JPS63115851A - Haloacetamide compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is aryl; R2 and R3 are H or alkyl; R4 is alkyl, aryl, alkenyl or alkynyl; A is O or S; Y is Cl, Br or I). EXAMPLE:N-[1-(p-phenoxyphenyl)-2,2-(dimethyl)ethenyl]-N-chloroaceto-2' -metho xyethylamide. USE:A herbicide exhibiting excellent activity especially against cockspur-grass which is a gramineous weed. It has excellent activity at a low concentration and is free from phytotoxicity to crops and toxicity to man and animals. PREPARATION:The compound of formula I can be produced by reacting a Schiff base compound of formula II with a chloroacetohalogenide of formula YCH2COX (X is halogen) at -20-+150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel haloacetamide compound represented by a specific general formula, and a herbicide containing the above compound as an active ingredient.

(Prior Art) Many compounds have been synthesized as chloroacetamide compounds, and some of them are known to be useful as herbicides. For example, in JP-A-58-947,
General formula (where R5 is a hydrogen atom or an alkyl group, R5 is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyalkyl group, or a benzyl group, and R1 is a hydrogen atom, an alkyl group, an alkenyl group) , an alkoxy group, or an alkoxyl group, and X, , Xt
, X3' are each independently a hydrogen, fluorine, chlorine or bromine atom or a straight or branched alkyl group having 1 to 4 carbon atoms. ) It has been described that N-(1-alkenyl)-croacetanilide represented by the following is useful as a herbicide.
Regarding compounds in which R3 is an atomyl group such as a phenyl group, no examples have been reported due to the difficulty of the manufacturing method.

(Means for Solving the Problems) The present inventors have been carrying out synthetic research on a wide variety of compounds having valuable physiological activities for many years. In recent years, we have focused on specific compounds with an enamine structure, particularly haloacetylated vinylamine compounds, and have conducted intensive research on their synthesis and physiological activities.As a result, we have discovered that a specific new group of haloacetamide compounds has been found in various species occurring in rice fields and fields. The present inventors have discovered that it is an extremely useful compound that has excellent activity against weeds even at low concentrations and is not harmful to crops or toxic to humans and livestock, leading to the completion of the present invention. - That is, the present invention is based on the general formula (1) (wherein R1 represents a substituted or unsubstituted aryl group,
R2 and R1 represent the same or different hydrogen atoms or alkyl groups; R4 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkenyl group; It represents an alkynyl group, A represents an oxygen atom or a sulfur atom, and Y represents a chlorine atom, a bromine atom or an iodine atom. The present invention provides a haloacetamide compound represented by the following formula and a herbicide containing the compound as an active ingredient.

In the general formula (1) of the present invention, the group represented by R1 is not particularly limited as long as it is an unsubstituted or substituted aryl group. To give more specific examples of the substituents that are generally preferably used, examples of unsubstituted aryl groups include aryl groups such as phenyl, naphthyl, anthranyl, and phenanthrenyl.

Further, the substituted aryl group includes methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl,
Alkylphenyl groups such as propylphenyl, dipropylphenyl, butylphenyl, pentylphenyl, hexylphenyl, methyl (ethyl) phenyl, methyl (propyl) phenyl, and ethyl (propyl) phenyl; fluorophenyl, difluorophenyl, chlorophenyl, dichlorophenyl, Halophenyl groups such as bromophenyl, iodophenyl, trichlorophenyl and chloro(fluoro)phenyl; alkoxyphenyl groups such as methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, jetoxyphenyl, propoxyphenyl, and butoxyphenyl; chloro( methyl)
Substituted phenyl groups such as phenyl, chloro(ethoxy)phenyl, methyl(methoxy)phenyl, methylthiophenyl, (trifluoromethyl)phenyl, chloromethylphenyl, chloro(trifluoromethyl)phenyl and diphenyl; methylnaphthyl, dimethylnaphthyl, ethyl Examples include substituted naphthyl groups such as naphthyl, chloronaphthyl, dichloronaphthyl, methoxynaphthyl, methylthionaphthyl, nitronaphthyl, and cyanonaphthyl.

In addition, in the general formula (1), the alkyl groups represented by R2 and R5 are not particularly limited and known ones can be used, but
In general, linear or branched alkyl groups having 1 to 6 carbon atoms are preferred.

Specific examples include methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, is.

-butyl group, n-pentyl group, n-hexyl group, etc.

In the general formula (1), R4 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituent is a substituted or unsubstituted alkynyl group. It is. The alkyl group preferably has 1 to 12 carbon atoms, and the alkenyl group and alkynyl group preferably have 2 to 12 carbon atoms.

