JPS61286358A - N-acylamino and derivative and use thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is 1,5-dicarboxypentyl, carboxymethyl, 1-carboxy-1-phenylmethine, etc.; R<2> is chloro or bromo). EXAMPLE:N-(p-Chlorophenoxy)acetyl-L-alpha-aminoadipic acid. USE:A safe phenoxy based herbicide having high selectivity for monocotyledonous and broad-leaved plants without phytotoxicity to useful crops, e.g. rice plant, wheat, barley, etc. PREPARATION:An amino acid derivative expressed by the formula R<3>-NH2 (R<3> is 1,5-dicarboxypentyl, 1,4-dicarboxybutyl, etc.) is reacted with an acid halide active ester compound or acid anhydride expressed by formula II or III (A is halogen or active ester) in the presence or absence of a base, e.g. alkali hydroxide, in water or an organic solvent - at room temperature or below to afford the aimed compound expressed by formula I.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is based on the general formula (1) (wherein R is a 1.5-dicargoxypentyl group, 1.4
-Dikal? Gysibutyl group, 1,3-dical is oxypropyl group, cargyxymethyl group, 1-carboxy-1-tzenylmethine group, 1-dyeyl group? Xyzolobyl group, 3-carboxybutyl group, 1-carboxy-2-ethanol group, 1
-carboxy-3-dironognol group, 1-cal is xyethyl group, 1-cal is xypentyl group, 1-carboxybutyl group, 1-carboxyheptyl group or 1-carboxy-2-N -(]R4 dichlorophenyl Oxy)
The present invention relates to a novel compound N-acylamino acid derivative having an acetylaminoethyl group (R represents chlor or pro-broad atom), its agrochemically acceptable salts, and uses thereof.

More specifically, the general formula (1) according to the present invention
The novel N-acylamino acid salt conductor represented by has strong herbicidal activity and is therefore a compound widely used as a herbicide.

[Conventional technology]

Conventionally, a series of phenoxy compounds such as 2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, and 4-chloro-0-)oxyacetic acid have been used as herbicides important in agriculture and horticulture. The primary effect of these phenoxy herbicides is the loss of auxin balance in the body, which affects the basic and physiological activities of plants such as abnormal division, abnormal morphology, inhibition of chlorophyll formation, and increased permeability of cell membranes. Herbicidal activity is discovered through disturbance phenomena.Auxin hormone type herbicides have not only soil treatment ability but also foliage treatment ability, and because they move freely within the plant body, they are difficult to control with other herbicides. In addition to being effective against perennial paddy field weeds, they also suppress the regeneration ability of controlled weeds and have many other characteristics, such as extremely high G.However, these phenoxy herbicides are useful for crops. Rice, wheat,
In addition, it causes chemical damage to plants such as barley, and is not effective against some perennial weeds, so its application and usage are extremely limited.

[Problem that the invention seeks to solve]

The present inventor has developed a stable auxin hormone type that has no phytotoxicity against useful crops such as rice, wheat, or barley, and is highly selective for monocots and broad-leaved plants, while maintaining the characteristics of these phenoxy herbicides. In the course of conducting research to develop herbicides, we discovered compounds with very strong herbicidal activity against condensation compounds of phenoxyacetic acid and various amino acids, and their derivatives, with good selectivity.

[Means for solving problems]

According to the present invention, a novel N-acylamino acid derivative having the general formula (1), which is a new compound having a strong herbicidal effect, or a pesticide-acceptable salt thereof, and its use as a herbicide are provided. Ru.

The compounds of the present invention differ from conventionally well-known herbicides in that they contain amino acids or analogues thereof and phenoxy groups in their skeletons, and therefore have extremely low toxicity to living organisms.

The N-acylamino acid derivative having the general formula (1) according to the present invention can be produced, for example, by the following method.

