Spirocyclic 3-phenyl-3-substituted 4-ketolactams and 4-ketolactones

摘要

#CMT# #/CMT# 3-phenyl-2,4-dioxo-spiro-heterocyclic compounds (I) are new. #CMT# : #/CMT# 3-phenyl-2,4-dioxo-spiro-heterocyclic compounds of formula (I) are new. #CMT#[Image]#/CMT# W' : cyano, halo, (halo)alkyl, (halo)alkoxy, alkenyl or alkynyl; X', Y' and Z' : H, halo, (halo)alkyl, (halo)alkoxy or cyano; -A'-B'- : -CH 2CH(OR 1)-, -O-CH 2- or -CHR 2-O-; G : halo or nitro; R 11-6C alkyl; R 2, R 3H or 1-4C alkyl; and Q : NH, O or S. Provided that where -A'-B'- is -CHR 2-O- : at least one of X, Y and Z is other than H, and W, X and Y are not all Me if Z = H. An independent claim is also included for two methods for preparing (I). #CMT#ACTIVITY : #/CMT# Insecticide; Acaricide; Nematocide; Fungicide; Herbicide; Antibacterial; Antifouling; Plant Growth Regulant. The compound 3-chloro-3-(2-chloro-5-methylphenyl)-5-(spiro-4-methoxycyclohexane)-2,4-dioxo- pyrrolidine was tested as a 500 ppm spray against larvae of Phaedon cochleriae, and gave 100% kill after 7 days. #CMT#MECHANISM OF ACTION : #/CMT# None given. #CMT#USE : #/CMT# (I) are useful (claimed) as pesticides (particularly insecticides, acaricides and nematocides, including ectoparasites on animals), herbicides (total or selective, depending mainly on application rate) and fungicides (including clinical antimycotics against Candida, Aspergillus, Trichophyton and Microsporon), useful in agriculture, forestry, protection of stored materials (e.g. plastics, glues, leather, wood etc.), and in hygienic applications, most preferably for plant protection. Also (not claimed) they are useful as bactericides, marine antifouling agents and plant-growth regulators, or as intermediates for other active compounds. #CMT#ADVANTAGE : #/CMT# (I) are well tolerated by plants; have low toxicity to warm-blooded animals; and are active against normally sensitive and resistant pests at one or more stages of the life cycle. They have excellent residual activity of wood and clay and are stable to alkali on white-washed surfaces. #CMT#ORGANIC CHEMISTRY : #/CMT# Preparation: The enol (II) is reacted (a) with a halogenating agent in presence of solvent and optionally radical initiator (e.g. benzoyl peroxide) to give (I) where G = halo, or (b) with fuming nitric acid in solvent to give (I) with G = nitro. Suitable halogenating agents included sulfuryl chloride or bromide, thionyl chloride or N-bromosuccinimide, generally at 1 mole per mole (II), with reaction at -40 to 150, preferably 0-100, [deg]C. Nitration is with 1 mole nitric acid at -50 to 150, preferably 0-80, [deg]C. #CMT#[Image]#/CMT# #CMT#AGRICULTURE : #/CMT# Preferred Compositions: These are usually in the form of e.g. solutions, emulsions, powders and may include a very wide range of other active agents (fungicides, bactericides, insecticides, acaricides, nematocides, antifoulants etc.). #CMT#DEFINITIONS : #/CMT# Preferred definitions: W' : chloro, bromo, 1-3C linear alkyl, (m)ethoxy, trifluoromethyl, di- or tri-fluoromethoxy or cyano; Y' and Z' : chloro, bromo, 1-3C linear alkyl, (m)ethoxy, trifluoromethyl, di- or tri-fluoromethoxy,cyano, H or fluoro; X' : H, chloro, bromo, 1-3C linear alkyl or (m)ethoxy; R 11-3C alkyl or (iso)butyl; and R 2, R 3H or Me. #CMT#ADMINISTRATION : #/CMT# (I) are administered at 0.1-10 4>, preferably 10-10 3>, g/hectare to plants; at 0.001-50, preferably 0.01-10, g/kg as a seed dressing, and at 0.1-10 4>, preferably 1-5X10 3>, g/hectare to soil. #CMT#SPECIFIC COMPOUNDS : #/CMT# About 70 (I) are disclosed, e.g. 3-chloro-3-(2-chloro-5-methylphenyl)-5-(spiro-4-methoxycyclohexane)-2,4-dioxo- pyrrolidine (Ia). #CMT#[Image]#/CMT# #CMT#EXAMPLE : #/CMT# A mixture of tetramic acid (0.96 g) (see Example I-1-a-16 of ) in dry chloroform (10 ml) was treated at 0[deg]C with sulfuryl chloride, then stirred for 30 minutes before adding saturated sodium hydrogencarbonate (5 ml). The organic phase was separated, dried and evaporated in vacuo to give 0.6513 g (48%) of 3-chloro-3-(2-chloro-5-methylphenyl)-5-(spiro-4-methoxycyclohexane)-2,4-dioxo- pyrrolidine, m. pt. 225[deg]C.