As the alkyl group, those specifically exemplified for Rt and R1 are preferable, but in addition to these, for example, heptyl group, octyl group, nonyl group, decyl group, etc. are preferable.

Further, the alkyl group may be substituted with a substituent that can substitute one or more hydrogen atoms on the carbon atoms constituting the alkyl group. The substituent is not particularly limited and may be selected from known substituents, but the following are particularly suitable from an industrial production method.

For example, halogen atom; alkoxy group having 1 to 6 carbon atoms; alkylthio group having 1 to 6 carbon atoms; cyano group; alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, carbon atom Alkylthio group having 1 to 6 carbon atoms or substituted or unsubstituted phenoxy group with halogen atom: alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms , or a phenyl group substituted or unsubstituted with a halogen atom; an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a heteroaryl group substituted or unsubstituted with a halogen atom; carbon Heterocycloalkyl group having 2 to 6 atoms; alkoxycarbonyl group having 1 to 6 carbon atoms; halogen atom-substituted or unsubstituted alkylcarbonyloxy group having 1 to 6 carbon atoms; 2 to 6 carbon atoms 6 alkenyloxy group; an alkynyloxy group having 2 to 6 carbon atoms, and the like.

Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. In addition, the alkoxy group includes a methoxy group, an ethoxy group, a propoxy group,
Butoxy, pentyloxy, hexyloxy, and the like are preferred. Further, as the alkylthio group, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, etc. are suitable.

In addition, the substituent of the substituted phenoxy group, substituted phenyl group, substituted heteroaryl group shown as a substituent in the substituted alkyl group of R4 is ゛, alkyl group, alkoxy group,
The types of alkylthio group and halogen atom are preferably the same as the above substituents.

Furthermore, the above-mentioned unsubstituted heteroaryl groups include furyl, chenyl, pyrrolyl, pyridyl, pyrimidyl, benzofuryl, benzochenyl, indolyl, quinolyl,
These include thiazolyl, pyrazolyl, benzothiazolyl, thiadiazolyl, and oxacylyl. The substituted heteroaryl groups include substituted furyl groups such as methylfuryl, dimethylfuryl, ethylfuryl, propylfuryl, chlorofuryl, bromofuryl, methoxyfuryl, ethoxyfuryl, and propoxyfuryl; methylchenyl, ethylchenyl, propylchenyl, butylchenyl; Substituted chenyl groups such as , fluorochenyl, chlorochenyl, bromochenyl, iodochenyl, methoxychenyl, ethoxychenyl, and propoxychenyl; N-methylpyrrolyl, N-ethylpyrrolyl, methyl-N-methylpyrrolyl, chloro-N-ethylpyrrolyl, methoxy -N-
Methylpyrrolyl, methoxyprolyl, ethylpyrrolyl,
and substituted pyrrolyl groups such as chloropyrrolyl; substituted pyridyl groups such as methylpyridyl, ethylpyridyl, chloropyridyl and methoxypyridyl; substituted benzofuryl groups such as methylbenzofuryl, chlorobenzofuryl, and ethoxybenzofuryl; ethylbenzochenyl, fluorobenzothyl Substituted benzochenyl groups such as nyl and methoxybenzochenyl; substituted quinolyl groups such as methylquinolyl, ethylquinolyl, chloroquinolyl, and methoxyquinolyl; and methylthiazolyl groups.

Furthermore, examples of the unsubstituted heterocycloalkyl group include tetrahydrofuryl, tetrahydrochenyl, pyrrolidyl, tetrahydropyryl, tetrahydrothiopyryl, and piperidyl.

Suitable examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, and pentoxycarbonyl group.

The above-mentioned alkylcarbonyloxy groups include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, butylcarbonyloxy group, pentylcarbonyloxy group, (chloromethyl)carbonyloxy group, (bromoethyl)carbonyloxy group, (fluorocarbonyloxy group) (propyl)carbonyloxy group, (dichloropropyl)carbonyloxy group and (trifluorobutyl)
Specific examples include carbonyloxy group.

In addition, as alkenyloxy groups, ethynyloxy groups,
Propenyloxy groups, butenyloxy groups, pentenyloxy groups, hexenyloxy groups, and the like are preferred.

Suitable examples of the alkynyloxy group include ethynyloxy, propynyloxy, butynyloxy, pentynyloxy, and hexynyloxy groups.

More specific examples of particularly preferred substituted alkyl groups are as follows. For example, linear or branched haloalkyl groups such as fluoromethyl, trifluoromethyl, chloromethyl, trichloromethyl, chloroethyl, bromoethyl, fluoropropyl, chloropropyl, chlorobutyl, bromopentyl, and chlorohexyl; methoxymethyl, methoxyethyl , dimethoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, ethoxymethyl, ethoxyethyl, jetoxyethyl, ethoxypropyl, jetoxypropyl, ethoxybutyl, propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl, butoxy Straight-chain or branched alkoxyalkyl groups such as methyl, butoxyethyl, butoxypropyl, butoxybutyl, and pentoxyethyl; methylthiomethyl, methylthioethyl, methylthiopropyl, ethylthiomethyl, ethylthioethyl, ethylthiobutyl, and Alkylthioalkyl groups such as propylthioethyl; cyanoalkyl groups such as cyanoethyl, cyanopropyl, and cyanobutyl; phenoxymethyl, phenoxyethyl, (methylthiophenoxy)methyl, (bromophenoxy)ethyl, (chlorophenoxy)ethyl, (methylphenoxy) ethyl,
Phenoxyalkyl groups such as (propoxyphenoxy)ethyl and (chlorophenoxy)propyl; phenylalkyl groups such as phenylmethyl, phenylethyl, phenylpropyl, (methylphenyl)methyl, (ethylthiophenyl)methyl, ゛ and (chlorophenyl)propyl Groups: Heteroarylalkyl groups such as chenylmethyl, chenylethyl, methoxychenylmethyl, furylmethyl, furylethyl, chlorofurylmethyl, pyrrolylmethyl, pyrrolylethyl, pyrazolylmethyl, pyrazolylethyl, and imidazolylethyl; tetrahydrofurylmethyl, tetrahydrofurylethyl, Heterocycloalkylalkyl groups such as methyltetrahydrofurylethyl, pyrrolidylethyl, piperidylethyl, tetrahydrochenylmethyl and tetrahydrochenylethyl; methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylcatyl, Alkoxycarbonylalkyl groups such as ethoxycarbonylpropyl and butoxycarbonylpropyl; methylcarbonyloxymethyl, methylcarbonyloxyethyl, methylcarbonyloxypropyl, ethylcarbonyloxymethyl, ethylcarbonyloxyethyl, ethylcarbonyloxypropyl, propylcarbonyloxyethyl, Alkylcarbonyloxyalkyl groups such as (chloromethyl)carbonyloxymethyl, (chloromethyl)carbonyloxyethyl, (chloroethyl)carbonyloxyethyl, and (fluoroethyl)carbonyloxyethyl; ethynyloxymethyl, ethynyloxyethyl, propenyloxymethyl ,
propenyloxyethyl, propenyloxyprovil,
Alkenyloxyalkyl groups such as propenyloxybutyl, butenyloxyethyl, and butenyloxypropyl; ethynyloxymethyl, ethynyloxyethyl, propynyloxymethyl, propynyloxyethyl, propynyloxypropyl, propynyloxybutyl, and butenyloxyethyl Examples include alkynyloxyalkyl groups such as.

The above-mentioned substituted or unsubstituted aryl group is preferably one specifically exemplified for R3 above.

Examples of the unsubstituted alkenyl group include various positional isomer alkenyl groups such as ethynyl, propenyl, butenyl, pentenyl, hexenyl, and octenyl. Examples of the substituted alkenyl group include haloalkenyl groups such as chloroethynyl, fluoroethynyl, bromopropenyl, chlorobutenyl, chloropentenyl, and fluorohexenyl;

Alkoxyalkenyl groups such as toxyethenyl, methoxypropenyl, ethoxybutenyl, ethoxyhexenyl, and propoxybutenyl; cyanoethynyl, cyanopropenyl, nitropropenyl, dimethylaminoethynyl,
and methylthiopropenyl.

Furthermore, the above-mentioned unsubstituted alkynyl group includes ethynyl,
Alkynyl groups such as propynyl, butynyl, pentynyl, and hexynyl. Examples of the substituted alkynyl group include chloropropynyl, bromobutynyl, methoxybutynyl, cyanopropynyl, and methylthiobutynyl.

Compounds having the groups listed above often exist in various positional isomers, but the methylphenyl group, which can be used in the present invention without any particular limitation, includes 0-
Examples of the butyl group include a methylphenyl group, a m-methylphenyl group, and a p-methylphenyl group, and examples of the butyl group include an n-butyl group, a sec-butyl group, and a tert-butyl group.

Furthermore, the substituents are not limited to the above specific examples, and can be appropriately selected and used as necessary as long as the desired haloacetamide compound can be obtained by the production method of the present invention.

The structure of the compound represented by the general formula (RI) of the present invention can be confirmed by the following means.

