Patent GB-1042639-A (GB)
Title: Substituted phenols
IPC: C09K15/14
Filed: 1964-08-04
Abstract: As antioxidants for fats, use is made of compounds containing a substituted benzyl radical of either of the formula <FORM:1042639/C4-C5/1> <FORM:1042639/C4-C5/2> in which R4 and R5 are identical or different alkyl, cycloalkyl or aralkyl groups, in which compounds two such benzyl radicals are linked by a sulphur atom or one or two such radicals are linked to the residue of a compound of any of the formulae ROH, R1SH, NH2R2, NHR2A, NHR2R3 or HSXSH, in which formulae R represents an alkyl, cycloalkyl, aralkyl or hydroxyalkyl group of up to 12 carbon atoms, R1 represents an alkyl, hydroxyalkyl, aryl, cycloalkyl, or aralkyl group of up to 18 carbon atoms, R2 and R3, which may be identical or different, represent hydrogen or hydroxy, alkyl, cycloalkyl, hydroxyalkyl, aralkyl or aryl groups of up to 12 carbon atoms or represent NR6R7, R6 and R7 being identical or different and representing hydrogen or alkyl, cycloalkyl, aralkyl or aryl groups of up to 12 carbon atoms, and X represents a divalent radical of 2 to 18 carbon atoms (see Division C2).  The radical X may be (1) an unsubstituted or substituted polymethylene radical, (2) an aralkyl radical of the formula <FORM:1042639/C4-C5/3> (3) an aralkyl radical of either of the formulae <FORM:1042639/C4-C5/4> (4)  a phenylene or substituted phenylene radical, (5) a radical of the formula <FORM:1042639/C4-C5/5> in which Z is -O-, -S- or -SO2-, (6) a diphenylene radical, (7) a radical of the formula <FORM:1042639/C4-C5/6> in which R is hydrogen or an alkyl group and n is 0-6, (8) a radical of the formula <FORM:1042639/C4-C5/7> in which R is hydrogen or alkyl, n is 1-6 and X1 is -O-, -S-, -SO2- or -NR1-, R1 being alkyl group, (9) or radical of the formula -CH2CH2OCH2CH2OCH2CH2-or -CH2CH2OCH2OCH2CH2- or (10) a radical of the formula <FORM:1042639/C4-C5/8> in which R is hydrogen or alkyl and n is 1-5, Compounds described in typical examples are 1) bis(3 - methyl - 4 - hydroxy - 5 - t. - butyl - benzyl)sulphide (2) bis(2-hydroxy-3-t.-butyl-5-methylbenzyl) sulphide, (3) a ,a 1-bis(2-hydroxy-3 - t. - butyl - 5 - methylbenzylthio) - p - xylene, p,p1 - bis(2 - hydroxy - (4) 3 - t. - butyl -5 - methylbenzylthio)biphenyl, (5) 1,4 - bis(3-methyl - 4 - hydroxy - 5 - t. - butyl -benzylthio) butane, (6) 3,4-bis(3,5-di-t.-butyl-4-hydroxybenzylthio) toluene, (7) 2,6-di-t.-butyl-4-(b -hydroxyethylthiomethyl) phenol, (8) 2-t.-butyl - 4 - methyl - 6 - (p - t. - butylphenyl-thiomethyl) phenol, (9) 2-t.-butyl-4methyl-6-(b -hydroxyetholxymethyl) phenol, (10) 2-t.-butyl-4-methyl-6(methoxymethyl) phenol, (11) N - (2 - hydroxy - 3 - t. - butyl - 5 - methyl-benzyl) aniline, (12) N,N-bis(2-hydroxy-3-t.-butyl-5-methylbenzyl) hydroxylamine, (13) p-bis(3,5 - di - t. - butyl -a 4 - hydroxybenzyl)amino diphenylamine, and (14) N,N-bis(3,5-di-t.-butyl-4 - hydroxybenzyl) - a  - naphthylamine.  Many other products of the invention are also described. An example (No. 37) is given of the use of some of the products in the treatment of lard.ALSO:The invention relates to the manufacture of compounds containing a substituted benzyl radical of either of the formulae <FORM:1042639/C2/1> <FORM:1042639/C2/2> in which R4 and R5 are identical or different alkyl, cycloalkyl or aralkyl groups.  