Process for preparing 2-hydroxyphenyl alkenyl benzotriazole compounds; use of the said compounds obtained via the process in the synthesis of siloxane compounds containing a 2-hydroxyphenylbenzotriazole function

Patent metadata

Field	Value
Publication number	US-9447123-B2
Application number	US-201013814539-A
Country	US
Kind code	B2
Filing date	Oct 25, 2010
Priority date	Oct 25, 2010
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

The process for preparing 2-hydroxyphenyl alkenyl benzotriazole compounds and the process for preparing siloxane compounds containing 2-hydroxyphenyl benzotriazole function are disclosed.

First claim

The invention claimed is:

1. A process for preparing a 2-hydroxyphenyl alkenyl benzotriazole compound, the process comprising:
1) reacting a 2-hydroxyphenylbenzotriazole compound in water, at least one organic solvent with a boiling point of greater than 200° C., or both, with an alkenyl halide in the presence of at least one phase-transfer agent and at least one base to obtain a 2-O-alkenylphenylbenzotriazole compound; and
2) heating a reaction mixture comprising the 2-O-alkenylphenylbenzotriazole compound and at least one organic solvent with a boiling point of greater than 200° C. to a temperature above 170° C. to form a 2-hydroxyphenyl alkenyl benzotriazole compound.

2. The process according to claim 1 , comprising:
i) the reacting 1) to obtain the 2-O-alkenylphenylbenzotriazole;
ii) cooling the reaction mixture comprising the 2-O-alkenylphenylbenzotriazole compound to room temperature and optionally diluting a resulting reaction medium with water, the organic solvent with a boiling point of greater than 200° C., or both;
iii) removing water from the reaction medium;
iv) heating a resulting reaction mixture comprising the 2-O-alkenylphenylbenzotriazole compound to a temperature of greater than 170° C. in the presence of at least one organic solvent with a boiling point of greater than 200° C. to form a 2-hydroxylphenyl alkenyl benzotriazole compound;
v) removing at least one solvent from the 2-hydroxyphenyl alkenyl benzotriazole compound; and
vi) recrystallizing the 2-hydroxyphenyl alkenyl benzotriazole compound in the presence of at least one recrystallization solvent.

3. The process according to claim 1 , which occurs in a single reactor.

4. The process according to claim 1 , wherein:
a 2-hydroxyphenyl alkenyl benzotriazole compound of formula (1) below is prepared:

n represents an integer between 0 and 3 inclusive;
T independently represents a linear or branched C 1 -C 8 alkyl radical, a halogen, or a linear or branched C 1 -C 4 alkoxy radical;
R 1 represents hydrogen or a methyl radical; and
the process comprises:
1) reacting a compound of formula (5):

in the water, the at least one organic solvent with a boiling point of greater than 200° C., or both, in the presence of the at least one phase-transfer agent and the at least one base, with an alkenyl halide of formula (6):

wherein X represents a halogen atom, and R 1 represents hydrogen or methyl, to obtain a compound of formula (7):

 and
(2) heating a reaction mixture comprising the compound of formula (7) to a temperature of greater than 170° C. in the presence of at least one organic solvent with a boiling point of greater than 200° C.

5. The process according to claim 1 , wherein the organic solvent is a water-immiscible solvent having a boiling point of greater than 200° C.

6. The process according to claim 1 , wherein:
a temperature of the reaction mixture during the reacting 1) is between 20° C. and 150° C.; and
a temperature of the reaction mixture during the heating 2) is between 170° C. and 250° C.

7. The process according to claim 1 , wherein the 2-hydroxyphenylbenzotriazole compound is selected from the group consisting of 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2-(2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole.

8. The process according to claim 1 , wherein the alkenyl halide is selected from the group consisting of 1-chloro-2-propene, 1-bromo-2-propene, 1-chloro-2-methyl-2-propene and 1-bromo-2-methyl-2-propene.

9. The process according to claim 1 , wherein, in the reacting 1):
the alkenyl halide is present in a ratio ranging from 1.05 to 1.7 equivalents relative to the 2-hydroxyphenylbenzotriazole compound; and
a concentration of the 2-hydroxyphenylbenzotriazole compound ranges from 5% to 80% by weight relative to the total weight of the reaction medium.

10. The process according to claim 1 , wherein the phase-transfer agent is at least one selected from the group consisting of a tetrabutylammonium halide, tetrabutylammonium hydrogenosulfate, benzyltrimethyl-ammonium chloride and a preformed catalyst formed by reacting tributylamine with an alkenyl halide.

11. The process according to claim 1 , wherein the at least one phase-transfer agent is present in a ratio ranging from 3 mol % to 15 mol % relative to the 2-hydroxyphenylbenzo-triazole compound.

12. The process according to claim 1 , wherein the base is an alkaline-earth metal base.

13. Process according to claim 1 , wherein the at least one base is present in a ratio ranging from 0.7 to 1.5 equivalents relative to the 2-hydroxyphenylbenzotriazole compound.

14. The process according to claim 1 , wherein the organic solvent is at least one selected from the group consisting of benzyl alcohol, diethylene glycol monobutyl ether, diphenyl ether, tetralin, methylnaphthalene and a biphenyl/diphenyl ether mixture.

15. The process according to claim 2 , wherein the recrystallization solvent is selected from the group consisting of isopropanol, methanol, ethanol, benzyl alcohol, and mixtures thereof.

16. A process for preparing a siloxane compound containing a benzotriazole, the process comprising hydrosilylating the 2-hydroxyalkenylphenylbenzotriazole compound prepared according to claim 1 in the presence of a catalyst and of a solvent with a siloxane comprising an SiH function.

17. The process according to claim 16 , wherein:
the siloxane compound is represented by formula (4):

wherein:
R independently represents a linear or branched and optionally halogenated or unsaturated C 1 -C 30 alkyl radical, a C 6 -C 12 aryl radical, a linear or branched C 1 -C 10 alkoxy radical or a group —OSi(CH 3 ) 3 ;
a represents an integer between 0 and 2 inclusive;
n represents an integer between 0 and 3 inclusive;
T independently represents a linear or branched C 1 -C 8 alkyl radical, a halogen, or a linear or branched C 1 -C 4 alkoxy radical;
R 1 represents hydrogen or a methyl radical;
the siloxane compound of formula (4) optionally further comprises at least one unit of formula:

wherein
b represents 1, 2 or 3; and
the process comprises at least
hydrosilylating a 2-hydroxyalkenylphenylbenzotriazole compound of formula (1):

with a siloxane of formula (2):

in the presence of the catalyst and the solvent.

18. The process according to claim 17 , wherein:
the compound Drometrizole Trisiloxane corresponding to formula (C):

is prepared; and
t

Assignees

• Richard Herve
• Xu Jinzhu
• Guerreiro Patricio
• Wang Yuan
• Guo Jianping
• Oreal

Inventors

• Richard Herve
• Xu Jinzhu
• Guerreiro Patricio
• Wang Yuan
• Guo Jianping

Classifications

• C07F7/0838

  Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21) · CPC title

• C07D249/20 Primary

  with aryl radicals directly attached in position 2 · CPC title

• C07F7/0879 Primary

  Hydrosilylation reactions · CPC title

• A61Q17/04

  Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations · CPC title

• C07F7/0849

  Chemistry & Metallurgy · mapped topic