That is, general formula (2) % formula % (2 (2) (wherein R is a 1.5-dicardegycypentyl group, 1
4-radical is xybutyl group, 1,3-di, carboxypropyl group, carboxymethyl group, 1-carboxy-1-
Tzenylmethyl group, 1-carboxypropyl group, 3-cal xypropyl group, 1-carboxy-2-ethanol group, 1-carboxy-3-propanol group, 1-cal?
Xyethyl group, 1-force? xypentyl group, 1-force is xybutyl group, 1-carboxyheptyl group or 1-
Cal? xy-2-aminoethyl group) and the general formula (3g).

(3b) (In the above formula, R is as defined above, and A represents a halodane atom or an active ester group) in the presence or absence of a base, an acid halide active ester compound or an acid anhydride, The compound (1) of the present invention can be obtained in high yield by reacting in water or an organic solvent.

The base used here is preferably an alkali hydroxide or a trialkylamine.

There are no particular limitations on the reaction conditions, but generally the reaction conditions are below room temperature.
Proceed by stirring for ~12 hours.

In the amino acid derivative having the aforementioned general formula (2),
When the carboxyl group contained in the group R is esterified, the above-mentioned general formula (3a) is used.

(3b) is reacted with an acid halide, active ester compound, or acid anhydride in water or an organic solvent in the presence or absence of a base to obtain a condensed compound in high yield, and then the ester group is The compound of the present invention represented by the general formula (1) can be obtained by hydrolysis.

In addition, when the carboxyl group contained in the group R3 in the above formula is esterified, it is condensed with a compound having the general formula (in the formula, R2 is as defined above) or in the peptide synthesis. By using common condensing agents such as N-ethyl-N', N'-dimethylaminozolobylcardiimide, dicyclohexylcal diimide, etc., the condensation reaction can easily occur, and then the ester group is hydrolyzed. The compound of the present invention can be obtained by doing so.

The method for producing the compound of the present invention involves using an easily available acid chloride having the general formula (3d) (wherein R is as defined above) as a raw material, and combining this with an amino acid derivative having the general formula (2). A method of reaction in an aqueous alkali hydroxide solution is preferable.

The compound of the present invention thus obtained can be purified using a general purification method after the reaction is completed.

Examples of common purification methods include recrystallization, column chromatography, and preparative thin layer chromatography.

In addition, after the reaction is completed, the obtained compound can be treated with alkali hydroxide,
For example, a salt can be formed by treatment with sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide or aqueous ammonia.

The compounds of the present invention obtained in this manner have low toxicity to the human body and to the family, and have extremely specific and strong growth regulating activity against broad-leaved and monocotyledonous plants.

This strength suggests that the compound of the present invention is widely used as an agricultural chemical.

When applying the compound of the present invention as a herbicide,
Generally, it can be applied in combination with a suitable carrier, such as a solid carrier such as clay or diatomaceous earth, or a liquid carrier such as water, alcohols, aromatic hydrocarbons, ethers, ketones, or esters.

In addition, emulsifiers, dispersants, suspending agents, spreading agents, stabilizers, etc. can be added as desired, and the formulation can be provided in the form of emulsions, wettable powders, powders, granules, etc. It may be applied in combination with other herbicides, various insecticides, fungicides, plant growth regulators, etc.

In the practice of the present invention, the concentration of the compounds of the present invention can vary over a wide range, but is generally less than
It is preferable to use it within the range of 0.9 to 50011. When manufacturing the various preparations described above, the active ingredients are mixed at 0.
It can be manufactured to contain in the range of 5 to 90 inches.

〔Example〕

Next, the present invention will be explained in more detail with reference to herbicidal tests and examples, but it goes without saying that the present invention is not limited to these examples.

In addition, SUAM numbers were used to identify compounds in the following examples and activity tests. Further, physical data of the examples are shown in Table 3.

Herbicidal test In order to evaluate the selectivity of herbicidal activity of the synthesized compound,
The compounds were tested using the broad-leaved plants cucumber, radish, monocots rice, wheat, and Japanese millet.

