Patent GB-812901-A (GB)
Title: Derivatives of 1,2,3,4,5,6,7,8-octahydronaphthalene and their preparation
IPC: C07C2/52
Filed: 1957-08-21
Abstract: 6 - Methylene - 1,2,3,4,5,6,7,8 - octahydronaphthalenes having on at least one of the carbon atoms in the 2- and 3-positions at least one substituent which is -NO2, -CN, -CHO, -COOH, -COOR, -CO-O-CO, -CONH2, -COCl, -COR, -SO2R, -C6H5 or -CH= CH2 wherein R is hydrocarbon free from aliphatic unsaturation, any other substituents in the 2- and/or 3-positions being hydrocarbon when spread as a film set hard on continued air drying and may be applied as coating compositions on wood, plaster and particularly metals.  Where the compounds contain ester or esterifying constituents they can be reacted with glycol or glycerol to give viscous polyesters which can be applied to substrates, e.g. metal, and polymerized to give protective coatings by baking.  In Example X a thin layer of 2(3) - methyl - 2(3) - carbomethoxy - 6 - methylene - 1,2,3,4,5,6,7,8 - octahydronaphthalene containing a cobalt drying agent is exposed on a glass plate to air at room temperature.  A solid film is formed after a few days. Specification 812,902 is referred to.ALSO:Substances of the formula <FORM:0812901/IV (a)/1> where at least one X is -NO2, -CN, -CHO, -COOH, -COOR, -CO-O-CO-, -CONH2, -COCl, -COR, -SO2R, -C6H5 or -CH = CH2, wherein R is hydrocarbon free from aliphatic unsaturation, other X's being hydrogen or hydrocarbon tend to polymerize spontaneously. They polymerize on exposure to air in thin layers gradually becoming tack-free.  In examples: (5) in an attempt to prepare the anhydride of 6-methylene-1,2,3, 4,5,6,7,8 - octahydronaphthalene - 2,3 - dicarboxylic acid by reaction of allene with maleic anhydride (see Group IV (b)) a polymer of molecular weight 1530 is recovered; (10) a thin layer of 2(3) - methyl - 2(3) - carbomethoxy - 6-methylene - 1,2,3,4,5,6,7,8 - octahydronaphthalene containing a cobalt drying agent was exposed to air at room temperature.  After a few days the polymer formed a soft tack-free film partially resistant to toluene and petroleum ether.  Compounds containing two or more ester or esterifying substituents such as the anhydride of 2,3 - dicarboxylic acid - 6 - methylene - 1,2,3,4, 5,6,7,8 - octahydronaphthalene can be reacted with ethylene glycol or glycerol to give viscous polyesters which can be applied to substrates and polymerized thereon by baking. Specification 812,902 is referred to.ALSO:The Specification comprises 6-methylene-1,2,3,4,5,6,7,8 - octahydronaphthalenes containing in the 2- and/or 3-position at least one substituent which is an unsaturated group having a multiple bond attached to an atom alpha to the ring carbon, any other substituents in the 2- and 3-positions being hydrocarbons. Specified unsaturated substituents are cyano, nitro, aldehydic carbonyl, ketonic carbonyl, carboxyl, ester carbonyl, dicarbonyl anhydride, carbonamido, sulphone sulphony, phenyl and vinyl. These compounds may be prepared by a Diels-Alder condensation between 1,2,4-trimethylenecyclohexane and a dienophilic ethylenic compound which is alphabeta-unsaturated with respect to the ethylenic bond suitable dienophilic compounds being listed in "The Diols-Alder Reaction," by H. L. Holmes in "Organic Reactions," Vol. IV, 60-173 (Wiley and Sons Inc., 1948).  The dienophile is preferably of less than 9 carbon atoms and has a terminal methylene; it may have the formula CX2=CX2 where at least one X is -CN, -NO2,-CHO,-COOH,-COOR,-CO-O-CO-, -CONH2, -COCl, -COR, -SO2R, -C6H5 or -CH=CH2, where R is hydrocarbon free from aliphatic unsaturation, other X's being hydrogen or hydrocarbon groups, each of such groups preferably containing 1 to 6 carbon atoms; the dienophile is preferably free from aromatic groups and the unsaturated X group is preferably carboxyl or a group which can be hydrolysed to carbonyl. The 1,2,4-trimethylenecyclohexane may be formed in situ by the polymerization of allene in the presence, as catalyst, of a complex of nickel carbonyl and an organic phosphine or phosphite of formula [(ROm)3P]nNi(CO)4-n, where m is 0 or 1, n is 1, 2 or 3 and R is a hydrocarbon radical free from aliphatic unsaturation; the dienophile and allene in this case are reacted together in the presence of the catalyst.  In either case temperatures of 10-175 DEG  C. are used.  A polymerization inhibitor such as phenthiazine, hydroquinone or resorcinol may be added to the reaction mixture if desired.  The dienophile is preferably employed in excess.  An inert solvent such as tetrahydrofuran, benzene, toluene or dioxane can be used.  All ingredients should be anhydrous.  In examples: (1) methyl methacrylate is reacted with allene in the presence of bis-(triphenyl phosphite) nickel dicarbonyl at 100-105 DEG  C. for 6 hours to give 2(3)-methyl-2(3) - carbomethoxy - 6 - methylene - 1,2,3,4,5, 6,7,8-octahydronaphthalene; (2) methyl acrylate is reacted with allene using the same catalyst at 145-155 DEG  C. for 4 hours to give the 2(3)-carbomethoxy-derivative; (3) acrylonitrile is reacted with allene using the same catalyst at 80-85 DEG  C. for 6 hours to give the 2(3)-cyanoderivative; (4) 1,3-butadiene is reacted with allene using the same catalyst in tetrahydrofuran in the presence of calcium carbide to absorb moisture at 115-140 DEG  C. for 7 hours to give the 2(3)-vinyl derivative; (5) maleic anhydride is reacted with allene using the same catalyst in tetrahydrofuran at 80-88 DEG  C. for 6 hours to give a polymer of the 2,3-di-carboxylic acid anhydride derivative of molecular weight 1530; (6) maleic anhydride is reacted with a mixture of the isomers 1,2,4- and 1,3,5-trimethylenecyclohexanes in about 80 : 20 ratio in benzene at 20 DEG  C. for 16 hours to give the monomeric 2,3-dicarboxylic acid anhydride derivative; (7) methyl methacrylate is reacted with a mixture of trimethylenecyclohexanes at 100 DEG  C. for 16 hours to give a product identical with that of (1); (8) tetracyanoethylene is reacted with a mixture of trimethylenecyclohexanes in acetone to give spontaneously the 2,2,3,3 - tetracyano - derivative.  Specification 812,902 is referred to.