Benzotriazole derivative compound

Abstract

Provided are benzotriazole derivative compounds of the general formula that are novel compounds capable of strongly absorbing light in the ultraviolet range, particularly 300-330 nm, while strongly absorbing light in the visible light short-wavelength range up to around 450 nm and being used suitably as a light absorber having high light fastness with a light-blocking function over an extended period of time. Preferably, R.sub.1 is a hydrogen atom or alkyl group, R.sub.2 is a C1-8 alkyl group, R.sub.3 is a hydrogen atom, alkyl group, acryloyloxyalkyl group, or methacryloyloxyalkyl group.

Claims

1. A benzotriazole derivative compound represented by the following general formula (1): ##STR00011## wherein R.sub.1 in the above general formula (1) a branched alkyl group whose carbon number is 3 to 8, wherein R.sub.2 in the above general formula (1) is an alkyl group whose carbo number is 1 to 8, and wherein R.sub.3 in the above general formula (1) is a hydrogen atom, an alkyl group whose carbon number is 1 to 8, an acryloyl oxyalkyl group whose alkyl carbon number is 1 to 2, or a methacryloyl oxyalkyl group whose alkyl carbon number is 1 to 2.

2. A light-absorber inducing the benztriazole derivative compound according to claim 1.

3. A light-absorbing rain composition wherein the benzotriazole derivative compound according to claim 1 is compounded in a rein.

4. The benzotriazole derivative compound according to claim 1, wherein R.sub.1 is tert-butyl.

Description

EXAMPLES

(1) Hereinafter, a method of synthesizing the benzotriazole derivative compound experimented in the present invention, and properties of the compound are shown. However, the present invention is not limited to these embodiments.

Example 1

Synthesis of Compound (a); 2-methacryloyloxyethyl 2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

(2) ##STR00005##

(3) To a four-neck flask of 200 ml, a balled condenser, a thermometer, and a mixing device were attached, in which 100 ml of water, 6.5 g (0.061 mol) of sodium carbonate, 20.0 g (0.110 mol) of 4-amino-3-nitro benzoic acid were put and dissolved, to which 22.7 g (0.118 mol) of an aqueous solution of 36% sodium nitrite were added. To a four-neck flask of 500 ml, a balled condenser, a thermometer, and a mixing device were attached, in which 100 ml of water and 43.0 g (0.274 mol) of 62.5% sulfuric acid and cooled to 3 to 7 C., onto which the mentioned solution was dripped, followed by mixing it at the same temperature for 2 hours to obtain an aqueous solution of diazonium salt. To a four-neck flask of 1000 ml, a balled condenser, a thermometer, and a mixing device were attached, in which 18.0 g (0.100 mol) of 2-tert-butyl-4-methoxyphenol, 10 ml of isopropyl alcohol, and 140 ml of water were put and mixed, onto which an aqueous solution of diazonium salt was dripped at 5 to 10 C. for 2 hours, further followed by mixing for 12 hours at 10 to 15 C. to obtain a slurry liquid of 2-tert-butyl-6-(4-carboxy-2-nitrophenylazo)-4-methoxyphenol. 27.8 g (0.222 mol) of an aqueous solution of 32% sodium hydroxide and 200 ml of isopropyl alcohol were added thereto, followed by removing a water layer in a bottom layer at 70 C. 30.0 g (0.222 mol) of an aqueous solution of 32% sodium hydroxide, 200 ml of water, and 0.4 g of hydroquinone were added thereto, followed by dripping 6.0 g (0.072 mol) of 60% hydraxine-hydrate at 40 to 50 C. for 1 hour, followed by mixing at the same temperature for 2 hours. Then the pH value was adjusted to 4 by 62.5% sulfuric acid, followed by filtering, rinsing, and drying the generated sediment to obtain 23.6 g of 5-carboxy-2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole N-oxide.

