JPH01228944A - Hydroxylamine derivative, its production and insecticide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is phenyl which may be substituted with lower alkyl; R2 is H or lower alkyl; R3 is lower alkyl; X is O or methylene; Y is lower alkylene). EXAMPLE:O-propyl-N-[2-(4-phenoxyphenoxy)ethyl]hydroxylamine. USE:An insecticide having excellent juvenile hormone activity and exhibiting extremely high controlling effect against insects of order Diptera, Lepidoptera, Coleoptera, etc. PREPARATION:The compound of formula I can be produced by reducing a compound of formula II (n is 2-4) with hydrogen in the presence of a catalyst such as palladium-carbon or with a reducing agent such as sodium cyanoborohydride in a solvent such as methanol at a temperature between 0 deg.C and the boiling point of the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel hydroxylamine derivative having excellent dibenyl hormone activity, a method for producing the same, and an insecticide containing the compound as an active ingredient.

[Conventional technology]

A large number of organic synthetic chemicals are used to control agricultural and sanitary pests, but they have various problems such as residual toxicity, environmental pollution, and the emergence of resistant pests. Therefore, in recent years, pesticide development has been progressing with a focus on substances produced by living organisms.

[Problem that the invention seeks to solve]

The purpose of the present invention is to focus on juvenile hormone (dibenyl hormone) related to the metamorphosis phenomenon peculiar to insects, and to show excellent efficacy.
Moreover, the objective is to find a compound that can be produced industrially advantageously.

[Means for solving problems]

The present invention is based on the general formula (wherein R3 is a phenyl group optionally substituted with a lower alkyl group, h is a hydrogen atom or a lower alkyl group, R1 is a hydrogen atom or a lower alkyl group, and X is an oxygen atom or a methylene group, Y represents a lower alkylene group),
The present invention is an insecticide characterized by its production method and containing the compounds as active ingredients.

The compound of the present invention has excellent dibenyl hormone activity and exhibits extremely high control efficacy against insects such as Diptera, Lepidoptera, and Coleoptera.

The compound of the present invention can be produced by reducing the compound represented by -Funzo [+11] below.

R, -x(preo-(cHt)am CH-NOR3[n
]-→R+
．． 3 or 4) As a reduction method, palladium-
Methods include hydrogen reduction using carbon as a catalyst, or methods using a reducing agent, but when using a reducing agent,
Since some compounds of the present invention or raw material compounds are unstable to certain reducing agents, it is preferable to use a reducing agent such as sodium cyanoborohydride.

When sodium cyanoborohydride is used, the reaction is carried out in a solvent such as methanol, without adjusting the pH, from 0° C. to the boiling point of the solvent used, preferably around room temperature.

After the completion of the reaction, the desired product can be obtained in good yield by performing a usual post-treatment.The structure of the compound of the present invention is IR,
Determined from NMR, elemental analysis, etc.

Moreover, the compound of the present invention can also be produced according to the following reaction formula.

(In the formula, Hal represents a halogen atom.) The raw material compound represented by -Funazura [11] can be produced, for example, according to the following reaction formula.

R+ -X 80 (CHt)--+ CHO or (in the formula, r' and r''4 each represent a lower alkyl group) (Examples) The present invention will be described in more detail with reference to Examples.

Example 10-Propyl-N-(2-(4-phenoxyphenoxy)ethyl)hydroxylamine (compound number 1): eosha0CHzCH-NOCsHt -1→(□O+0CHzCHx NHOCsHt4-phenoxyphenoxyacetaldoxime O-propyl ether 0 .31 g (1,09 mmol) of methanol solution 5 was added with a small amount of bromcresol green and 1-2 drops of hydrogen chloride in methanol.To this solution was added 0.10 g (1,5 mmol) of sodium cyanoborohydride.
9 mmol) was added at room temperature, and the methanol solution of hydrogen chloride was added dropwise while keeping the pH at which bromcresol green turned yellow (4 or less). The reaction solution was stirred for 2 hours at room temperature and neutralized with 2N sodium hydrogen carbonate. After that, water was added and extracted with ether. The ether layer was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography to obtain 0.30 g (yield 96%) of 0-propyl-N-(2-(4-phenoxyphenoxy)ethyl)hydroxylamine as a colorless oil.

