JP2637061C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION       [0001]     [Industrial applications]   The present invention is effective as an insecticide for both growing and harvested crops.
New substituted diacylhydrazines and unsubstituted diacylhydras
About Jin.       [0002]     [Prior art]   Certain hydrazine compounds are known, but their use as insecticides.
No use is taught or suggested. For example, Porter, Q.N
. And Seif, AE, "Mass Spectrometric Studies
(Mass Spectroscopic Studies), XI, Skeletal Rearrangements In
・ Acylhydrazines (Skeltal Rearrangements in Acylhydrazines)
Aust. J. Chem.,25Go to 523-529 (1972)
Several 1,2-dibenzoyl-1-alkylhydrazines are disclosed. In addition
Maerky et al., “The Photochemistry of Sidnons and 1
, 3,4-oxodiazolin-2-one (The Photo-chemistry of Sydnones and
1,3,4-oxdiazolin-2-one) ", Helv. Chem. Act.
a.),61(4), 1477-1510 (1978) is 4-nitrobenzoic acid 2-
Benzoyl-1- (1,1-dimethylethyl) hydrazine
, Does not include its use.       [0003]   Japan dated November 2, 1972 and published as No. 49-047,528
No. 91048 discloses certain benzoylhydrazine derivatives as acaricides.
Describes the use of diacylhydrazine to control insect attack.
Neither has it been submitted, proposed or disclosed. As of April 17, 1980
Japanese Patent Application No. 50819 published as No. 56-147,066 is N, N¹−
Dibenzoyl-N, N¹-Detect blood in body fluids of dialkyl-alkylenediamine
No indication of its pesticidal activity or effectiveness
Not. Published March 18, 1969 and as No. 7,302,770
Japanese Patent Application No. 20216 discloses certain N-substituted compounds having insecticidal and acaricidal activity.
Although reference is made to N-phenyl-hydrazine, this reference is dibenzoyl.
Does not teach that -N-alkylhydrazines are effective insecticides;
Not even. Finally, German Patent Application No. 3228631 describes insecticidal, miticide, disinfection and
Or thiophosphate-containing compounds for use as nematicides and nematicides
, 1-phosphorylthioacetyl-2-acyl-hydrazine is disclosed.       [0004]     [Problems to be solved by the invention]   It is thus understood that the present invention presents the compound as an insecticide without exception.
.       [0005]   The present invention also relates to compounds that are useful intermediates in the preparation of dibenzoylhydrazine
You. These dibenzoylhydrazines are effective insecticidal gastric poisons and
It is effective in systematically protecting growing plants.       [0006]   Further, the compounds of the present invention are effective as insecticides themselves. These new compounds
Objects have been found to control insects and protect growing plants from insect attack.
Was.       [0007]   The present invention is effective as an insecticide against both growing and harvested crops
The present invention relates to a novel diacylhydrazine compound. The present invention also relates to these novel compounds
And the use of unsubstituted diacylhydrazines as insecticides and their intermediates
About the body.       [0008]   Therefore, it is an object of the present invention to provide novel substituted diacylhydrazine compounds
Is Rukoto. A further object is to provide these compounds as effective insecticides.
And       [0009]   In addition, unsubstituted diacylhydrazines protect growing plants from insect attack.
It is a useful and effective insecticide to protect.       [0010]   Another object of the present invention is to provide novel substituted 1-alkyl-, 2-alkyl benzoates.
-And 2-cycloalkyl hydrazides, preferably 1- or 2-tert-butyl
Providing ruhydrazide as an insecticide, and dibenzoylhydrazine insecticide
To provide many such compounds useful in the preparation of       [0011]   These and other objects of the invention will be apparent from the following more detailed description of the invention.
Will be clear.       [0012]     [Means for Solving the Problems]   The novel diacylhydrazine compound of the present invention has the following formula:       [0013] Embedded image       [0014] [Wherein R is C_Two~ C₆X, Y, M and N are each independently H,
C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy, C₁~ C_ThreeAlkylthio, C₁~ C_ThreeAl
Killsulfinyl, C₁~ C_ThreeAlkylsulfonyl, cyano, F, Cl, Br, I
, Nitro, CF_Three, R₁CF_TwoZ-, 1,1-difluoro-2,2-dichloroethoxy
Si, R_TwoCO or R_ThreeR_FourN and X and Y are taken together and XY is a structural formula       [0015] Embedded image       [0016] May form a ring represented by the formula: and M and N are taken together to form MN having the structural formula       [0017] Embedded image       [0018] May form a ring represented by; Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn
R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H
Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2; Provided that at least one of X, Y, M or N is a substituent other than hydrogen, and M is p
-In the case of nitro, at least one of X, Y or N must be a substituent other than hydrogen
Absent] Is exemplified by       [0019]   Preferably R is-(CH_Three)_ThreeOr -CH (CH_Three)_TwoWhere X, Y, M and N
Is as described above, and at least one of X, Y, M and N is a substituent other than hydrogen
It is.       [0020]   These compounds have an effective insecticidal effect on insects, their habitats, their food or their spawning grounds.
It is a very effective insecticide for suppressing the distribution of insects when applied in the field. now
Times, having a basic structure as described above, provided that X, Y, M and N are each hydrogen
Alternatively, other compounds wherein one of X, Y, M and N is nitro and R is as described above.
The compound has also been found to be a very effective insecticide. Further substitution and non-placement as described above
The substituted diacylhydrazines affect growing plants over the long term of their active growth.
It has been found to be particularly useful for systemic protection from attack by plant-harming insects.
Was seen. Such protection is provided by the growing soil or water of the plant.       [0021] Embedded image       [0022] [Wherein R is C_Two~ C₆X, Y, M and N are each independently H,
C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy, C₁~ C_ThreeAlkylthio, C₁~ C_ThreeAl
Killsulfinyl, C₁~ C_ThreeAlkylsulfonyl, cyano, F, Cl, Br, I
, Nitro, CF_Three, R₁CF_TwoZ-, 1,1-difluoro-2,2-dichloroethoxy
Si, R_TwoCO or R_ThreeR_FourN and X and Y are taken together and XY is a structural formula       [0023] Embedded image       [0024] May form a ring represented by the formula: and M and N are taken together to form MN having the structural formula       [0025] Embedded image       [0026] May form a ring represented by; Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn
R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2] By applying a systemically effective amount of the compound of formula (I).       [0027]   More particularly, the protection of the growing plants is effected on the leaves of the plants and / or on the soil in which they grow.