The samples were divided into two types: pre-emergence and post-emergence tests. In the pre-germination test for Kili and Japanese radish, a liquid preparation of the test compound was sprayed on the soil where the seeds had just been sown. For the post-germination test, the seeds were grown in pots in a greenhouse.
When the test plants grew to the 2-3 leaf stage, a liquid preparation of the test compound was sprayed on them. Cucumbers and daikon 6x1
5X10crn PVC A? Transplant 5 seeds or 2 test plants to Tsuku, 10 ares, 200150I
A compound was prepared, diluted in an amount of acetone water equivalent to 60 cc of one pack, and sprayed.

Rice, wheat, and thyme vinyl are made of 20x10x6m PVC/
Paddy soil was filled in a 17-hole tank, and seeds or plants grown in a greenhouse at the 2-3 leaf stage were mixed into the soil surface layer 1 to 2 cn1 and flooded to a depth of about 3 crn. A predetermined amount of the compound (1
An acetone solution of 20011.50 g (per 0 are) diluted 100 times or more with water was treated with fiQcc per 1.00 m in water, and post-germination tests were conducted only on representative compounds.

After 30 days of treatment, the growth status of the plants was observed, and the degree of herbicidal effect was judged in 6 stages from 5 to 0 (complete withering to no effect).
The results shown in Tables 1 and 2 were obtained.

The following margin Example 1 (SUAM 3650) H-(,,*lachlorophenoxy)acetyl-L-α-
Aminoadipic acid L-α-aminoadipic acid (10 mmol) was dissolved in 1N hydroxide solution and diluted with water to 30 mmol.
- diluted. Parachlorophenoxyacetyl chloride (10 mmol) was added to this aqueous solution in advance while stirring while cooling it with water. A solution of 100% dissolved in benzene was slowly added dropwise. Immediately thereafter, an additional 10 liters of 1N sodium hydroxide solution was added. After returning to room temperature, the mixture was stirred overnight.

After the reaction was completed, the mixture was extracted twice with ethyl ether to remove unreacted acid chloride. The aqueous layer was acidified with hydrochloric acid, the precipitated compound was extracted three times with ethyl acetate, the solvent was distilled off under reduced pressure, and the residue was recrystallized with a solvent system of ethyl acetate/benzene/hexane to form colorless crystals. Chlorophenoxy)acetyl-L-α-aminoadipic acid was obtained.

In the same manner as in Example 1, N-()gurachlorophenoxy)acetyl-D,L-α-amino gimelic acid (SUAM
Example 2
(SUAM 3652) N-() or labromophenoxy)acetyl-L-glutamic acid (1N hydroxylation of L-glutamic acid (10 mmol))
IJum solution 20m7! Dissolve this in 30m7 of water.
! diluted to This aqueous solution was cooled with water and stirred, and 107 mmol of bromophenoxyacetyl chloride (10 mmol) was added in advance to this aqueous solution. A solution of 100% dissolved in benzene was slowly added dropwise. Immediately after that, further 1N hydroxide) IJ
A total of 10% of the solution was added.

After returning to room temperature, the mixture was stirred all day and night.

After the reaction was completed, the mixture was extracted twice with ethyl ether to remove unreacted acid chloride. The entire aqueous layer was acidified with hydrochloric acid, the precipitated compound was extracted three times with ethyl acetate, the solvent was distilled off under reduced pressure, and the residue was recrystallized in a solvent system of ethyl acetate/benzene/hexane to form colorless crystals of N -(z9 Phenoxy)acetyl-glutamic acid was obtained.

Example 3 (SU Notification 3655) N-(/J?Lachlorophenoxy)acetyl-glycineglycine (10 mmol) was dissolved in 1N sodium hydroxide solution, and this was diluted to 20 ml with water. While cooling this aqueous solution with stirring, add 10 mg of parachlorophenoxyacetyl chloride (10 mmol) in advance.
A solution of 100% dissolved in benzene was slowly added dropwise. Immediately after that, add another 10 m7 of 1N sodium hydroxide solution!
added. After returning to room temperature, the mixture was stirred overnight.

