Patent GB-441457-A (GB)
Title: Organic condensation products and their manufacture
IPC: C07C43/16
Filed: 1934-04-16
Abstract: Addition products are obtained by the reaction of compounds containing an alcoholic hydroxy group, or aliphatic or aromatic mercaptans, with hydrocarbons containing conjugated unsaturated linkages, one at least of which is an acetylenic linkage. Specified hydrocarbons are mono- and di-vinylacetylene.  The hydroxy compounds treated may be primary, secondary or tertiary monohydric alcohols or their substitution products, such as aminoalcohols, or polyhydric alcohols or derivatives thereof such as partly esterified polyhydric alcohols and esters of hydroxy acids; specified hydroxy compounds are methanol, ethanol, isopropanol, n-butanol, tertiary butanol, benzyl alcohol, cyclohexanol, ethylene glycol and its monomethyl ether, diethylene glycol, glycerol, dimethyldimethylolmethane, monoethylin, monobenzylin, mannitol, sugars, starch and cellulose.  Specified mercaptans are thiocresols, benzyl mercaptan, n-butyl mercaptan, diethylthiocarbinol, cyclohexyl mercaptan, mono- and di-thioglycols, and thioglycollic acid.  The reaction of an alcohol ROH with monovinylacetylene is believed to yield first a diolefinic ether CH2 : C : CHCH2OR, which is then converted into an acetylenic ether CH3C­CCH2OR; the reaction with divinylacetylene is believed to yield a triolefinic ether CH3CH : C : C(OR) CH : CH2; in each case, addition products from two mols. of alcohol and one of hydrocarbon are also obtainable.  The products are useful as perfume ingredients, solvents, insecticide ingredients, and plasticizers; the mercaptan addition products are useful as "rubber chemicals."  In the examples: (1) methanol containing p  dissolved sodium is heated with monovinylacetylene to yield a product of the probable formula CH3C­CCH2OCH3, which yields methyl n-butyl ether on reduction; (2) ethanol and monovinylacetylene, reacted as in example 1, yield a similar product which gives ethyl n-butyl ether on reduction; (3) butanol and monovinylacetylene are reacted as in example 1 to yield a product of unstated constitution; (4) benzyl alcohol and monovinylacetylene are reacted as in example 1 to yield an addition product and a resinous by-product; (5) ethylene glycol and monovinylacetylene are reacted as in example 1 to yield an equimolecular addition product and a resinous by-product; (6) cyclohexanol or (example 7) ethylene glycol monomethyl ether or (example 8) isopropanol, or (example 9) tertiary butanol is reacted with monovinylacetylene as in example 1; addition products of unspecified constitution are obtained; (10) methanol containing sodium methylate is heated with divinylacetylene to yield methoxy - 4 - hexatriene - 2 : 3 : 5; (11) methanol and divinylacetylene are reacted as in example 10, but for a longer time; an addition product from two mols. of alcohol and one of hydrocarbon is obtained, as well as the product of example 10; (12) a mixture of p - thiocresol and monovinylacetylene is irradiated with an electric lamp to yield products of the probable formul  CH3C6H4SCH2CH2C­CH, (CH3C6H4SH)2C4H4, and (CH3C6H4SH)3C4H4; (13) a mixture of benzyl mercaptan and monovinylacetylene is irradiated with artificial light to yield a product of the formula C6H5CH2SH.C4H4 and other products of higher boiling point; (14) a mixture of p-thiocresol and divinylacetylene is allowed to stand; a product of the formula <FORM:0441457/IV/1> is obtained.ALSO:Products useful as "rubber chemicals" are obtained by the reaction of aliphatic or aromatic mercaptans with hydrocarbons containing conjugated unsaturated linkages, one at least of which is an acetylenic linkage.  Specified mercaptans are thiocresols, benzyl mercaptan, n-butyl mercaptan, diethylthiocarbinol, cyclohexyl mercaptan, mono- and di-thioglycols, and thioglycollic acid.  Examples are given in which (1) p-thiocresol and monovinylacetylene yield products of the probable formul CH3C6H4SCH2CH2C= CH,(CH3C6H4SH)2C4H4, and (CH3C6H4SH)3C4H4; (2) benzyl mercaptan and monovinylacetylene yield a product of the formula C6H5CH2SHC4H4; (3) p-thiocresol and divinylacetylene yield a product of the formula CH3C6H4SCH2CH2C= CCH2CH2SC6H4CH3.