Alternatively, in water, about 0.01 to about 10.0 kg / ha of the diacylhydrazine as described above,
Preferably achieved by applying at 0.028-4.0 kg / ha.
it can.       [0028]   The present invention relates to compounds of formula (II) which are effective as insecticides       [0029] Embedded image       [0030] [Wherein, R and R₆Is independently hydrogen, C_Two~ C₆Alkyl or C_Five~ C₆Shiku
X and Y are each independently H, C₁~ C_ThreeAlkyl, C₁~
C_ThreeAlkoxy, C₁~ C_ThreeAlkylthio, C₁~ C_ThreeAlkylsulfinyl, C₁~
C_ThreeAlkylsulfonyl, cyano, F, Cl, Br, nitro, CF_Three, R₁CF_TwoZ
-1,1-difluoro-2,2-dichloroethoxy, R_TwoCO or R_ThreeR_FourN
X and Y are joined together, and XY is a structural formula       [0031] Embedded image       [0032] May form a ring represented by Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn
R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H
Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2;
R is hydrogen₆Is C_Two~ C_FiveAlkyl or C_Five~ C₆A cycloalkyl, and
R₆R is C when is hydrogen_Two~ C_FiveAlkyl or C_Five~ C₆Cycloalkyl; and
And when R is tert-butyl and Y is chloro at the para position of the ring, X is
A substituent other than hydrogen] A novel substituted 1-alkyl-, 2-alkoxybenzoate having the structural formula
It also relates to kill- and 2-cycloalkyl hydrazides.       [0033]   The novel substituted 1-alkyl-, 2-alkyl- and benzoates of the formula (II) and
2-cycloalkylhydrazide is a 1-alkyl-, 2-alkyl- of the formula (1).
And 2-cycloalkyl hydrazide. Therefore these
The hydrazides of formulas (I) and (II) effectively reduce the number of insects present and
Remove from insect attack. The insecticidally effective amount of this active compound is
To the leaves or to the soil, water or other medium in which the plants grow. This
These compounds may be provided to insects in the form of food or to the spawning or habitat of insects.
May be applied.       [0034]   Further halogen, CH_Three, CF_Three, -OCH_Three, -OCH_TwoO-, -OCF_TwoO-,
NH_Two, NO_TwoOr a novel compound of formula (II) substituted with -CH = CH-CH = CH-
Of 1-alkyl-, 2-alkyl- and 2-cycloalkylhydrazides of benzoic acid
Many are dibenzoylhydrazines that are effective as insecticides and systemic soil insecticides
Useful as an intermediate for the production of       [0035]   1-alkyl-, 2-alkyl- and 2-cyclobenzoates of the formula (II) according to the invention Roalkyl hydrazides have the structural formula       [0036] Embedded image       [0037] [Wherein, R and R₆Is independently hydrogen, C_Two~ C₆Alkyl or C_Five~ C₆Shiku
X and Y are each independently H, C₁~ C_ThreeAlkyl, C₁~
C_ThreeAlkoxy, C₁~ C_ThreeAlkylthio, C₁~ C_ThreeAlkylsulfinyl, C₁~
C_ThreeAlkylsulfonyl, cyano, F, Cl, Br, nitro, CF_Three, R₁CF_TwoZ
-1,1-difluoro-2,2-dichloroethoxy, R_TwoCO or R_ThreeR_FourN
X and Y are joined together, and XY is a structural formula       [0038] Embedded image       [0039] May form a ring represented by Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn
R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H
Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2;
R is hydrogen₆Is C_Two~ C_FiveAlkyl or C_Five~ C₆A cycloalkyl, and
R₆R is C when is hydrogen_Two~ C_FiveAlkyl or C_Five~ C₆Cycloalkyl] Is indicated by       [0040]   The 2-alkyl- and 2-cycloalkylhydrazides of the formula (I) of the present invention are
Alkyl- or cycloalkylhydrazine hydrochloride can be converted to benzoyl in the presence of an aqueous base.
It is produced by reacting with a halide.       [0041]   Generally, alkyl or cycloalkyl hydrazine hydrochloride is converted to an organic solvent such as chloride
Disperse in methylene, ether, etc. and mix the resulting mixture with aqueous base
You. Ordinarily, to achieve benzoylation of alkyl hydrazines,
About 2 to 6 molar equivalents of base, such as sodium carbonate, per equivalent of hydrazine hydrohalide
Thorium or sodium hydroxide is used. The mixture thus produced is then
With an organic solvent, preferably an alkyl- and cycloalkyl-hydrazine halide.
A suitable benzene dissolved or dispersed in the same solvent used to dissolve the hydrobromide
Mix with Zoyl halide.       [0042]   This mixture is used for the production of the alkyl- or cycloalkyl-hydrazide benzoate.
Stir for sufficient time. This product separates the aqueous phase from the organic phase and removes the organic solvent
Is easily recovered from the mixture by evaporating from the organic phase.       [0043]   This reaction is used schematically below:       [0044] Embedded image       [0045] Wherein Q is a halogen, preferably chlorine, and R, X and Y are As described for the compound of (I)].       [0046] Structural formula       [0047] Embedded image       [0048] Wherein R is hydrogen;₆Is C_Two~ C₆Alkyl or C_Five~ C₆Cycloalkyl
And X and Y are as described above. 1-alkyl and 2-cycloalkyl benzoates of the formula (II) according to the invention represented by
Lucyl hydrazide is an alkyl hydrazine or cycloalkyl hydrazine
It is produced by reacting with tons. After leaving the mixture for a short time,
Treat with ether and potassium hydroxide pellets. This ether phase is separated from the mixture.
Separate and evaporate to give 1-alkyl-2-isopropylidenehydrazide or 1-cyclohexane.
This gives chloroalkyl-2-isopropylidenehydrazide.       [0049]   Subsequently, the obtained 1-alkyl- or 1-cycloalkyl-isopropylidene hydrogen
Reacting drazide with benzoyl halide in the presence of 10% sodium hydroxide
1-alkyl or 1-cycloalkyl-2-isopropylidenehydra of benzoic acid
Get Zid. The product prepared in this way is diluted with a dilute mineral acid such as 1 in the presence of an alcohol.
Hydrolysis with 0% HCl yields 1-alkyl or 1-cycloalkyl of benzoic acid.
Hydrazide is formed.       [0050]   These reactions are illustrated as follows:       [0051] Embedded image       [0052] [Wherein, R₆, X and Y are as described above]   R₆Alkyl and cycloalkyl of formula (II) of the present invention wherein
The production of hydrazide is based on the comparison of the appropriate alkylidene hydrazide
It is also carried out, for example, by reduction with hydrogen in the presence of platinum or palladium. Anti
The lower alkyl (C) is preferably reacted under a hydrogen atmosphere maintained at about 20-60 psig.₁
~ C_Four) Done in alcohol. This reaction is illustrated below:       [0053] Embedded image       [0054] [Wherein, R₁, X and Y are as described for the compounds of formula (II) above.
].       [0055]   Benzoic acid 2-alkylhydrazide and 2-cycloalkylhydra of formula (II)
Zide is a highly potent insect gastric poison and systemic insecticide, a dizide of formula (I).
Useful as an intermediate for the production of benzoylhydrazine. These dibens
Zoilhydrazines include, but are not limited to, Lepidoptera, Homoptera, Orthoptera, Coleoptera
It is effective in controlling various insects, including dipteran and dipteran, as well as controlling various crops.
