4-aryl-4-substituted pyrazolidine-3, 5-dione derivatives

Details 4-aryl-4-substituted pyrazolidine-3, 5-dione derivatives 4-aryl-4-substituted pyrazolidine-3, 5-dione derivatives

2000-04-19

2001-01-30

Ramsuer, Robert W. (Department: 1626)

Plant protecting and regulating compositions

Plant growth regulating compositions

Organic active compound containing

C548S366400

Reexamination Certificate

active

06180568

ABSTRACT:

TECHNICAL FIELD
The present invention relates to novel 4-aryl-4-substituted pyrazolidine-3,5-dione derivatives and to a miticide, an insecticide or a herbicide each containing the derivative as their active component.
BACKGROUND ART
Heretofore some kinds of 4-aryl-4-halopyrazolidine-3,5-dione derivatives have been known. For example, An. Quim. vol. 71, 396 to 399 (1975) discloses that compounds A, B and C to be described later, i.e. 4-aryl-4-halopyrazolidine-3,5-dione derivatives, can be prepared by Diels-Alder reaction between 4-chloro-4-phenylpyrazoline-3,5-dione and diene. Further An. Quim. vol. 75, 931 to 935 (1979) describes the under-mentioned compounds D and E as an intermediate for preparing 13,14-azasteroid, the compounds being prepared by Diels-Alder reaction between 4-chloro-4-phenylpyrazoline-3,5-dione and diene. In addition, Comment., Pontif. Acad. Sci. vol.2, 8 (1975) sets forth that compounds A, B and C to be described later can be prepared by chlorination of the corresponding 4-phenylpyrazolidine-3,5-dione derivative.
However, the compounds of the invention represented by the formula (1) are novel compounds which are not included in conventional compounds.
On the other hand, 4-aryl-4-nitropyrazolidine-3,5-dione derivatives are entirely novel compounds.
With insecticides and miticides in use for many years, pest insects have acquired resistance in recent years and become difficult to control with conventional insecticides. Accordingly it is expected to develop novel insecticides. Also in the herbicide field, the development of novel herbicides are expected.
An object of the present invention is to provide 4-aryl-4-substituted pyrazolidine-3,5-dione derivatives which have not only extremely high insecticidal and miticidal activities but a high herbicidal activity.
DISCLOSURE OF THE INVENTION
The present invention provides a 4-aryl-4-substituted pyrazolidine-3,5-dione derivative represented by the formula (1), a process for preparing the same and a miticide, an insecticide or a herbicide each containing the derivative
wherein R
1
and R
2
are each independently alkyl group having 1 to 4 carbon atoms, or R
1
and R
2
, when taken together, represent saturated or unsaturated bivalent hydrocarbon group having 3 or 4 carbon atoms which may optionally be substituted with alkyl group having 1 to 4 carbon atoms or halogen atom, X is alkyl group having 1 to 4 carbon atoms, haloalkyl group having 1 to 4 carbon atoms or halogen atom, Y is halogen atom or nitro group, and n is an integer of 0 to 3.
Examples of alkyl groups having 1 to 4 carbon atoms in the formula (1) are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
Examples of haloalkyl groups having 1 to 4 carbon atoms are fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, pentafluoroethyl, 1-fluoropropyl, 2-chloropropyl, 3-fluoropropyl, 3-chloropropyl, 1-fluorobutyl, 1-chlorobutyl and 4-fluorobutyl.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Saturated or unsaturated divalent hydrocarbon groups having 3 or 4 carbon atoms include trimethylene, tetramethylene and propenylene groups.
The compounds of the present invention exhibit a high effect against various harmful organisms even when used at a low dose. These harmful organisms include, for example, the following agricultural harmful insects:
those of the order Tetranychus, e.g. spider mites such as
Tetranychus urticae, Panonychus citri, Panonychus ulmi, Tetranychus kanzawai
, etc. and Tarsonemidae such as
Polyphagotarsonemus latus;
those of the order Hemiptera, e.g. planthoppers such as
Laodelphax striatellus
and
Nilaparvata lugens
, leafhoppers such as
Nephotettix cincticeps
and
Arboridia apicalis
, aphides such as
Myzus persicae, Aphis gossyii
and
Ovatus malicolens
, shield-bugs, scales and whiteflies;
