Patent GB-1439491-A (GB)
Title: Aromatic long chain alkenyl ethers and thioethers
IPC: A01N37/10
Filed: 1973-08-08
Abstract: 1439491 Benzodioxole-substituted and aryl-substituted ethers SANDOZ Ltd 8 Aug 1973 [10 Aug 1972 9 June 1973] 37574/73 Heading C2C The invention comprises compounds (I) wherein R 1  is alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms, alkynyl of 3 to 6 carbon atoms, cycloalkyl of 5 to 7 ring carbon atoms or cycloalkyl of 5 to 7 ring carbon atoms substituted by alkyl of 1 to 6 carbon atoms; R 2 , R 3  and R 4  are each, independently, hydrogen or alkyl of 1 to 4 carbon atoms; Z is a divalent group -CR 5 = CH-, -CH= CR 5 - or wherein R 5  is hydrogen or alkyl of 1 to 4 carbon atoms; Y is oxygen and sulphur; w and n are, independently, zero or an integer 1 to 4; and R 6  is an aromatic radical Ar 1  of Formula (A) or an aromatic radical Ar 2  of Formula (B); wherein U is alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkenyloxy of 3 to 6 carbon atoms, formyl, alkylcarbonyl of 2 to 6 carbon atoms, alkoxycarbonyl of 2 to 6 carbon atoms, carbamoyl mono- or di-substituted by alkyl of 1 to 6 carbon atoms, alkoxymethyl of 2 to 7 carbon atoms, alkylthio of 1 to 6 carbon atoms, cyano, nitro, chlorine, bromine or phenyl, R 7  and R 8  are, independently, hydrogen or alkyl of 1 to 6 carbon atoms; r is 1, 2 or 3; p is 1 or 2 and is 0, 1 or 2, and its preparation by (a) eliminating, by known methods, HX, where X is a group capable of being eliminated as HX, from a compound (II) where one of X 1  and X 2  is hydrogen and the other is X, by an elimination reaction; (b) selectively condensing a compound (III), wherein R<SP>1</SP> 2  and R<SP>1</SP> 3  are each, independently, alkyl of 1 to 4 carbon atoms, and W<SP>1</SP> is an integer 1 to 4, with a compound of formula wherein R<SP>1</SP> 1  is primary alkyl of 1 to 4 carbon atoms, to produce a compound of Formula Ia; (c) condensing a compound V where M is hydrogen, sodium or potassium, with a compound of formula wherein R<SP>11</SP> 1  is primary or secondary alkyl of 1 to 6 carbon atoms, primary or secondary alkenyl of 3 to 6 carbon atoms, primary or secondary alkynyl of 3 to 6 carbon atoms, cycloalkyl of 5 to 7 ring carbon atoms or cycloalkyl of 5 to 7 ring carbon atoms substituted by alkyl of 1 to 6 carbon atoms, and Q is chlorine, bromine or tosyl, in the presence of an acid acceptor when M of Formula V is hydrogen, to produce a compound of Formula Ib; (d) condensing a compound VII with a compound in the presence of an acid acceptor, when M is hydrogen to produce a compound (Ib); or (e) condensing a compound (IX) with a suitable Wittig reagent under Wittig conditions. Substituted ethers (II) may be by condensing a compound where Hal is Cl, Br or I, with a compound under Grignard conditions to form a compound where X<SP>1</SP> 1  is hydrogen and X<SP>1</SP> 2  is -OH; or by condensing a compound where R<SP>1</SP> 6  is an aromatic group Ar<SP>1</SP> 1  of Formula (C) or Ar<SP>1</SP> 2  of Formula (D), wherein U<SP>1</SP> is alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkenyloxy of 3 to 6 carbon atoms, alkoxymethyl of 2 to 7 carbon atoms, alkylthio of 1 to 6 carbon atoms, or phenyl, with a compound (IX) under Grignard condition to give a compound where X<SP>11</SP> 7  is -OH and X<SP>11</SP> 2  is hydrogen. Dienes (III) may be made by eliminating HX from a compound Haloethers used for making the Grignard compounds (XII) may be made by reacting an alcohol  with a halogenating agent or by reacting a compound where w<SP>111</SP>, Z<SP>111</SP> ,  R<SP>111</SP> 4  and n<SP>111</SP> have the same significances as w, Z, R 4  and n respectively, with the proviso that the portion is symmetrical, e.g. when R<SP>111</SP> 4  is H, and Z<SP>111</SP> is -CH 2 -, with a compound (VIII), in the presence of an acid acceptor, where M is hydrogen, or by reacting a compound (XX) with 48% HBr to form a compound and, if desired, replacing the terminal Br by Cl or I. Alcohols XVIII may be made by reacting a compound with a compound VI, in the presence of an acid acceptor when M is hydrogen or by hydrogenating a compound where Ac is a group which protects the hydroxy group and removing the protecting group, to form a compound where R 1 <SP>IV</SP> is alkyl of 1 to 6 carbon atoms, cycloalkyl of 5 to 7 carbon atoms or cycloalkyl of 5 to 7 ring carbon atoms substituted by alkyl of 1 to 6 carbon atoms. The protected alcohols (XXII) may be made by adding a compound to a compound and replacing the terminal Cl of the resulting compound by a protected hydroxy group. The Diols XXI may be made by reacting a compound with a compound (XXVIII), where Hal is Cl or Br. The invention includes insecticidal and acaricidal compositions comprising a compound of Formula (I) and a suitable carrier or diluent and a method of combating insects or acaricids by applying a compound (I) to a suitable locus.