(4) To a four-neck flask of 500 ml, a balled condenser, a thermometer, and a mixing device were attached, in which 23.6 g (0.066 mol) of 5-carboxy-2-(3-tert-butyl-2-hydroxy-5-5methoxyphenyl)-2H-benzotriazole N oxide, 100 ml of isopropyl alcohol, 100 ml of water, and 24.0 g (0.192 mol) of an aqueous solution of 32% sodium hydroxide were put, to which 12.0 g (0.11 mol) of a thiourea dioxide was added at 70 to 80 C. taking for 3 hours. It was mixed at the same temperature for 1 hour, followed by removing the water layer in the bottom layer by separating it, followed by adjusting the pH value to 4 by using 62.5% sulfuric acid, further followed by filtering, rinsing, and drying the generated sediment, thereby obtaining 20.3 g of 5-carboxy-2-(3-tert-butyl-2-hydroxy-5-5methoxyphenyl)-2H-benzotriazole.

(5) To a four-neck flask of 300 ml, a balled condenser, a thermometer, and a mixing device were attached, to which 20.3 g (0.059 mol) of 5-carboxy-2-(3-tert-butyl-2-hydroxy-5-5methoxyphenyl)-2H-benzotriazole, 100 ml of toluene, 13.0 g (0.109 mol) of thionyl chloride, and 2.0 ml of N,N-dimethylformamide were put and were mixed at 60 to 70 C. for 3 hours. Subsequently, by depression, the solvent was recovered, followed by adding 100 ml of toluene, 14.0 g (0.108 mol) of methacrylic acid 2-hydroxyethyl, and 8.3 g (0.105 mol) of pyridine, and were mixed at 60 to 70 C. for 1 hour. 20 ml of water and 9.0 g(0.057 mol) of 62.5% sulfuric acid were added thereto and the water layer of the bottom layer were separated at 60 to 70 C. and removed, followed by recovering the toluene by depression, to which 90 ml of isopropyl alcohol was added, further followed by filtering, rinsing, and drying the generated sediment thereby obtaining a coarse crystal. This coarse crystal was recrystallized to obtain 22.2 g of compound (a). The yield was 49% (from 2-tert-butyl-4-methoxyphenol). A melting point was 124 C.

(6) In the meantime, by HPLC analysis, a purity of the compound (a) was measured.

(7) <Condition of Measurement>

(8) Apparatus: L-2130 (Hitachi High-Technologies Corporation)

(9) Column used: SUMIPAX ODS A-212 6.0150 mm 5 m

(10) Column temperature:40 C.

(11) Mobile phase: methanol/water=95/5 (3 ml phosphoric acid/L)

(12) Flow velocity: 1.0 ml/min

(13) Detection: UV250 nm

(14) <Result of Measurement>

(15) HPLC surface purity: 98.5%

(16) For information, the HPLC measurement was conducted under the same measurement condition as above in the following Examples 2 to 5.

(17) The ultraviolet-visible absorption spectrum of the compound (a) was measured, and it was found that the maximum absorption wavelength Imax was 313.2 nm and 382.8 nm, respectively, and the molar extinction coefficient of the wavelength was 14800 and 12700, respectively. The spectrum is shown in FIG. 1. The measurement condition of the spectrum is as follows:

(18) <Condition of Measurement>

(19) Apparatus: UV-2450 (Shimadzu Corporation)

(20) Measurement wavelength: 250 to 500 nm

(21) Solvent: chloroform

(22) Concentration: 10 ppm

(23) For information, the ultraviolet-visible absorption spectrum was measured under the same measurement condition as above in the following Examples 3 to 6.

(24) Further, as the result of the NMR measurement of the compound (a), the above structure was supported. The measurement condition is as follows:

(25) <Condition of Measurement>

(26) Apparatus: JEOL JNM-AL300

(27) Resonant frequency: 300 MHz (1H-NMR)

(28) Solvent: chloroform-d

(29) As an internal standard substance of 1H-NMR, tetramethylsilane was used, and the chemical shift value was represented by value (ppm) and the coupling constant was represented by Hertz. Further, s represents an abbreviation of singlet, d that of doublet, t that of triplet, and m that of multiplet. The same is applied to the following Examples 2 to 6. For information, in the following Examples 2 to 6, the NMR measurement was conducted as in the present Example. The content of the NMR spectrum obtained is as follows:

