Patent GB-959123-A (GB)
Title: Novel sulphur-containing aromatic hydroxy compounds, process for preparing these compounds and use thereof as stabilisers
IPC: C07C323/16
Filed: 1962-03-28
Abstract: An aromatic hydroxy compound containing a group: <FORM:0959123/C2/1> in which R is a hydrogen atom or an alkyl group and m is zero or an integer, is reacted with a compound QSH, in which Q is hydrogen or an organic radical.  The term "aromatic hydroxy compound" covers not only carbocyclic hydroxy compounds, e.g. those derived from benzene, naphthalene, anthracene or phenanthrene, but also heterocyclic analogues, e.g. hydroxy compounds of pyridine, quinoline, acridine, pyrimidine, furan, thiophine or benzothiazole, and in the formula above, when m is an integer, the carbon atoms or some of the carbon atoms may together form one or more rings. The aromatic hydroxy compound may contain one or more additional substituents, e.g. an alkyl, aralkyl or cycloalkyl group, an alkoxy group or an additional hydroxy group. Specified aromatic hydroxy compounds are o-allylphenol, 4, 6-dinorbornyl-2-allylphenol, 4-tert-butyl-2, 6-diallylphenol, 4-tert-butyl-2-allylphenol, 2, 4, 6-triallylphenol, 4, 6-ditert-butyl-2-allylphenol, and o -cyclohexenyl-p-tert-butylphenol, and reference is made also to the use of alkyl derivatives of 2-allyl-1-naphthol or of 1-allyl-2-naphthol, 1, 5-diallyl-2, 6-dihydroxyanthracene, 1 - allyl - 2 - hydroxyphenanthrene, 3-allyl-4-hydroxybiphenyl and 3-allyl-2-hydroxybiphenyl, the alkyl groups being preferably cyclohexyl, norbornyl or tert-butyl groups. The use of vinyl, isopropenyl, 3-butenyl, methallyl and crotyl derivatives of phenols is also mentioned. The aromatic hydroxy compound may be obtained by a Claisen re-arrangement of allyl ethers (or substituted allyl ethers) of aromatic hydroxy compounds or by a variation of the Claisen re-arrangement in which an allyl (or substituted allyl) ether of an aromatic hydroxycarboxylic acid, e.g. the allyl ether of salicylic acid, is used as the starting material, whereupon decarboxylation occurs and the carboxy group is replaced by the allyl group.  The compound QSH mentioned above may be hydrogen sulphide or Q may denote an alkyl, alkenyl or aralkyl group which may contain hetero atoms, e.g. nitrogen, oxygen or sulphur, and may also contain additional substituents, e.g. halogen atoms or hydroxy or sulph-hydryl groups, the use of dithiols, e.g. 1, 4-butanedithiol, being particularly mentioned.  Alternatively Q may represent a group R1CO, R1CS or R12NCS, where R1 is hydrogen or an alkyl radical.  The products contain the grouping: <FORM:0959123/C2/2> in which X is an organic radical, R is hydrogen or an alkyl group and n is at least 2, the carbon atoms of the CRR groups, or a part thereof, possibly forming one or more rings. The reaction is preferably effected under irradiation or in the presence of a non-peroxidic catalyst, e.g. a metal alkyl or an azo compound, particularly azodiisobutyronitrile, at 70-100 DEG C., preferably under an inert gas, e.g. nitrogen. In the examples (1) 4-tert-butylphenyl allyl ether is prepared from p-tert-butylphenol and allyl bromide and is then converted into 4-tert-butyl-2-allyl phenol by heating to 240 DEG C.; the latter product is heated with n-dodecyl mercaptan in a nitrogen atmosphere in the presence of azodiisobutyronitrile to yield 4 - tert - butyl - 2 - (4 - thiahexadecyl)phenol; (2) 2-(4-thiahexadecyl) phenol is prepared similarly from o-allylphenol and n-dodecylmercaptan; (3) 4-tert-butyl-2, 6-bis(4-thiahexadecyl) phenol is prepared from 4-tert-butyl-2, 6-diallylphenol and 2 mols of n-dodecylmercaptan: (4) 2, 6-bis(4-thiahexadecyl) phenol is prepared similarly from 2, 6-diallyphenol and n-dodecylmercaptan; (5) 2, 4-dinorbornylphenol is treated with allyl bromide to yield 2, 4-dinorbornyl phenyl allyl ether, which is heated to 250 DEG C. to convert it into 4, 6-dinorbornyl-2-allylphenol; the latter product is treated with n-dodecyl mercaptan, as in Example 1, to yield 4, 6-dinorbornyl-2-(4-thiahexadecyl) phenol; (6) 1, 12-bis(3, 5-dinorbornyl-2-hydroxyphenyl)-4, 9-dithiadodecane is prepared similarly from two mols. of 4, 6-dinorbornyl-2-allylphenol and butane-1, 4-dithiol.  