Patent GB-1377219-A (GB)
Title: Aryl-alkenyl and aralkyl-alkenyl ether and thioether derivatives
IPC: C07D317/64
Filed: 1971-12-10
Abstract: 1377219 Alkene bis-ethers or-thioethers SANDOZ Ltd 10 Dec 1971 [14 Dec 1970 17 Sept 1971 6 Oct 1971 11 Nov 1971] 57379/71 Heading C2C  The invention comprises compounds of Formula (I) where Ar is a group of Formula (Ia) or (Ib), wherein Q is hydrogen; W is alkyl of 1 to 5 carbon atoms, fluorine, chlorine or bromine; Z is alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkenyloxy of 2 to 12 carbon atoms, formyl, alkylcarbonyl of 2 to 6 carbon atoms, alkoxycarbonyl of 2 to 6 carbon atoms, mono- or dialkyl (of 1 to 5 carbon atoms) substituted carbamoyl, alkoxymethyl of 2 to 6 carbon atoms, alkylthio of 1 to 5 carbon atoms, fluorine, chlorine, bromine, cyano or nitro; R 10  and R 11 , which may be the same or different, are each hydrogen or alkyl of 1 to 5 carbon atoms; n and p, which may be the same or different, are each 1 or 2; q is 0 or 1; m and n, which may be the same or different, are each 0, 1, 2, 3, or 4; with the proviso that n+m+r is 5; R 1  is alkyl of 1 to 11 carbon atoms, non-cyclic hydrocarbon of up to 11 carbon atoms having at least one double and/or triple bond, cycloalkyl of 4 to 7 carbon atoms, alkyl substituted cycloalkyl (of 4 to 7 ring carbon atoms) the alkyl substituent having 1 to 5 carbon atoms, cycloalkenyl of 4 to 7 carbon atoms, alkyl substituted cycloalkenyl (of 4 to 7 ring carbon atoms) the alkyl substituent having 1 to 5 carbon atoms, phenyl, Ar 2  which has the same definition as Ar 1  above, wherein Ar 1  and Ar 2  may be the same or different; R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 , which may be the same or different, are each hydrogen, alkyl of 1 to 5 carbon atoms or alkenyl of 2 to 6 carbon atoms; Y is oxygen or sulphur; X is oxygen or sulphur, -OCH 2 - or -SCH 2 ; s, v and w, which may be the same or different, are each 0, or 1; and z is 1, 2 or 3, and their preparation by reacting a compound (II), wherein Hal is chlorine or bromine, with a compound of formula MX-Ar (III); wherein M is hydrogen, potassium or sodium, with the proviso that when M is hydrogen, the reaction is effected in the presence of an acid binding agent, (b) reacting a compound (IV), wherein z is 1, with the proviso that v + w is 0 or 2 or when v + w is 1, R 6  and R 7 , or R 8  and R 9  are other than hydrogen, with an alcoholate or thioalcoholate R 1 (CH 2 ) s YM<SP>1</SP> (V), wherein R 1 , Y and s are as defined in relation to Formula I, and M<SP>1</SP> is sodium or potassium, to produce a compound of Formula I, wherein z is 1, v and w are each 0 or 2, or when v and w are each 1, R 6  and R 7 , or R 8  and R 9  are other than hydrogen, (c) condensing a compound (VIa) with a compound Ar,OH (IIIa), in the presence of dicyclohexylcarbodiimide to produce a compound (I) where x is oxygen or (d) reacting a compound (VIa) or (VIb) or an alkali metal salt thereof with a compound Hal-CH 2 -Ar 1  (VII), with the proviso that when a compound of Formula VIa or VIb is reacted in the free alcohol or thioalcohol form thereof respectively, the reaction is effected in the presence of an acid-binding agent, to produce a compound of Formula I wherein X is OCH 2 - or -SCH 2 -. Halides (II) may be made (a<SP>1</SP>) by reacting a compound VIII with a halide transmitter, (b<SP>1</SP>) by reacting a compound R 1 (CH 2 ) s OC(R 4 )(R 5 )Cl (XI) with a compound (XII), if required, in the presence of a catalyst, to produce a compound II where Y is oxygen, Hal is chlorine, z and v are 1 and w is 0; (c<SP>1</SP>) reacting a compound (Via) where z is 3 with a halide transmitter, in the presence of an acid binding agent, to produce a compound II where z is 3; (d<SP>1</SP>) reacting a compound (XIII) wherein each of R 4 , R 5 , R 6 , R 7 , R 8  and R 9  is hydrogen, and each of v and w is 0 or 1, with a compound of Formula V, to produce a compound II, wherein R 4  and R 5  are hydrogen, and each of v and w is 0; (e<SP>1</SP>) reacting a compound (XIV) with concentrated HCl or HBr to give a compound II where z is 2. Enols (VIII) may be made by reacting a compound (IX) with a compound CH 2 =C(R 3 )Mt (X); where Mt is -MgCl, a -MgBr or Li, in a suitable solvent, and hydrolysing the product. Enols VIa may be made, where Z is 3, by reducing a compound XVI with NaBH 4 ; where z is 1 or 3, by reacting a suitable compound II with an alkali metal hydroxide; or, where z is 2, by reacting a suitable compound (II) with potassium acetate and hydrolysing the result acetate with methanolic KOH. Enethiols (VIb) may be made, where z is 2, as above for enols (VIa), where z is 2 but using potassium thioacetate or, where z is 1 or 3, by reacting a suitable compound (II) with thiourea or ammonium dithiocarbamate and hydrolysing the product with alkali. Aldehydes (XVI) may be made by reacting compounds (VTII) with alkyl vinyl ethers in the presence of mercury (II) acetate and transposing the product by heating to 160-190 C. Cyclopropyl derivatives (XIV) may be made by reacting compounds (IX) with a Grignard compound (XV) and hydrolysing the product. Halides (IV) may be made by reacting a compound XIII with a compound MX-Ar, (III), where M is hydrogen, potassium or sodium, with the proviso that when M is hydrogen, the reaction is performed in the presence of an acid binding agent. Insecticidal compositions comprise compounds of the invention with suitable carriers, diluents or adjuvants, and the invention includes a method of combating insects at a locus by treatment with the compounds of'the invention.