(30) =11.44 (s, 1H, phenol-OH), 8.73 (m, 1H, benzotriazole-H), 8.13 (d, 1H, J=9.0 Hz, benzotriazole-H), 7.98 (d, 1H, J=11.1 Hz, benzotriazole-H), 7.82 (s, 1H, phenol-H), 7.05 (s, 1H, phenol-H), 6.18 (s, 1H, CCH.sub.2H), 5.62 (s, 1H, CCH.sub.2H), 4.65 (m, 2H, methacryloyl-OC H.sub.2H), 4.56 (m, 2H, benzotriazole-COOCH.sub.2H), 3.93 (s, 3H, phenol-OCH.sub.3H), 1.98 (s, 3H, CH.sub.2CCH.sub.3H), 1.56 (s, 9H, tert-butyl-1H)

Example 2

Synthesis of Compound [b]; 2-acryloyloxyethyl 2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

(31) ##STR00006##

(32) Compound (b) was obtained with the yield of 46% (from 2-tert-butyl-4-methoxyphenyl) in the same manner as in Example 3 except that acrylate acid 2-hydroxyethyl was used instead of methacrylate acid 2-hydroxyethyl. The melting point was 126 C. and the HPLC surface purity was 98.1%.

(33) Further, when the ultraviolet-visible absorption spectrum of the compound (b) was measured, the maximum absorption wavelength max was 313.2 nm and 380.6 nm, respectively, and the molar extinction coefficient of the wavelength was 15400 and 13100, respectively. The spectrum is shown in FIG. 2. The measurement condition of the spectrum is as follows:

(34) <Condition of Measurement>

(35) Apparatus: UV-1850 (Shimadzu Corporation)

(36) Measurement wavelength: 250 to 500 nm

(37) Solvent: chloroform,

(38) Concentration: 10 ppm

(39) Further, as the result of the NMR measurement of the compound (b), the above structure was supported. The measurement condition is as follows:

(40) =11.39 (s, 1H, phenol-OH), 8.72 (s, 1H, benzotriazole-H), 8.12 (d, 1H, J=9.0 Hz, benzotriazol-H), 7.96 (d, 1H, J=9.0 Hz, benzotriazole-H), 7.81 (s, 1H, phenol-H), 7.05 (s, 1H, phenol-H), 6.46 (m, 1H, CHCH.sub.2H), 6.20 (m, 1H, CH.sub.2=CHH), 5.89 (m, 1H, CHCH.sub.2H), 4.64 (m, 2H, acryloyl-OCH.sub.2H) 4.57 (m, 2H, acryloyl-OCH.sub.2CH.sub.2H), 3.81 (s, 3H, phenyl-OCH.sub.3H),

Example 3

Synthesis of Compound (c); methyl 2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

(41) ##STR00007##

(42) Compound (c) was obtained with the yield of 53% (from 2-tert-butyl-4-methoxyphenyl) in the same manner as in Example 1 except that methy alcohol was used instead of met acrylate acid 2-hydroxyethyl. The melting point was 154 C. and the HPLC surface purity was 99.4%. The maximum absorption wavelength max was 312.6 nm and 381.6 nm, respectively, and the molar extinction coefficient of the wavelength was 14800 and 13000, respectively. The spectrum is shown in FIG. 3.

(43) Further, as the result of measuring the NMR of the compound (c), the above structure was supported. The content of the obtained NMR is as follows:

(44) =11.40 (s, 1H, phenol-OH), 8.69 (s, 1H, benzotriazole-H), 8.10 m, 1H, benzotriazole-H), 7.96 (m, 1H, benzotriazole-H), 7.80 (s, 1H, phenol-H), 7.04 (s, 1H, phenol-H), 4.04 (s, 3H, benzotriazole-COOCH.sub.3H), 3.84 (s, 3H, phenol-OCH.sub.3H), 1.50 (s, 9H, tert-butyl-H)

Example 4

Synthesis of Compound (d); octyl 2-3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

(45) ##STR00008##

(46) Compound (d) was obtained with the yield of 32% (from 2-tert-butyl-4-methoxyphenyl) in the same manner as in Example 1 except that octyl alcohol was used instead of methacrylate acid 2-hydroxyethyl. The melting point was 130 C. and the HPLC surface purity was 99.7%. The maximum absorption wavelength max was 312.8 nm and 379.8 nm, respectively, and the molar extinction coefficient of the wavelength was 14600 and 13000, respectively. The spectrum is shown in FIG. 4.

