Patent GB-1105537-A (GB)
Title: Improvements in or relating to the ozonisation of organic compounds
IPC: C07C51/34
Filed: 1965-08-20
Abstract: Homo- or co-polymers of polymerizable compounds, e.g olefines, styrene or acrylates, are converted into derivatives containing nitrile and hydroxy groups by ozonization in admixture with at least two mols of hydrogen cyanide per mol. of polymer, the ozonization being effected in a liquid medium under basic conditions. Derivatives containing nitrile and amino groups may be obtained by including in the reaction mixture up to five mols. of ammonia per mol. of hydrogen cyanide.  The hydrogen cyanide may be used as such or formed from cyanide-generating compounds, e.g. potassium or sodium cyanide.  The reaction mixture may be aqueous or anhydrous and, if aqueous, may include an emulsifier.  The nitriles may be isolated or they may be converted directly in the reaction mixture into other products, e.g. hydroxy acids. Examples 30-35 describe the treatment of polybutene, polypropylene, polyisobutylene and polyethylene grease.ALSO:Hydroxynitriles are obtained by ozonizing unsaturated organic compounds (including aromatic compounds) in admixture with at least two mols. of hydrogen cyanide per mol. of unsaturated compound, the ozonization being effected in a liquid medium under basic conditions. Aminonitriles may be obtained by including in the reaction mixture up to five mols. of ammonia per mol. of hydrogen cyanide.  The hydrogen cyanide may be used as such or formed from cyanide-generating compounds such as potassium or sodium cyanide. The reaction mixture may be aqueous or anhydrous and, if aqueous, may include an emulsifier.  The nitriles may be isolated or they may be converted directly in the reaction mixture into other products, e.g. hydroxy- or amino-acids. In examples: (1) cyclododecene yields 1,12-dihydroxydodecane - 1,12 - dicarboxylic acid; (2) cyclooctene yields 2,9-dihydroxysebacic acid; (3) cyclooctene yields 1,8 - dihydroxy - 1,8 - dicyanooctane; (4) indene yields 1 - oxoisochroman-3-carboxylic acid of the formula (5) acenaphthylene yields naphthalide-3-carboxylic acid of the formula <FORM:1105537/C2/1> (6) cyclododecene yields 1,12-diaminododecane-1,12 - dicarboxylic acid; (7) 1 - octadecene yields 2 - hydroxystearonitrile, which is converted into 2-aminostearic acid, 2-hydroxystearic acid or 2 - hydroxystearamide; (8) 5-norbornene - 2,3 - dicarboxylic anhydride yields the lactone of 1,2-dicarboxycyclopentane - 3,5 - diglycolic acid; (9) 1,5,9 - cyclododecatriene yields a product of the formula <FORM:1105537/C2/2> (10) a -pinene yields a product of the formula <FORM:1105537/C2/3> (11) 1 - dodecene yields 2 - acetaminolauronitrile; (12) 1 - dodecene yields 2 - acetoxylauronitrile, (13) 1,5 - cyclooctadiene yields 1,8 - dicyano - 1,8 - diacetoxyoctene - 4; (14) cyclooctene yields 2,9 - diacetoxysebaconitrile; (15) cholesterol yields a product of the formula <FORM:1105537/C2/4> (16) methyl abietate yields a product of the formula <FORM:1105537/C2/5> (17) 1 - methylcyclohexene - 1 yields an acetylated mixture of mono- and di-cyanoheptane derivatives; (18) cyclohexene yields 2,6-diacetoxysuberonitrile; (19) 1 - hexadecene yields 2-hydroxypalmitonitrile, from which 2-hydroxypalmitamide may be obtained by treatment with hydrogen chloride; the amide yields N-n-butyl - 2 - hydroxypalmitamide when treated with n-butylamine; (20) 1-hexadecene yields 2-aminopalmitonitrile; (21) methyl oleate yields 2 - acetoxycapronitrile and methyl 9-cyano - 9 - acetoxypelargonate; (22) stilbene yields mandelonitrile acetate; (23) allylbenzene yields phenylalanine; (24) norbornylene yields a product of the formula <FORM:1105537/C2/6> (25) an adduct of 1,5-hexadiene and hexachlorocyclopentadiene, of the formula <FORM:1105537/C2/7> yields a product of the formula <FORM:1105537/C2/8> (26) an adduct of (2,2,1)-bicyclo-2,5-heptadiene and hexachlorocyclopentadiene of the formula <FORM:1105537/C2/90> yields a product of the formula <FORM:1105537/C2/101> (27) an adduct of 1,5-cyclooctadiene and hexachlorocyclopentadiene, of the formula <FORM:1105537/C2/112> yields a product of the formula <FORM:1105537/C2/123> (28) dicyclopentadiene yields a mixture of products of the formulae <FORM:1105537/C2/134> <FORM:1105537/C2/145> Reference is made also to the treatment of benzene, naphthalene, anthracene, phenanthrene, chrysene, rubrene, coronene, styrene, divinylbenzene, 2 - and 4 - vinylpyridine, vinylquinoline, 1,2 - dipyridylothylene, allyl alcohol, 1 - butene - 4 - ol, oleyl alcohol, allyl methyl ether, crotyl butyl ether, phenyl allyl ether, methyl vinyl ketone, 1-cyclohexene-3-one, benzylidene acetone, oleic acid, crotonic acid, cinnamic acid, propenylsuccinic anhydride, dodecenylsuccinic anhydride, N - allylacetamide, N - oleylbenzamide, allyl chloride, p - bromostyrene, hexachloronorbornylbutene, sulpholene, divinyl sulphone, camphene, dipentene, cholesterone and ergosterol.