After the reaction was completed, the mixture was extracted twice with ethyl ether to remove all unreacted acid chloride. The aqueous layer was acidified with hydrochloric acid, the precipitated compound was extracted three times with total ethyl acetate, the solvent was distilled off under reduced pressure, and the residue was recrystallized in a solvent system of ethyl acetate/benzene/hexane to form colorless crystals of N-(/4 ml). Chlorophenoxy)acetyl-glycine was obtained.

H-(),e-lachlorophenoxy)acetyl-γ-aminobutyric acid (SUAM 3658) was prepared in the same manner as in Example 3.
was obtained as colorless crystals using γ-aminobutyric acid.

Example 4 (SUA+V[3663) N-(z+lachlorophenoxy)acetyl-L-norleucine L-norleucine (10 mmol) was dissolved in 1N sodium hydroxide solution 10-, and this was diluted with water to 20- . This aqueous solution was cooled with water and stirred.
A solution dissolved in benzene was slowly added dropwise. Immediately after that, add 1N sodium hydroxide solution 'klO
wl! added.

After returning to room temperature, the mixture was stirred overnight.

After the reaction was completed, the mixture was extracted twice with ethyl ether to remove unreacted acid chloride. The aqueous layer was acidified with hydrochloric acid, the precipitated compound was extracted three times with total ethyl acetate, the solvent was distilled off under reduced pressure, and the residue was recrystallized in a solvent system of ethyl acetate/benzene/hexane. Chlorophenoxy)acetyl-L-norleucine was obtained.

N-(A?Lachlorophenoxyacetyl)-DL-norvaline (SUAM 3664) was prepared in the same manner as in Example 4.
), N-(/#lachlorophenoxyacetyl)-DL
-2-aminooctanoic acid (SUAM 3665),
N-(parachlorophenoxyacetyl)L-2-aminobutyric acid (SUAM 3657), N-(parachlorophenoxyacetyl)-L-alanine (SUAM 36)
62) and the corresponding DL-norvaline and DL, respectively.
It was obtained as colorless crystals by using -2-amine octanoic acid, L-2-aminobutyric acid, and L-alanine.

Example 5 (SUAM 3656) N-(A?Lachlorophenoxy)acetyl-DL-phenylglycine DL-phenylglycine (10 mmol) was dissolved in 10-kl normal sodium hydroxide solution and diluted to 20-kl with water. did. While cooling the aqueous solution with water and stirring, a solution of Lavala chlorophenoxyacetel chloride (10 mmol) previously dissolved in 10-penzene was slowly added dropwise. Immediately thereafter, a further 1N hydroxide solution (10rnI2) was added. After returning to room temperature, the mixture was stirred overnight.

After the reaction was completed, the mixture was extracted twice with ethyl ether to remove unreacted acid chloride. The aqueous layer was acidified with hydrochloric acid, the precipitated compound was extracted three times with ethyl acetate, the solvent was distilled off under reduced pressure, and the residue was recrystallized in a solvent system of total ethyl acetate/benzene/hexane to form colorless crystals such as N-() and R. Chlorophenoxy)acetyl-DL-phenylglycine was obtained.

N-(parachlorophenoxy)acetyl-L-homoserine-homoserine (10 mmol) k 1 m hydroxylation) 1. The solution was dissolved in 10 parts of 1+7ml solution, and diluted with water to 20 parts. While cooling and stirring this aqueous solution, parachlorophenoxyacetyl chloride (10 mmol) was added in advance to 10 m/! A solution of 100% dissolved in benzene was slowly added dropwise. Immediately after that, further 1N hydroxide) IJ
Um solution 110tn! ,added. After returning to room temperature, the mixture was stirred overnight.

After the reaction was completed, the mixture was extracted twice with ethyl ether to remove unreacted acid chloride. The aqueous layer was acidified with hydrochloric acid, the precipitated compound was extracted three times with ethyl acetate, the solvent was distilled off under reduced pressure, and the residue was recrystallized in a solvent system of ethyl acetate/benzene/hexane to form colorless crystals of N-(parachlorophenoxylate). ) Acetyl-homoserine was obtained.

In the same manner as in Example 6, N-(parachlorophenoxy)
Acetyl-L-serine (SUAM 3659), N
-(z9lachlorophenoxy)acetyl-DI, -homoserine (SUAM 3660) all L-serine.

It was obtained as colorless crystals by using DL-homoserine.

Example 7 (SUAM3666) N(c4.N(b)-di(parachlorophenoxy)acetyl-DL-αβ-diaminozolopionic acid DL-αβ-
Diaminopropionic acid (10 mmol) was 1N hydroxylated) IJum solution 101n1. Dissolve this in water and dilute it with water.
Diluted to 01nt. While stirring this aqueous solution while cooling it with water, a solution of parachlorophenoxyacetyl C"J" (20 mmol) previously dissolved in 10 g of benzene was slowly added dropwise. Immediately thereafter, an additional 1 N water was added dropwise. 20rnt of sodium oxide solution was added.After returning to room temperature,
The mixture was stirred overnight.

After the reaction was completed, the mixture was extracted twice with ethyl ether to remove unreacted acid chloride. The aqueous layer was acidified with hydrochloric acid, the precipitated compound was extracted three times with ethyl acetate, the solvent was distilled off under reduced pressure, and the residue was recrystallized with a solvent system of ethyl acetate/benzene/hexane to form colorless crystals of N((1), N(A
-di(parachlorophenoxy)acetyl-DL-αβ-
Obtain diaminopropionic acid 1°
JJ,...,Fe2 Next, examples of formulations in which the compounds of the present invention are specifically used will be shown.

After uniformly mixing and pulverizing the granules, a small amount of water was added, the mixture was stirred, and the mixture was granulated and dried to obtain granules.

emulsion The above was mixed uniformly to form an emulsion.

hydrating agent The above was mixed and crushed to make an irrigation agent.

〔Effect of the invention〕

As is clear from Tables 1 and 2, the compound of the present invention not only has a strong herbicidal effect, but also has SUAM 3
652.3653.3657.3661.3662.3
663°3664 and 3665, it is clear that it has good selectivity and can be widely used as a herbicide.

Claims (1)

[Claims] 1. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1 is a 1,5-dicarboxypentyl group, 1
, 4-dicarboxybutyl group, 1,3-dicarboxypropyl group, carboxymethyl group, 1-carboxy-1-
Phenylmethine group, 1-carboxypropyl group, 3-carboxypropyl group, 1-carboxy-2-ethanol group, 1-carboxy-3-propanol group, 1-carboxyethyl group, 1-carboxypentyl group, 1-carboxybutyl group group, 1-carboxyheptyl group or 1-
An N-acylamino acid derivative having a carboxy-2-N-(parachlorophenyloxy)acetylaminoethyl group, in which R^2 represents a chlor or bromine atom), and a pesticide-acceptable salt thereof. 2. The compound according to claim 1, wherein the N-acylamino acid derivative having general formula (1) is an optically active compound. 3. The compound according to claim 1 or 2, wherein the agrochemically acceptable salts are sodium, potassium, calcium, lithium, and ammonium salts. 4. General formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1 is a 1,5-dicarboxypentyl group, 1
, 4-dicarboxybutyl group, 1,3-dicarboxypropyl group, carboxymethyl group, 1-carboxy-1-
Phenylmethine group, 1-carboxypropyl group, 3-carboxypropyl group, 1-carboxy-2-ethanol group, 1-carboxy-3-propanol group, 1-carboxyethyl group, 1-carboxypentyl group, 1-carboxybutyl group group, 1-carboxyheptyl group or 1-
Contains an N-acylamino acid derivative having a carboxy-2-N-(parachlorophenyloxy)acetylaminoethyl group, where R^2 represents a chlor or bromine atom) and its agriculturally acceptable salt as an active ingredient. herbicide. 5. The herbicide according to claim 1, wherein the N-acylamino acid derivative having general formula (1) is an optically active derivative.