Patent ID: 12227898

I. SYNTHESIS EXAMPLES

Example 1.1

Synthesis of the Compound

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).

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.

λmax=280 nm/352 nm.

Example 1.2

Synthesis of the Compound

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).

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).

λmax=280 nm/354 nm.

Examples 1.3-1.16

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

TABLE 1CompoundR1R2R3VWXY(105)HHHNCHCHCH(106)HCH3HNCHCHCH(107)HOCH3HNCHCHCH(108)HClHNCHCHCH(109)HBrHNCHCHCH(110)HHHCHCHCHN(111)HOHHCHCHCHN(112)HCH3HCHCHCHN(113)HOCH3HCHCHCHN(114)HClHCHCHCHN(115)HBrHCHCHCHN(116)HHHCHCHNCH(117)HCH3HCHCHNCH(118)HOCH3HCHCHNCH(119)HClHCHCHNCH(120)HBrHCHCHNCH(121)HHHCHNNCH(122)HCH3HCHNNCH(123)HOCH3HCHNNCH(124)HClHCHNNCH(125)HBrHCHNNCH(126)HHCH3NCHCHCH(127)HHOCH3NCHCHCH(128)HHCNNCHCHCH(129)HHCF3NCHCHCH(130)HHClNCHCHCH(131)HHBrNCHCHCH(132)HHCH3CHCHCHN(133)HHOCH3CHCHCHN(134)HHCNCHCHCHN(135)HHCF3CHCHCHN(136)HHClCHCHCHN(137)HHBrCHCHCHN(138)HHCH3CHCHNCH(139)HHOCH3CHCHNCH(140)HHCNCHCHNCH(141)HHCF3CHCHNCH(142)HHClCHCHNCH(143)HHBrCHCHNCH(144)HHCH3CHNNCH(145)HHOCH3CHNNCH(146)HHCNCHNNCH(147)HHCF3CHNNCH(148)HHClCHNNCH(149)HHBrCHNNCH(150)HOHCH3NCHCHCH(151)HOHOCH3NCHCHCH(152)HOHCF3NCHCHCH(153)HOHClNCHCHCH(154)HOHBrNCHCHCH(155)HOHCH3CHCHCHN(156)HOHOCH3CHCHCHN(157)HOHCF3CHCHCHN(158)HOHClCHCHCHN(159)HOHBrCHCHCHN(160)HOHCH3CHCHNCH(161)HOHOCH3CHCHNCH(162)HOHCF3CHCHNCH(163)HOHClCHCHNCH(164)HOHBrCHCHNCH(165)HOHCH3CHNNCH(166)HOHOCH3CHNNCH(167)HOHCF3CHNNCH(168)HOHClCHNNCH(169)HOHBrCHNNCH(170)CH3HHNCHCHCH(171)CH3HCH3NCHCHCH(172)CH3HOCH3NCHCHCH(173)CH3HCNNCHCHCH(174)CH3HCF3NCHCHCH(175)CH3HClNCHCHCH(176)CH3HBrNCHCHCH(177)CH3HHCHCHCHN(178)CH3HCH3CHCHCHN(179)CH3HOCH3CHCHCHN(180)CH3HCNCHCHCHN(181)CH3HCF3CHCHCHN(182)CH3HClCHCHCHN(183)CH3HBrCHCHCHN(184)CH3HHCHCHNCH(185)CH3HCH3CHCHNCH(186)CH3HOCH3CHCHNCH(187)CH3HCNCHCHNCH(188)CH3HCF3CHCHNCH(189)CH3HClCHCHNCH(190)CH3HBrCHCHNCH(191)CH3HHCHNNCH(192)CH3HCH3CHNNCH(193)CH3HOCH3CHNNCH(194)CH3HCNCHNNCH(195)CH3HCF3CHNNCH(196)CH3HClCHNNCH(197)CH3HBrCHNNCH(198)OCH3HHNCHCHCH(199)OCH3HCH3NCHCHCH(200)OCH3HOCH3NCHCHCH(201)OCH3HCNNCHCHCH(202)OCH3HCF3NCHCHCH(203)OCH3HClNCHCHCH(204)OCH3HBrCHCHCHN(205)OCH3HHCHCHCHN(206)OCH3HCH3CHCHCHN(207)OCH3HOCH3CHCHCHN(208)OCH3HCNCHCHCHN(209)OCH3HCF3CHCHCHN(210)OCH3HClCHCHCHN(211)OCH3HBrCHCHCHN(212)OCH3HHCHCHNCH(213)OCH3HCH3CHCHNCH(214)OCH3HOCH3CHCHNCH(215)OCH3HCNCHCHNCH(216)OCH3HCF3CHCHNCH(217)OCH3HClCHCHNCH(218)OCH3HBrCHCHNCH(219)OCH3HHCHNNCH(220)OCH3HCH3CHNNCH(221)OCH3HOCH3CHNNCH(222)OCH3HCNCHNNCH(223)OCH3HCF3CHNNCH(224)OCH3HClCHNNCH(225)OCH3HBrCHNNCH(226)CH3OHCH3NCHCHCH(227)CH3OHOCH3NCHCHCH(228)CH3OHCF3NCHCHCH(229)CH3OHClNCHCHCH(230)CH3OHBrNCHCHCH(231)CH3OHCH3CHCHCHN(232)CH3OHOCH3CHCHCHN(233)CH3OHCF3CHCHCHN(234)CH3OHClCHCHCHN(235)CH3OHBrCHCHCHN(236)CH3OHCH3CHCHNCH(237)CH3OHOCH3CHCHNCH(238)CH3OHCF3CHCHNCH(239)CH3OHClCHCHNCH(240)CH3OHBrCHCHNCH(241)CH3OHCH3CHNNCH(242)CH3OHOCH3CHNNCH(243)CH3OHCF3CHNNCH(244)CH3OHClCHNNCH(245)CH3OHBrCHNNCH(246)OCH3OHOCH3NCHCHCH(247)OCH3OHCF3NCHCHCH(248)OCH3OHClNCHCHCH(249)OCH3OHBrNCHCHCH(250)OCH3OHOCH3CHCHCHN(251)OCH3OHCF3CHCHCHN(252)OCH3OHClCHCHCHN(253)OCH3OHBrCHCHCHN(254)OCH3OHCF3CHCHNCH(255)OCH3OHClCHCHNCH(256)OCH3OHBrCHCHNCH(257)OCH3OHOCH3CHNNCH(258)OCH3OHCF3CHNNCH(259)OCH3OHClCHNNCH(260)OCH3OHBrCHNNCH

II. APPLICATION EXAMPLES

II.1. Dyeing of Polyester

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 containing1.0 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 containing2.0 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.

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

The results are summarised in Table 2.

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

TABLE 2Hot ligthfastness ratings* of grey dyeingsobtained with different amounts of UVAAmount UVA(103)(111)(127)0%2.52.52.52%3.13.13.34%3.43.63.76%3.63.63.8*1 to 5 decimal rating according to grey scale ISO 105-A02
II.2. Dyeing of Polyester

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 containing1.0 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.).

After cooling to about 80° C. the specimens are subjected to a reductive aftertreatment (20 min/75° C.) with a clearing liquor containing2.0 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.

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

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

TABLE 3Hot ligthfastness ratings* of grey dyeings obainedwith different amounts of UVAAmount UVA(110)(116)(121)(133)(145)0%2.62.62.72.72.72%3.53.83.63.83.84%3.84.03.93.94.16%3.94.13.94.24.1*1 to 5 decimal rating according to grey scale ISO 105-A02