Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
1999-11-01
2001-08-21
Killos, Paul J. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S416000, C564S417000, C564S418000, C564S419000, C564S310000, C564S314000
Reexamination Certificate
active
06278022
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to novel process for the preparation of phenylhydrazine derivatives that exhibit activity as insecticides, acaricides, and nematicides. The present invention is also directed to processes for the preparation of intermediates useful in the manufacture of such phenylhydrazine derivatives.
2. Description of Related Art
Destruction by insects, acarids, and nematodes presents a serious problem to agriculture. A wide variety of field crops are in need of protection from nematodes, acarids, and insects including such valuable crops as soybeans, corn, peanuts, cotton, alfalfa, rice, and tobacco. In addition, vegetables, such as, tomatoes, potatoes, sugar beets, carrots, peas, and the like, as well as fruits, nuts, ornamentals, and seed bed crops, such as, apples, peaches, almonds, citrus fruit, and grapes may also require protection from the ravages of such pests.
Consequently, the development of new, more effective, pesticides, including insecticides, acaricides, and nematicides, and processes for the preparation thereof represent an ongoing scientific activity.
Chemical Abstracts 105(17):152686c refers to various phenylhydrazines said to have activity against insects and mites.
Chemical Abstracts 108(19):163280d refers to alkyl phenylhydrazinecarboxylates said to be useful as acaricides.
DerWent abstract 88-312695/44 refers to arylhydrazides of trifluoroacetic acid said to have fungicidal, bactericidal, acaricidal, and antiseptic activity.
WO 98/17637 is directed to compounds having the structural formula
wherein:
R is C
1
-C
6
hydroxyalkyl, C
1
-C
6
haloalkyl, C
1
-C
6
alkyl, C
7
-C
9
aralkyl, or nitroso; R′ is C
1
-C
4
alkyl; and R″ is C
1
-C
4
alkyl. These compounds exhibit insecticidal and miticidal activity.
European Patent 0 067 471 refers to 7-substituted 2,3-dihydrobenzofurans said to be useful as pesticides or chemical intermediates.
U.S. Pat. No. 4,725,302 refers to substituted phenylhydrazines and phenyloxadiazolinones said to be useful as pesticides.
U.S. Pat. Nos. 5,367,093 and 5,438,123 and WO 93/10083 relate to compounds having the structural formulae (I) or (II) described below. These compounds are effective for controlling mites, nematodes, rice planthopper, tobacco budworm, and southern corn rootworm. Methods for making these compounds are also set forth.
WO 97/40692 discloses a composition for insects and representatives of the order Acarina, which comprises a combination of variable amounts of one or more compounds of the formula
in which A is an unsubstituted or, depending on the possibility of substitution on the ring system, mono- to tetrasubstituted, aromatic or non-aromatic monocyclic or bicyclic heterocyclic radical, in which the substituents of A can be chosen from the group consisting of C
1
-C
3
alkyl, C
1
-C
3
alkoxy, halogen, halo-, cyclopropyl, halocyclopropyl, C
2
-C
3
alkenyl, C
2
-C
3
alkynyl, halo-C
1
-C
3
alkoxy, C
1
-C
3
alkylthio, halo C
1
-C
3
alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano, and nitro; R is hydrogen, C
1
-C
6
alkyl, phenyl-C
1
-C
4
alkyl, C
3
-C
6
cycloalkyl, C
2
-C
6
alkenyl or C
2
-C
6
alkynyl; and X is N—NO
2
or N—CN, in the free form or in the salt form, if appropriate tautomers, in the free form or salt form, and one or more compounds mentioned in the specification and at least one auxiliary. A method of controlling pests, a process for the preparation of the composition, its use and plant propagation material treated with it, and use of the compound of the above formula for the preparation of the composition are also described.
Dekeyser et al.,
Brighton Crop Prot. Conf.—Pests Dis
. Vol. 2:487-492 (1996) discloses N′-(4-methoxybiphenyl-3-yl)hydrazinecarboxylic acid, iso-PR ester (D2341) as a novel acaricide for mite control in agricultural and ornamental crops. The compound has a good toxicological and environmental profile. D2341 shows no cross-resistance with currently available acaricides and provides excellent control at low rates against all stages of tetranychid mites and motile forms of Panonychus species. Proposed field rates are 0.15-0.60 kg/ha for the control of Panonychus urticae. D2341 has outstanding knockdown and residual activity for control of many phytophagous mites. It shows minimal impact on beneficial insects and mites. It is therefore recommended in integrated pest management programs. In trials on apples and citrus, D2341 has shown no crop injury at rates well in excess of proposed field rates.