(b) By measuring the infrared absorption spectrum (IR), absorption based on CH bond in the vicinity of 3200 to 2800 es-', strong absorption based on the carbonyl group of amide in the vicinity of 1680 to 1660 cm-', and strong absorption in the vicinity of 1640 to 1620 cm-'
A weak absorption based on the C=C bond can be observed near cm-'.

(II) If! Measure the spectrum (flIs),
By calculating the composition formula corresponding to each observed peak (generally the mass number expressed as m/e, which is the ion molecular weight m divided by the ion charge number e), the molecular weight of the compound subjected to measurement and the internal content of the molecule can be calculated. You can know the bonding mode of each atomic group in . That is, when the sample subjected to measurement is represented by the general formula (I), a molecular ion peak (hereinafter M
) is observed in the intensity ratio according to the isotope abundance ratio depending on the number of halogen atoms contained in the molecule, so the molecular weight of the compound subjected to measurement can be determined. Further, for the compound of the present invention represented by the general formula (1), characteristic peaks corresponding to M■-Y and M■-COCH,Y are observed, and the bonding mode of the molecule can be known.

(c)'l(-nuclear magnetic resonance spectrum ('H-nmr
), it is possible to know the bonding mode of hydrogen atoms present in the compound of the present invention represented by the above general formula. 'H- of the compound represented by the general formula (1)
As a representative example of nmr (δ, ppm: based on tetramethylsilane, in deuterated chloroform solvent), the analysis results of the following compound are as follows.

(龜) That is, 1.85 ppm is a doublet of 6 protons based on methyl group (bl), 3.22ppm is a singlet of 3 protons based on methoxy group (f), 4.15ppm
m is a doublet of 2 protons based on the chloroacetyl group (C), 6.80 to 7.22 ppm is a multiplet of 9 protons based on a benzene ring, and 3.42pp- is a methylene group (el is a doublet of 2 protons). Based on the triplet of two protons, 2.99
A multiplet of two protons based on the methylene group (d) was observed at 3.90 ppm.

(iv) Determine the weight percent of each of carbon, hydrogen, nitrogen, and halogen (and sulfur if it contains sulfur) by elemental analysis, and then subtract the sum of the weight percent of each recognized element from 100 to determine the oxygen content. It is possible to calculate the weight% of
Therefore, the compositional formula of the compound can be determined.

The haloacetamide compound of the present invention has R in the general formula
Although the properties vary somewhat depending on the types of 7, R2, R3, R4, A and Y and the degree of purification, they are generally colorless to pale yellow to blackish viscous liquids or solids at room temperature and normal pressure. Specifically, the compounds of the present invention shown in the Examples below are soluble in most organic solvents such as benzene, ether, alcohol, chloroform, acetonitrile, dimethylformamide, and dimethyl sulfoxide, but are difficult to dissolve in water. ? It is accommodating.

The method for producing the compound represented by the general formula (1) of the present invention is not particularly limited. A typical manufacturing method is described below.

General formula (II) (However, R1 represents a substituted or unsubstituted aryl group, R2 and R2 represent the same or different hydrogen atoms or a narkyl group, R4 is a substituted or unsubstituted alkyl group, A Schiff base compound represented by a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and A represents an oxygen atom or a sulfur atom. General formula (m)YC
By reacting a chloroacetohalogenide represented by H2COX (where X is a halogen atom and Y is a chlorine atom, a bromine atom, or an iodine atom), the compound represented by the general formula (I) can be obtained. .

The Schiff base compound represented by the general formula (n) used as a raw material for this method may be obtained by any method. Generally, it is obtained by dehydration condensation of a corresponding carbonyl compound and an amine compound as shown in the following formula.

In the reaction between the Schiff base compound represented by the general formula (n) and the haloacetyl halide, the molar ratio of both compounds to be charged may be appropriately determined as necessary, but usually equimolar or 10 acetyl halide is used. It is generally used in a slight molar excess.

Since hydrogen halide is produced as a by-product in this reaction, it is usually preferable to use a hydrogen halide scavenger in the reaction. A suitable scavenger may be selected depending on the reaction conditions (solvent, temperature, etc.), and generally preferred scavengers include triethylamine, pyridine, sodium carbonate, and the like.

In the reaction in the present invention, it is generally preferable to use an organic solvent. Examples of those preferably used include benzene, toluene, xylene, hexane, petroleum ether, chloroform, methylene chloride, ethyl ether, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, acetonitrile, N,N-dimethylformamide, and hexamethyl phosphor. and dimethyl sulfoxide.

In particular, when a basic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, etc. is used as the solvent for the reaction, a scavenger for by-produced hydrogen halide may be used. Even without coexistence, the reaction proceeds easily and the desired haloacetamide compound can be obtained in high yield in many cases, which is extremely suitable.

