH N (181) CH3 H CF.sub.3 CH CH CH N (182) CH3 H Cl CH CH CH N (183) CH3 H Br CH CH CH N (184) CH3 H H CH CH N CH (185) CH3 H CH.sub.3 CH CH N CH (186) CH3 H OCH.sub.3 CH CH N CH (187) CH3 H CN CH CH N CH (188) CH3 H CF.sub.3 CH CH N CH (189) CH3 H Cl CH CH N CH (190) CH3 H Br CH CH N CH (191) CH3 H H CH N N CH (192) CH3 H CH.sub.3 CH N N CH (193) CH3 H OCH.sub.3 CH N N CH (194) CH3 H CN CH N N CH (195) CH3 H CF.sub.3 CH N N CH (196) CH3 H Cl CH N N CH (197) CH3 H Br CH N N CH (198) OCH3 H H N CH CH CH (199) OCH3 H CH.sub.3 N CH CH CH (200) OCH3 H OCH.sub.3 N CH CH CH (201) OCH3 H CN N CH CH CH (202) OCH3 H CF.sub.3 N CH CH CH (203) OCH3 H Cl N CH CH CH (204) OCH3 H Br CH CH CH N (205) OCH3 H H CH CH CH N (206) OCH3 H CH.sub.3 CH CH CH N (207) OCH3 H OCH.sub.3 CH CH CH N (208) OCH3 H CN CH CH CH N (209) OCH3 H CF.sub.3 CH CH CH N (210) OCH3 H Cl CH CH CH N (211) OCH3 H Br CH CH CH N (212) OCH3 H H CH CH N CH (213) OCH3 H CH.sub.3 CH CH N CH (214) OCH3 H OCH.sub.3 CH CH N CH (215) OCH3 H CN CH CH N CH (216) OCH3 H CF.sub.3 CH CH N CH (217) OCH3 H Cl CH CH N CH (218) OCH3 H Br CH CH N CH (219) OCH3 H H CH N N CH (220) OCH3 H CH.sub.3 CH N N CH (221) OCH3 H OCH.sub.3 CH N N CH (222) OCH3 H CN CH N N CH (223) OCH3 H CF.sub.3 CH N N CH (224) OCH3 H Cl CH N N CH (225) OCH3 H Br CH N N CH (226) CH3 OH CH.sub.3 N CH CH CH (227) CH3 OH OCH.sub.3 N CH CH CH (228) CH3 OH CF.sub.3 N CH CH CH (229) CH3 OH Cl N CH CH CH (230) CH3 OH Br N CH CH CH (231) CH3 OH CH.sub.3 CH CH CH N (232) CH3 OH OCH.sub.3 CH CH CH N (233) CH3 OH CF.sub.3 CH CH CH N (234) CH3 OH Cl CH CH CH N (235) CH3 OH Br CH CH CH N (236) CH3 OH CH.sub.3 CH CH N CH (237) CH3 OH OCH.sub.3 CH CH N CH (238) CH3 OH CF.sub.3 CH CH N CH (239) CH3 OH Cl CH CH N CH (240) CH3 OH Br CH CH N CH (241) CH3 OH CH.sub.3 CH N N CH (242) CH3 OH OCH.sub.3 CH N N CH (243) CH3 OH CF.sub.3 CH N N CH (244) CH3 OH Cl CH N N CH (245) CH3 OH Br CH N N CH (246) OCH3 OH OCH.sub.3 N CH CH CH (247) OCH3 OH CF.sub.3 N CH CH CH (248) OCH3 OH Cl N CH CH CH (249) OCH3 OH Br N CH CH CH (250) OCH3 OH OCH.sub.3 CH CH CH N (251) OCH3 OH CF.sub.3 CH CH CH N (252) OCH3 OH Cl CH CH CH N (253) OCH3 OH Br CH CH CH N (254) OCH3 OH CF.sub.3 CH CH N CH (255) OCH3 OH Cl CH CH N CH (256) OCH3 OH Br CH CH N CH (257) OCH3 OH OCH.sub.3 CH N N CH (258) OCH3 OH CF.sub.3 CH N N CH (259) OCH3 OH Cl CH N N CH (260) OCH3 OH Br CH N N CH

