Patent GB-951669-A (GB)
Title: Improvements in or relating to condensation products
IPC: C08F2/38
Filed: 1961-05-19
Abstract: A product of general formula: <FORM:0951669/C2/1> where R and R2 are hydrogen, alkyl radicals of 1 to 8 carbon atoms, alkenyl radicals of up to 8 carbon atoms or cycloalkyl, aralkyl, aryl or heterocyclic radicals, R1 is hydrogen, an alkyl radical of 1 to 5 carbon atoms or a cycloalkyl, aralkyl, aryl or heterocyclic radical and m is a whole number from 1 to 20 is prepared by reacting an alkylidene diacylate of formula: <FORM:0951669/C2/2> with an unsaturated compound of formula: <FORM:0951669/C2/3> at -50 DEG C. to 150 DEG C. in the presence of 0.05 to 30% (of the weight of diacylate) of a Lewis acid addition catalyst the molar ratio of unsaturated compound to alkylidene diacylate being from 1:1 to 20:1.  The alkylidene diacylate, which may be a benzal diacylate, may be made in situ by reacting a carboxylic acid anhydride with an aldehyde in the presence of the acidic catalyst. Aldehydes which may be so used are aliphatic saturated or unsaturated aldehydes, mono and polynuclear aromatic aldehydes, araliphatic aldehydes, cyclo-aliphatic and heterocyclic aldehydes. While the anhydrides may be of aliphatic saturated or unsaturated mono, di or polycarboxylic acids, halogenated products of the monocarboxylic acids, dimeric, fatty acids, maleic acid, benzoic acid, substituted benzoic acids, phenylacetic acid, cinnamic acid and phthalic acid.  In a modification the reaction products of alkylidene diacylates and another aldehyde may also be used.  Specified unsaturated compounds are styrene, alpha-methyl styrene, ethyl styrene and chlorostyrenes, divinyl benzene, butadiene, isoprene, 2-3-dimethyl butadiene, chlorobutadiene, 1-vinylcyclohexene, 1-2-dimethylenecyclohexane, 1-11-bicyclohexenyl and the endocyclic dienes described in Specifications 796,133 and 796,135.  The catalysts must act as a Lewis acid and have a strength greater than acetic acid.  A long list is given including sulphuric, chloroacetics, benzene sulphonic, sulphonated polymers having a base of divinyl benzene cross-linked polystyrene, sulphonation products of phenol formaldehyde resins, boron trifluoride, phosphorus trichloride and sulphurated chlorides.  Referring to the examples (1) 510 parts of acetic anhydride are added dropwise to a mixture of 530 parts benzaldehyde and 60 parts polystyrene sulphonic acid cross-linked with 2% divinyl benzene and the mixture heated to give the benzaldiacetate which is then cooled and 520 parts styrene (stabilized with 0.1% hydroquinone added dropwise. Agitation follows then filtration to remove the acid catalyst and distillation giving a first distillate corresponding to 1-3-diphenyl-propanediol-1.3-diacetate, (2) 212 parts benzaldehyde, 204 parts acetic anhydride, 20 parts volume-boron trifluoride/etherate and 208 parts styrene are similarly reacted, the catalyst removed and unreacted material distilled off to give a product similar to that of Example 1. This product is saponified with KOH in ethanol under reflux producing 1-3-diphenyl-propane-1-3-diol, (3) benzaldiacetate replaces the benzaldehyde and acetic acid of (2), (4) 104 parts styrene are added dropwise to a mixture of 102 parts acetic anhydride, 30 parts paraformaldehyde and 10 parts conc. sulphuric acid at 40 DEG C. Then potassium acetate is added with agitation, the mixture filtered and distilled to give an ester which is refluxed with KOH in ethanol giving on fractional distillation 4-phenyl-1-3-dioxane and an alcohol boiling between 105 and 127 DEG C./0.1 mm.Hg.(20) 93 parts 2-6-dichlorobenzaldiacetate in 50 parts absolute benzene are first treated with 10 parts boron trifluoride etherate and than at 40 DEG C. with 34 parts styrene.  Later extraction with dilute sodium bicarborate and distillation yields a distillate which on saponification gives 1-phenyl-3-(21-61-dichlorophenyl)-propanediol-1-3. (22) The crude 1-3-diphenyl-propane 1-3-diol diacetate of Ex. 1 was saponified to give crude 1-3-diphenyl-1-3-propane-diol isomer mixture and finally (23) 100 parts benzaldehyde, 102 parts acetic anhydride and 20 parts polystyrene sulphonic acid of Example 1 were reacted with styrene to give an ester.ALSO:An alkylidene diacylate of formula: <FORM:0951669/C3/1> where R and R2 are hydrogen, alkyl radicals of 1 to 8 carbon atoms, alkenyl radicals of up to 8 carbon atoms, cycloalkyl, aralkyl, aryl or heterocyclic radicals is reacted with an olefinically unsaturated compound of formula: <FORM:0951669/C3/2> where R1 is hydrogen, an alkyl radical of 1 to 5 carbon atoms, or a cycloalkyl, aralkyl, aryl or heterocyclic radical at -50 to 150 DEG C. in the presence of 0.05 to 30%, on the weight of diacylate, of a Lewis acid addition catalyst, the molar ratio of unsaturated compound to diacylate being from 1:1 to 20:1. The alkylidene diacylate may be prepared in situ by reacting a carboxylic acid anhydride with an aldehyde in the presence of the acidic catalyst. List of aldehydes including formaldehyde trichloroacetaldehyde, acrolein, benzaldehyde, nitrobenzaldehydes, cinniamic aldehyde, furfural and hexahydrobenzaldehyde and carboxylic acids including acetic acid, oleic acid, acrylic acid, their halogenation products, succinic acid, sebacic acid, maleic acid, cinnamic acid and phthalic acid are given. Specified olefinically-unsaturated compounds are styrene, alpha-methyl-styrene, ethyl styrene and chlorostyrene, divinyl benzene, butadiene, isoprene, 2.3-dimethylbutadiene, chloro-butadiene, 1-vinyl cyclohexene, 1-2-dimethylene-cycloalkanes and polycyclic dienes.  A long list of Lewis acid catalysts includes strong inorganic acids, organic carboxylic acids, aliphatic and aromatic sulphonic acids, cation exchangers of the sulphonated polymer type, and halides of non-metals. Specifications 796,133 and 796,135 are referred to.