The order of adding the raw materials in the reaction is not particularly limited, but generally the Schiff base compound represented by the general formula (n) may be dissolved in a solvent, and the haloacetyl halide may be added with stirring.

The reaction temperature in the above reaction can be selected from a wide range, generally from -20°C to 150°C, preferably from -10°C to 12°C.
It should be selected within the range of 0°C. Although the reaction time varies depending on the raw materials and the reaction temperature, it is usually sufficient to select the reaction time from 5 minutes to 10 days, preferably from 1 hour to 50 hours. Further, it is preferable to stir the reaction mixture during the reaction.

The method for isolating and purifying the target product, ie, the compound represented by the general formula (I) from the reaction system, is not particularly limited, and any known method can be employed. For example, after the reaction, the reaction solvent and hydrogen halide scavenger are distilled off, water is added, and the residue is extracted with benzene, ether, chloroform, or the like. Furthermore, the desired product can be obtained by drying the organic layer with a desiccant such as sodium sulfate or calcium chloride, distilling off the solvent, and vacuum distilling the residue. In addition to isolation and purification by vacuum distillation, it can be purified by chromatography, recrystallization, and the like.

Furthermore, when the reaction is carried out using an amide polar solvent such as N,N-dimethylformamide as a reaction solvent, a hydrogen halide scavenger is often unnecessary, and low-boiling substances are distilled off after the reaction is completed. However, if the desired product can be obtained simply by vacuum distillation, after the reaction is completed, water is added to the reaction solution and then extracted with benzene, ether, chloroform, etc. After drying the organic layer with a drying agent such as sodium sulfate, the solvent is distilled off and the residue is purified by vacuum distillation, chromatography, or recrystallization to obtain the desired product.

The compound represented by the general formula (I) of the present invention exhibits an excellent herbicidal effect as a herbicide. For example, it exhibits an excellent herbicidal effect in soil treatment before and after germination of grass weeds, broad-leaved weeds, and perennial weeds. Demonstrate. Particularly, it exhibits a remarkable herbicidal effect on grass weeds, and for example, it exhibits an excellent herbicidal effect on weeds, which are highly harmful, not only when they germinate, but also when they grow at the 1.5-leaf stage. Moreover, it is highly safe for paddy rice. As described above, the compound of the present invention has a highly selective herbicidal effect, making it an excellent herbicide with a significantly longer suitable treatment period than conventional herbicides.

It also exhibits a selective herbicidal effect when used as a herbicide in fields, so it can be applied not only to broad-leaved crops such as soybeans, cotton, and beets, but also to gramineous crops such as wheat, barley, corn, and upland rice. be able to. Furthermore, it can be used as a herbicide for lawns as well as for paddy fields and fields.

Representative examples of specific embodiments in which the compound represented by the general formula (1) is used as a herbicide will be described below.

When the compound represented by the general formula (I) is used for wildflowers and paddy rice that are sown at the same time in paddy soil, 10
When treated at a concentration of 30g per area, germination of wild plants is completely inhibited, but paddy rice is not affected at all even when treated with 1000g. Therefore, generally per 10 ares, 6.25
The active ingredient may be used in paddy fields in an amount of 30 g to 500 g, preferably 30 g to 500 g.

As mentioned above, the present invention has selective herbicidal activity between wild grasses and paddy rice, so it can be applied during the long-term growth stage from the germination period to the growth period of paddy rice, and in particular, it can be applied to warm-water direct-seeded paddy rice. This is a major feature of

Although the compounds represented by the above general formula (R) of the present invention have slightly different herbicidal effects depending on their functional groups, they have little phytotoxicity against gramineous crops, and especially extremely little phytotoxicity against paddy rice. Examples of weeds on which the compound of the present invention exhibits herbicidal effects are as follows.

As mentioned above, it has a high herbicidal effect on grass family weeds, especially grasshopper, and has a remarkable herbicidal effect on Cyperaceae, especially Cyperaceae, Cyperus japonica, firefly, etc., and it has a herbicidal effect on broad-leaved weeds next to these, but the amount of active ingredient used is It is also possible to use a mixture of known herbicides such as phenoxy compounds, amide compounds, virazole compounds, sulfonylurea compounds, etc. to increase the Weeds that can be particularly effectively weeded are, for example, Japanese grasshopper, Japanese grasshopper, Japanese cypress, Japanese firefly, Japanese cypress, Japanese cypress, Japanese black bream, pine flycatcher, black-and-white chickadee, black-and-white chickadee, Japanese staghorn pear, yellow-spotted chickadee, Japanese cypress, Japanese parsley, Japanese parsley, willow knotweed,
These are paddy field weeds such as Japanese thornweed, Japanese privet, Japanese chickweed, Japanese chickweed, Japanese commonweed, Kikashigusa, Japanese knotweed, Japanese knotweed, Japanese japonica, American chiliflower, Japanese horsetail, Japanese azalea, and Japanese red pepper. In addition, the field weeds can be applied to, for example, blackberry, hackberry, pigweed, Japanese knotweed, Japanese cyperus, cyperus japonica, Japanese commonweed, purslane, red-spotted grass, oxalis, sycamore, sycamore, japonica, japonica, japonica, japonica, shepherd's purse, etc.