The compounds are prepared from compounds AZ, in which A is a substituted benzyl radical as formulated above and Z is a group -S-C(S)-NR8R9 R8 and R9 being identical or different lower alkyl groups, or, when A has the second formula above, Z may be a group <FORM:1042639/C2/3> The process of the invention comprises treating the compound AZ with an alkali-metal sulphide, or with an alkali-metal hydroxide and a compound of any of the formulae ROH, R1SH, NH2R2, NHR2A, NHR2R3 or HSXSH, in which formulae R represents an alkyl, cycloalkyl, aralkyl or hydroxyalkyl group of up to 12 carbon atoms, R1 represents an alkyl, hydroxyalkyl, aryl, cycloalkyl or aralkyl group of up to 18 carbon atoms, R2 and R3, which may be identical or different, represent hydrogen or hydroxy, alkyl, cycloalkyl, hydroxyalkyl, aralkyl or aryl groups of up to 12 carbon atoms or represent NR6R7, R6 and R7 being identical or different and representing hydrogen or alkyl, cycloalkyl, aralkyl or aryl groups of up to 12 carbon atoms, and X represents a divalent radical of 2 to 18 carbon atoms.  The radical X may be (1) an unsubstituted or substituted polymethylene radical, (2) an aralkyl radical of the formula <FORM:1042639/C2/4> (3) an aralkyl radical of either of the formulae <FORM:1042639/C2/5> <FORM:1042639/C2/6> (4) a phenylene or substituted phenylene radical, (5) a radical of the formula <FORM:1042639/C2/7> in which Z is -O-, -S- or -SO2-, (6) a diphenylene radical, (7) a radical of the formula <FORM:1042639/C2/8> in which R is hydrogen or an alkyl group and n is 0-6, (8) a radical of the formula <FORM:1042639/C2/9> in which R is hydrogen or alkyl, n is 1-6, and X1 is -O-, -S-, -SO2- or -NR1-, R1 being an alkyl group, (9) a radical of the formula -CH2CH2OCH2CH2OCH2CH2-or -CH2CH2OCH2OCH2CH2-or (10) a radical of the formula <FORM:1042639/C2/100> in which R is hydrogen or alkyl and n is 1-5. In typical examples, (1) 3-methyl-5-t.-butyl-4-hydroxybenzyl N,N - dimethyldithiocarbamate and sodium sulphide yield bis(3-methyl-4-hydroxy - 5 - t. - butylbenzyl) sulphide, (2) 2-hydroxy - 3 - t. - butyl - 5 - methylbenzyl 2-benzothiazolyl sulphide and sodium sulphide yield bis(2-hydroxy-3-t.-butyl-5-methylbenzyl) sulphide, (3) 2-hydroxy-3-t.-butyl-5-methylbenzyl 2-benzothiazolyl sulphide, a ,a 1-dimercapto-p-xylene and potassium hydroxide yield a ,a 1 - bis(2 - hydroxy - 3 - t. - butyl - 5 - methylbenzylthio) - p - xylene, (4) 2 - hydroxy - 3 - t.-butyl - 5 - methylbenzyl 2 - benzothiazolyl sulphide, p,p1-dimercaptobiphenyl and potassium hydroxide yield p,p1-bis(2-hydroxy-3-t. butyl - 5 - methylbenzylthio)biphenyl, (5) 3-methyl - 4 - hydroxy - 5 - t. - butylbenzyl N,N-dimethyldithiocarbamate, 1,4 - dimercaptobutane and sodium hydroxide yield 1,4-bis(3-methy - 4 - hydroxy - 5 - t. - butylbenzylthio)-butane, (6) 3,5 - di - t. - butyl - 4 - hydroxybenzyl N,N-dimethyldithiocarbamate, toluene-3,4-dithiol and potassium hydroxide yield 3,4-bis(3,5 - di - t. - butyl - 4 - hydroxybenzylthio) toluene, (7) 3,5 - di - t. - butyl - 4 - hydroxybenzyl N,N-dimethyldithiocarbamate, b -mercaptoethanol and potassium hydroxide yield 2,6 - di - t. - butyl - 4 - (b  - hydroxyethylthiomethyl)phenol, (8) 2 - hydroxy - 3 - t. - butyl-5 - methylbenzyl N,N - dimethyldithiocarbamate, p - t. - butylthiophenol and sodium hydroxide yield 2 - t. - butyl - 4 - methyl - 6 -(p - t. - butylphenylthiomethyl)phenol, (9) 2-hydroxy - 3 - t. - butyl - 5 - methylbenzyl 2-benzothiazolyl sulphide, ethylene glycol and potassium hydroxide yield 2-t.