Patent GB-806211-A (GB)
Title: Improvements in or relating to stabilizing organic compounds subject to oxidative deterioration
Inventor: THOMPSON RALPH BREWSTER
IPC: C10G29/22
Filed: 1956-05-09
Abstract: Motor fuels (e.g. cracked or polymer gasoline), diesel oils, fuel oils, lubricating oils, mineral oils, drying oils, greases, paraffin waxes and edible fats and fatty oils are stabilized against oxidative deterioration by the addition of 0.0001-1 per cent by weight of a hydroxyspirochroman having a spiro linkage in the 2-position, for example 6,61-dihydroxy-4,4,41,41-tetramethyl - bis - 2,21 - spirochroman of formula: <FORM:0806211/III/1> The spirochromans are prepared by reaction between hydroquinone, hydroxy-hydroquinone or substitution derivatives thereof and saturated or unsaturated aliphatic or cyclic ketones Substituent groups which may be attached to the ring of the hydroquinone or hydroxy-hydroquinone are alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxy, amino and RS- (where R is alkyl) groups. Fats and fatty oils mentioned are linseed, menhaden, codliver, castor, olive, rapeseed, coconut, palm, corn, sesame, peanut and babassu oils, lard and beef tallow, as well as hydrogenated, air-blown and heat-treated fats and fatty oils.  In the case of edible fats and fatty oils, a synergist such as phosphoric acid or ascorbic acid may be used along with the spirochroman.  In the case of gasoline, the spirochroman may be used in conjunction with lead tetraethyl, dyes and inhibitor activators such as alkylene polyamines.  In examples: (i) the spirochromans formed by reaction of hydroxy-hydroquinone with acetone, methyl ethyl ketone, methyl n-amyl ketone, diethyl ketone or cyclohexanone are added to lard with or without phosphoric acid as a synergist; and (ii) the spirochromans formed by reaction of hydroxy-hydroquinone with methyl ethyl ketone or cyclohexanone, or the spirochroman formed by the reaction of hydroquinone with acetone, are added to cracked gasoline.ALSO:Natural or synthetic rubber is stabilized against oxidative deterioration by the addition of 0.0001-1 per cent by weight of an hydroxy-spirochroman having a spiro linkage in the 2-position, for example 6,61-dihydroxy-4,4,41,41-tetramethyl - bis - 2,21 - spirochroman of formula <FORM:0806211/IV (a)/1> The spirochromans are prepared by reaction between hydroquinone, hydroxy-hydroquinone or substitution derivatives thereof and saturated or unsaturated aliphatic or cyclic ketones.  Substituent groups which may be attached to the ring of the hydroquinone or hydroxy-hydroquinone are alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkoxy, amino and RS- (where R is alkyl) groups.  In an example, bis-(6,7-dihydroxy - 3 - trimethylene - 4,4 - pentamethylene - 2 - spirochroman) is added to the latex resulting from the emulsion copolymerization of butadiene and styrene, after which the latex is coagulated and dried.ALSO:Hydroxyspirochromans having a spiro linkage in the 2-position are prepared by reacting hydroquinone, hydroxyhydroquinone or substitution derivatives thereof with saturated or unsaturated aliphatic or cyclic ketones.  The hydroquinone or hydroxy-hydroquinone may contain one or more substituents attached to the ring, provided that a position ortho to the hydroxyl group is not substituted.  Substituent groups mentioned are alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxy, amino and RS- (where R is alkyl) groups. The acetate of hydroquinone or hydroxyhydroquinone may be used in the preparation of the spirochromans, the acetyl groups splitting off during the preparation.  Ketones mentioned are acetone, methyl ethyl ketone and other dialkyl ketones, phorone, mesityl oxide, methyl heptenone, cyclopentanone, cyclohexanone, cycloheptanone, 3-methyl-cyclohexanone, 4 - methyl - cyclohexanone, pulegone and carvone.  In examples, hydroxyhydroquinone triacetate is reacted with acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone or diethyl ketone, in the presence of glacial acetic acid and concentrated hydrochloric acid.  In a further example, hydroquinone is reacted with acetone in the presence of glacial acetic acid and concentrated hydrochloric acid.  The product in this case is 6,61 - dehydroxy - 4,4,41,41 - tetramethyl - bis-2,21-spirochroman of formula <FORM:0806211/IV (b)/1> Polymerizable hydrocarbon monomers, such as styrene and butadiene, are stabilized against oxidative deterioration by the addition of 0.0001-1 per cent by weight of the hydroxyspirochromans.ALSO:Edible fats and fatty oils are stabilized against oxidative deterioration by the addition of 0,000-1 per cent. by weight of a hydroxy-spirochroman having a spiro linkage in the 2-position, for example 6,61-dihydroxy-4,4,41,41 tetramethyl-bis-2,21-spirochroman of formula:- <FORM:0806211/I/1> The spirochromans are prepared by reaction between hydroquinone, hydroxy-hydroquinone or substitution derivatives thereof and saturated or unsaturated aliphatic or cyclic ketones.  Substituent groups which may be attached to the ring of the hydroquinone or hydroxy-hydroquinone are alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxy, amino and RS-(where R is alkyl) groups.  Fats and fatty oils mentioned are (butter, beef tallow, lard, and linseed, menhaden, cod liver, castor, olive, rapeseed, coconut, palm, corn, sesame, peanut and babassu oils, as well as hydrogenated, air-blown and heat-treated fats and fatty oils.  A synergist such as phosphoric acid or ascorbic acid may be used along with the spirochroman.  In examples, the spirochromans formed by reaction of hydroxy-hydroquinone with acetone, methyl ethyl ketone, methyl n-amyl ketone, diethyl ketone or cyclohexanone are added to lard with or without phosphoric acid as synergist.ALSO:Edible fats and fatty oils are preserved against against oxidative deterioration by the addition of 0.0001-1 per cent by weight of a hydroxyspirochroman having a spiro linkage in the 2-position, for example 6,61-dihydroxy-4,4,41,41 - tetramethyl - bis - 2,21 - spirochroman of formula <FORM:0806211/VI/1> The spirochromans are prepared by reaction between hydroquinone, hydroxy-hydroquinone or substitution derivatives thereof and saturated or unsaturated aliphatic or cyclic ketones. Substituted groups which may be attached to the ring of the hydroquinone or hydroxyhydroquinone are alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxy, amino and RS-(where R is alkyl) groups.  Fats and fatty oils mentioned are linseed, menhaden, cod liver, castor, olive, rapeseed, coconut, palm, corn, sesame, peanut and babassu oils, butter, lard and beef tallow, as well as hydrogenated, air-blown and heat-treated fats and fatty oils.  A synergist such as phosphoric or ascorbic acid may be used along with the spirochroman.  In examples, the spirochromans formed by reaction of hydroxyhydroquinone with acetone, methyl ethyl ketone, methyl n-amyl ketone, diethyl ketone or cyclohexanone are added to lard with or without phosphoric acid as synergist.