SULFUR-CONTAINING PHENOL DERIVATIVES

Abstract

The present invention relates to a novel process for preparing sulfur-containing phenolic compounds, and to novel phenol derivatives substituted with at least one radical comprising a sulfur atom. Said sulfur-containing phenolic compounds are of use in numerous industrial fields, particularly the chemical industry, and said compounds are particularly suitable as, for example, antioxidant agents, UV stabilizers, heat stabilizers, and for other uses.

Claims

1. A process for preparing, from raw materials of renewable origin, sulfureous phenolic compounds corresponding to formula (1) below: ##STR00019## in which: A represents a radical R.sup.1 or a radical of formula A.sup.m: ##STR00020## R.sup.1 is chosen from a hydrogen atom, a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms and a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; R.sup.2 is chosen from a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms and a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; R.sup.3 represents a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms; R.sup.4, R.sup.7 and R.sup.8, which may be identical or different, are chosen, independently of each other, from a hydrogen atom, a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms and a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; G is chosen from S.sub.c, (CH.sub.2).sub.a, C(CH.sub.3).sub.2, [S(O).sub.b].sub.c and W, in which W is an aromatic group, optionally substituted with one or more alkyl groups; T is chosen from a single bond, S.sub.v, (CH.sub.2).sub.t, C(CH.sub.3).sub.2, and [S(O).sub.u].sub.v; X and Y, independently of each other, each represent a radical chosen from a hydrogen atom and linear or branched hydrocarbon-based groups, comprising from 1 to 20 carbon atoms, and optionally comprising one or more heteroatoms chosen from oxygen, nitrogen and sulfur; a and t, which may be identical or different and independently of each other, each represent an integer between 1 and 9 and preferably between 1 and 3, limits inclusive; b and u, which may be identical or different and independently of each other, each represent an integer equal to 1 or 2; c and v, which may be identical or different and independently of each other, each represent an integer between 1 and 6, limits inclusive; m represents 0, or an integer between 1 and 20, limits inclusive; n represents an integer between 8 and 20, limits inclusive; p represents an integer between 1 and 10, limits inclusive; it being understood that at least one of the groups R.sup.1, R.sup.2 or R.sup.4 represents a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3, in which R.sup.3, X, Y, n and p are as defined above, said process comprising at least steps a) to c) below: a) reacting a mercapto alkoxide of formula (2): ##STR00021## in which R.sup.3, X, Y and n are as defined previously, with an amine compound of formula (3): ##STR00022## in which R.sup.4 and p are as defined previously and R and R, which may be identical or different, are chosen, independently of each other, from a hydrogen atom, a linear or branched alkyl radical comprising from 1 to 6 carbon atoms, or form, together with the nitrogen atom that bears them, a heterocycle, R.sup.5 represents a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms or a group (CH.sub.2).sub.pNRR, and R.sup.6 is chosen from a hydrogen atom, a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms, and a group (CH.sub.2).sub.pNR/R, b) optionally, reacting the compound obtained in step a) with a compound of formula (4): ##STR00023## in which R, R.sup.7, R.sup.8, m and G are as defined previously, via an aromatic electrophilic substitution reaction, and c) extracting and then optionally purifying the compound of formula (1).

2. The process according to claim 1, wherein the radicals X and Y of the compound of formula (1) each represent a hydrogen atom.

3. The process according to claim 1, wherein the radical R.sup.4 of the compound of formula (1) represents a hydrogen atom.

4. The process according to claim 1, wherein the compound of formula (1) has at least one of the following characteristics: R.sup.1 is chosen from a hydrogen atom and a linear or branched hydrocarbon-based group comprising from 1 to 6 carbon atoms; R.sup.2 represents a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; R.sup.3 represents methyl or ethyl; R.sup.4 represents a hydrogen atom; T is chosen from a single bond, S.sub.v, (CH.sub.2).sub.t and C(CH.sub.3).sub.2; X represents a radical chosen from a hydrogen atom and methyl, ethyl, propyl and butyl radicals; Y represents a hydrogen atom; t represents an integer between 1 and 3, limits inclusive; v represents an integer between 1 and 6, limits inclusive; m represents 0, or an integer between 1 and 6, limits inclusive; n represents an integer between 8 and 12, limits inclusive; and p is equal to 1.

5. The process according to claim 1, wherein the compound of formula (4) is selected from the group consisting of phenol/aldehyde resins, sulfureous phenolic resins and phenolic resins with gem-dimethyl bridges derived from the oligomerization reaction of ortho-isopropenyl-para-alkylphenol.

