JPH0219353A - Imino((3-fluorophenyl)amino)acetic acid derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X1-X4 are H, halogen or methyl; R is H or lower alkyl). USE:A herbicide exhibiting excellent herbicidal effect especially against paddy field weeds such as water chestnut, flatstage, cockspur-grass and bulrush and free from phytotoxicity to paddy rice plant. It also exhibits excellent effect against cockspur-grass of 3-leaved stage. PREPARATION:The compound of formula I having the form of an alkyl ester derivative can be produced by reacting an amine of formula II with a compound of formula III and neutralizing the product. The hydrolysis of the obtained compound of formula I gives another compound of formula I wherein R is H. The starting compound of formula III can be produced by reacting H2NC(S)C (O)OR' with a Meerwein reagent (triethyloxonium tetrafluoroborate) in methylene chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel imino[(3-fluorophenyl)amino]acetic acid derivative and a herbicide containing H as an active ingredient.

[Conventional technology]

Conventionally, regarding imino[(substituted or unsubstituted phenyl)amino]acetic acid, Japanese Patent Publication No. 48-539
8-14041. Japanese Patent Publication No. 49-20197. Special Public Service 1977
-10287, Special Publication Showa 50-22018. Japanese Unexamined Patent Publication No. 1973-
108933, JP-A-57-88158. Japanese Unexamined Patent Publication No. 1983
-85351. JP-A-57-85352° JP-A-58-
38249 and Journal of Organic Chemistry (J, Org, Chew, ) 43° 4485-4487 (I978), but the 3-fluorophenyl compound is not disclosed. Also, imino [(substituted or unsubstituted phenyl)amino]
Although acetic acid ester is described as a reaction intermediate in Japanese Patent Publication No. 57-88157, its isolated structure has not been determined, and no 3-fluorophenyl compound is known. Further, some of the above-mentioned documents include descriptions of the general possibility of herbicidal activity or pesticide activity, but there is no specific description and it cannot be said that they are disclosed as herbicides.

[Problem to be solved by the invention]

On the other hand, regarding paddy field herbicides, there is a demand for agents having the following characteristics.

■) It should not cause chemical damage to paddy rice; 11) It should be able to control problem weeds such as black bream and Japanese cyperus; iii) it should show herbicidal activity even when treated at the 3-leaf stage of wild grass.

Therefore, the object of the present invention is to develop a novel imino[(3-fluorophenyl)amino]acetic acid derivative having excellent herbicidal activity, particularly the above characteristics.

[Means for Solving the Problems and Outline of the Invention] The present invention is based on the general formula [where xl, x2 . x3. x4 represents a hydrogen atom, a halogen atom or a methyl group, and R represents a hydrogen atom or a lower alkyl group. The present invention provides an imino[(3-fluorophenyl)amino]acetic acid derivative, which is a new compound not described in literature, represented by the following formula, and a herbicide containing the same as an active ingredient.

Here, examples of halogen atoms include chlorine atom, fluorine atom, and bromine atom, and examples of lower alkyl groups include methyl group, ethyl group, low propyl group, i-propyl group, n-butyl group, -butyl group, 5ec-butyl group, t-butyl group, n-amyl group and i-amyl group.

Although the compound of -killing (I) has tautomers such as the following formula (I'), in the present invention, both are represented by the general formula (I).

[In the formula, X to X4. R is as described above. 〕■ The compound of general formula (I) exhibits strong herbicidal activity against a wide range of weeds, and the compound is used as an active ingredient at 0.1 per hectare just before the weeds germinate or at the early or middle stage of their growth. Approximately 1 to 10 kg is applied.
Within two weeks, a wide range of weeds as described below can be killed or controlled.

In addition, by limiting the amount of this compound applied or applying an appropriate application method, corn, potato, etc.
Sugarcane, peanuts, soybeans, sunflowers, barley, wheat,
Weeds can be selectively controlled in fields where specific crops such as turgid gum, paddy rice, cotton, and fruit trees are grown. In particular, in paddy fields, it can control the strong weeds of grasshoppers, fireweeds, black grubs, and watermelons without causing chemical damage to paddy rice, and it also shows excellent herbicidal effects even when applied during the second and third leaf stages of rice fields. It is said that

The compound of the present invention can be produced, for example, according to the following reaction route (wherein Xl to X4 are as described above, and R' represents a lower alkyl group).

(Space below) Route a Roux (n) (II) (I: R lower alkyl group) (I) R-H (Space below) Route a is the method described in 1-1 Japanese Patent Application Laid-Open No. 108933/1989. was applied. In route b, the amine of general formula (II) and the compound of general formula (IV) are reacted, and then neutralized to obtain an alkyl ester derivative of the compound of the present invention. Further, by hydrolyzing this alkyl ester derivative, the RH acid of the compound (I) of the present invention is obtained. In addition, the compound of general formula (IV) is H2NC(S)
It is obtained by reacting C(0)OR' with Meerwein's reagent (triethyloxonium tetrafluoroborate) in methylene chloride.

Typical examples of the compounds of the present invention are shown in Table-
Examples include those shown in 1. The following explanation is shown in Table-1.
Use the compound number (&) inside.

In addition, the compound is indicated by the symbol in the above general formula. In addition, NMR in the physical properties column represents nuclear magnetic resonance spectrum,
1t)J constant solvent is shown in parentheses, and the unit is pp+s. IR stands for infrared spectrum, unit is Cl11-1
It is.

(Margin below) (continuation) (continuation) table (continuation) Next, the method for producing the compound of the present invention will be specifically described.

Synthesis Example 1 Compound No, IO 3-fluoro-2-methylaniline hydrochloride (20a+no
1.3.2g) and ethyl cyanoformate (20mao1
．． 2.0g) and sodium perchlorate (0.0a+s
of! , 0.73g) was added to l/10 normal perchloric acid acetic acid solution (2.0gmo1.20ml) and heated to 100℃ for 4 hours.
Heat for an hour. After cooling, 6N hydrochloric acid (40 ml) was added and heated at 100°C for 1 hour. After concentrating the reaction solution under reduced pressure,
The resulting mixture was mixed with water (40 ml) and ethyl acetate (30 ml).
ml) and then neutralize by adding sodium bicarbonate. After standing still for 3 hours, the white powder produced was collected by tP,
Wash with water and ethanol. Recrystallized from methanol. Colorless crystal (5, Jmsoi), 1. Og) was obtained. Yield 26%.

Synthesis Example 2 Compound No. 1O Ethylimino(ethylthio)acetate borohydrofluoride (400tso, 77) in methylene chloride solution (2
00ml), 3-fluoro-2-methylaniline (40ml)
methylene chloride solution (IO
After adding 0 ml') and shaking well, leave it at room temperature overnight. Furthermore, n-hexane (OOOml) was added to the reaction mixture.
), shake well and leave for 2 hours. The upper layer solution was removed by decantation, and methylene chloride (300 ml) was added to the resulting reaction mixture, followed by an aqueous sodium bicarbonate solution and shaken well to neutralize. The obtained methylene chloride solution was concentrated under reduced pressure and diluted with 3N hydrochloric acid (400 m
Add 1) and ethanol (200 ml) and mix well while heating to 60°C. The reaction mixture was concentrated under reduced pressure, water (300 ml) was added, and the mixture was shaken well. What about the white powder produced by adding an aqueous sodium bicarbonate solution? Tori.

Wash with water and ethanol. Recrystallize using 2N hydrochloric acid. White crystals (I90mn+oIl, 37g) were obtained. Yield 48%.

Synthesis Example 3 Compound Nα5 4-bromo-3-fluoro-2-methylaniline ((io
mllloN, 12FC) of methylene chloride (25m
l) Mix the solution with a methylene chloride solution (25 ml) of ethylimino(ethylthio)acetate borohydrofluoride (GO+gnoj7) and continue stirring at room temperature for 5 hours.
- After standing overnight, wash twice with cold 5% aqueous sodium bicarbonate solution.

After drying the methylene chloride solution with Glauber's salt, si! lcagel
(Wakogel C-200) After passing through column chromatography,
The eluate was concentrated under reduced pressure to obtain 15 g of crude crystals.

Recrystallize from methylene chloride-n-hexane.

One white crystal (43 mIIoN, 13 g) was collected. Yield 72%.

Synthesis Example 4 Compound N (L4 ethylimino[(4-bromo-3-fluoro-2-methylphenyl)aminocoacetate (6.6ml1of,
2.0 g) in methanol (20 ml), 2N sodium hydroxide (4 ml) was added thereto, heated to 60°C, and stirred for 10 minutes. Methanol is distilled off under reduced pressure, and the mixture is neutralized with water-cooled 2N hydrochloric acid.

The obtained precipitate is collected and washed with water and n-hexane. Recrystallized from methanol. Transparent plate crystal (2,9a+
moN, 0.80 g) was obtained. Yield 44%.

When the compound of the present invention is applied as a herbicide, it can be formulated into various formulations such as emulsions, wettable powders, powders, granules, flowables, etc. together with a solid or liquid carrier by applying a formulation method commonly used in agricultural chemical formulations. Preferably, it is formulated into a dosage form. At that time, as necessary, use of emulsifiers, spreading agents, various surfactants for other purposes, and other herbicides and agricultural chemicals other than herbicides, such as insecticides and fungicides, to expand the range of action. , nematicides, etc., plant growth regulators, fertilizers, etc. can also be mixed.

Next, typical formulation examples are given. "Parts" in the description indicate parts by weight.

Example 1 Wettable powder active ingredients: 50 parts of the compounds shown in Table 1, 35 parts of talc, 5 parts of diatomaceous earth, 5 parts of white carbon, and 5 parts of polyoxyethylene alkyl allyl ether were mixed and ground to obtain 50 parts of the active ingredient compound. A hydrating agent containing % is obtained.

Example 2 Granules 10 parts of the compound shown in Table 1 and 3 parts of bentonite as active ingredients
0 parts, 58 parts of talc, and 2 parts of polyoxyethylene alkyl allyl ether were mixed, about 25 parts of water was added, and the mixture was kneaded in a kneader, then granulated through a granulator, and then dried and sized to obtain an active ingredient of 10%. Granules containing a are obtained.

〔Effect of the invention〕

The compounds of the present invention can be used, for example, to control the following weeds: That is, broad-leaved ramids, such as Stellarla media, Ch.
enopodlua album), Sag
I najaponlca), Coacaza (Cheno
podlua rlcifollum), Polygonum nodosum, Portulaca olcracea, Capscillabursapastorls, Lcpldiuivjrgi nic
um), Rorippa 1ndlca
), Tanetsukebana (Cardailnc I'1exu
osa), Ichibi (Abutllon Lhcoph)
rasti), American Golden Deer (Sida 5p)
lnosa), Malva morning glory (Iposoeapu)
rpurea), Senecl. vu
lgirls), Sonchus asp
er), a, Bldens l'
rondosa), brosla a
rtesislaerolia), broom daisy (As
ter 5ubulaLus), Hotokenoza (Laml
Oxalis (Oxa)
lls corniculata), Ama
ranthus rctroflcxus), Gallum aparlnc (Hcla 5ativa), Gallum aparlnc (S.
Poa annua), Poa annua, etc.
, Opeculus aequ
alis), Diglariadsc.
endens), Ohishiba (Eleuslne 1n)
dlca), wild foxtail (SeLaria vlrl)
dls), Golden millet (EchJnochloa cru
s-galli), Agropyron
Kamoji), Loliu + * pere
nne), dogwheat (Bromus unloroid)
es), Oat (^vena ratua), Polypogonllgegaverl (Polypogonllllgegaverl)
) Panicum dlchotom
if'1oru■), Cyperaceae weeds, such as Cyperus m1crolria, Cyperus 1ria, Elcocharjsaclurals
,etc.

In order to demonstrate the herbicidal effect of the moth killer according to the present invention, some representative test examples will be given and explained in more detail. In addition,
In the test examples, herbicidal effects and phytotoxicity were observed with the naked eye and expressed on an 11-level index from 0: no effect or phytotoxicity to 10: complete death.

In order to demonstrate the herbicidal effects of the compounds of the present invention, some representative test examples will be given and explained in more detail.

Test example 1 Flooded soil treatment (before weed emergence) area 80c
Fill J's pot with paddy soil, and grow the Echlnoc.
Seeds of Amn+annla multif'1ora, Amn+annla multif'1ora, and Sclrpus juncordas were mixed into the soil to a depth of about 2 cm above the surface.
perus 5 crotinus) and paddy rice at the two-leaf stage were transplanted to two locations each, and the water depth was maintained at 3 cm. One day later, a hydrating agent of the compound of the present invention prepared according to Example 1 was administered into water. Three weeks after the chemical treatment, the herbicidal effect and damage to paddy rice were visually observed, and the results are shown in Table 2.

Test example 2 Flooded soil treatment (after weed emergence) Area 80c
Fill paddy soil in a gf pot, provide weeds and paddy rice according to Test Example 1, grow in a greenhouse for 10 days, and then administer a hydrating powder of the compound of the present invention prepared according to Example into water. did. Three weeks after the chemical treatment, the herbicidal effect and damage to paddy rice were investigated. The results are shown in Table-3.

(Margin below)

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X_1, X_2, X_3, and X_4 are hydrogen atoms,
It represents a halogen atom or a methyl group, and R represents a hydrogen atom or a lower alkyl group. ] A compound represented by 2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X_1, X_2, X_3, and X_4 are hydrogen atoms,
It represents a halogen atom or a methyl group, and R represents a hydrogen atom or a lower alkyl group. ] A herbicide characterized by containing a compound represented by the following as an active ingredient.