Patent GB-957241-A (GB)
Title: Process for producing mono-ethylenic oxy compounds
IPC: C07C409/20
Filed: 1962-05-07
Abstract: Mono-ethylenic oxy compounds are obtained by treating an organic free radicle precursor with a diene, and, as solvent, water or an alcohol, or a mixture thereof, in the presence of 0.01 to 0.6 equivalents of cupric ion per mole of precursor. The products, some of which are new, are especially ethers and hydroxy compounds having an ether or hydroxyl group linked to a saturated carbon atom to which a carbon atom of an ethylenic group is directly attached. With conjugated dienes the reaction is: <FORM:0957241/C2/1> <FORM:0957241/C2/2> where R. is the free radicle and R1-OH the solvent. Products from 1, 4-addition e.g. <FORM:0957241/C2/3> , are also obtained but generally in smaller amounts. Illustrative of specified dienes, 1, 3-conjugated dienes being preferred, are 1, 3-butadiene, isoprene, 1, 3-cyclohexadiene, 2-phenyl-1, 3-butadiene, 1, 3-dodecadiene, 2, 3-dichloro-1, 3-butadiene, 2, 4-pentadienol and its ethyl ethers, b -vinylacrylic acid and sorbic acid and its methyl ester. Mixtures of dienes may be used. When hydroxyl-group containing products are desired, water is an adequate solvent.  For ethers, however, the corresponding organic hydroxy solvent should be used.  Thus t-butyl ethers are made in t-butanol. The proportion of alcohol used may effect the nature of the product.  Thus with ethylene glycol either b hydroxyethyl ether or dioxyethane compounds are obtained. Preferred solvents are water or saturated aliphatic mono or polyhydroxy alcohols. Representative of other specified polyols are trimethylene glycol, glycerol and sorbitol. Preferably the cupric ions are derived from a salt, which must be soluble in the chosen solvent, such as salts of polybasic inorganic acids e.g. the sulphate.  Cupric chloride may result in chlorine containing products. Other cupric salts specified include the nitrate and benzenesulphonate. Preferably 0.06 to 0.25 equivalents of cupric ion are used. Amounts of diene of 3 to 100 moles, preferably 5 to 15 moles, per mole of precursor are usually used.  Desirably at least one equivalent of hydroxy solvent should be present per mol of precursor.  Preferably less than 500, especially 10 to 150, moles of solvent per mole of precursor are used. Organic peroxides are the preferred source of free radicles, e.g. cyclic or t-alkyl peroxides.  The peroxides may contain substituents e.g. hydroxyl, cyano, alkoxy, carboxy and halogen groups.  Illustrative of specified reactions are the production of 3-methoxy-heptene-1 from 1, 1-dimethylbutyl-hydroperoxide and butadiene in methanol and 1-cyclohexyl-2-methoxybutene-3 when 1, 11-dicyclohexyl-hydroperoxide replaces the former peroxide, 3-methoxy-8-acetoxy-1-and 1-methoxy-8-acetoxy-2-octenes from 2-t-butyl-peroxy-2-methyltetrahydropyran and butadiene and aqueous methanol, 3-ethoxy-1- and 1-ethoxy-2-hexenes and -heptenes-1 from 3-t-butylperoxy-3-methyl-hexane and butadiene and ethanol, 10-keto-3-methoxy-1 and -1-methoxy-2-undecenes from 1-t-butylperoxy-1-methylcyclohexane, butadiene and methanol. Substituted peroxides may be used e.g. bis (1, 1-dimethyl-4-hydroxybutyl) peroxide which gives 5-methoxy-6- and 7-methoxy - 5 - heptenol from butadiene and methanol, 3-methoxy-6-cyanohexene-1 and 1-methoxy-6-cyanohexene-2 from t-butyl-3-cyano-t-amyl peroxide and butadiene and methanol, 3-methyl-3-ethoxy-7-methoxy-1- and some 3-methyl-1-ethoxy-7-methoxy-2-octene from 2-t-butylperoxy-2-methyl-5-methoxy-hexane, isoprene and ethanol and 7-chloro-3-ethoxy-3-methyl-1- and 7-chloro-1-ethoxy-2-methyl-2-heptene from 1, 1-bis-(4-chlorobutylperoxy)-1-phenyl-ethane from isoprene and ethanol.  Other free radicle precursors indicated are azo and carbonyl compounds.  The free radicles are generated by usual methods, e.g. photolyns and the addition of redox-reducing agents, the latter method being preferred, especially when using ferrous salts in the presence of a strong polybasic acid.  The products are especially useful in the preparation of dienic acids by the removal of the hydroxy or ether groups.  Thus 8-methyldecadienoic acid may be made from methoxy-8-methyldecenoic acid esters.  The dienoic acids may be polymerized e.g. with peroxide catalysts (see Division C3). Compounds of formula: <FORM:0957241/C2/4> where x is 4 or 5 and R is H or an alkyl group of up to 3 carbon atoms are preferred together with their esters of alkanols of 1 to 4 carbon atoms, since these compounds may be condensed, using acid catalysts and removing water as formed, to produce polyesters which can be cured at the allylic ethylenic bond.  The compounds of the above formula may also be subjected to ether exchange with allyl alcohol and the products epoxidised.  Examples are provided of the reaction of methyl omega caproate, omega-heptanone-2, omega-formyloxybutane, omega-hexane and t-butoxy precursors with butadiene, isoprene and chloroprene and methanol or ethanol, a wide variety of products being obtained.ALSO:Mono-ethylenic oxy compounds, obtained by treating an organic free radicle precursor with a diene and, as solvent, water or an alcohol, or a mixture thereof, in the presence of 0.01 to 0.6 equivalents of cupric ion per mole of precursor (see Division C2) may, by the removal of hydroxy or ether groups by e.g. dehydration, hydrolysis or pyrolysis, yield dienoic acids which may be polymerised or copolymerised in the presence of a peroxide catalyst.  The products may be crosslinked through their carboxylic acid groups by means of polyols e.g. ethylene and hexamethylene glycol or diisocyanates. Styrene, divinyl benzene, butadiene, methyl methacrylate and vinyl chloride are specified for copolymer formation. Indicated starting dienoic acids are 8-methyl-decadienoic acid and products made by hydrolysis with sulphuric acid and pyrolysis at 500 DEG C. of compounds obtained when the methyl o -caproate radicle precursor is reacted with butadiene and methanol in the presence of cupric sulphate and the dehydration of products obtained in a similar fashion when water is used instead of methanol. Monoethylenoic oxy compounds of formula <FORM:0957241/C3/1> where x is 4 or 5 and R is H or an alkyl group of 1-3 C atoms, obtained as above, may be condensed, using acid catalysts and preferably removing the water produced as fast as it is formed, to form polyesters which may be cured by treatment at the allylic bond.