Another specified product is 2, 4, 6-tris(4-thiahexadecyl) phenol. The products, especially those obtained from hydrogen sulphide, may be further reacted, e.g. by the oxidation of a mercaptan to a disulphide, possibly by reaction with a second molecule of an unsaturated phenol.  The products are useful as anti-oxidants and may be added to lubricating oils, rubber and synthetic resins.ALSO:As anti-oxidants for addition to rubber and synthetic resins, particularly to polymers and co-polymers of ethylenic hydrocarbons, e.g. ethylene, propylene and the butylenes, use is made of aromatic hydroxy compounds containing the grouping <FORM:0959123/C3/1> in which X is an organic radical, R is hydrogen or an alkyl group and n is at least 2, the carbon atoms of the CRR groups, or a part thereof, possibly forming one or more rings. In the examples, 2-(4-thiahexadecyl) phenol, 2-(4-thiahexadecyl) -4- norbornyl phenol, 4, 6-dinorbornyl -2- (4-thiahexadecyl) phenol, 4-tert. butyl -2- (4-thiahexadecyl) phenol, 2, 6-bis (4-thiahexadecyl) phenol, 4-tert. butyl-2, 6-bis (4-thiahexadecyl) phenol and 1, 12-bis (3, 5-dinorbornyl-2-hydroxyphenyl) 4,9-dithiadodecane optionally with dicetyl sulphide or 2, 4, 6-trinorbornyl phenol are used to stabilize polypropylene.ALSO:As anti-oxidants for mineral lubricating oils, use is made of products obtained by reacting an aromatic hydroxy compound containing a group <FORM:0959123/C3/1> in which R is a hydrogen atom or an alkyl group and m is zero or an integer, with a compound QSH, in which Q is hydrogen or an organic radical.  The term "aromatic hydroxy compound" covers not only carbocyclic hydroxy compounds, e.g. those derived from benzene, naphthalene, anthracene or phenanthrene, but also heterocyclic analogues, e.g. hydroxy compounds or pyridine, quinoline, acridine, pyrimidine, furan, thiophene or benzothiazole, and in the formula above, when m is an integer, the carbon atoms or some of the carbon atoms may together form one or more rings.  The aromatic hydroxy compound may contain one or more additional substituents, e.g. an alkyl, aralkyl or cycloalkyl group, an alkoxy group or an additional hydroxy group.  The compound QSH may be hydrogen sulphide or Q may denote an alkyl, alkanyl or aralkyl group which may contain hetero atoms, e.g. nitrogen, oxygen or sulphur, and may also contain additional substituents, e.g. halogen atoms or hydroxy or sulph-hydryl groups, the use of dithiols, e.g. 1,4-butanedithiol, being particularly mentioned.  Alternatively Q may represent a group R1CO, R1CS or R12NCS, where R1 is hydrogen or an alkyl radical.  The anti-oxidants may be used alone or with other anti-oxidants, e.g. 2,4,6-trinorbornylphenol or organic sulphides. Specified types of organic sulphides are (a) sulphides of the types R1CH2CH2SxR2\t or R1CH2CH2SxCH2CH2R2 where x is an integer and R1 and R2 are aliphatic aromatic radicals, e.g. b -thio ethers of propionic esters, dodecylcetyl sulphide didodecyl disulphide, dicetyl monosulphide or dicetyl disulphide, (b) polyalkoxyalkyl sulphides (-R1OR1S-)x, polyalkoxyalkoxyalkyl sulphides (R1OR2OR2 OR1S-)x or polyhydroxyalkyl sulphides (-R1(OH)S-) obtainable by reacting an unsaturated ether, e.g. diallyl ether, with hydrogen sulphide, and (c) thiuram disulphide and particularly its tetra-alkyl derivatives.