Effective for protecting against insects.       [0056]   The dibenzoylhydrazine compound of formula (I) has the structural formula       [0057] Embedded image       [0058] [Wherein R is C_Two~ C₆X, Y, M and N are each independently H,
C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy, C₁~ C_ThreeAlkylthio, C₁~ C_ThreeAl Killsulfinyl, C₁~ C_ThreeAlkylsulfonyl, cyano, F, Cl, Br, I
, Nitro, CF_Three, R₁CF_TwoZ-, 1,1-difluoro-2,2-dichloroethoxy
Si, R_TwoCO or R_ThreeR_FourN and X and Y are taken together and XY is a structural formula       [0059] Embedded image       [0060] May form a ring represented by the formula: and M and N are taken together to form MN having the structural formula       [0061] Embedded image       [0062] May form a ring represented by; Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn
R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H
Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2; Provided that at least one of X, Y, M or N is a substituent other than hydrogen, and M is p
-In the case of nitro, at least one of X, Y or N must be a substituent other than hydrogen
Absent] Having.       [0063]   These compounds of formula (I) include alkyl benzoate hydrazide and benzoyl hae
About an equimolar amount of the ride is added to a neutral solvent such as ether, chlorinated hydrocarbon, etc.
It is produced by reacting in the presence of a neutral base. Generally alkyl benzoate About 2-6 molar equivalents of base per equivalent of hydrazide is sufficient to complete the reaction.
You. This reaction is schematically illustrated below:       [0064] Embedded image       [0065] Wherein Q is halogen and R, X, Y, M and N are relative to formula (I)
As described above]   As mentioned above, the compounds of the invention can advantageously be prepared in a fairly rapid manner.
it can. According to the method of the present invention, C_Two~ C₆Alkyl hydrazine hydrohalic acid
Disperse the salt in an organic solvent such as methylene chloride, ether, etc.
The mixture is mixed with an aqueous base. Achieve benzoylation of ordinary alkyl hydrazines
About 2 to 6 molar equivalents per equivalent of alkyl hydrazine hydrohalide
For example, sodium carbonate or sodium hydroxide is used. Then like this
An organic solvent, preferably an alkyl hydrazine hydrogen halide
A suitable benzoyl halide dissolved or dispersed in the same solvent used for dissolution of the acid salt
Mix with ride.       [0066]   Stir the mixture for a time sufficient to produce the alkyl benzoate hydrazide
. The product separates the aqueous phase from the organic phase and evaporates the organic solvent from the organic phase.
And is easily recovered from the mixture.       [0067]   This reaction is schematically illustrated below:       [0068] Embedded image       [0069] Wherein Q is halogen, preferably chlorine; R is C_Two~ C₆Alkyl;
X and Y are independently H, C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy, C
₁~ C_ThreeAlkylthio, C₁~ C_ThreeAlkylsulfinyl, C₁~ C_ThreeAlkylsulfo
Nil, cyano, F, Cl, Br, nitro, CF_Three, R₁CF_TwoZ-, 1,1-diflu
Or-2,2-dichloroethoxy, R_TwoCO or R_ThreeR_FourN and X and Y
Are connected together and XY is a structural formula       [0070] Embedded image       [0071] May form a ring represented by Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn
R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H
Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2].       [0072] As used herein, R is C_Two~ C₆In the case of alkyl, it is straight-chain and branched-chain Lucyl group C_Two~ C₆And cycloalkyl group C_Three~ C₆It is intended to include       [0073]   The production of alkyl benzoate hydrazide is carried out with the appropriate alkylidene hydrazide benzoate.
Is reduced with hydrogen in the presence of a noble metal catalyst such as platinum or palladium.
Is also achieved. The reaction is preferably run under hydrogen maintained at about 20-60 psig.
Lower alkyl C₁~ C_FourPerformed in alcohol. This reaction is illustrated below:       [0074] Embedded image      [0075] [Wherein R is C_Two~ C₆X and Y are each independently H, C₁~ C_Three
Alkyl, C₁~ C_ThreeAlkoxy, C₁~ C_ThreeAlkylthio, C₁~ C_ThreeAlkylsul
Finil, C₁~ C_ThreeAlkylsulfonyl, cyano, F, Cl, Br, nitro, C
F_Three, R₁CF_TwoZ-, 1,1-difluoro-2,2-dichloroethoxy, R_TwoCO
Is R_ThreeR_FourN and X and Y are taken together and XY is a structural formula       [0076] Embedded image       [0077] May form a ring represented by Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H
Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2].       [0078]   The above-mentioned alkyl hydrazide benzoate is useful as an insecticide, and is a lepidopteran
Particularly effective when used to control insects. These compounds are dibenzoylhydra
It has the additional advantage of being useful as an intermediate for the preparation of gin compounds. This is very
Insect stomach toxicant and systemic insecticide useful for insects, Lepidoptera, Homoptera, Orthoptera, Sheath
It is effective in controlling a variety of insects, including Coleoptera and Diptera, and also in a variety of crops
Has been found to be effective in protecting against insect attack. These compounds
Has also been found to have some activity as a contact insecticide.       [0079]   The novel benzoylhydrazine compound of the present invention has the structural formula       [0080] Embedded image       [0081] [Wherein R is C_Two~ C₆X, Y, M and N are each independently H,
C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy, C₁~ C_ThreeAlkylthio, C₁~ C_ThreeAl
Killsulfinyl, C₁~ C_ThreeAlkylsulfonyl, cyano, F, Cl, Br, I
, Nitro, CF_Three, R₁CF_TwoZ-, 1,1-difluoro-2,2-dichloroethoxy
Si, R_TwoCO or R_ThreeR_FourN and X and Y are taken together and XY is a structural formula       [0082] Embedded image       [0083] May form a ring represented by the formula: and M and N are taken together to form MN having the structural formula       [0084] Embedded image       [0085] May form a ring represented by; Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn
R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H
Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2; Provided that at least one of X, Y, M or N is a substituent other than hydrogen, and M is p
-In the case of nitro, at least one of X, Y or N must be a substituent other than hydrogen
Absent] Having. These are approximately the alkyl benzoates and benzoyl halides.
Equimolar amounts of neutral solvents such as ethers, chlorinated hydrocarbons and the presence of aqueous bases
Manufactured by reacting below. Generally, benzoic acid is required to complete the reaction.
About 2-6 molar equivalents of base per equivalent of acid alkyl hydrazide is sufficient. This anti
The response is schematically illustrated in the equation:       [0086] Embedded image       [0087] Wherein Q is halogen and R is C_Two~ C₆X, Y, M and N
Are independently H and C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy, C₁~ C_ThreeArchi
Lucio, C₁~ C_ThreeAlkylsulfinyl, C₁~ C_ThreeAlkylsulfonyl, cyano
, F, Cl, Br, I, nitro, CF_Three, R₁CF_TwoZ-, 1,1-difluoro-2
, 2-Dichloroethoxy, R_TwoCO or R_ThreeR_FourN and X and Y together
Nate XY is a structural formula       [0088] Embedded image       [0089] May form a ring represented by the formula: and M and N are taken together to form MN having the structural formula       [0090] Embedded image      [0091] May form a ring represented by; Z is S (O) n or O;₁Is H, F, CHF_Two, CHFCl or CF_ThreeIn
R;_TwoIs C₁~ C_ThreeAlkyl, C₁~ C_ThreeAlkoxy or R_ThreeR_FourN; R_ThreeIs H
Or C₁~ C_ThreeAlkyl; R_FourIs H, C₁~ C_ThreeAlkyl or R_FiveCO;
R_FiveIs H or C₁~ C_ThreeAlkyl and n is 0, 1 or 2].       [0092]Composition with other compounds   The diacylhydrazines of the present invention are effective insecticides for synergists.
