Patent GB-191317193-A (GB)
Title: Improvements in or relating to the Manufacture of Synthetic Caoutchoucs and Intermediate Products.
Inventor: HENRY DREYFUS
IPC: C07C1/30
Filed: 1913-07-26
Abstract: 17,193. Dreyfus, H. Aug. 5, 1912, [Convention date]. Void. [Published under Section 91 of the Act.] Hydrocarbons; alcohols; aldehydes; amino, cyano, imino, and nitroso compounds; carboxylic acids and esters; chlor and chlorhydroxy compounds ; ketones; furfurane, pyrrol, and thiophene derivatives.-The Specification describes the production of olefines, dienes, and their derivatives by the following series of processes: - (1) Condensation of two molecules of halogen compounds with elimination of halogen; suitable halogen compounds are, hydroxyhalogen compounds, their ethers and esters (for instance chlorhydrins), ketohalogen, aldehydohalogen and polyhalogen compounds, acid chlorides, non- saturated halogen derivatives of hydrocarbons, &c. The removal of halogen can be effected by means of metallic salts such as cuprous chloride, or metals such as copper (copper powder, copper wool, or colloidal copper), zinc, lead, iron, etc.; alkali metals, such as sodium or potassium, are less suitable; mixtures of other metals with traces of copper or copper salts may be used. The reaction may be carried out under pressure or not, and with or without employment of solvents, diluents, or emulsifying agents, or by passing the liquid or vaporized products through heated tubes containing halogen-removing substances. Hydroxy derivatives, such as glycols, can be converted into olefine or diolefine hydrocarbons by elimination of water, for example by means of sodium or potassium bisulphate, potassium pyrosulphate, zinc chloride, copper sulphate, zinc sulphate, oxalic acid, aluminium, chromium, or iron sulphate, acid salts of mono and polysulphonic acids of the aromatic or aliphatic series, aluminium oxide, &c. The halogen compounds can be transformed into the olefine or diolefine hydrocarbons by elimination of halogenhydride, for example by heating with alkali phenolates, salts of fatty acids, borates, aluminates, pyridine, quinoline, aniline, carbonates, oxides, hydroxides, &c. Compounds which are both halogenated and hydroxylated can be converted into the diolefine hydrocarbons by a combined elimination of water and halogenhydride. Ketones, diketones, aldehydes, ketonealdehydes, ketonealcohols, &c. can be converted by reduction into alcohols and then into halogenated products, or they can be transformed directly into halogenated products by means of chlorides of sulphur, snlphuryl chloride, chlorides of phosphorus, &c. ; halogendiolefines are thus obtained and converted into the hydrocarbons by treatment with zinc &c. Ketones &c. may be converted into imines, iminoketones, isonitrosoketones, pyrrols, &c. by means of ammonia, hydroxylamine, &c., and then by appropriate treatment yield dienes. Non-saturated hydroxy or halogen derivatives can be reduced to saturated compounds, or the halogen derivatives may be converted first into hydroxy derivatives, or the corresponding furfuranes may be first produced; these products can be transformed into diolefines. The following are suitable parent materials: - (a) Halogenhydrins such as ethylene chlorhydrin, ethylidene chlorhydrin, propylene chlorhydrin, their homologues and isomers, ethers, esters, such as #-chlorethyl ester and their substitution products; these products may be prepared from acetylene or ethylene by addition of halogen or halogenhydride in the presence of contact substances such as aluminium chloride, antimony chloride, &c., or they may be prepared from acetic aldehyde, which may be formed from acetylene by the action of' halogenhydrides, in the presence or absence of mercury salts &c., or by the action of chlorine or halogenhydride or hypochlorous acid on ether or ethylene, or by the energetic action of chlorine on ethyl alcohol in the absence of water. Condensation of these products yields butandioles, their homologues and isomers. Glycol oxides also, by elimination of water, form mono- and di-olefines. Or the glycols can be converted by partial elimination of water into butenols; these products can also be obtained bv condensing a ehlorhydrin with an halogenolefine. (b) Polyhalogen derivatives of hydrocarbons of the fatty or aliphatic-aromatic or hydroaromatic series such as ethylene chloride, ethylidene chloride, their homologues, isomers, and substitution products. These products may be prepared from ethylene or from acetylene or alcohol, &c., for example by acting on acetylene with hydrochloric acid in presence of aluminium chloride, antimony chloride, &c., ethylidene chloride is obtained; this product is also obtained on treating acetaldehyde with chlorides of sulphur, chlorides of phosphorus, or sulphuryl chloride, &c. By condensation of these products there result halogenated derivatives of the butane series. By elimination of hydrochloric acid, non-saturated hydrocarbons result. The halogen derivatives can