The disclosures of the foregoing are incorporated herein by reference in their entirety.
SUMMARY OF THE INVENTION
The present invention relates to an improved method for making compounds having the structural formulae (I) or (II):
wherein: X is a) phenyl; lower phenylalkoxy; phenoxy; or benzyl; or b) one substituent from group a) and one or more substituents selected from C
1
-C
4
alkoxy; halogen; lower alkyl; and lower alkylthio; or c) along with the phenyl to which it is attached, forms a multiple fused ring heterocycle such as dibenzofuranyl; Y is H, C
1
-C
4
alkanoyl, C
1
-C
4
haloalkenoyl, dialkoxyphosphoryl, alkylaminocarbonyl, haloalkylsulfonyl, or C
1
-C
4
alkoxy carbonyl; and R is H, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
3
-C
6
cycloalkoxy, haloalkyl, alkoxyalkyl, arylalkoxy, alkenyl, alkylthio, alkoxycarbonyl, alkylamino, heteroaryl, (e.g., 2-thiophenyl or 2-furyl) arylalkyl, haloalkoxy, aryloxy, or C
3
-C
6
cycloalkyl; and Z is O or S. Further, when X includes a substituent having a phenyl ring (i.e., is phenyl, phenylalkoxy, phenoxy or benzyl), the phenyl ring is optionally substituted with one or more of halogen, nitro, lower alkyl, lower alkoxy, lower haloalkyl, or dialkylamino.
More particularly, the present invention is directed to an improvement in a method for making compounds having the structural formulae (I) or (II):
wherein: X is a) phenyl; lower phenylalkoxy; phenoxy; or benzyl; or b) one substituent from group a) and one or more substituents selected from C
1
-C
4
alkoxy; hydroxyl; halogen; lower alkyl; and lower alkylthio; or c) along with the phenyl to which it is attached, forms a multiple fused ring heterocycle such as dibenzofuranyl; Y is H, C
1
-C
4
alkanoyl, C
1
-C
4
haloalkenoyl, dialkoxyphosphoryl, alkylaminocarbonyl, haloalkylsulfonyl, or C
1
-C
4
alkoxy carbonyl; and R is H, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
3
-C
6
cycloalkoxy, haloalkyl, alkoxyalkyl, arylalkoxy, alkenyl, alkylthio, alkoxycarbonyl, alkylamino, heteroaryl, arylalkyl, haloalkoxy, aryloxy, or C
3
-C
6
cycloalkyl; and Z is O or S, wherein the improvement comprises the steps of:
A) selecting as a starting material a compound of the structural formula
B) dissolving compound III in an organic solvent selected from the group consisting of methyl t-butyl ether, ethylene glycol dimethyl ether, 2-methoxyethyl ether, acetonitrile, and acetic acid, and
C) nitrating with nitric acid to form a compound of the structural formula
In a preferred embodiment, the present invention is directed to an improvement in a method for making compounds having the structural formula I:
wherein R is C
1
-C
6
alkoxy, wherein the improvement comprises the steps of:
A) selecting as a starting material a compound of the structural formula
B) dissolving compound II in an organic solvent selected from the group consisting of methyl t-butyl ether, ethylene glycol dimethyl ether, 2-methoxyethyl ether, acetonitrile, and acetic acid,
C) nitrating with nitric acid to form a compound of the structural formula
D) reacting compound III with dialkylsulfate to form a compound of the structural formula:
wherein R′ is C
1
-C
6
alkyl;
E) reducing compound IV to form a compound of the structural formula
and,
F) adding hydrochloric acid solution to precipitate a compound of the structural formula:
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The compounds prepared by the process of the present invention have the structure (I) or (II) defined above.
CK Witco Corporation
Grandinetti Paul
Killos Paul J.
Thompson Raymond D.
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