-butyl-4-methyl-6 - (b  - hydroxyethoxymethyl) phenol, (10) 2-hydroxy - 3 - t. - butyl - 5 - methylbenzyl benzothiazolyl sulphide, sodium hydroxide and methanol yield 2 - t. - butyl - 4 - methyl - 6-(methoxymethyl)phenol, (11) 2 - hydroxy - 3-t. - butyl - 5 - methylbenzyl 2 - benzothiazolyl sulphide, aniline and sodium hydroxide yield N - (2 - hydroxy - 3 - t. - butyl - 5 - methylbenzyl)aniline, (12) 2 - hydroxy - 3 - t. - butyl-5 - methylbenzyl 2 - benzothiazolyl sulphide, hydroxylamine hydrochloride and sodium hydroxide yield N,N - bis(2 - hydroxy - 3 - t.-butyl - 5 - methylbenzyl)hydroxylamine, (13) 3,5 - di - t. - butyl - 4 - hydroxybenzyl N,N-dimethyldithiocarbamate, p - aminodiphenylamine and sodium hydroxide yield p-bis(3,5-di-t. - butyl - 4 - hydroxybenzyl)amino diphenylamine, and (14) 3,5 - di - t. - butyl - 4 - hydroxybenzyl N,N - dimethyldithiocarbamate, a -naphthylamine and sodium hydroxide yield N,N - bis(3,5 - di - t. - butyl - 4 - hydroxybenzyl)-a  - naphthylamine.  Many other products of the invention are also described.  The products are useful as antioxidants (see Divisions C3 and C5).  The preparation of the following intermediates is described.  3 - Methyl - 5 - t. - butyl - 4 - hydroxybenzyl N,N - dimethyldithiocarbamate is prepared from sodium dimethyldithiocarbamate, 2-methyl-6-t.-butylphenol and formaldehyde.  3,5 - Di - t. - butyl - 4 - hydroxybenzyl N,N-dimethyldithiocarbamate is prepared from 2,6-di-t.-phenol, formaldehyde, dimethylamine and carbon disulphide.  3,5 - Dimethyl - 4 - hydroxybenzyl N,N - dimethyldithiocarbamate is prepared similarly from 2,6-xylenol.  2 - Hydroxy - 3 - (1,1,3,3 - tetramethylbutyl) - 5-methylbenzyl N,N - dimethyldithiocarbamate is prepared by treating 2 - (1,1,3,3 - tetramethylbutyl) - p - creso with formaldehyde and dimethylamine, and treating the 2-(1,1,3,3-tetramethylbutyl) - 4 - methyl - 6 - dimethylaminomethylphenol so obtained with carbon disulphide.  2 - Hydroxy - 3 - (a ,a  - dimethylbenzyl) - 5-methylbenzyl N,N - dimethyldithiocarbamate is prepared from 2 - (a ,a  - dimethylbenzyl) - 4-methyl - 6 - dimethylaminomethyl phenol and carbon disulphide.  2 - Hydroxy - 3 - t. - butyl - 5 - methylbenzyl 2-benzothiazolyl sulphide is prepared from 2-mercaptobenzothiazole, formaldehyde and 2-t.-butyl-p-cresol.  2 - Hydroxy - 3 - (1,1,3,3 - tetramethylbutyl) - 5-methylbenzyl 2 - benzothiazolyl sulphide is prepared similarly from 2-(1,1,3,3-tetramethylbutyl)-p-cresol.  2 - Hydroxy - 3 - (a ,a  - dimethylbenzyl) - 5-methylbenzyl 2-benzothiazolyl sulphide is prepared similarly from 2-(a ,a -dimethylbenzyl)-p-cresol.  2 - Hydroxy - 3 - t. - butyl - 5 - methylbenzyl N,N-dimethyldithiocarbamate is prepared similarly to 2-hydroxy-3-(1,1,3,3-tetramethylbutyl)-5 - methylbenzyl N,N - dimethyldithiocarbamate above.ALSO:As antioxidants, use is made of compounds containing a substituted benzyl radical of either of the formulae <FORM:1042639/C3/1> and <FORM:1042639/C3/2> in which R4 and R5 are identical or different alkyl, cycloalkyl or aralkyl groups, in which compounds two such benzyl radicals are linked to a sulphur atom or one or two such radicals are linked to the res