II. APPLICATION EXAMPLES

(14) II.1. Dyeing of Polyester

(15) Specimens of 10 g of a PES knit-fabric (5-4212) are dyed by a laboratory high temperature dyeing machine Labomat BFA-16 (Mathis) with a dyeing liquor containing 1.0 g/l ammonium sulphate, 0.5 g/l wetting agent, 1.0 g/l dispersing agent,
as well as the 0.218% by weight, based on the weight of the fabric, of the dyestuff Teratop Yellow HL-G-01 150% (supplied by Huntsman), 0.112% by weight, based on the weight of the fabric, of the dyestuff Teratop Red HL (supplied by Huntsman), and 0.142% by weight, based on the weight of the fabric, of the dyestuff Teratop Blue HL-B 150% (supplied by Huntsman) and the compound of formula (103), (111) or (127), respectively, in the amounts given in Table 2 according to the exhaust method (liquor ratio 1:20, 60 min/135 C.). After cooling to about 80 C. the specimens are subjected to a reductive aftertreatment (20 min/75 C.) with a clearing liquor containing 2.0 g/l sodium hydrosulfite, 5.0 g/l 30% NaOH, 1.0 g/l soaping agent (Eriopon OS, supplied by Huntsman) and subsequently rinsed with water and dried.

(16) The dyeings so obtained are tested for hot lightfastness according to DIN 75202 (FAKRA).

(17) The results are summarised in Table 2.

(18) The percentages in Table 2 are % by weight and relate to the weight of the fabric.

(19) TABLE-US-00002 TABLE 2 Hot ligthfastness ratings* of grey dyeings obtained with different amounts of UVA Amount UVA (103) (111) (127) 0% 2.5 2.5 2.5 2% 3.1 3.1 3.3 4% 3.4 3.6 3.7 6% 3.6 3.6 3.8 *1 to 5 decimal rating according to grey scale ISO 105-A02
II.2. Dyeing of Polyester

(20) Specimens of 10 g of a PES knit-fabric (5-4212) are dyed by a laboratory high temperature dyeing machine Labomat BFA-16 (Mathis) with a dyeing liquor containing 1.0 g/l ammonium sulphate, 0.5 g/l wetting agent, 1.0 g/l dispersing agent,
as well as the 0.20% by weight, based on the weight of the fabric, of the dyestuff Teratop Yellow HL-G-01 150% (supplied by Huntsman), 0.11% by weight, based on the weight of the fabric, of the dyestuff Teratop Red HL (supplied by Huntsman), and 0.26% by weight, based on the weight of the fabric, of the dyestuff Teratop Blue HL-GR (supplied by Huntsman) and the compound of formula (110), (116), (121), (133) or (145), respectively, in the amounts given in Table 3 according to the exhaust method (liquor ratio 1:20, 60 min/135 C.).

(21) After cooling to about 80 C. the specimens are subjected to a reductive aftertreatment (20 min/75 C.) with a clearing liquor containing 2.0 g/l sodium hydrosulfite, 5.0 g/l 30% NaOH, 1.0 g/l soaping agent (Eriopon OS, supplied by Huntsman) and subsequently rinsed with water and dried.

(22) The dyeings so obtained are tested for hot lightfastness according to DIN 75202 (FAKRA). The results are summarised in Table 3.

(23) The percentages in Table 3 are % by weight and relate to the weight of the fabric.

(24) TABLE-US-00003 TABLE 3 Hot ligthfastness ratings* of grey dyeings obained with different amounts of UVA Amount UVA (110) (116) (121) (133) (145) 0% 2.6 2.6 2.7 2.7 2.7 2% 3.5 3.8 3.6 3.8 3.8 4% 3.8 4.0 3.9 3.9 4.1 6% 3.9 4.1 3.9 4.2 4.1 *1 to 5 decimal rating according to grey scale ISO 105-A02