Patent GB-754968-A (GB)
Title: Improvements in and relating to spirocyclic esters
IPC: C07D317/72
Filed: 1954-05-20
Abstract: The invention comprises spirocyclic esters of sulphurous acid of the general formula <FORM:0754968/IV(a)/1> where X represents a divalent saturated hydrocarbon radical having from 4-17 carbon atoms which together with the quaternary C atom forms a 5 to 7 membered ring, and R represents a chlorosubstituted alkyl radical containing 2 or 3 carbon atoms. The radical X may be substituted by halogen atoms or alkoxy groups, and may be a cycloaliphatic or a straight- or branched-chain aliphatic radical.  The esters may be obtained by reacting a spirocyclic alcohol of the general formula <FORM:0754968/IV(a)/2> with a chloroalkyl chlorosulphite of the general formula R-O-SO-Cl, in the presence of a base such as pyridine, triethylamine or dimethylaniline, in a solvent such as ether or benzene.  The spirocyclic alcohol may first be obtained by acetalizing cycloaliphatic ring ketones with glycerine using an acid condensation agent such as hydrochloric acid, in a solvent such as toluene which enables the removal by azeotropic distillation of water formed.  In examples: (1) glycerol is reacted with 4-tertiary butyl hexanone to form 1,4-dioxa-8-tert.-butyl-spiro-[4,5]-decyl-(2) methanol, which is then reacted with b -chloroethyl-chlorosulphite to form {1,4-dioxa-8-tert.-butyl-spiro-[4,5] - decyl - (2) - methyl} - (b  - chloroethyl) - sulphite, and (2) glycerol is reacted with cyclohexanone to form 1,4-dioxa-spiro-[4,5]-decyl-(2)-methanol, which is reacted with b ,b 1 - dichloro-isopropylchlorosulphite to form {1,4-dioxa - spiro - [4,5] - decyl - (2) - methyl} - (b ,b 1-dichloro-isopropyl) sulphite.  A further example gives a list of spirocyclic alcohols and the b -chloro-ethyl sulphite esters obtained from them.ALSO:Pesticidal compositions comprise a spirocyclic ester of sulphurous acid of formula: <FORM:0754968/VI/1> where X is a divalent, saturated hydrocarbon radical having 4 to 17 carbon atoms which together with the quaternary C atom forms a five to seven membered ring and R is a chlorosubstituted alkyl radical containing 2 or 3 carbon atoms, and a carrier therefor. The radical X may be substituted by halogen atoms or alkoxy groups and may be a cycloaliphatic or a straight or branched-chain aliphatic radical. The carrier may be a powder, ointment, liquid, water emulsion of a propelling agent such as difluorodichloromethane or methyl chloride. Compositions may contain talc, kaolin, ground limestone, bentonite, chalk, precipitated magnesium carbonate, diacetone alcohol, xylene, petroleum, and blood albumen; emulsifying agents and wetting agents such as high molecular ethylene oxide condensation products, sulphite waste liquor, and the sodium salt of dibutylnaphthalene sulphonic acid.  Esters used in Examples (4 to 10) are [1 : 4-dioxa-8-tertiary butyl-spiro-[4,5]-decyl-(2)-methyl]- (b  - chlorethyl) - sulphite, [1 : 4 - dioxa - 8 - cyclohexylspiro - [4,5] - decyl - (2) - methyl] - (b  - chlorethyl) - sulphite, [1 : 4 - dioxa - 8 - amyl - spiro - [4,5] - decyl - (2) - methyl] - (b  - chlor-ethyl) - sulphite, and [1 : 4 - dioxa - 7 : 9 : 9 - trimethyl - spiro - [4,5] - decyl - (2) - methyl] - (b  - chlor - ethyl) - sulphite.  The compositions may also include other active ingredients such as a  : a  - bis - (chlorophenyl) - b  : b  : b  - trichlorethane or - b  : b  - dichlorethane, 1 : 2 : 4 : 5 : 6 : 7 : 8 : 8 - octachloro - 3a : 4 : 7 : 7a - tetra - hydro - 4 : 7 - methano - indane, diethyl - p - nitrophenyl thiophosphate, 5 : 5 - dimethyl - dihydroresorcin - dimethyl carbamate, dinitrocresol, nitrated naphthylamines, mercury compounds, copper compounds, mercuric chloride or sulphur.