Alkoxy enones and enamino ketones and a process for preparation thereof
View Patent ↗The present invention relates to novel alkoxy enones and enamino ketones, and to a novel process for preparation thereof. Alkoxy enones and enamino ketones are valuable intermediates for preparation of pyrazoles and anthranilamides, which can be used as insecticides.
1. A process for preparing a compound of formula (I),
in which
R 4 is hydrogen, —(C═O)alkyl, (C═O)haloalkyl, —(C═O)O-alkyl, SO 2 alkyl, SO 2 -haloalkyl, SO 2 -aryl,
X is halogen,
R 5 is alkoxy, dialkylamino where the alkyl groups may optionally form a ring which may optionally contain 1-2 further heteroatoms from the group of O, N, S, or is cycloalkylamino, thioalkyl,
said process comprising reacting a compound of formula (III)
in which R 5 is as defined above and X and Y are independently fluorine, chlorine, bromine or iodine, with a compound of formula (II)
KatOR 4 (II)
in which
Kat is a cation, and is Li, Na, K, Cs, (alkyl) 4 N, (alkyl) 4 P, (aryl) 4 P,
R 4 is hydrogen, —(C═O)alkyl, (C═O)haloalkyl, —(C═O)O-alkyl, SO 2 alkyl, SO 2 -haloalkyl, SO 2 -aryl.
2. A compound of formula (I)
wherein
R 4 is hydrogen, —(C═O)alkyl, (C═O)haloalkyl, —(C═O)O-alkyl, SO 2 alkyl, SO 2 -haloalkyl, SO 2 -aryl,
X is halogen, and
R 5 is alkoxy, dialkylamino, where the alkyl groups may optionally form a ring which may optionally contain 1-2 further heteroatoms from the group of O, N, S or is cycloalkylamino, or is thioalkyl.
3. A compound of formula (I) according to claim 2 ,
wherein
R 4 is —(C═O)(C 1 -C 6 )alkyl, (C═O)halo(C 1 -C 6 )alkyl, —(C═O)O—(C 1 -C 6 )alkyl, SO 2 (C 1 -C 6 )alkyl, SO 2 -halo(C 1 -C 6 )alkyl, SO 2 -aryl,
X is fluorine, chlorine or bromine, and
R 5 is alkoxy.
4. A compound of formula (I) according to claim 3 ,
wherein
R 4 is —(C═O)(C 1 -C 6 )alkyl,
X is chlorine or bromine, and
R 5 is (C 1 -C 6 )alkoxy.
5. The process according to claim 1 wherein the reaction is effected in the presence of an acid.
6. The process according to claim 5 wherein the acid is selected from the group consisting of HCl, H 2 SO 4 , CH 3 COOH and CF 3 COOH.
7. The process according to claim 1 wherein the reaction is effected in the presence of a catalyst.
8. The process according to claim 6 wherein the acid is CH 3 COOH.
9. The process according to claim 7 wherein the catalyst is tetrabutylammonium bromide.
10. The process according to claim 1 wherein the reaction is effected in the presence of an acid wherein said acid is selected from the group consisting of HCl, H2SO4, CH3COOH and CF3COOH.