6. The process according to claim 1, comprising at least the following steps: a1) transesterifyinq at least one triglyceride, in the presence of an alcohol, and removing the glycerol formed, to obtain an unsaturated ester; a1) optionally, treating said unsaturated ester by metathesis or pyrolysis; a2) sulhydratinq the unsaturated ester from step a1) or a1) to obtain the mercapto ester of formula (2) as defined previously; a) reacting the mercapto ester of formula (2) with an amine phenolic compound of formula (3); b) optionally, reacting the compound obtained in step a) with a compound of formula (4), optionally in the presence of a reagent bearing the group T; c) extracting and then optionally purifying the compounds obtained in step b).

7. The process according to claim 1, wherein the raw material of renewable origin is a triglyceride originating from animal or plant oils or fats, selected from the group consisting of soybean oil, sunflower oil, linseed oil, rapeseed oil, castor oil, palm oil, palm kernel oil, coconut oil, jatropha oil, cotton seed oil, groundnut oil, olive oil, vernonia oil, cuphea oil, hevea oil, lunaria oil, safflower oil, camellina oil, Calophyllum inophyllum oil, Pongamia pinnata oil, beef tallow, and cooking oil and grease.

8. A compound of formula (1): in which: ##STR00024## A represents a radical R.sup.1 or a radical of formula A.sup.m: ##STR00025## R.sup.1 is chosen from a hydrogen atom, a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms and a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; R.sup.2 is chosen from a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms and a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; R.sup.3 represents a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms; R.sup.4, R.sup.7 and R.sup.8, which may be identical or different, are chosen, independently of each other, from a hydrogen atom, a linear or branched hydrocarbon-based group comprising from 1 to 20 carbon atoms and a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; G is chosen from S.sub.c, (CH.sub.2).sub.a, C(CH.sub.3).sub.2, [S(O).sub.b].sub.c and W, in which W is an aromatic group, optionally substituted with one or more alkyl groups; T is chosen from a single bond, S.sub.v, (CH.sub.2).sub.t, C(CH.sub.3).sub.2 and [S(O).sub.u].sub.v; X and Y, independently of each other, each represent a radical chosen from a hydrogen atom and linear or branched hydrocarbon-based groups, comprising from 1 to 20 carbon atoms, and optionally comprising one or more heteroatoms chosen from oxygen, nitrogen and sulfur; a and t, which may be identical or different and independently of each other, each represent an integer between 1 and 9 and preferably between 1 and 3, limits inclusive; b and u, which may be identical or different and independently of each other, each represent an integer equal to 1 or 2; c and v, which may be identical or different and independently of each other, each represent an integer between 1 and 6, limits inclusive; m represents 0, or an integer between 1 and 20, limits inclusive; n represents an integer between 8 and 20, limits inclusive; p represents an integer between 1 and 10, limits inclusive; subject to the proviso that at least one of the groups R.sup.1, R.sup.2 or R.sup.4 represents a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3, in which R.sup.3, X, Y, n and p are as defined above, and subject to the proviso that when p=1, then A represents a radical of formula A.sup.m.

9. The compound according to claim 8, wherein the radicals X and Y each represent a hydrogen atom.

10. The compound according to claim 8, wherein the radical R.sup.4 represents a hydrogen atom.

11. The compound according to claim 8, having at least one of the following characteristics: R.sup.1 is selected from a hydrogen atom, a linear or branched hydrocarbon-based group comprising from 1 to 12 carbon atoms or a group (CH.sub.2).sub.p13 SC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; R.sup.2 is selected from a linear or branched hydrocarbon-based group comprising from 1 to 12 carbon atoms or a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; R.sup.3 represents a linear or branched hydrocarbon-based group comprising from 1 to 6 carbon atoms; R.sup.4 is selected from a hydrogen atom or a linear or branched hydrocarbon-based group comprising from 1 to 6 carbon atoms; T is selected from a single bond, S.sub.v, (CH.sub.2).sub.t or C(CH.sub.3).sub.2; X and Y, independently of each other, each represent a radical selected from a hydrogen atom or linear or branched alkyl radicals comprising from 1 to 6 carbon atoms; t represents an integer between 1 and 3, limits inclusive; v represents an integer between 1 and 6, limits inclusive; m represents 0, or an integer between 1 and 10, limits inclusive; n represents an integer between 8 and 20, limits inclusive; p represents 2; subject to the proviso that at least one of the groups R.sup.1 or R.sup.2 represents a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3, in which R.sup.3, X, Y, n and p are as defined above.