Although not required to be present, they are 5- [1- [2- (2-ethoxy-ethoxy)
C) ethoxy] ethoxy] -1,3-benzodioxole; n- (2-ethyl
Xyl) -5-norbornene-2,3-dicarboximide; 5- (2-octyl)
Sulfinyl) propyl] -1,3-benzoxol or piperonyl butoxy
Can be advantageously used in combination with a synergist such as They kill other normal
Insecticides such as pyrethroids, phosphates, carbamates, chlorinated hydrocarbons, halo
In combination with other common insecticides such as benzoyl urea, and formamidine or
They can be used together.       [0093]   Insecticides intended for use in combination with the diacylhydrazines of the present invention include:
There are;   (RS) -α-cyano (3-phenoxyphenyl) methyl (RS) -4-chloro
Ru-α- (1-methylethyl) benzene acetate;   (RS) -α-cyano (3-phenoxyphenyl) methyl (I-RS) -cis
-, Trans-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopro
Pan carboxylate;   (±) -α-cyano (3-phenoxyphenyl) methyl (+)-4- (diflu
Olomethyxi) -α- (1-methylethyl) benzene acetate;   (3-phenoxyphenyl) methyl (I-RS-cis, trans-3- (2,
2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate;   2,2-bis (p-methoxyphenyl) -1,1,1-trichloroethane;   4,4'-dichloro-α-trichloromethylbenzhydrol;   3- (dimethoxyphosphinyloxy) -N, N-dimethyl-cis-crotona
Mid;   Diethyl (dimethoxyphosphinothiothio) succinate;   O, O-dimethyl O- [3-methyl-4- (methylthio) phenyl] -phospho
Rothioate;   S-6-Chloro-2,3-dihydro-2-oxobenzoxazol-3-yl-
Methyl-O, O-diethyl phosphorodithioate;   N, N-dimethyl-2-methylcarbamonoximino-2- (methylthio)-
Acetamide;   1-methylethyl (E, E) -11-methoxy-3,7,11-trimethyl-2,
4-dodecadienoate;   S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiasol
-3-ylmethyl O, O-dimethyl phosphorodithioate;   O, S-dimethylphosphoramide thioate;   2- (diethoxyphosphinylimino) -4-methyl-1,3-dithiolane;   (RS) -α-cyano-3-phenoxybenzyl N- (2-chloro-α, α, α
-Trifluoro-p-tolyl] -D-valinate;   4-chlorophenyl-3- (2,6-difluorobenzoyl) urea;   O, O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate
G;   N '-(4-chloro-2-methylphenyl) -N, N-dimethylmethanimide door
Mid;   1,3-di (carbamoylthio) -2-dimethylaminopropane;   N-methylbis (2,4-xylyliminomethyl) amine;   O, S-dimethylacetylphosphoramide thioate;   (RS-α-cyano-4-fluoro-3-phenoxybenzyl) (I-RS)
-Cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropyl
Lopan carboxylate;   S-methyl N- (methylcarbamoyloxy) thio-acetimidate;   2,3-dihydro-2,2-dimethyl-7-benzofuranylmethyl carbamate
;   2-methyl-2- (methylthio) propanal O-[(methylamino) carboni
Ru] -oxime;   O, O-diethyl-S- (tert-butylthiomethyl) phosphorodithioe
G;   O, O-dimethyl S-phthalimidomethyl phosphorodithioate;   O-2,4-dichlorophenyl O-ethyl S-propyl phosphorodithioate
;   O-4-bromo-2-chlorophenyl O-ethyl S-propyl phosphorothioe
To;   2- (dimethylamino-5,6-dimethyl-4-pyrimidinylmethylcarbamine
To;   O, O-diethyl Sp-chlorophenylthiomethyl phosphorodithioate;   6,7,8,9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydride
B-6,9-methano-2,4,3-benzodioxathiepine-3-oxide;   α-methylbenzyl 3- (dimethoxyphosphinyloxy) -cis-crotonay
G;   2- (2-butoxyethoxy) ethyl ester;   Bis (dialkylphosphinothionyl) disulfide;   O, O-dimethyl O-2-chloro-4-nitrophenyl phosphorodithioate ;   S-α-cyano-3-phenoxybenzyl (IR) -cis-3- (2,2-
Dibromovinyl) -2,2-dimethylcyclopropanecarboxylate;   (±) -α-cyano-4-fluoro-3-phenoxybenzyl (±) -4-di
Fluoromethoxy-α- (1-methylethyl) benzene acetate;   O, O-diethyl Op-nitrophenyl phosphorothioate;   O, O-dimethyl Op-nitrophenyl phosphorothioate;   O, O-dimethyl O- (3-methyl-4-nitrophenyl) thionophosphate G;   O, O-dimethyl Sp-chlorophenylthiomethyl phosphorodithioate;   4-dimethylamino-3,5-xylylmethylcarbamate;   2,2-bis (p-chlorophenyl) -1,1,1-trichloroethane;   Dichlordiphenyldichloroethane;   Chlorinated camphorene;   Terpene polychlorinate;   O, O, O ', O'-tetramethyl-O, O'-thiodi-p-phenylene phosphoro
Thioate;   O, O, O ', O'-tetraethyl S, S'-methylenebis-phosphorodithioate
G;   Dimethyl 2-methoxycarbonyl-1-methylvinyl phosphate;   Dimethyl 2,2-dichlorovinyl phosphate;   Dimethyl-1,2-dibromo-2,2-dichloroethylphosphate;   2,4-dinitro-6- (2-octyl) phenylcrotonate;   Dimethyl 2-chloro-2-diethylcarbamoyl-1-methylvinylphosphe
To;   N-methyl-1-naphthyl carbamate;   O, O-diethyl-S- (ethylthiomethyl) phosphorodithioate;   O, O-dimethyl-S- (ethylthiomethyl) phosphorodithioate;   O, O-dimethyl S- (4-oxobenzotriazine-3-methyl) phosphoro
Dithioate;   2,3-p-dioxane S, S-bis (O, O-diethyl phosphorodithioate
);   O, O-diethyl O- (2-isopropyl-4-methyl-6-pyrimidinyl)
Phosphorothioate;   O, O-dimethyl S- (N-methylcarbamoylmethyl) phosphorodithioie
G.       [0094] Preparation   As described above, the diacylhydrazine of the present invention and the 1-alkyl benzoate,
-Alkyl and 2-cycloalkylhydrazines are excellent insect stomach poisons
Has a contact insecticidal action. They are applied to the leaves of the plant to be protected from insect attack
It is effective when applied to insect spawning soil, food sources or habitats. This
These diacylhydrazines are present in the rhizomes of plants to be protected from insect attack.
It is also a very effective systemic insecticide. Active dia when used systemically
Silhydrazine is easily dispersed in soil or water where plants grow, usually in the soil or water.
