Patent GB-1394864-A (GB)
Title: Unsaturated ethers and thioethers
IPC: C07C49/255
Filed: 1972-05-31
Abstract: 1394864 Unsaturated ethers and thioethers SANDOZ Ltd 31 May 1972 [2 June 1971] 25476/72 Heading C2C Compounds of Formula I wherein R 1  is alkyl of 1 to 10 carbon atoms; alkenyl of 3 to 10 carbon atoms; alkynyl of 3 to 10 carbon atoms; cycloalkyl of 3 to 6 carbon atoms; cycloalkyl of 3 to 6 carbon atoms substituted by alkyl of 1 to 4 carbon atoms; cycloalkenyl of 5 to 7 carbon atoms; cycloalkenyl of 5 to 7 carbon atoms substituted by alkyl of 1 to 4 carbon atoms; cycloalkyl (of 3 to 6 carbon atoms) alkyl (of 1 to 4 carbon atoms); cycloalkyl (of 3 to 6 carbon atoms) alkyl (of 1 to 4 carbon atoms) ring substituted by alkyl of 1 to 4 carbon atoms; cycloalkenyl (of 5 to 7 carbon atoms) alkyl (of 1 to 4 carbon atoms); or cycloalkenyl (of 5 to 7 carbon atoms) alkyl (of 1 to 4 carbon atoms) ring substituted by alkyl of 1 to 4 carbon atoms; R 2  and R 3 , which are the same or different, are each hydrogen or alkyl of 1 to 4 carbon atoms, Y is cyano; -CONR 4 R 5  wherein R 4  and R 5 , which are the same or different, are each hydrogen of alkyl or 1 to 4 carbon atoms, or R 4  and R 5  together with the nitrogen atom constitute a 5 to 6 membered heterocycle containing either one ring nitrogen atom or one ring nitrogen atom and one ring oxygen atom; -COOR 6  wherein R 6  is alkyl of 1 to 5 carbon atoms; or COR 7  wherein R 7  is alkyl of 1 to 5 carbon atoms; Q is oxygen or sulphur; is or and n is an integer 1, 2 or 3, with the proviso that when Y is -COOR 6  then R 3  is alkyl, are produced by (a) reacting a compound of Formula II wherein R 1 ,R 2 , R 3 , Q, and n are as defined above with a compound of Formula III wherein Y is as defined above and R 8  and R 9  which are the same or different, are each phenyl, alkoxy of 1 to 4 carbon atoms or aryloxy, in the presence of a strong base, or (b) reacting a compound of Formula II with a compound of Formula IV wherein Y is as defined above and R 10 , R 11  and R 12  are each aryl or dialkylamino of 2 to 8 carbon atoms or (c) reacting a compound of Formula V wherein R 1 , R 2 , Q and n are as defined above is or and X is chlorine or bromine, with a compound of Formula VI wherein R 3  and R 7  are as defined above and R 13  is alkyl of 1 to 4 carbon atoms with subsequent acid hydrolysis and dehydration to produce a compound of Formula Ia wherein R 1 , R 2 , R 3 , R 7 , Q, and n are as defined above, or (d) reacting a compound of Formula Ib wherein R 1 , R 2 , R 3 , R 6 , Q, and n are as defined above with a compound of Formula VII MNR 4 R 5  wherein R 4  and R 5  are as defined above and M is hydrogen, lithium or MgBr to produce a compound of Formula Ic wherein R 1 , R 2 , R 3 , R 4 , R 5 , Q, and n are as defined above. The compounds of Formula I are used in insecticidal compositions. The compound of Formula II employed as starting material in processes (a) and (b) above may be produced as follows viz: (a<SP>1</SP>) the compounds of Formula IIa wherein R 1 , R 2 , R 3 , Q and n are as defined above may be produced by reacting a compound of Formula VIII  wherein R 1 , R 2 , Q and n are as defined above with a compound of Formula XIII wherein R 3  is as defined above and R 14  is methyl or ethyl, in manner known per se, (b<SP>1</SP>) the compounds of Formula IIb wherein R 1 , R 2 . R 3  Q and n are as defined, above and is  or  may be produced by etherifying a compound of Formula IX wherein R 1 , R 2 , Q, and n are as defined above, with a compound of Formula X wherein R 3  is as defined above, in manner known per se, (c<SP>1</SP>) the compounds of Formula IIc wherein R 1 , R 2 , R 3 , Q, and n are as defined above, may be produced by reacting a compound of Formula XI wherein R 1 , R 2 , Q, n and X are as defined above. with a compound of Formula XIII with subsequent hydrolysis and decarboxylation, in manner known per se, (d<SP>1</SP>) the compounds of Formula IId wherein R 1 , R 2 , Q and n are as defined above, may be produced by reacting a compound of Formula VIII, with an alkylvinyl ether of 3 to 7 carbon atoms, in the presence of mercuric acetate. The reaction may be effected at elevated temperature and over a prolonged period, e.g. 4 days, with subsequent rearrangement while heating at a temperature of, for example, 160-190 C., over a period of, for example, 1 to 2 hours, (e<SP>1</SP>) the compounds of Formula IIe wherein R 1 <SP>1</SP> is alkyl of 1 to 10 carbon atoms; cycloalkyl of 3 to 6 carbon atoms; cycloalkyl of 3 to 6 carbon atoms substituted by alkyl of 1 to 4 carbon atoms; cycloalkyl (of 3 to 6 carbon atoms) alkylene (or 1 to 4 carbon atoms); or cycloalkyl (of 3 to 6 carbon atoms) alkyl (of 1 to 4 carbon atoms) ring substituted by alkyl of 1 to 4 carbon atoms; and R 2 , R 3 , Q and n are as defined above, may be produced by catalytic hydrogenation of a compound of Formula IIf wherein R 1 <SP>1</SP>, R 2 , R 3 , Q and n are as defined above, in conventional manner. The compounds of Formula VIII may, for example, be produced by reacting a compound of Formula XII wherein R 1 ,  2 R, Q and n are as defined above, with vinyl magnesium chloride or bromide. The compounds of Formulae III, IV, V, VI, VII, IX, X, XI, XII and XIII are either known or may be produced in analogous manner to the process for producing the known compounds.