Patent GB-759416-A (GB)
Title: Improvements relating to cleavage products of aliphatic compounds
IPC: C11C3/00
Filed: 1954-05-11
Abstract: The invention comprises the new compounds 11 - acetoxy - 9 - undecenoic acid, methyl - 11 - acetoxy - 9 - undecenoate, 11 - hydroxy - 9- undecenoic acid, 1 - acetoxy - 9 - undecen - 1 - ol and 1.11-dihydroxy-9-undecene.  They may be made, among other products, by reacting an aliphatic compound having a group <FORM:0759416/IV(a)/1> in which R is H, COOH or alkyl, R1 is H or alkyl and R11 is H, OH or alkyl, with a tetravalent lead salt of an aliphatic carboxylic acid having from 2 to 6 carbon atoms per molecule in the presence of a solvent.  The lead salt may be prepared in situ from a lead compound and an aliphatic carboxylic acid having from 2 to 6 carbon atoms.  Typical aliphatic compounds which may be used as starting materials are allyl carbinol, b -hydroxy propionaldehyde, hydracrylic acid, citric acid and the alkali metal salts, malic acid, citramalic acid, agaracinic acid, norcaperatic acid (n - C14H29CH(COOH)C(OH) (COOH)CH2COOH), b  - hydroxybutyric acid, b -hydroxyvaleric acid, b -hydroxyisovaleric acid, b -acetylethyl alcohol, 2.5-hexanedion-3-ol, diacetone alcohol, methyl acetonyl, carbinol and aldol condensation products such as acetaldol and heptaldol. Castor oil and ricinoleyl derivatives, such as methyl ricinoleate, butyl ricinoleate, ricinoleic acid, ricinoleyl alcohol, ricinoleic acid salts and ricinoleic amide may also be used. Suitable tetravalent lead salts are those of acetic acid, propionic acid, pivalic acid and caproic acid.  Suitable solvents are aliphatic carboxylic acids having from 2 to 6 carbon atoms, aromatic hydrocarbons, nitro aromatic hydrocarbons and chlorinated aliphatic hydrocarbons.  The cleavage reaction takes place at temperatures from 10 DEG  C. to 200 DEG  C.  In the examples (a) a solution of sodium citrate in acetic acid is heated with lead tetra-acetate to give a mixture of oxaloacetic acid and acetoxy acetic acid; (b) a solution of diacetone alcohol in acetic acid is treated with lead tetra-acetate to give acetone and acetoxyacetone; (c) a solution of heptaldol in benzene is treated with lead tetra-acetate to give heptaldehyde and a -acetoxy-heptaldehyde; (d) methyl ricinoleate is dissolved in acetic acid and treated with lead tetra-acetate to give heptaldehyde and methyl-11-acetoxy-9-undecenoate which on saponification gives 11-hydroxy-9-undecenoic acid and on oxidation with potassium permanganate give azelaic acid; (e) methyl ricinoleate is dissolved in caproic acid and treated with lead tetracaproate to give heptaldehyde and methyl-11 - acetoxy - 9 - undecenoate; (f) ricinoleyl alcohol dissolved in acetic acid is treated with lead tetra-acetate to give heptaldehyde and 11-acetoxy - 9 - undecene - 1 - ol which on saponification gives 1.11-dihydroxy-9-undecene; (g) castor oil is treated with lead tetra-acetate in acetic acid to give heptaldehyde and glycery tri - (11 - acetoxy - 9 - undecenoate); (h) the butyl ester of castor oil fatty acids is reacted with lead tetra-acetate in acetic acid to give heptaldehyde and butyl-11-acetoxy-9-undecenate; (j) castor oil fatty acids are treated with lead tetra acetate in acetic acid to give 11-acetoxy-9-undecenoic acid; and (k) methyl ricinoleate is treated with lead tetra-acetate using benzene and dichlorethylene as solvents to give heptaldehyde and methyl-11-acetoxy-9-undecenoate.  The lead tetra-acetate used is prepared by adding red lead to a mixture of glacial acetic acid and acetic anhydride and heating.