And / or applied in the form of a solid or liquid preparation which dissolves.       [0095]   Emulsifiable concentrates, wet and dry flowable compositions, granular preparations, microemulsions and water
All compatible dusts are suitable for soil and / or water applications and provide the desired insect control and
Provide necessary plant protection.       [0096]   A typical emulsifiable thickener is about 31 W / V% diacylhydrazine such as 1-t
tert-butyl-1,2-bis (p-chlorobenzoyl) hydrazine; 1-te
rt-butyl-1,2-bis (3,4-dichlorobenzoyl) hydrazine, or 1
, 2-Dibenzoyl-1-tert-butylhydrazine was treated with 49 W / V% of 2-
Pyrrolidone; 10 W / V% n-butanol; 7 W / V% polyalkylene glycol
Coal ethers such as Westvaco-Polychemica
ls, Charleston Heights, South, Carolina)^R) S
320 and 3.0 W / V% from Rohm & Haas
Toriton^R) Nonylphenoxypolyethoxy commercially available as N101
It can be produced by dispersing in ciethanol.       [0097]   Because emulsifiable concentrates are easily dispersed in water for application as a liquid spray
It is particularly useful for dispersing the active diacyl hydrazines of the present invention. Those
May be added to irrigation water or paddy water as used for rice cultivation or undiluted
For ultra low volume (ULV) or low volume (LV) applications where the thick material is finely divided droplets
Me Plants to be protected by using a pneumatic application machine or ground equipment designed in
It may be applied directly to the area.       [0098]   The particulate preparation is dissolved in a solvent that boils diacylhydrazine, for example, methylene chloride.
And dissolve the solution thus prepared in about 2-20 weights based on the total weight of the granular product.
% Of the adsorbent carrier, preferably in an amount sufficient to provide about 3 to 15% of the active ingredient.
For example, spray on kaolin, bentonite, attapulgite, montmorillonite, etc.
Can be manufactured.       [0099]   The wettable powder preparation contains about 30-75% by weight of the active diacylhydrazine in about 5%.
10 to 10% by weight of an anionic surfactant such as a naphthalene sulfonate condensate or
Is a sodium or ammonium salt of condensed mononaphthalenesulfonic acid, about 3 to 5 times
% Of an anionic surfactant such as alkyl naphthalene sulfonate, i.e.
Sodium n-butyl naphthalene sulfonate, diisopropyl naphthalene sulfo
Sodium diacid and the like and the remaining inert diluents of the composition such as attapulgite,
Grinding with kaolin, montmorillonite, talc, diatomaceous earth, etc.
Can be manufactured.       [0100]   In practice, the protection of growing plants can be the leaves of the plants and / or the soil in which they grow,
In water or other medium, 2-alkyl- or 2-alkylbenzoate of formula (I) or (II)
About 0.1 to about 10.0 kg / ha of cycloalkyl hydrazide, preferably
Achieved by applying in an amount of about 0.28-4.0 kg / ha. Advantageously
Habitat, food source and / or spawning soil of these preparations in the proportions mentioned above
Application reduces the viability of insects in such treated areas.       [0101]   Do not apply active compounds of formula (I) or (II) as a spray of diluent.
The spray may be used for 10 to about 10,000 to provide the desired protection and insect control.
It should contain 0 ppm of active ingredient.       [0102]   A typical emulsifiable concentrate preparation contains about 30 W / V% of the inventive benzoic acid 1-al
The kill-, 2-alkyl- and 2-cycloalkylhydrazines are converted to 50 W / V%
2-pyrrolidone, 10 W / V% n-butanol, 7 W / V% polyalkylene
Glycol ethers, such as Polyfar S from Westbaco-Polychemicals
320 and 3.0 W / V% from Rohm and Haas from Triton N101
Disperse in Nonylphenoxypolyethoxyethanol, commercially available as
It is manufactured by this.       [0103]   Because emulsifiable concentrates are easily dispersed in water for application as a liquid spray
The active 1-alkyl, 2-alkyl and 2-cycloalkyl benzoates of the present invention
It is particularly useful for dispersing hydrazides. They are used for cultivation of rice
Concentrates that may or may not be added to water or field water are combined with finely divided droplets
Pneumatic applications designed for ultra low volume (ULV) or low volume (LV) applications
Applied directly to the plant or area to be protected by using a machine or ground equipment
Is also good.       [0104]   Particulate preparations are solvents which boil the active hydrazide of formula (I) or (II)
For example, dissolve in methylene chloride and apply the solution thus prepared to the total weight of the granular product.
About 2-20% by weight, based on the weight of the active ingredient, preferably about 3-15%.
A small amount of adsorbent carrier such as kaolin, bentonite, attapulgite, montmo
It can be manufactured by spraying on rilonite or the like.       [0105]   The wettable powder preparation is about 30-75% by weight of the active compound of formula (I) or (II).
Drazide is added to about 5-10% by weight of an anionic surfactant such as naphthalene sulfo.
Sodium or ammonium nitrate condensate or condensed mononaphthalenesulfonic acid
Salt, about 3-5% by weight of an anionic surfactant such as alkyl naphthalene sulfo
, Ie, sodium di-n-butylnaphthalenesulfonate, diisopropyl
Inert diluents such as sodium naphthalene sulfonate and the rest of the composition e.g.
Powder with attapulgite, kaolin, montmorillonite, talc, diatomaceous earth, etc. It can be produced by crushing.       [0106]   The following examples are merely illustrative of the present invention and are not limiting.
No.       [0107]     【Example】Reference Example 1 Preparation of 2-tert-butyl hydrazide benzoate   Tert-butylhydrazine hydrochloride (15.6 g, 0.125 mol) was added to methyl chloride.
Dissolved in 350 ml of ren. 240 ml of 10% aqueous sodium hydroxide in this solution
(24 g, 0.60 mol) was added. Then, benzoyl chloride (d = 1.211,
(14.5 ml, 17.6 g, 0.125 mol) in methylene chloride was rapidly stirred.
It was added at a moderate rate to the stirring two-phase system.       [0108]   After the mixture was stirred at room temperature for 24 hours, the methylene chloride phase was removed and 5% aqueous
Wash with sodium hydroxide, water, saturated sodium chloride solution, then sodium sulfate
Dried. 19.3 g of a white solid, mp 87-94 ° C. by evaporation under vacuum
I got This was recrystallized from 2-propanol-water to give a product having a melting point of 92-94 ° C.
13.0 g were obtained.       [0109]   In the above reaction, p-chlorobenzoyl chloride was used instead of benzoyl chloride.
By using p-chloride, p-chlorobenzoic acid 2-te having a melting point of 116 to 122 ° C is used.
rt-Butyl hydrazide was obtained. Similarly, p-fluorobenzoyl chloride, p
-Nitrobenzoyl chloride, o-toluyl chloride, m-fluorobenzo
Yl chloride, p-bromobenzoyl chloride, p-trifluoromethyl
Nzoyl chloride, o-anisyl chloride, p-toluyl chloride, o-
Chlorobenzoyl chloride, p-iodobenzoyl chloride, o-iodobe
Nzoyl chloride, p-ethylbenzoyl chloride and o-fluorobenzo
Il chloride, o-nitrobenzoyl chloride, o-bromobenzoyl chloride And N-methylanthraniloyl chloride with benzoyl chloride
Alternatively, 2-tert-butyl p-fluorobenzoate may be used.
