Patent GB-984012-A (GB)
Title: New substituted thiazoles and the stabilisation of organic materials therewith
IPC: C09K15/30
Filed: 1961-05-02
Abstract: The invention comprises thiazoles of the formula <FORM:0984012/C2/1> wherein R1 represents C4-18 alkyl or C7-24 alkylphenyl, R2 represents hydrogen, R1 and R2 taken jointly represent -CH2-CH2-CH2 -CH2- and X represents naphthyl, hydroxyphenyl, aminophenyl, alkylamidophenyl, alkylhydroxyphenyl, (C1-6 alkoxy) phenyl, (C1-6 alkylamino) phenyl, phenylaminophenyl, aminobiphenyl, acenaphthyl or thiazolyl of the formula <FORM:0984012/C2/2> wherein R3 represents C1-18 alkyl or phenyl and R4 represents alkyl, phenyl or C1-18 alkanoyl; <FORM:0984012/C2/3> wherein R5 represents hydrogen or C1-18 alkyl, R6 represents C1- 18 alkyl and X represents hydroxyphenyl; <FORM:0984012/C2/4> wherein R7 and R8 independently represent C1-18 alkyl, phenyl or C7-24 alkylphenyl, R9 and R10 each represent hydrogen or phenyl, at least one group always representing hydrogen, X1 represents phenylene and n represents 1 or 2; <FORM:0984012/C2/5> wherein R11 represents methyl, ethyl or propyl, and X represents aminophenyl or C7-24 alkylhydroxyphenyl; and <FORM:0984012/C2/6> wherein R12 represents hydroxy, amino, alkylamino, C1-18 alkyl or C1- 18 alkylamido, and R13 represents hydrogen, or, when R12 is alkyl represents hydroxy.  The above compounds may be prepared by the following reaction schemes <FORM:0984012/C2/7> <FORM:0984012/C2/8> <FORM:0984012/C2/9> <FORM:0984012/C2/100> <FORM:0984012/C2/111> wherein Y represents halogen, R1 represents hydrogen or R4, R11 represents X or the group <FORM:0984012/C2/122> R111 represents R1, R3, R5, R7, R8 or R11, and R1111 represents R2 or R6.  Aldehydes such as heptaldehyde; perfluorohydrocarbons; and esters such as dihexyl azelate, di(2-ethylhexyl) azelate, di(3,5,5-trimethylhexyl) glutarate, di(3,5,5 - trimethylpentyl) glutarate, di(2 - ethylhexyl) pimelate, di(2-ethylhexyl) adipate, diisoamyl adipate, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate and 1,5 - pentanediol - di (2-ethylhexanoate) are stabilized against oxidative deterioration by the addition thereto of one or more of the above thiazoles.  1 - (2 - Hydroxy - 5 - tertiary - octylphenyl) -2- thiourea, 1 - (para - aminobiphenyl) - 2 - thiourea, 1,11 - para, para1 - biphenylene - bis - 2-thiourea, 1 - (para - anilinophenyl) - 2 - thiourea, 1 - phenyl - 1, 11 - para - phenylene - bis - 2-thiourea, 1 - (para - acetamidophenyl) - 2 - thiourea, 1 - (meta - acetamidophenyl) - 2 - thiourea, 1 - (para - lauramidophenyl) - 2 - thiourea, 1 - (para - stearamidophenyl) - 2 - thiourea and 1-(para-aminophenyl) - 1 - methyl - 2 - thiourea are prepared by reacting an appropriately substituted arylamine with sodium, potassium or ammonium thiocyanate.ALSO:Polyolefins such as polyethylenes, polypropylenes and polystyrene; polyhaloolefins such as polyvinyl chloride polyamides such as nylon; natural rubber; neoprene, nitrile, butyl, polyisoprene and styrene-butadiene rubbers; polyalkylene oxides such as polyisopropylene oxide, polyisopropylene oxide diether and polyisopropylene oxide diester; silicones such as methyl silicone and methyl phenyl silicone and esters of silicic acid such as tetraisooctyl silicate are stabilized against oxidative deterioration by the addition of a compound of the formula <FORM:0984012/C3/1> wherein R1 represents C4- 18 alkyl or C7- 24 alkylphenyl, R2 represents hydrogen, R1 and R2 taken jointly represent -CH2-CH2-CH2-CH2 and X represents naphthyl, hydroxyphenyl, aminophenyl, alkylamidophenyl, alkylhydroxyphenyl, (C1- 6 alkyl) phenyl, (C1- 6 alkylamino) phenyl, phenylaminophenyl, aminobiphenyl, acenaphthyl or thiazolyl of the formula <FORM:0984012/C3/2> (2) wherein R3 represents C1- 18 alkyl or phenyl and R4 represents