Patent GB-581303-A (GB)
Title: Manufacture of new nitrosulphones
IPC: C07C317/14
Filed: 1944-08-31
Abstract: Nitrosulphones are prepared by causing a compound of formula RR1CHNO2 to react with a sulphone of formula R11SO2R111 in the presence of an alkaline reacting substance, where R and R1 may be hydrogen or substituted or unsubstituted hydrocarbon radicals or together may form part of a cycloaliphatic ring and where R11 and R111 are substituted or unsubstituted hydrocarbon radicals at least one of which carries an ethylenic double bond in a position a  : b  to the sulphone group or is a b -chlor or b -brom alkyl group.  If one or both of the groups R and R1 are hydrogen, then secondary products may be obtained by reaction with further molecules of sulphone.  The reaction may be carried out in the presence of a solvent which may be, for example, dioxan or ethylene glycol ethers.  In the examples: (1) an aqueous ethanol solution of n-butylvinylsulphone and nitroethane is refluxed in the presence of potassium hydroxide.  On cooling, 3-nitro-1 : 5-di-(butanesulphonyl)-3-methylpentane crystallizes out; (2) a solution of potassium hydroxide in methanol is added slowly to an ice-cold solution of 1-nitropropane in methanol, n-butylvinylsulphone is added and the mixture heated.  The product is diluted with water and cooled, the deposit consisting of 3 - nitro - 1 : 5 - dibutanesulphonyl - 3 - ethyl - pentane is filtered off, and the filtrate acidified with acetic acid and extracted with ether.  The extract is dried and the ether distilled off, giving n-butyl-g -nitroamylsulphone; (3) an aqueous solution of sodium hydroxide is slowly added to a cooled, stirred solution of 1-nitropropane in methanol, n-butyl-b -chloroethylsulphone is then added and the mixture stirred at room temperature.  The product is poured into aqueous sodium hydroxide when a precipitate of 3-nitro-1 : 5-dibutanesulphonyl-3-ethylpentane is obtained; (4) the process of example (1) is repeated using nitromethane and methylvinylsulphone giving a product of tris-(b -methanesulphonylethyl) nitromethane; (5) the process of example (1) is repeated using 2-nitropropane and divinylsulphone giving a product of g  : g 1-dinitro-g  : g 1-dimethyldibutylsulphone; (6) aqueous sodium hydroxide solution is added slowly to a cooled, stirred mixture of nitroethane and water. The mixture is stirred and then n-butylvinylsulphone added.  Crystals of 3-nitro-1 : 5-di-(n-butanesulphonyl)-3-methylpentane separate. The filtrate is acidified with acetic acid when g -nitro-di-n-butylsulphone separates; (7) isobutylvinylsulphone is added to an aqueous solution of the sodium salt of p-bromophenylnitromethane, the mixture being warmed and stirred.  The product is filtered after the addition of kieselguhr and the filtrate acidified with acetic acid giving isobutyl-3-nitro-3-p-bromophenylpropylsulphone; (8) an aqueous methanol solution of p-bromophenylnitromethane and methylvinylsulphone is allowed to stand in the presence of b -hydroxyethyltrimethylammoniumhydroxide.  A deposit of 3-nitro-1 : 5-di-(methanesulphonyl)-3-p-bromophenylpentane is obtained; (9) a solution containing p-nitrophenyl-b -bromoethylsulphone (obtained by hydrogen peroxide oxidation of p-nitrophenyl-b -bromoethylsulphide), nitrocyclohexane and potassium hydroxide in methanol is refluxed, the alcohol distilled off, and the residue diluted with water when p-nitrophenyl-b -1-nitrocyclohexylethylsulphone is precipitated. Other nitro-compounds which may be used are stated to be 1- and 2-nitrobutane, 1-nitrohexane, nitroneopentane, 1-nitro-2 : 2-dimethylbutane, 1-nitrohexadecane, 2 - nitroethanol, 1 - nitro - 2 - propanol, phenyl - nitromethane, p-nitrophenylnitromethane and a -naphthylnitromethane.  Unsaturated sulphones which may be used, also include, ethylvinyl-, tert-amylvinyl-, n-dodecylvinyl-, n-cetylvinyl-, phenylvinyl-, p - chlorophenylvinyl-, benzylpropenyl-, p-tolylstyryl- and p-methoxyphenylvinylsulphone.  Halogenated sulphones which may be used also include b  : b 1-dichlorodiethyl-, b -bromodiethyl- and b -chloroethylmethylsulphone.  In the Provisional Specifications, the sulphone used may be unsaturated in a position b : g  to the sulphone group.  Benzylallyl-, ethylallyl- and diallylsulphones are mentioned.  b -Chlorethylsulphones may be prepared by treating the sodium salt of the corresponding mercaptan with ethylene chlorhydrin, reacting the resulting b -hydroxyethylsulphide with thionylchloride and oxidising with hydrogen peroxide.  The b -chlorethylsulphones are converted to the corresponding vinylsulphones by treating them in benzene solution with triethylamine.  1-Nitrohexadecane may be prepared by reacting nitroethylene with tetradecylmagnesiumbromide in ether as described in Specification 571,804.  Specification 442,524 also is referred to. Samples have been furnished under Sect. 2 (5) of (1) 2 - nitro - 1 : 5-di - p - toluenesulphonyl - 3 - ethylpentane, from 1-nitropropane and p-tolylvinylsulphone, and (2) 3-nitro-1-p-toluenesulphonyl-3-ethylbutane from 2-nitropropane and p-tolylvinylsulphone.