Hydraside, mp 136-138 ° C; 2-tert-butyl p-nitrobenzoate
Hydraside; 2-tert-butylhydraside o-toluic acid; m-fluoro ammonium
2-tert-butyl hydrazide benzoate, melting point 119-120 ° C; p-bromoamine
2-tert-butyl hydrazide benzoate; p-trifluoromethylbenzoic acid 2-
tert-butylhydraside; 2-tert-butylhydraside o-anisic acid;
p-toluic acid 2-tert-butylhydraside; o-chlorobenzoic acid 2-te
rt-butyl hydrazide, melting point 68-70 ° C; p-iodobenzoic acid 2-tert
-Butyl hydrazide; o-iodobenzoic acid 2-tert-butyl hydrazide; p
-Ethylbenzoic acid 2-tert-butylhydraside; and o-fluorobenzoic acid
2-tert-butylhydrazide, melting point 58-59 ° C; o-nitrobenzoic acid 2-
tert-butyl hydrazide, melting point 116-118 ° C; o-bromobenzoic acid 2-
tert-butyl hydrazide, melting point 85-87 ° C .; and N-methylanthranyl
This gave acid 2-tert-butylhydrazide, mp 125-129 ° C.       [0110]   The above reaction is illustrated below:       [0111] Embedded image       [0112] Wherein Q is halogen, preferably chlorine; R is tert-butyl or te
rt-amyl; and X is hydrogen, halogen, C₁~ C_ThreeAlkyl, methoxy
, Methylamino, NH_Two, Nitro or CF_ThreeIs] Other methods that can be prepared using appropriately substituted benzoyl halides according to the methods described above.
The compound was 2-tert-butylhydraside m-chlorobenzoate, melting point 120-
123 ° C; p-cyanobenzoic acid 2-tert-butylhydrazide, melting point 135-
136 ° C; anthranilic acid 2-tert-butylhydrazide, melting point 165-16
Including 7 ° C.       [0113]Reference example 2 Production of 3,4-dichlorobenzoic acid 2-tert-butyl hydrazide   Sodium carbonate (23.3 g, 0.2 ml in 100 ml of water and 250 ml of ether)
Tert-butylhydrazide hydrochloride (12.4 g, 0.1 mol)
Was added. Then 3,4-dichlorobenzoyl chloride (20.9 g, 0.1
(Mol) in 50 ml of water at 0-15 ° C. Reaction mixture after 1 hour
The material was filtered and the filtrate was separated. The organic layer was washed with 100 ml of water and dried over anhydrous MgSO._Four
, Filtered and evaporated. For recrystallization of the residue from 2-propanol
As a result, white crystals having a melting point of 144 to 145 ° C were obtained.       [0114]   2,4-dichlorobenzoyl chloride instead of 3,4-dichlorobenzoyl chloride
The method described above except for using chloride or 2,6-dichlorobenzoyl chloride
Accordingly, 2,4-dichlorobenzoic acid 2-tert-butylhydrazide,
Point 115-117 ° C and 2-tert-butylhydra 2,6-dichlorobenzoate
Azide, mp 173-174 ° C.       [0115]   Similarly, 2-chloro-4-nitrobenzoyl chloride, 3-bromo-4-methyl
Lebenzoyl chloride, 2,6-difluorobenzoyl chloride, 2,5-di
Chlorbenzoyl chloride, 3,5-dichlorobenzoyl chloride or naph
Using toyl chloride instead of 3,4-dichlorobenzoyl chloride
To give 2-tert-butylhydra 2-chloro-4-nitrobenzoate
Zide; 3-bromo-4-nitrobenzoic acid 2-tert-butylhydrazide, melting point
95-97 ° C; 2,6-difluorobenzoic acid 2-tert-butylhydrazide; 2,5-dichlorobenzoic acid 2-tert-butylhydrazide, 3,5-dichloroammonium
2-tert-butyl hydrazide, melting point 163-165 [deg.] C .;
There was obtained tert-butyl hydrazide melting point 148-150 ° C.       [0116]   These reactions are exemplified below:       [0117] Embedded image      [0118] Wherein Q is halogen, preferably chlorine; X and Y are each independently halo
Gen, C₁~ C_ThreeAlkyl, methoxy, nitro or CF_ThreeAnd XY is one
In the beginning       [0119] Embedded image       [0120] Represents].       [0121]Reference Example 3 Production of 1,2-dibenzoyl-1-tert-butylhydrazine   In 31 flasks with mechanical stirring, t-butylhydrazine hydrochloride (101 g, 0.18 mol) in 970 ml of 10% sodium hydroxide (97 g, 2.
4 mol). After the addition of water 11, attach the condenser and the addition funnel to the flask.
I did.       [0122]   Then benzoyl chloride (176 ml, 213 g, 1
.52 mol) was added over about 1 hour. The reaction starts with the formation of a white solid.
Progressed thermally. After stirring overnight, the mixture was filtered and the resulting solid was dried,
Then recrystallized from isopropyl alcohol. Collect white crystals, dry and weigh
Weighed. 147.0 g of product with a melting point of 174.degree.-176.degree. C. were obtained.       [0123]   In the above reaction, 2,6-difluorobenzoyl chloride, 4-ethylbenzene
Nzoyl chloride, 4-nitrobenzoyl chloride, 4-iodobenzoyl
Chloride, 2-chloro-4-nitrobenzoyl chloride, 3-bromo-4-
Toluoyl chloride, 2,5-dichlorobenzoyl chloride or 3,4- (meth
Tylenedioxy) benzoyl chloride or 3,4-naphthoyl chloride
By substituting for benzoyl chloride, 1-tert-butyl
1,2-bis (2,6-difluorobenzoyl) hydrazine, melting point 193-1
94 ° C; 1-tert-butyl-1,2-bis (p-ethylbenzoyl) hydra
Gin, melting point 178 ° C .; 1-tert-butyl-1,2-bis (p-nitrobenzo
Yl) hydrazine, melting point> 240 ° C .: 1-tert-butyl-1,2-bis (p
-Iodobenzoyl) hydrazine, melting point> 230 ° C; 1-tert-butyl-1
, 2-Bis (2-chloro-4-nitrobenzoyl) hydrazine, melting point 155-1
58C; 1-tert-butyl-1,2-bis (3-bromo-p-toluoyl)
Hydrazine, mp 177-178 ° C; 1-tert-butyl-1,2-bis (2,
5-Dichlorobenzoyl) hydrazine, mp 198-200 ° C; 1-tert-
Butyl-1,2-bis [3,4- (methylenedioxy) -benzoyl] hydrazine
Mp> 235 ° C; and 1-tert-butyl-1,2-di-2-naphthoylch.
Drazine, melting point 235 ° C. was obtained.       [0124]   These reactions are exemplified below:       [0125] Embedded image      [0126] Wherein Q is halogen, preferably chlorine; and X and Y are each independently
Hydrogen, halogen, C₁~ C_ThreeAlkyl, methoxy, nitro, CF_ThreeOr R₁CF_Two
Z and X and Y are taken together to form XY having the structural formula -OCH_TwoO-, -OCF_Two
O- or       [0127] Embedded image       [0128] R may form a ring represented by the formula: Z is S or O;₁Is H, F, CH_TwoF
Or CF_ThreeIs].       [0129]Reference example 4 2-benzoyl-1-tert-butyl-1- (3,4-dichlorobenzoyl)
Hydrazine   50 ml of methylene chloride and 25 ml of 10% aqueous sodium hydroxide (2.5 g,
0.063 mol) of benzoyl-2-tert-butylhydra in a two-phase system.
