Patent GB-990304-A (GB)
Title: Phenolic substitution products
Inventor: MEIER ERIC A
IPC: C07C47/27
Filed: 1963-01-04
Abstract: The invention relates to the manufacture of compounds of the formula <FORM:0990304/C2/1> in which R1 is a secondary or tertiary alkyl group, R2 is an alkyl group, R13 and R14, which may be the same or different, are hydrogen atoms or alkyl, aryl, alkaryl, aralkyl or carbalkoxy groups and R15 is a hydrogen atom, an alkoxy, alkylthioalkyloxy, amino, alkylamino, dialkylamino, alkyl, aryl, alkaryl or aralkyl group or a group <FORM:0990304/C2/2> in which Z is a straight or branched alkylene group.  The compounds are made by additive reaction an appropriate 2,6-dialkylphenol and an unsaturated compound of the formula CH(R13)=C(R14)COR15, the reaction being effected in the presence of a basic catalyst, e.g. a quaternary ammonium base, an alkali-metal amide, alkoxide or hydroxide or an alkaline-earth metal alkoxide or hydroxide, and optionally in a solvent, e.g. a tertiary alkanol, tetrahydrofuran, dimethyl formamide or acetone. The reaction may be effected at 25-200 DEG  C. at atmospheric or raised pressure. Examples are given in which (1) 2,6-di-tert.-butylphenol and methyl acrylate yield methyl (3.5-di-tert.-butyl - 4 - hydroxyphenyl) propionate, (2) 2.6-di-tert.-butylphenol and lauryl (or octadecyl) acrylate yield dodecyl (or octadecyl) 3,5 - di - tert. - butyl - 4 - hydroxyphenyl) propionate, (3) 2,6 - di - tert. - butylphenol and diethyl maleate yield diethyl (3,5-di-tert.-butyl - 4 - hydroxyphenyl) succinate, (4) 2.6-di - tert. - butylphenol and acrylamide yield 3,5 - di - tert. - butyl - 4 - hydroxyphenyl propionamide, (5) 2.6 - di - tert. - butylphenol and N - octadecyl acrylamide yield N - octadecyl-3,5 - di - tert. - butyl - 4 - hydroxyphenyl propionamide, (6) 2.6 - di - tert. - butylphenol and methyl vinyl ketone yield 4-(3.5-di-tert.-butyl-4 - hydroxyphenyl) butan - 2 - one, and (7) 2.6 - di - tert. - butylphenol and ethylene bis-acrylate yield ethylene bis(3,5 - di - tert. - butyl - 4 - hydroxyphenyl) propionate.  Other specified phenols are 6-tert.-butyl-o-cresol, 6-(1,1,3,3 - tetramethylbutyl) - o - cresol, 2 - sec.-butyl - 6 - tert. - butylphenol, 2,6 - bis(1,1 - dimethyl - n - propyl)phenol and 2.6 - bis(1-methyl - n - nonyl)phenol.  Other alkyl groups which may constitute or form part of the radicals R1, R2, R13, R14 and R15 in the first formula above are specified, and it is stated that R13, R14 and R15 may also be naphthyl or acenaphthyl groups.  The products are useful as stabilizing agents for hydrocarbon polymers, e.g. polyethylene or polypropylene, waxes, soaps, greases, natural and synthetic rubbers and animal, vegetable or mineral oils, including lubricating oils, fuel oils and gasoline. Specification 965,373 is referred to.ALSO:As stabilizing agents for hydrocarbon polymers, e.g polyethylene or polypropylene, and for natural and synthetic rubbers, use is made of compounds of the formula <FORM:0990304/C3/1> in which R1 is a secondary or tertiary alkyl group, R2 is an alkyl group, R13 and R14, which may be the same or different, are hydrogen atoms or alkyl, aryl, alkaryl, aralkyl or carbalkoxy groups and R15 is a hydrogen atom, am alkoxy, alkylthioalkyloxy, amino, alkylamino, dialkylamino, alkyl, aryl, alkaryl or aralkyl group or a group <FORM:0990304/C3/2> in which Z is a straight or branched alkylene group (see Division C2).  Typical compounds are methyl (3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionate, dodecyl (or octadecyl) (3,5 - di - tert. - butyl - 4 - hydroxyphenyl) propionate, diethyl (3,5 - di - tert. - butyl - 4 - hydroxyphenyl) succinate, 3,5 - di - tert. - butyl - 4 - hydroxyphenyl propionamide, N - octadecyl - 3,5 - di - tert. - butyl - 4 - hydroxyphenyl propionamide, 4 - (3,5 - di - tert. - butyl - 4 - hydroxyphenyl) butan-2-one, and ethylene bis-(3,5 - di - tert. - butyl - 4 hydroxyphenyl) propionate. Specification 965,373 is referred to.ALSO:As stabilizing agents for waxes, soaps, greases and vegetable and mineral oils, including lubricating oils, fuel oils, and gasolene, use is made of compounds of the formula <FORM:0990304/C4-C5/1> in which R1 is a secondary or tertiary alkyl group, R2 is an alkyl group, R13 and R14, which may be the same or different, are hydrogen atoms or alkyl, aryl, alkaryl, aralkyl or carbalkoxy groups and R15 is a hydrogen atom, an alkoxy, alkylthioalkyloxy, amino, alkylamino, dialkylamino, alkyl, aryl, alkaryl or aralkyl group or a group <FORM:0990304/C4-C5/2> in which Z is a straight or branched alkylene group (see Division C2).  Typical compounds are methyl (3,5 - di - tert. - butyl - 4 - hydroxyphenyl) propionate, dodecyl (or octadecyl) (3,5-di - tert. - butyl - 4 - hydroxyphenyl) propionate, diethyl (3,5 - di - tert. - butyl - 4 - hydroxyphenyl) succinate, 3,5-di-tert.-butyl-4-hydroxyphenyl propionamide, N-octadecyl-3,5-di-tert.-butyl-4-hydroxyphenyl propionamide, 4-(3,5-di - tert. - butyl - 4 - hydroxyphenyl) butan - 2 - one and ethylene bis(3,5-di-tert.-butyl-4-hydroxyphenyl) propionate. Specification 965,373 is referred to.