Patent GB-762340-A (GB)
Title: Unsaturated polycarbonyl compounds and a process for preparing them
IPC: C07C49/203
Filed: 1954-12-07
Abstract: Diethylenic dicarboxylic acids of the formula <FORM:0762340/IV(a)/1> wherein each R represents a hydrogen atom, a halogen atom or a hydrocarbon radical comprising 1-12 carbon atoms, and n is an integer equalling 3-9 (inclusive) and esters thereof are suitable for use as plasticisers for nitrocellulose and polyvinyl chloride resins.  These compounds may be obtained by reacting a compound having 4-18 carbon atoms and having 2 conjugated double bonds, e.g. butadiene, chloroprene, isoprene and derivatives thereof with a cyclic peroxide obtained, for example, by reacting hydrogen peroxide with cyclohexanone, methyl cyclohexanone, cyclopentanone, and methyl cyclopentanone, in the presence of a redox reducing agent. Octadecadiene-7,11-dicarboxylic acid-1,18 and others are mentioned.ALSO:The invention comprises an unsaturated polycarbonyl compound of the general formula: <FORM:0762340/IV(b)/1> in which R represents a hydrogen atom, a halogen atom or a hydrocarbon radical comprising 1-12 carbon atoms, each symbol A represents a bivalent hydrocarbon radical having a carbon chain of 3-9 (inclusive) carbon atoms and each symbol X represents an hydroxyl, cyano, hydrocarbon, alkoxy, cycloalkoxy or aryloxy group, the last four of which may contain each 1-12 (inclusive) carbon atoms, and the preparation thereof by reacting a compound containing 4-18 (inclusive) carbon atoms in its molecule and having two conjugated double bonds, in the presence of a redox reducing agent, with a cyclic peroxide of the general formula: <FORM:0762340/IV(b)/2> in which the additional symbols X1 and Y1 are such that X1 represents an hydroxyl, hydroperoxy, cyano, hydrocarbon, alkoxy, cycloalkoxy or aryloxy group, the last four of which may each comprise 1-12 carbon atoms, and Y represents a hydrogen atom or an <FORM:0762340/IV(b)/3> radical.  The cyclic peroxides used as starting materials and having the formulae: <FORM:0762340/IV(b)/4> and <FORM:0762340/IV(b)/5> can be obtained by reacting a cyclic ketone with hydrogen peroxide, e.g. by reacting cyclohexanone, cyclopentanone, methyl cyclopentanone, methyl cyclohexanone with hydrogen peroxide. Additionally compounds of the formula: <FORM:0762340/IV(b)/6> wherein R1 represents a hydrocarbon radica containing 1-12 carbon atoms and compounds of the formula: <FORM:0762340/IV(b)/7> wherein Z represents a hydrocarbon radical, a cyano, carboxy or alkoxy group may be utilized.  The other starting material may comprise butadiene, chloroprene, isoprene and derivatives thereof.  As redox reducing agent there may be used ferrous ions, chromous irons, vanadous ions, sodium bisulphite, sodium formaldehyde sulphoxylate and l-ascorbic acid.  The reaction may be effected in acid medium between -15 DEG  and 50 DEG  C. Examples disclose the production of (1) the diethylenic dibasic acid HOOC-(CH2)5-(C4H6)2 -(CH2)5-COOH and dichloro-octadecadiene 7,11-dicarboxylic acids-1,18; (2) octadecadiene-7,11-dicarboxylic acid - 1,18, the dimethyl esters of 7-vinyl-hexadecene-9-dicarboxylic acid-1,16, esters of dimethyl-octadecadiene-7,11-dicarboxylic acids-1,18, 7,9- and 7,10-dimethyl-7-vinylhexadecene-9-dicarboxylic acid-1,16 and 9 and 10-methyl-7-isopropenyl - hexadecene - 9 - dicarboxylic acid-1,16; (3) the same dimethyl esters of the C20-diethylenic dicarboxylic acids as Example (2); (4) the dimethyl esters of hexadecadiene-6,10-dicarboxylic acid-1,16 and 6-vinyl-tetradecene-8-dicarboxylic acid-1,14, the dimethyl ester of dichlorohexadecadiene-6,10-dicarboxylic acid-1,16, the methyl ester of octadecadiene-7,11-dicarboxylic acid-1,18, and the C22-diketonitrile having the formula NC-CO-(CH2)6-CH = CH-(CH2)2-CH = CH-(CH2)6-CO-CN; (5) a mixture of the methyl esters of 3,16-dimethyl - octadecadiene - 7,11 - dicarboxylic acid - 1,18 and 3,14 - dimethyl - 7 - vinyl-hexadecene - 9 - dicarboxylic acid - 1,16; (6) compounds having the formulae: <FORM:0762340/IV(b)/8> (7) the diketone <FORM:0762340/IV(b)/9>