12. The compound according to claim 8, having at least one of the following characteristics: R.sup.1 is selected from a hydrogen atom or a linear or branched hydrocarbon-based group comprising from 1 to 6 carbon atoms; R.sup.2 represents a group (CH.sub.2).sub.pSC(XY)(CH.sub.2).sub.nC(O)OR.sup.3; R.sup.3 represents methyl or ethyl; R.sup.4 represents a hydrogen atom; T is selected from a single bond, S.sub.v, (CH.sub.2).sub.t or C(CH.sub.3).sub.2; X represents a radical selected from a hydrogen atom or methyl, ethyl, propyl or butyl radicals; Y represents a hydrogen atom; t represents an integer between 1 and 3, limits inclusive; v represents an integer between 1 and 6, limits inclusive; m represents 0, or an integer between 1 and 6, limits inclusive; n represents an integer between 8 and 12, limits inclusive; and p is equal to 1.

13. A method, comprising using at least one sulfureous phenolic compound of formula (1) according to claim 8 as an antioxidant, UV stabilizer or heat stabilizer.

14. The method according to claim 13, wherein the method prepares a product selected from the group consisting of plastics, synthetic fibres, elastomers, adhesives, additives and lubricants.

Description

[0186] The examples that follow illustrate the invention without limiting it.

EXAMPLE 1

Preparation of 2-(10-methyl(ethylthio)decanoate)phenol from Soybean Oil

[0187] ##STR00018##

[0188] Soybean oil is treated with aluminium so as to reduce its peroxide content to less than 10 milliequivalents per kg of soybean oil. The soybean oil is then degassed by sparging with nitrogen for 30 minutes. The treated soybean oil is then stored in a container under a nitrogen atmosphere until the time of use.

[0189] 250 ml of deperoxidized and degassed (as previously) soybean oil are placed in a 500 ml stainless-steel autoclave, equipped with a magnetic stirring device, a heating device, a gas introduction valve and a relief valve.

[0190] A sealed glass tube containing 35 mg of (tricyclohexylphosphine)(benzylidene)ruthenium chloride dissolved in 5 ml of toluene is placed in the autoclave. The autoclave is closed and then placed under an inert atmosphere of nitrogen via 3 cycles of flushing under vacuum/placing under a slight pressure of nitrogen (550 kPa). The system is then flushed under vacuum a final time, followed by introduction of ethylene into the medium, while maintaining a pressure of 2.7 MPa, which will be maintained throughout the test.

[0191] Stirring is started to break the glass tube containing the catalyst, and the temperature of the medium is then raised to 30 C. and maintained for 10 hours.

[0192] At the end of the test, the autoclave is cooled and returned to atmospheric pressure, and the contents are purified by passage through alumina to remove the (tricyclohexylphosphine)(benzylidene)ruthenium chloride. The reaction medium is then purified by distillation to separate the side products from the glyceryl tris(9-decenoate). The expected product is obtained in a yield of greater than 70%.

[0193] A step of methanolysis of the products is performed on the glyceryl tris(9-decenoate) in order to recover the glycerol, on the one hand, and methyl 9-decenoate, on the other hand.

[0194] The methyl 9-decenoate thus obtained (156 g) is placed in a photochemical reactor comprising a reaction loop, with 100 g of pentane and 60 molar equivalents of liquefied hydrogen sulfide (1806 g condensed at 20 C. under a pressure of 17.5 bar, i.e. 1.75 MPa). The mixture is recirculated at a rate of 601/hour in the reaction loop, in which it is subjected to UV radiation (wavelength: 254 nm, power: 12 watts) for 3 hours at a temperature of 38 C. and at a pressure of 23 bar (2.3 MPa).

[0195] The excess hydrogen sulfide is then flushed out towards a thermal oxidizer by decompression of the medium, followed by stripping with nitrogen. The mixture is then distilled so as to remove the solvent and the sulfides formed, at a temperature of 130 C., under a pressure of 5 mbar (500 Pa). The methyl 9-mercaptodecanoate is obtained in a purity of greater than 98.5%.

[0196] 115.7 g (0.7 mol) of 2-(dimethylaminoethyl)phenol and 152.7 g of methyl 10-mercaptodecanoate (0.7 mol) are mixed in a jacketed reactor equipped with a stirring system and a condenser for a time of 36 hours at 150 C. The dimethylamine is removed continuously from the medium by gentle stripping with nitrogen.

[0197] The crude reaction product is removed from the medium and washed with water, and the organic phase is distilled under reduced pressure to give the expected 2-(10-methyl(ethylthio)decanoate)phenol.