Furthermore, since the compound represented by the general formula (1) of the present invention affects the growth of plants, it can also be used as a defoliant, a germination inhibitor, and a growth regulator.

The manner of use of the general formula (1) of the present invention is not particularly limited, and the manner of use of known herbicides can be used as is. For example, it can be used in any dosage form such as granules, powders, emulsions, wettable powders, tablets, oils, aerosols, smokes, etc. using inert solid carriers, liquid carriers, emulsifying dispersants, etc. Of course,
Formulation auxiliaries such as spreading agents, diluents, surfactants,
・Solvents and the like can be added as appropriate.

The compound represented by the general formula (1) of the present invention can also be used in combination with insecticides, fungicides, other agricultural chemicals, fertilizer substances, soil conditioners, and the like.

EXAMPLES In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but the present invention is not limited to these Examples.

Reference Example In a flask, p-phenoxy-isobutyrophenone (1
3,30 g, 0.055 mol), 2-methoxyethylamine (8,20 g, 0.11 mol), toluene (4
Azeotropic dehydration was performed by adding 0 gm and a small amount of p-toluenesulfonic acid and heating under reflux on an oil bath overnight. By distilling the liquid obtained by removing low boiling point components under reduced pressure, the boiling point is 144-148℃/0.2 mm11
g of pale yellow liquid (12.41 g) was obtained.

Instrumental analysis of the product revealed that it was a Schiff base having the following structural formula. The yield was 76%.

Example 1 N-(1-(p-phenoxyphenyl)-2-methylpropylidene)-2'-methoxyethylamine (2.18 g, 0.0073 mol) obtained in Reference Example was mixed with dimethylformamide (hereinafter referred to as DMF). (abbreviated as ) (dissolved in 20 mj and stirred at room temperature, chloroacetyl chloride (1.03 g, 0.0091 mol) was dissolved in DMF (
5+d) The solution was added gradually.

After stirring for a while at room temperature, it was heated in an oil bath (50°C) for 2 hours.
The mixture was heated and stirred for hours. After cooling the reaction solution to room temperature, water (
The organic layer was washed twice with ether (100 mi) and the organic layer was washed with ether (10
0m+/). After drying the ether layer with sodium sulfate, the viscous liquid obtained by removing the ether was purified by column chromatography (silica gel) to obtain a colorless viscous liquid (1.86 g).

When the infrared absorption spectrum of the compound was measured, it was found that 31
Absorption based on C-H bond from 00 to 2800 cm-', 1
670c+m-' showed strong absorption based on the >C=0 bond of amide.

Also, when we measured the mass spectrum, m/C37
Molecular ion peak (M ■) at 3, M at m/e 358
■-CHx peak, M■-α at m/e338
A peak corresponding to m/e223 was shown.

A 1H-nuclear magnetic resonance spectrum (δ; ppm: tetramethylsilane standard, deuterium chloroform solvent) was measured, and the results are shown in FIG. The analysis results are as follows.

ν Product (a) Its elemental analysis values are C67,41%, H6,45%, N3
．． 71%, and the composition formula is Cz s Hz a N CJ
! Calculated value C67,46 for O5(373,87)
%, H6, 47%, and N3.75%.

From the above results, it is clear that the isolated product is N-(1-(p-phenoxyphenyl)-2,2-(dimethyl)ethynyl)-N
-chloroaceto-2'-methoxyethylamide. The yield was 68%. The compound disease of this compound is defined as 1.

Example 2 N-(1-(p-phenoxyphenyl)-2-methylpropylidene-2'-methoxyethylamine (2,00 g, 0.0067 mol) obtained in Reference Example was dissolved in toluene (20 m). Sodium carbonate (0.70g,
Bromoacetyl chloride (1.20 g, 0.0076 mol) was added to toluene 57% while stirring at room temperature. The solution was added gradually. After stirring at room temperature for a while, the mixture was heated and stirred in an oil bath (60° C.) for 3 hours.

