Patent GB-424659-A (GB)
Title: Process for the treatment of unsaturated organic halogenated compounds
IPC: C07C209/08
Filed: 1933-09-22
Abstract: Unsaturated organic compounds containing at least four carbon atoms and at least one halogen atom linked to a saturated carbon atom are treated under pressure with basic compounds.  When a strong base such as an alkali or alkaline earth hydroxide is used, the main product is an unsaturated alcohol obtained by substitution of a hydroxy group for halogen.  When a weak basic compound is used, such as basic lead acetate, bismuth subnitrate, bismuth subcarbonate, lead hydroxide, ferrous hydroxide or ferric hydroxide, or preferably an alkali or alkaline earth carbonate or bicarbonate, the main product is an aldehyde or ketone isomeric with the unsaturated alcohol referred to above.  When ammonia or a primary or secondary amine is used, unsaturated amines are obtained.  Suitable halogenated compounds are 3-chlorobutene-1, 3-chloromethylbutene-2, 1-chloro-3-methylbutene - 2, 3 - chloro - 2 - hydroxymethylpropene-1, 3-chloro-2-chloromethylpropene-1, isobutenyl chloride, 4-chloro-2-methylbutene-1, 3-chloro-2-methylbutene-1, 1-phenyl-2-chloromethyl-3-chloropropene-2, 1-phenyl-1-chloro-2-chloro-methylpropene-1, and 1-phenyl-1-chloro-2-methyl-3-chloropropene-2.  When mixtures of such halogenated compounds with compounds containing halogen linked to an unsaturated carbon atom are treated, the compounds of the latter class are unaffected; similarly, when a compound containing one halogen atom linked to a saturated carbon atom and another halogen atom linked to an unsaturated carbon atom is treated, the first halogen atom only reacts.  The reaction is preferably effected at 80--250 DEG  C. and may be carried out in an autoclave or in baffled tubes through which the reagents are caused to flow.  In the examples: (1) isobutenyl chloride, admixed or not with dimethylvinyl chloride, is heated under pressure with aqueous sodium hydroxide; isobutenol is formed, and dimethylvinyl chloride, if present initially, is recovered unchanged; if calcium carbonate is used in place of sodium hydroxide, isobutyraldehyde is obtained as the main product, with subordinate amounts of isobutenol, isobutyraldol, 2 : 2 : 4-trimethylpentadiol-1 : 3, isobutyl alcohol, and salts of isobutyric and hydroxyoctylic acids; (2), (3) and (4) isobutenol is obtained as in example 1, but under different reaction conditions; (5) a chlorinated amylene mixture consisting mainly of isopentenyl chlorides is heated with aqueous caustic soda under pressure; 2-methylbutene-1-ol-3 and 2-methylbutene-2-ol-4 are the main products; (6) a mixture of 1-phenyl-2-chloromethyl-3-chloropropene-2, 1 - phenyl - 1 - chloro - 2 - chloromethylpropene - 1, and 1 - phenyl - 1 - chloro - 2 - methyl - 3 - chloropropene - 2 is heated under pressure with aqueous caustic soda; the products are 1-phenyl-2-hydroxymethyl-3-chloropropene-2, 1-phenyl-1-chloro-2-hydroxymethylpropene-1, and 1-phenyl-1-hydroxy-2-methyl-3-chloropropene-2; (7) isobutenyl chloride is heated under pressure with an aqueous slurry of calcium carbonate; isobutyraldehyde and a subordinate amount of isobutenol are obtained; (8) isobutenyl chloride is heated under pressure with aqueous caustic soda; a mixture of isobutenol, isobutyl alcohol, isobutyraldehyde, isobutyric acid, and 2 : 2 : 4-trimethylpentadiol-1 : 3 is obtained; (9) isobutenyl chloride is heated under pressure with aqueous ammonia; a mixture of amines is obtained, from which mono-, di- and tri-isobutenylamines can be isolated; the compound (CH3)2CHN : C4H7 is also formed; (10) monochlorinated tertiary amylenes are heated under pressure with an aqueous sludge of marble; methylisopropyl ketone and isovaleraldehyde are the main products. The Specification states that the starting materials may contain alkoxy or amino groups.  Specification 339,675, [Class 2 (iii)], is referred to.  3-Chlorobutene-1 is prepared from butene-1-o1-3 and anhydrous hydrogen chloride.  3-Chloromethylbutene - 2, 1-chloro - 3 - methylbutene-2, 4-chloro-2-methylbutene-1, and 3-chloro-2-methylbutene-1 are the chief components of the mixture obtained by chlorinating technical tertiary amylenes. 3-Chloro-2-chloromethylpropene-1 occurs in the higher chlorination products of isobutylene.  3-Chloro-2-hydroxymethylpropene-1 is obtainable by careful hydrolysis of 3-chloro-2-chloromethyl-propene-1.  Phenylchloropropenes.  The phenylchloropropenes used in example 6 are obtained by chlorinating a mixture of phenylisobutenes of the formul  C6H5CH : C(CH3)2 and C6H5CH2C (CH3) : CH2 ; the phenylisobutene of the second formula is prepared by treating isobutenyl chloride with phenyl magnesium bromide, and decomposing the product with aqueous hydrochloric acid. The Specification as open to inspection under Sect. 91 is not restricted to the treatment of compounds containing at least four carbon atoms, and refers to the treatment of allyl halides, 2 : 3-dihalogenpropene-1, 2 : 3 : 3-trimethyl-3-halogenpropene-1, and 2-methyl-1 : 3-dihalogenbutene-1.  This subject-matter does not appear in the Specification as accepted.