Gin (4.8 g, 0.025 mol) was stirred vigorously until all had dissolved. This In a solution of 3,4-dichlorobenzoyl chloride in methylene chloride (7.3 g, 0
.025 mol) was added. After stirring this two-phase mixture at room temperature for several hours,
The solid was removed and washed with water and methylene chloride. For recrystallization from 2-propanol
Thus, 7.1 g (78%) of a product having a melting point of 234 to 235.5 ° C. was obtained.       [0130]   This reaction can be schematically illustrated as follows:       [0131] Embedded image       [0132]Reference Example 5 1-benzoyl-1-tert-butyl-2- (3,4-dichlorobenzoyl)
Manufacture of hydrazine   40 ml of methylene chloride and 20 ml of 10% aqueous sodium hydroxide (2 g,
3,4-dichlorobenzoyl-2-t).
tert-Butylhydrazine (5.63 g, 0.0215 mol) was added. Then
Benzoyl chloride in methylene chloride (d = 1.211, 2.5 ml, 3.03 g
, 0.0215 mol) was added and the reaction mixture was stirred vigorously at room temperature for approximately 3 hours.
. The resulting solid was collected and washed with water and methylene chloride.       [0133]   The dried solid weighed 6.18 g and had a melting point of 206.5-208.5 ° C.       [0134]   This reaction is illustrated below:       [0135] Embedded image       [0136]   Suitable in place of 3,4-dichlorobenzoyl-2-tert-butylhydrazine
Substituted benzoyl-2-tert-butylhydrazine and benzoyl chloride
The above method except that appropriately substituted benzoyl chloride is used instead of the ride
1-tert-butyl-2- (p-chlorobenzoyl) -1-p-toluene
Oil hydrazine, melting point 232.5-224.0 ° C; 1-p-anisoyl-1-t
tert-butyl-2- (3,4-dichlorobenzoyl) hydrazine, melting point> 23
0 ° C; 1-tert-butyl-2- (3,4-dichlorobenzoyl) -1-o-
Toluoylhydrazine, melting point 133-136 ° C; 1-tert-butyl-2- (
3,4-dichlorobenzoyl) -1- (p-nitrobenzoyl) hydrazine, fused
Point> 230 ° C; 1-tert-butyl-2- (3,4-dichlorobenzoyl)-
1- (α, α, α-trifluoro-p-toluoyl) hydrazine, melting point 212-2
13 [deg.] C; and 1-tert-butyl-2- (3,4-dichlorobenzoyl) -1.
-(Α, α, α-trifluoro-o-toluoyl) hydrazine, melting point 171-17
2.5 ° C. was obtained.       [0137]Reference example 6 Process for producing 3,4-dichloroisopropylidenehydrazine benzoate   3,4-Dichlorobenzoic acid hydrazide (11.7 g, 0.060 mol)
Place in the thimble of the sleigh extractor and remove
Extracted with hot acetone. After refluxing overnight, the reaction mixture is concentrated in vacuo to a white
A colored solid was obtained. The title compound was obtained by recrystallization from ethyl acetate petroleum ether 9.
5 g were obtained as white crystals with a melting point of 141-144 ° C.       [0138]   This reaction is illustrated below:       [0139] Embedded image       [0140]   Follow the above procedure except that an appropriate aldehyde or ketone is used instead of acetone
The following compound was obtained: benzoic acid (1-ethylpropylidene) hydrazide, melting point 8
9-91 ° C; and benzoic acid (2,2-dimethylpropylidene) hydrazide, melting point
168-169 ° C.       [0141]Reference Example 7 Production of 3,4-dichlorobenzoic acid 2-isopropylhydrazide   In a Parr hydrogenation unit, 3,4-dichloro ammonium in 100 ml of methanol
Isopropylidene hydrazide benzoate (9.2 g, 0.040 mol) and platinum oxide 1
00 mg was shaken under an initial hydrogen pressure of 40 psig for 1 hour 30 minutes. Filtered reaction
The mixture is concentrated under vacuum and the resulting solid is crystallized three times from isopropyl alcohol To give 2.6 g of the title compound as a white crystalline product with a melting point of 112.5 ° -115 ° C.
As obtained.       [0142]   The reaction is illustrated below.       [0143] Embedded image       [0144]Reference Example 8 1-benzoyl-2- (3,4-dichlorobenzoyl) -1-isopropylhydrido
Razine production   3,4-dichlorobenzoic acid 2-isopropylhydrazide (0.98 g, 0.004
Mol) and benzoyl chloride (0.56 g, 0.004 mol)
Stirred overnight in 1.2 ml of methylene and 6.5 ml of 10% sodium hydroxide.
The organic phase was removed and the aqueous mixture was extracted with 25 ml of methylene chloride. Organic extract
Combine and concentrate to give a yellow oil, which was taken in hot isopropyl alcohol
. Cool the alcohol solution to precipitate the title compound as a white solid
And collected by filtration. It had a melting point of 157 ° C.       [0145]   the abovereferenceIn accordance with one or more of the methods described in Examples 1-8, shown in Table 1 below
Compounds were prepared. This reaction is schematically illustrated below:       [0146] Embedded image       [0147] [Table 1]       [0148] [Table 2]       [0149] [Table 3]       [0150] [Table 4]       [0151] [Table 5]      [0152]Reference Example 9 Preparation of acetone tert-butylhydrazone   To 6.6 g of acetone cooled in an ice bath was added 5.0 g of tert-butylhydrazine.
Added. The mixture was stirred and then left for a few minutes. The mixture is then
Tell and sodium hydroxide pellets were added. The mixture is stirred and then
The ether layer was separated from the mixture. The boiling point of the ether layer is 132 to 13 by distillation.
Acetone tert-butylhydrazone at 4 ° C. was obtained as product.       [0153]   This reaction is illustrated as follows:       [0154] Embedded image       [0155]Reference example 10 Preparation of 1-tert-butyl-2-isopropylidenehydrazide benzoate   Acetone tert-butylhydrazone (2.0 g) was added to benzoyl chloride 4.
4 g and 15 ml of 10% sodium hydroxide. And benzoylchlora
The mixture was stirred until the id odor was no longer felt. The resulting product is then
And dried over magnesium sulfate. Allow the solvent to evaporate from the mixture.
Acetone N-tert-butyl-N-benzo having a boiling point of 100 to 103 ° C.
I got Ilhydrazone. This product is also obtained from 1-tert-butyl-2 of benzoic acid.
-Also referred to as isopropylidene hydrazide.       [0156]   Except that p-chlorobenzoyl chloride is used instead of benzoyl chloride
Following the method described above, the product 1-tert-butyl-2- of p-chlorobenzoic acid.