After cooling to room temperature, the reaction solution was washed with water, and the organic layer was extracted with ether. After drying the ether layer with sodium sulfate, the viscous liquid obtained by distilling off the low-boiling components was purified by column chromatography (silica gel) to obtain a pale yellow viscous liquid (1.56 g). Ta.

When the infrared absorption spectrum of the compound was measured, it was found that 31
Absorption based on C-H bond from 00 to 2800 cm-', 1
At 660 cm-', strong absorption based on the C=O bond of amide was observed.

Also, when we measured the mass spectrum, m/C41
Molecular ion beak (M■) at 8,420, m/e338
The peaks corresponding to M■-Br are shown.

IH-nuclear magnetic resonance spectrum (δ:ppn: tetramethylsilane standard, deuterated chloroform solvent) was measured. The analysis results are as follows.

(a) 6.80-7.28ppm (m, 9H)
(b) 1.85ppm (d, 6H
) (c) 4.15ppm (d, 2H
) (d) 2.92.3.92ppm (m, 2H)t
el 3.42ppm (t, 2H) (
f) 3.22 ppm (s, 3H) Its elemental analysis values are C60, 47%, H5, 88%, N3.
40%, and the composition formula Ct+HzaNBrCh (418
, 33) calculated values for C60, 29%, H5, 78%
, N3.61%.

From the above results, it is clear that the isolated product is N-(1-(p-phenoxyphenyl)-2,2-(dimethyl)ethynyl)-N
-bromoaceto-2'-methoxyethylamide. The yield was 56%. The compound number of the compound is 2.

Example 3 A reaction between N-(1-(m-phenoxyphenyl)-2-methylpropylidene-2'-methoxyethylamine and chloroacetyl chloride) was carried out in the same manner as in Example 1 to produce a pale yellow viscous liquid. Obtained.

When the infrared absorption spectrum of this compound was measured, it was found that 16
Strong absorption based on >C=O bond of amide was observed at 65 cm-'.

Also 'ff! When the spectrum was measured, m/e
Molecular ion peak (M■) at 373, m/e 358
The peaks corresponding to M■-CHl were shown.

IH-nuclear magnetic resonance spectra were measured. The analysis results are as follows.

(m) (a) 6.90-7.40pp+s (m, 9
)()(b) 1.84ppm (d, 6
H) (c) 4.12ppm (d, 2H
)(d12.92.3.88ppm (m, 2H)(
el 3.42ppm (t, 2H) (f)
3.20ppm (s, 3H) Its elemental analysis values are C67.18%, H6.24%, N3.81%, and the composition formula is Ct, Ht4N (JO3(37
Calculated value C67,46% for 3,87), 86.47
% and N3.75%.

From the above results, it is clear that the isolated product is N-(1-(m-phenoxyphenyl)-2,2-(dimethyl)ethynyl)-N
-chloroaceto-2'-methoxyethylamide. The yield was 72%. The compound disease of this compound is designated as 3.

Example 4 N-(1-(m-(p-chlorophenoxy)phenyl)
-2-Methylpropylidene-2'-methoxyethylamine and chloroacetyl chloride were reacted in the same manner as in Example 1 to obtain a colorless viscous liquid.

When the infrared absorption spectrum of this compound was measured, it was found that 16
Strong absorption based on the >c=o bond of 60cm-'niamide was shown.

Also, when we measured the mass spectrum, m/e40
Molecular ion peak (M■) at 7, peak corresponding to M■-CHs at m/e 392, M■- at m/e 372.
The peaks corresponding to α are shown.

1H-nuclear magnetic resonance spectra were measured. The analysis results are as follows.

(-1, -:9.) (c) Its elemental analysis values are C61,54%, H5,72%, N3
．． 62%, compositional formula Cz IHz a N C12
Calculated value C61,77% for 0z(408,31),
There was good agreement with N5.68% and N3.43%.

From the above results, it is confirmed that the isolated product is N(1-(m-(p-chlorophenoxy)phenyl)-2,2-(dimethyl)ethynyl)-N-chloroaceto-2'-methoxyethylamide. It became clear. The yield was 67%. The compound magnetism of this compound is 4.

Example 5 N-[1-(m-(p-chlorophenoxy)phenyl)
-2-Methylpropylidene]-2'-ethoxyethylamine and chloroacetyl chloride were reacted in the same manner as in Example 1 to obtain a pale yellow viscous liquid.

The infrared absorption spectrum value and elemental analysis value of the compound are shown below.

C62,40X: H6,08X; N 3.4
1% (62,56χ”) (5,97χ)
(3,32χ) The numbers in parentheses are theoretical values and other results of instrumental analysis. The isolated product is N-(1-(m-(p-chlorophenoxy)phenyl)-2,2-( It became clear that it was dimethyl)ethynyl)-N-chloroaceto-2'-methoxyethylamide. The yield was 70%. The compound number of this compound is 5.

Example 6 N-(1-(m-(p-chlorophenoxy)phenyl)
Example 1 Reaction of -2-methylpropylidene]-ethoxycarbonylmethylamine and chloroacetyl chloride
A yellow viscous liquid was obtained in the same reaction as above.

The measurement results of the infrared absorption spectrum and elemental analysis of the compound are shown below.

m/e=435(MO”), 420(MO-CN5)
, 400 (MO-a) CtzHz*NCJ! zoa =436.32C60,
45χ: N5.43χ: N 3.30χ” (60,
56χ) (5,31χ) (3,21χ)()
From the theoretical values and other instrumental analysis results, the isolated product has the following structural formula: N-, (1-(m-(p-chlorophenoxy)phenyl) to 2.2-(dimethyl)ethynyl- It was found that it was ethoxycarbonylmethylamide. The yield was 46%. The compound fish of this compound is designated as 6.

Formulation Example 1 (Wettable powder) N-(1-(p-phenoxyphenyl)-2,2-(dimethyl)ethynyl)-N-chloroaceto-2'-methoxyethylamide ( Compound 11h
l) 10 parts, 2:1 of Zikrite (trade name: Nijikrite Kogyo Co., Ltd.) and Kunilite (trade name: Kunimine Kogyo Co., Ltd.)
85 parts of the mixture, Tsurupol 800A (as a surfactant)
Product name: Toho Chemical Industry Co., Ltd.) 5 parts were uniformly mixed and pulverized to 1
A 0% permanent agent was obtained.

, Formulation Example 2 (emulsion) 2) A 20% emulsion was obtained by mixing and dissolving 20 parts, 70 parts of xylene, and 10 parts of Tsurpol 800A as a surfactant.

Formulation Example 3 (granules) N(1-(m-phenoxyphenyl)-2,2-(dimethyl)ethynyl)-N-chloroaceto-2'-methoxyethylamide (compound number 3) obtained in Example 3 5th part,
Bentonite (manufactured by Kunimine Industries) 50 parts, Dani 5414
After uniformly mixing and pulverizing 800 parts and 5 parts of Tsurupol as a surfactant, water was added and stirred uniformly to form a paste, and the diameter was 0.7111! It was extruded through a +I node hole, dried, and then cut into 1-2 ml lengths to obtain 5% granules.

Example 7 A 1/8850 are porcelain pot was filled with paddy soil (alluvial loam) stirred with water, and after sowing paddy weeds, rice seedlings at the 3-leaf stage (variety: Akinishiki) were placed at a depth of 1c+n. The weeds were transplanted and water was added to bring the temperature to 3CI+. Then, a predetermined amount of a water-diluted solution of a wettable powder of each compound prepared according to Formulation Example 1 was dropped at the time of weed germination. Average temperature after treatment 2
The herbicidal effects of each test compound were investigated after 3 weeks of growth in a greenhouse at 5° C. The results are shown in Table 1. However, the broad leaves shown in the table refer to azalea, azalea, red pepper, etc. The evaluation is in 6 stages, and in the numbers in the table -0 is normal, 1 to 4 is between normal and completely withered, and 5 is This indicates complete withering.

Example 8 Various haloacetamide compounds were synthesized using methods similar to those described in Examples 1 to 6. The structure, elemental analysis results, and herbicidal activity of the compound are listed in Table 2. The herbicidal effects in the table were determined in the same manner as in Example 7, and only the values at a dosage of 400 g/10a are listed. The criteria for herbicidal effect were also the same as in Example 7. Further, R+ -Rt -R, R4, A and Y in the table are RI, R2, R1, R4, A and Y in the following general formula.

[Brief explanation of the drawing]

FIG. 1 shows the 1H-nuclear magnetic resonance spectrum of the haloacetamide compound of the present invention obtained in Example 1.

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 represents a substituted or unsubstituted aryl group, R_2 and R_3 represent the same or different hydrogen atoms or alkyl groups, and R_4 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group;
represents an oxygen atom or a sulfur atom, and Y represents a chlorine atom, a bromine atom or an iodine atom. ) A haloacetamide compound represented by (2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 represents a substituted or unsubstituted aryl group, R_2 and R_3 represent the same or different hydrogen atoms or alkyl groups, and R_4 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group;
represents an oxygen atom or a sulfur atom, and Y represents a chlorine atom, a bromine atom or an iodine atom. ) A herbicide containing a haloacetamide compound as an active ingredient.