also be transformed into chlorhydroxy, dichlor, or polychlor derivatives or into chlorolefines such as chlorbutenes, all of which can be transformed into the diolefines. (c) The halogenolefines, such as vinyl chloride, vinyl bromide, # - chloropropylene, # -chlorbutylene, &c., their homologues, isomers, and substitution products. Vinyl chloride may be prepared from acetylene and hydrochloric acid in presence of contact substances preferably using excess of acetylene, or from ethylene chloride. The manufacture of #-chlorpropylene and of its homologues is preferably effected by treating the corresponding ketones with chlorides of sulphur, chlorides of phosphorus, &c. (d) The halogenketones such as chloracetone, their homologues, isomers, and substitution products. Condensation of chloracetone gives acetonylacetone which by reduction, for example with aluminium-, sodium-, or magnesium-amalgam, or hydrogen in presence of catalysts, forms a diglycol of the formula CH3-CH(OH)-CH2-CH2- CH(OH)CH, which by elimination of water gives a diene. Diketones may be converted by means of chlorides of sulphur or of phosphorus into chlorinated derivatives, which by elimination of hydrochloric acid form chlorinated dienes. These latter may be directly polymerized, or they may first be freed from chlorine by treatment with zinc &c. (e) The halogen derivatives of acids such as acid chlorides, for example acetyl chloride. By condensation diketones are formed which can be reduced to butandiols &c., or converted by means of chlorides of sulphur or of phosphorus &c, into chlorides. (f) The halogen derivatives of aldehydes such as mono-chloraldehyde, #-chlorpropionic aldehyde, &c. By condensation dialdehydes are formed, which by reduction are transformed into polyhydroxy alcohols, or are converted by treatment with chlorides of sulphur or phosphorus into halogen derivatives, or by ammonia into imines, all of which may be converted into corresponding dienes. These products can also be transformed into furfurane derivatives, which again by appropriate treatment will form olefines. (g) The halogen derivatives of unsaturated hydrocarbons or their homologues and substitution products, for example, dichlorethylene, perchlorethylene, chlorvinyl alcohol, acetylene-chlorhydrin, or chlorvinyl ether. Chlorvinyl alcohol and chlorvinyl ether may be obtained from the halogenated derivatives by treatment with agents capable ot eliminating chlorine and adding hydroxy or alkoxy groups, for example potassium and alcohol, or from acetylene by means of hypochlorous acid. By condensation halogen and hydroxy derivatives of the butadiene series are formed. By appropriate reduction there are formed saturated halogen or hydroxy derivatives which can be transformed into the dienes. (h) Mixtures of the different products indicated above, for example halogenated ketones with acid chlorides or with halogenated hydrocarbons &c. (2) Certain halogenated derivatives can also be transformed by the action of cyanides such as potassium cyanide, into intermediate products of the butadiene series. For example, by treatment of chloracetone with potassium cyanide a cyanacetone is formed which by reduction forms an aminoacetone; replacement of the amino group by hydroxyl gives a product which can be converted into a glycol, chlorbutanol, chlorbutene, or butenol, which by subsequent elimination of water form diolefines. Ethylene chloride yields ethylene cyanide which by reduction and diazotizing forms a butandiol. (3) Aldehydes or ketones may be caused to act on halogen derivatives of saturated or non- saturated hydrocarbons, or on the non-saturated hydrocarbons or their derivatives themselves in the presence of metals such as magnesium, zinc, &c. For example, vinyl bromide or chloride and acetone or its homologues in presence of magnesium yield isoprene alcohol or its homologues; with acetaldehyde a butenol is obtained. Acetone and #-chlorpropylene form a methylisopropene alcohol; acetaldehyde with #-chlorpropylene forms an isopropene alcohol. Dichlorethylene forms with acetone or acetaldehyde a chlorisopropene alcohol. Similarly, chlorvinyl ether or chlorvinyl alcohol give oxyethers of butadiene or isoprene. Ethylene chloride forms with acetone a product of the formula CR2Cl. CR2.C(CH3)2.OH; acrolein gives with chlorethyl a product of the formula CH2=CH-CH(OH) C2H5. By elimination of water or of halogenhydride the diolefines are formed. (4) Acetylene can be transformed into acetaldehyde by addition of water, for example in the presence of mercury salts and concentrated sulphuric acid &c. The acetic aldehyde can be condensed to aldol, which by reduction forms a glycol, which by elimination of water gives a diolefine. The reaction can also be conducted by passing through the halogen derivatives and splitting off halogenhydride as above described; chlorbutanols, chlorbutenes, or butenols may also be formed. Cretonic aldehyde can be similarly converted into diolefines or their chlor derivatives. Acetone or acetic aldehy