Isopropylidene hydrazide was obtained.       [0157]   In the above method, o-nitrobenzoyl chloride or o-fluorobenzo
When yl chloride was used instead of benzoyl chloride, o-
1-tert-butyl-2-isopropylidenehydrazide of nitrobenzoic acid and
1-tert-butyl-2-isopropylidenehydrazide of p-fluorobenzoic acid
Was obtained. These reactions are illustrated as follows:       [0158] Embedded image       [0159]Reference Example 11 Preparation of 1-tert-butyl hydrazide benzoate   0.5 g of 1-tert-butyl-2-isopropylidenehydrazide benzoate, 1
A solution of 0% hydrochloric acid (3 ml) and methanol (3 ml) was mixed and allowed to stand for 12 hours. this
The mixture was made basic with dilute sodium hydroxide. The methanol is evaporated from the mixture
Tert-butyl hydrazide of the product benzoic acid, melting point 117-123 ° C
I got       [0160]   Instead of 1-tert-butyl-2-isopropylidenehydrazide of benzoic acid
1-tert-butyl-2-isopropylidenehydrazide of p-chlorobenzoic acid
The above procedure was followed except that As a result, p-benzoic acid having a melting point of 134 to 136 ° C.
1-tert-butylhydrazide was obtained.       [0161]   Similarly, following the above reaction, an appropriately substituted benzoic acid, ie, its 1-tert-
By using butyl-2-isopropylidene hydrazide, the melting point of 141 to 1
1-tert-butylhydrazide of o-nitrobenzoic acid at 44 ° C and melting point 136
Preparation of 1-tert-butylhydrazide of p-fluorobenzoic acid at ~ 137 ° C
Was. The reaction is illustrated as follows:       [0162] Embedded image       [0163]Insecticidal activity of the compounds of the invention   The compounds of the present invention can be used at various concentrations of the active ingredient in acetone-water solution.
It shows insecticidal activity against various insects. An example of this insecticidal activity is Spodopte
La Eridania (Spodoptera eridania) [The third instar larva, Southern armyworm (Sou
thern, armyworm)], Spodoptera Eridania (7 days remaining), Spodoptera
Eridania (systemic test of third-stage stem cutting, southern armyworm), Anofueles
・ Anaphores quadrimaculatus (adult, ordinary malari)
Yaka), Heliotris virescense [3rd tobacco
・ Battworm (tobacco budworm)], Blattella germanica (Blattella
 germanica) [residual test, adult male cockroach (German cockroach
)], And Leptinotarsa decemlineata [
Colorado potate beetles].       [0164]   In addition, the systemic activity of the compound is determined by the colorado potato beetles (Leptinotal
Potato plants [Solanum tu (Solanum tu) from Sa desemlineata
berosum)] when tested for control. These beetles
Is resistant to carbamates, phosphates and pyrethroids, but
It was exterminated by the compound.       [0165]   The bean plant, Phaseolus limensis, is also
Potato leafhoppers, empoa, which can be protected from armyworm
It was systemically protected from Emposca abrupta.       [0166]   Sorghum plant [Zeamays L. Plants] are also young
Insects (Spodoptera eridania, third instar larva) are protected from attack and
-Corn corn rootworm (Southern corn rootworm) [Diabrotica un
From Diabrotica undecimpunctata howardi]
I was able to protect myself.       [0167]   The rice plant [Ozyza sativa] has been
By applying to leaves, armyworm [Spodoptera frugiperda]
And protected from leafhoppers (Empoaska Abruska).       [0168]   Cotton plants [Gossypium hirsutum] are also systemically average
Tobacco Batworm (Heliotris viresens)
Protected.

Claims (1)

Claims: 1. Insects, their habitats, spawning soil or food are represented by the formula: Wherein R is C ₂ -C ₆ alkyl; X, Y, M and N are each independently H,
C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, cyano, F, Cl, Br, I
, _{Nitro, CF 3, R 1 CF 2} Z-, 1,1- difluoro-2,2-dichlorophenyl ethoxy, R ₂ CO or R ₃ R ₄ N, and X and Y are the connexion XY such together Structural formula [Formula 2] In represented by it may form an atomic group ring and the M and N connexion MN structural formula ## STR3 ## such Together In represented by may form an atomic group ring; Z is S (O) n or O; R ₁ is an H, F, CHF _2, CHFCl or CF _3; R ₂ is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or R ₃ R ₄ N; R ₃ is H
Or be a C ₁ -C ₃ alkyl; R ₄ is H, be a C ₁ -C ₃ alkyl or R ₅ CO; R ₅ is H or C ₁ -C ₃ alkyl, and n is 0, 1 or 2 With the proviso that
, X and Y, or M and N, together form a structure
Drive removal of insects, characterized in that contacting a pesticidally effective amount of a compound having a forming an atomic group ring of formula -OCF ₂ O-]. 2. The compound according to claim 1, wherein [Wherein, R _{C (CH 3) 3, CH} (CH 3) 2 or _{C (CH 3) 2 C 2} H 5 in which] the a patented process range described first of claims. 3. A compound of the formula Wherein R is C ₂ -C ₆ alkyl; X, Y, M and N are each independently H,
C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, cyano, F, Cl, Br, I
, _{Nitro, CF 3, R 1 CF 2} Z-, 1,1- difluoro-2,2-dichlorophenyl ethoxy, R ₂ CO or R ₃ R ₄ N, and X and Y are the connexion XY such together Structural formula [Formula 6] In represented by may form an atomic group ring and the M and N connexion MN is structural formula 7], such together In represented by may form an atomic group ring; Z is S (O) n or O; R ₁ is an H, F, CHF _2, CHFCl or CF _3; R ₂ is C ₁ -C R ₃ is H, ₃ alkyl, C 1 -C ₃ alkoxy or R ₃ R ₄ N;
Or C ₁ -C ₃ alkyl; R ₄ is H, C ₁ -C ₃ alkyl or R ₅ CO;
R ₅ is H or C ₁ -C ₃ alkyl, and n is an 0, 1 or 2, provided that
, X and Y, or M and N, together form a structure
Pesticidal composition comprising forming an atomic group ring of formula -OCF ₂ O-]. 4. The method according to claim 1, wherein the soil or other medium in which the growing plant grows has the formula: Wherein R is C ₂ -C ₆ alkyl; X, Y, M and N are each independently H,
C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylsulfinyl, C ₁ -C ₃ alkylsulfonyl, cyano, F, Cl, Br, I
, _{Nitro, CF 3, R 1 CF 2} Z-, 1,1- difluoro-2,2-dichlorophenyl ethoxy, R ₂ CO or R ₃ R ₄ N, and X and Y are the connexion XY such together Structural formula [Formula 9] In represented by may form an atomic group ring and the M and N connexion MN is structural formula 10], such together In represented by may form an atomic group ring; Z is S (O) n or O; R ₁ is an H, F, CHF _2, CHFCl or CF _3; R ₂ is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or R ₃ R ₄ N; R ₃ is H
Or C ₁ -C ₃ alkyl; R ₄ is H, C ₁ -C ₃ alkyl or R ₅ CO;
R ₅ is H or C ₁ -C ₃ alkyl, and n is an 0, 1 or 2, provided that
, X and Y, or M and N, together form a structure
Insect harming the long term cotton connexion plant of active growth of plants, which comprises applying a systemic effective amount of a compound of forming an atomic group ring of formula -OCF ₂ O-] How to protect systemically. 5. The method according to claim 1, wherein said systemically active compound is present in an amount of about 0.01 to about 10.0 kg / ha.
The method according to claim 4 , wherein the method is applied at a ratio of: