Patent GB-1436621-A (GB)
Title: Aromatic alkyl ethers and thioethers and their use in insecticidal and acaricidal compositions
IPC: C07C67/00
Filed: 1973-06-18
Abstract: 1436621 Aromatic alkyl ethers and thioethers SANDOZ Ltd 18 June 1973 [23 June 1972] 28822/73 Heading C2C The invention comprises compounds of the formula (I) wherein R 1  is C 1  to C 9  alkyl, C 3  to C 9  alkenyl, C 3  toC 9  alkynyl, C 5  to C 7  cycloalkyl or C 5  to C 7  cycloalkyl substituted by C 1  to C 4  alkyl; R 2 , R 3 , R 4  and R 5  are H or C 1  to C 4  alkyl, w is 2, 3 or 4, z is an integer from 2 to 6, X is -O-, -S-, -OCH 2 - or -SCH 2 - and R 6  is an aromatic radical of the formula or of the formula wherein U is C 1  to C 6  alkyl, C 2  to C 6  alkenyl, C 1  to C 6  alkoxy, C 3  to C 6  alkenyloxy, CHO, C 2  to C 6  alkylcarbonyl, mono- or di- C 1  to C 6  alkylcarbamoyl, C 2  to C 7  alkoxymethylene, C 1  to C 6  alkylthio, CN, NO 2 , Cl, Br or phenyl; R 7  and R 8  are H or C 1  to C 6  alkyl, r is 1 or 2, p is 1 or 2 and q is 0, 1 or 2. They may be obtained by condensing (a) a compound of formula wherein L is Cl, Br or tosyl, with a compound of the formula wherein M is H, Na or K, in the presence of an acid binding agent when M is H; (b) a compound of formula with a compound of formula in the presence of dicyclohexyl carbodiimide to give a compound of Formula I wherein X is -O-; (c) a compound of formula with a compound of formula in the presence of an acid acceptor when M is H, to give a compound of Formula I wherein R 2  is H; (d) a compound of formula with a compound of formula wherein R<SP>1</SP> 1  is a primary or secondary C 1  to C 9  alkyl, primary or secondary C 3  to C 9  alkenyl, primary or secondary C 3  to C 9  alkynyl, C 5  to C 7  cycloalkyl or C 5  to C, cycloalkyl substituted by C 1  to C 4  alkyl, R<SP>1</SP> 1  being bonded to L through a primary or secondary carbon atom, in the presence of an acid acceptor when M is H, to give a compound of Formula I wherein R 1  is R<SP>1</SP> 1  and R 2  is H; (e) a compound of formula with a compound of formula in the presence of an acid acceptor when M is H, to produce a compound of Formula I in which R 4  is H; (f) a compound of formula with a compound of formula in the presence of an acid acceptor when M is H, to produce a compound of Formula I in which R 4  is H; or (g) a compound of formula wherein X<SP>1</SP> is -O- or -S-, with a compound of formula wherein L<SP>1</SP> is Cl or Br, in the presence of an acid acceptor when M is H, to give a compound of Formula I in which X is -OCH 2 - or -SCH 2 -. Examples are given for the preparation of the compounds. They are useful as insecticides and acaricides. 1 - Bromo - 4 - (4 - isobentyloxy - butyloxy)- butane is obtained by treating 4-isopentyloxybutanol with sodium hydride and adding thereto 1,4 - dibromobutane. 1 - Bromo - 6 - (4 - isopentyloxy - butyloxy) - hexane, 1 - bromo - 4- (5 - alkyloxy - 2 - hexyloxy) - butane 1 - bromo- 4 - isopropoxybutane and 6 - bromo - 6 - isopropoxy - hexane are obtained in an analogous manner. 6 - (4 - Isopentyloxy - butyloxy)- hexanol is obtained by treating 1,6-hexanediol with sodium hydride in 1,2-dimethoxyethane and adding thereto 1-bromo-4-isopentyloxybutane. 6 - (6 - Isopentyloxy - hexyloxy)hexanol is obtained in an analogous manner. 4-Isopentylozy-butanol is obtained by treating 1,4-butanediol with sodium hydride in 1,2- dimethoxy ethane and adding thereto isopentyl bromide. 6-Isopentyloxyhexanol, 4-isopropoxybutanol and 5-allyloxy-2-hexanol are obtained in an analogous manner. 1 - (4 - Bromo - butyloxy) - 4 - (methylthio)- benzene is obtained by treating 4-(methylthio)- phenol with KOH in DMF and adding thereto 1,4-dibromobutane. 1 - Bromo - 4 - isopentyloxy - butane is obtained by treating 4-isopentyloxy-butanol in chloroform with PBr 3  in the presence of pyridine. 1 - Bromo - 6 - isopentyloxy - hexane is obtained in an analogous manner. 2-Piperonylthio-ethanol is obtained by treating 2-mercapto-ethanol with sodium hydride in tetrahydrofuran and adding thereto piperonyl bromide in tetrahydrofuran.