(47) Further, as the result of measuring the NMR of the compound (d), the above structure was supported. The content of the obtained NMR is as follows.

(48) =11.44 (s, 1H, phenol-OH), 8.71 (s, 1H, benzotriazole-H), 8.11 (d, 1H, J=1.5 Hz, benzotriazole-H), 7.97 (m, 1H, benzotriazole-H), 7.81 (s, 1H, phenol-H), 7.05 (s, 1H, phenol-H), 439 (m, 2H, benzotriazole-COOCH.sub.2H), 3.90 (s, 3H, phenol-OCH.sub.3H), 1.50 (m, 21H, octyl-CH.sub.2, tert-butyl-H), 0.90 (m, 3H, octyl-CH.sub.3)

Example 5

Synthesis of Compound (e); 2-ethylhexyl 2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

(49) ##STR00009##

(50) Compound (e) was obtained with the yield of 37% (from 2-tert-butyl-4-methoxyphenyl) in the same manna as in Example 1 except that 2-ethylhexyl alcohol was used instead of methacrylate acid 2-hydroxyethyl. The melting point was 81 C. and the HPLC surface purity was 99.8%. The maximum absorption wavelength max was 312.8 nm and 379.8 nm, respectively, and the molar extinction coefficient of the wavelength was 15100 and 13100, respectively. The spectrum is shown in FIG. 5.

(51) Further, as the result of measuring the NMR of the compound (e), the above structure was supported. The content of the obtained NMR is as follows.

(52) =11.46 (s, 1H, phenol-OH), 8.73 (s, 1H, benzotriazole-H), 8.13 (d, 1H, J=9.0 Hz, benzotriazole-H), 7.97 (d, 1H, J=9.0 Hz, benzotriazole-H), 7.82 (s, 1H, phenol-H), 7.05 (s, 1H, phenol-H), 4.32 (m, 2K, benzotriazole-COOCH.sub.2H), 3.90 (s, 3H, phenol-OCH.sub.3H), 1.50 (m, 18H, tert-butyl)-H, 2-ethylhexyl-CH.sub.2, 2-ethylhexyl-CH), 0.96 (m, 6H, 2-ethylhexyl-CH.sub.3)

Example 6

Synthesis of Compound (f); 2-methacyloyl oxyethyl 2-(2-hydroxy-5methoxyphenyl)-2H-benzotriazole-5-carboxylate

(53) ##STR00010##

(54) Compound (f) was obtained with the yield of 5% (from 4-methoxyphenyl) in the same manner as in Example 1 except that 4-methoxyphenol was used instead of 2-tert-butyl-4-methoxyphenol. The melting port was 94 C. and the maximum absorption wavelength max was 309.8 nm and 373.2 nm, respectively, and the molar extinction coefficient of the wavelength was 14700 and 13100 respectively. The spectrum is shown in FIG. 6

(55) Further, by HPLC analysis, a purity of the compound (e) was measured.

(56) <Condition of Measurement>

(57) Apparatus: L-2130 Q-Hitachi High-Technologies Corporation)

(58) Column used: Inestsil ODS-3 4.6150 mm 5 m

(59) Column temperature:25 C.

(60) Mobile phase: acetonitrile/water 9/1 (phosphoric acid 3 ml/L)

(61) Flow velocity: 1.0 ml/min

(62) Detection: UV250 nm

(63) <Result of Measurement>

(64) HPLC surface purity: 93.4%

(65) Further, as the result of measuring the NMR of the compound (f), the above structure was supported. The content of the obtained NMR is as follows.