alkyl, phenyl or C1- 18 alkanoyl; <FORM:0984012/C3/3> wherein R5 represents hydrogen or C1- 18 alkyl, R1 represents C1- 18 alkyl and X represents hydroxyphenyl; <FORM:0984012/C3/4> wherein R7 and R8 independently represent C1- 18 alkyl, phenyl or C7- 24 alkylphenyl R9 and R10 each represent hydrogen or phenyl, at least one group always representing hydrogen, X1 represents phenylene and n represents 1 or 2; <FORM:0984012/C3/5> wherein R11 represents methyl, ethyl or propyl, and X represents aminophenyl or C7- 24 alkylhydroxyphenyl; and <FORM:0984012/C3/6> wherein R12 represents hydroxy, amino, alkylamino, C1- 18 alkyl or C1- 18 alkylamido, and R13 represents hydrogen or, when R12 is alkyl represents hydroxy.ALSO:Fat, lard, beef tallow; linseed, menhaden, cod liver, castor, olive, rapeseed, coconut, palm, corn, sesame, peanut and cotton seed oils; paraffin wax; resins; gasolines; jet fuel; diesel, fuel, paraffin and mineral oils; synthetic lubricating oils, e.g. aliphatic esters (including di-, tri-, and hindered esters), polyalkylene oxides and esters and ethers thereof, silicones, esters of phosphoric and silicic acids and highly fluorine-substituted hydrocarbons; tetra-hydronaphthalene and cyclohexene are stabilized against oxidative deterioration by the addition of a compound of the formula <FORM:0984012/C4-C5/1> wherein R1 represents C4- 18 alkyl or C7- 24 alkylphenyl, R2 represents hydrogen, R1 and R2 taken jointly represent -CH2-CH2-CH2-CH2- and X represents naphthyl, hydroxyphenyl, aminophenyl, alkylamidophenyl, alkylhydroxyphenyl, (C1- 6 alkoxy) phenyl, (C1- 6 alkylamino) phenyl, phenylaminophenyl, aminobiphenyl, acenaphthyl or thiazolyl of the formula <FORM:0984012/C4-C5/2> <FORM:0984012/C4-C5/3> (2) wherein R3 represents C1- 18 alkyl or phenyl and R4 represents alkyl, phenyl or C1- 18 alkanoyl; <FORM:0984012/C4-C5/4> wherein R5 represents hydrogen or C1- 18 alkyl, R6 represents C1- 18 alkyl and X represents hydroxylphenyl; <FORM:0984012/C4-C5/5> wherein R7 and R8 independently represent C1- 18 alkyl, phenyl or C7- 24 alkylphenyl R9 and R10 each represent hydrogen or phenyl, at least one group always representing hydrogen, X1 represents phenylene and n represents 1 or 2; <FORM:0984012/C4-C5/6> wherein R11 represents methyl, ethyl or propyl, and X represents aminophenyl or C7- 24 alkylhydroxyphenyl; and <FORM:0984012/C4-C5/7> wherein R12 represents hydroxy, amino, alkylamino, C1- 18 alkyl or C1- 18 alkylamide, and R13 represents hydrogen or, when R12 is alkyl, represents hydroxy.ALSO:Butter is stabilized against oxidative deterioration by the addition of a compound of the formula:-  <FORM:0984012/A1-A3/1> wherein R1 represents C4-18 alkyl or C7-24 alkylphenyl, R2 represents hydrogen, R1 and R2 taken jointly represent -CH2-CH2- -CH2-CH2-and X represents naphthyl, hydroxyphenyl, aminophenyl, alkylamidophenyl, alkylhydroxyphenyl, (C1-6alkoxy) phenyl, (C1-6 alkylamino) phenyl, phenylaminophenyl, aminobiphenyl, acenaphthyl or thiazolyl of the formula:-  <FORM:0984012/A1-A3/2> wherein R3 represents C1-18 alkyl or phenyl and R4 represents alkyl, phenyl or C1-18 alkanoyl; <FORM:0984012/A1-A3/3> wherein R5 represents hydrogen or C1-18 alkyl, R6 represents C1-18 alkyl and X represents hydroxylphenyl; <FORM:0984012/A1-A3/4> wherein R7 and R8 independently represent C1-18 alkyl, phenyl or C7-24 alkylphenyl, R9 and R10 each represent hydrogen or phenyl, at least one group always representing hydrogen, X1 represents phenylene and n represents 1 or 2; <FORM:0984012/A1-A3/5> wherein R11 represents methyl, ethyl or propyl, and X represents aminophenyl or C7-24 alkylhydroxyphenyl; and (6) <FORM:0984012/A1-A3/6> wherein R12 represents hydroxy, amino, alkylamino, C1-18 alkyl or C1-18 alkylamido, and R13 represents hydrogen, or, when R12 is alkyl represents hydroxy.