those of the order Thysanoptera such as
Scirtothrips dorsalis, Thrips palmi, Frankliniella occidentalis
and
Frankliniella intonsa
; and
those of the order Diptera such as
Phytobia cepae HERING
and
Liriomyza trifolii.
The compounds of the present invention have an activity against sanitary insect pests such as
Culex pipiens pallens, Musca domestica
and other insect pests as well as against agricultural harmful insects.
At a low dose, the compounds of the present invention can control weeds such as chickweed, Digitaria adscendens,
Monochoria vaginalis var. plantaginea, Echinochloa Crus-galli, Cyperus microiria Steud
. and
Cyperus serotinus Rottb
. which pose agricultural problems. The effectiveness of the compounds is specifically demonstrated in Test Examples on organisms to be described later.
Among the compounds of the present invention represented by the formula (1), a compound of the present invention represented by the formula (3) can be prepared according to the following reaction scheme
wherein R
1
, R
2
, X and n are as defined above and Y
1
is halogen atom.
According to the reaction scheme illustrated above, 4-arylpyrazolidine-3,5-dione derivative represented by the formula (2) is reacted with a halogenating agent in an inert solvent to give a compound of the invention represented by the formula (3).
The 4-arylpyrazolidine-3,5-dione derivative of the formula (2) can be prepared according to the method disclosed in JP-(PCT)-6-506201.
Examples of the halogenating agent used in halogenation are inorganic halides such as chlorine, thionyl chloride, sulfuryl chloride, phosgene, phosphorus trichloride, phosphorus pentachloride, bromine, thionyl bromide, sulfuryl bromide, phosphorus pentabromide and phosphorus oxybromide, organic halides such as N-chlorosuccinic acid imide (NCS) and N-bromosuccinic acid imide (NBS), alkali metal salts of hypochloric acid such as sodium hypochlorite, organic hypochlorine oxides such as tert-butyl hypochlorite. The amount of the halogenating agent used in the reaction is 1 to 10 equivalents, preferably 1 to 4 equivalents, per equivalent of the 4-arylpyrazolidine-3,5-dione derivative of the formula (2).
Examples of the solvent used in halogenation are halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane and carbon tetrachloride; aromatic hydrocarbons such as benzene, toluene, xylene and o-chlorobenzene; and ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane. The reaction temperature, although not specifically limited, is in the range of usually −30° C. to the boiling point of the solvent used. It is possible to carry out the reaction at a temperature in the range of from 0° C. to the reflux temperature of the halogenating agent without use of the solvent. Although variable depending on the above-mentioned concentration, temperature and other factors, the reaction time is in the range of about 0.1 to about 6 hours. Optionally the reaction may be conducted in the presence of a catalyst. Examples of useful catalysts are benzoyl peroxide (BPO), 2,2′-azobisisobutyronitrile (AIBN), 4,4′-azobis-4-cyanovaleric acid (ACVA) and like radical initiators. The amount of the catalyst used is 0.00001 to 1 equivalent, preferably 0.0001 to 0.1 equivalent, per equivalent of the compound of the formula (3).
The 4-aryl-4-halopyrazolidine-3,5-dione derivative of the invention having the formula (3) can be purified by conventional methods such as solvent extraction, recrystallization and chromatographies such as column chromatography and preparative thin layer chromatography.
Among the compounds of the invention represented by the formula (1), a compound of the invention represented by the formula (4) can be prepared according to the following reaction scheme
wherein R
1
, R
2
, X and n are as defined above and y
2
is nitro group.
According to the reaction scheme illustrated above, 4-arylpyrazolidine-3,5-dione derivative of the formula (2) is reacted with a nitrating agent in a solvent to give a compound of the invention represented by the formula (4).
Examples of the nitrating agent used herein are mixed acids, nitric acid, fuming nitric acid, and

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