(66) =10.71 (s, 1H, phenol-OH), 8.73 (s, 1H benzotriazole-H), 8.12 (d, 1H, J=9.6 Hz, benzotriazole-H), 7.98 (d, 1H, J=9.6 Hz, benzotriazole-H), 7.15 (m, 3H, phenol H), 6.18 (s, 1H, CCH.sub.2H), 5.62 (s, 1H, CCH.sub.2H), 4.65 (m, 2H, methacryloyl-OCH.sub.2H), 4.57 (m, 2H, benzotriazole-COOCH.sub.2H), 3.89 (s, 3H, phenol-OCH.sub.3H), 1.98 (s, 3H, CH.sub.2CCH.sub.3H)

Comparative Example

(67) As a comparative example, a compound (g); 3-(2H-benzotriazole-2-yl)-4-hydroxyphenethyl methacrylate that is a conventionally general ultraviolet light absorber was synthesized.

(68) (Preparation of a Light Absorbing Film)

(69) 0.1 g of compound (e) obtained in Example 5, 1.9 g of polymethyl methacrylate, 4.0 g of methylethylketone, and 4.0 g of toluene were mixed and dissolved to obtain a solution of a resin composition having a light absorber. Then the obtained solution of the resin composition having a light absorber was applied onto a glass plate (2 mm thick) by using a bar coater No. 20, followed by heating and drying at 90 C. for 2 minutes, then followed by heating and drying at 120 C. for 3 minutes. After that, drying under reduced pressure was implemented at 40 C. for 12 hours to remove the solvent thereby obtaining a film of polymethyl methacrylate having 5% light absorber with the film thickness of 4 m. In the meantime, the compounds (g) synthesized in Comparative Example was copolymerized with methyl methacrylate to prepare a copolymer that includes 5% light absorber, followed by filming them by the same method as in compound (e) thereby obtaining a film of polymethyl methacrylate having 5% light absorber with the film thickness of 4 m.

(70) [Light Blocking Test]

(71) By placing the film of polymethyl methacrylate having 5% light absorber of the compounds (e) and (g) that were obtained in the above mentioned methods on transfer films of yellow dyes, cyan dyes, and magenta dyes, that are used for commercially available sublimation transfer type compact photo printer (Canon SELPHY CP600) to protect the transfer films, followed by irradiating simulated solar light for 100 hours by a weather meter to see color fading Five criteria were set in which Level 5 signifies no fading, level 4 little fading, level 3 fading to some extent, level 2 much fading and level 1 complete fading. The results evaluated based on the above are shown in Table 1.

(72) TABLE-US-00001 TABLE 1 Light absorbing Compound (g) No film film Compound (e) (Comparison) (Comparison) Evaluation result 5 3 2 of light blocking test

(73) From Table 1, it is found that compared with the conventional light absorber, the product related to the present invention has higher light blocking function for a long term, and therefore, it can be said that the product related to the present invention is a useful light absorber. For information, the condition of the light blocking test for the films in which the compound obtained from Examples and Comparative Example is as follows.

(74) <Condition of Light Blocking Test>

(75) Apparatus: Superxenon weather meter SX-75 (Suga Test Instruments Co., Ltd)

(76) Irradiation intensity: 180 W/m.sup.2

(77) Irradiation time: 100 hours

(78) Black panel temperature: 63 C.

(79) Tank moisture: 50%

(80) Industrial Availability

(81) The benzotriazole derivative compound of the present invention exhibits a maximum absorption wavelength in a vicinity of 310 nm and 380 nm, with excellent ultraviolet light blocking function and excellent light blocking function for a visible light short wavelength range, and therefore, the light blocking function is not damaged even when exposed to solar light for a long time. Thus, it can be utilized for a material that deteriorates with ultraviolet light and the light of a visible light short wavelength range and for protection of a human body.

BRIEF EXPLANATION OF DRAWINGS

(82) FIG. 1 shows UVvisible absorption spectrum of a compound (a).

(83) FIG. 2 shows UVvisible absorption spectrum of a compound (b)

(84) FIG. 3 shows UVvisible absorption spectrum of a compound (c).

(85) FIG. 4 shows UVvisible absorption spectrum of a compound (d).

(86) FIG. 5 shows UVvisible absorption spectrum of a compound (e).

(87) FIG. 6 shows UVvisible absorption spectrum of a compound (f).