Example 20-Isopropyl-N-(3-+4-(3-methylphenoxy)phenoxy)propyl]hydroxylamine (Compound No. 10) CH.

3-(4-(3-methylphenoxyphenoxyphpropionic aldoxime O-isopropyl ether 0.20
g (0.64 mmol) in methanol 5? 8
A small amount of bromcresol green and 1-2 drops of hydrogen chloride in methanol were added. this? Add 0.07 g of sodium cyanoborohydride (1,
02 mmol), and while adding hydrogen chloride methanol solution dropwise, adjust the pH until the bromcresol green turns yellow.
(4 or less) and stirred at room temperature for 2 hours.
The mixture was neutralized with N-sodium hydrogen carbonate, water was added, and the mixture was extracted with ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, and then the ether was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography to obtain 0.19 g (yield 94%) of 0-isopropyl-N-(3-[4-(3-methylphenoxyphenoxy)-propyl]hydroxylamine as a colorless oil. I got it as a thing.

Table 1 shows representative examples of the compounds of the present invention produced in the same manner as in the above examples.

Table 1 [Means for solving the problem - Insecticide] The insecticide of the present invention contains the compound represented by the -S formula [1] as an active ingredient, Although it can be used as is, it is usually used in the form of general agricultural chemicals, such as wettable powders, powders, emulsions, and flowables.

As additives and carriers, if the purpose is to use solid agents,
Vegetable powders such as soybean flour and wheat flour, and mineral fine powders such as diatomaceous earth, Hanawa lime, gypsum, talc, pyrophyllite, and clay are used.

For liquid formulations, use kerosene, mineral oil, petroleum,
Solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, water, etc. are used as the solvent. In these preparations, a surfactant may be added if necessary in order to obtain a uniform and stable form. The wettable powders, emulsions, flowables, etc. obtained in this way can be diluted with water to a predetermined degree to make a suspension or emulsion, and powders and granules can be used as they are by spraying them on plants. be done.

[Example - Insecticide]

Next, examples of formulations will be shown, but the carriers, surfactants, etc. to be added are not limited to these examples.

Example 3 Emulsion Compound of the present invention 10 parts Alkylphene port polyoxyethylene 5
#dimethylformamide 35#xine
Mix and dissolve 50 # or more, dilute with water before use, and spray as an emulsion.

Example 4 Wettable powder Compound of the present invention 20 parts Higher alcohol sulfate ester 5#
stomach
74 White carbon
1 # or more is mixed and pulverized into a fine powder, and before use, it is diluted with water and sprayed as a suspension.

Example 5 Powder Compound of the present invention 5 parts Tal
the law of nature
91 #silica
3
#Alkylphenylpolyoxyethylene
Mix and pulverize 1 # or more, and sprinkle as is when using.

〔Effect of the invention〕

Next, test examples will be given to demonstrate the insecticidal activity of the compounds of the present invention.

Test example l 20 final instar larvae of Culex mosquito were taken in 100% water.
10μ of ethanol solution of each concentration of sample compound! administered. After rearing at 28°C for about one week, the inhibition rate of emergence was determined. As a control group, 10 μE of ethanol was administered, and the corrected eclosion inhibition rate 0〉 was determined using the average value of 17% of the eclosion inhibition rate of 10 times.

Using the probit conversion method from the corrected eclosion inhibition rate of each concentration, the inverse logarithm of the half eclosion inhibition concentration of the sample compound, 1
) 150 was completed in summer. The results are shown in Table 2.

Corrected emergence inhibition rate (χ) (However, if the value is negative, it is set to 0%.)
2 Applicant: Nippon Soda Co., Ltd.

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a phenyl group that may be substituted with a lower alkyl group, R_2 is a hydrogen atom or a lower alkyl group, and R_3 is a lower alkyl group. , X represents an oxygen atom or a methylene group, and Y represents a lower alkylene group). (2) A method for producing a compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_3, X and n have the same meanings as above.) (3) One or more compounds represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, R_3, X and Y have the same meanings as above.) An insecticide characterized by containing it as an ingredient.