WO2005037844A1

WO2005037844A1 - Substituted phenyl fused heterocycles as high efficiency herbicides

Info

Publication number: WO2005037844A1
Application number: PCT/CN2004/001176
Authority: WO
Inventors: Zhengquan Wang; Baoqi Li; Yanlong Li; Junchun Wang
Original assignee: Zhengquan Wang
Priority date: 2003-10-21
Filing date: 2004-10-18
Publication date: 2005-04-28
Also published as: CN1609110A; CN1259321C

Abstract

The inVention is related to new substituted phenyl fused heterocycle compounds having herbicidal activities, these compounds are characterized by high efficiency, low toxicity, high selectivity, and the like.

Description

Substituted phenyl heterocyclic super efficient herbicide

[Technical Field]

The invention belongs to a fine chemical pesticide herbicide.

[technical background]

In 1987, a new compound KJH-9201 was discovered, and its structural formula is:

The crops to which this compound is suitable are corn and soybeans.

In recent years, Japanese research and pharmaceutical companies, combinatorial chemical companies, German Cole, BASF, and DuPont of the United States have invented highly effective herbicides, such as: ET-751, KIH-9210, KPP-300, KPP-314, and so on. The molecular structure of such herbicides has substituents at positions 1, 2, 4, and 5 on the benzene ring, halogens at positions 2, 2, and 4, and a heterocyclic ring at position 1.

As human beings attach great importance to the environment, and put forward higher requirements for pesticide toxicity and environmental impact, chemical pesticides have entered a new era of "super high efficiency, low toxicity, and no pollution.

[Inventive Content]

The purpose of the present invention is to develop a non-polluting super-efficient herbicide.

The present invention is a substituted phenyl heterocyclic herbicide. The 1 position of the benzene ring is connected to the heterocyclic ring. The biggest feature of the structure is that:

1. The 5-position on the benzene ring consists of methallyloxy, N, N—diethylsulfonyl, N, N—dimethylsulfonyl, methoxycarbonylchlorovinyl, and allyloxy Substituting groups such as methoxycarbonylmethylthio, etc., can also form benzofuran with the 6-position.

2. The 4-position on the benzene ring is replaced by a chlorine atom.

3. The 2-position on the benzene ring is substituted by a fluorine atom and an ethoxy group.

Twelve new structured high-efficiency herbicides are synthesized as follows:

Confirm this

(X) (XI) (Xfl)

The twelve new compounds mentioned above belong to the class of protoporphyrinogen oxidase inhibitor herbicides, which have the following characteristics:

1. Excellent herbicidal effect.

2. Inhibit chlorophyll biochemical synthesis.

3. Inhibition of protoporphyrinogen oxidase and cause accumulation of protoporphyrin IX.

4. The photooxidation of thylakoid membrane is destroyed.

The method for synthesizing the compound of the present invention is as follows: 1. Synthesis of benzofuran

The corresponding benzofuran compounds are prepared from 2-fluoro-4, 4-chloro-5, methallyloxyaniline through translocation and ring closure, namely:

(A) (B) (C) The reaction proceeds in two steps:

(a) the methallyl group is transferred to the ortho position of the hydroxyl group to form an intermediate product (B);

(b) The hydroxyl group is added to the carbon-carbon double bond to form the product (C). The reaction proceeds in the presence of N, N-diethylaniline through a reflux reaction. Trifluoromethanesulfonic acid is used as a catalyst for ring closure.

2.Synthesis of heterocyclic part of compound I ''

The whole reaction uses dichloromethane as a solvent, and triamine and pyridine are used as catalysts respectively. After the reaction, the catalyst is washed away with water.

3. Synthesis of compound XI heterocyclic moiety

Synthesis of Heterocyclic Part of Compound X II

5. Synthesis of hexahydropyridazine

CICOOC ₂ H ₅ NHCOOC ₂ H ₅ CI (CH ₂ ) ₄ CI

NHCOOC H

, NH

The reaction uses ethanol as a solvent '

Because the tetra-substituted phenyl heterocyclic compounds use chlorophyll as the action point of plant cells, the selectivity of these compounds between plants and animals is ensured, which makes them super-efficient and low-toxic, which is related to published foreign Compared with the patented varieties, they have the same or higher herbicidal effect. The results of the pot experiment are as follows-Test plants:

Echinochloa crusgalli

Dutch (Abuti lon thephrasti)

Matang (Digitaria sanguinalis)

Acalypha austrl is

Dogtail (Setaria viridis)

Zinnia elegans Preliminary Screening Data Sheet:

Inhibition rate of fresh weeds by different dosages (15 days after treatment)

10g (ai) / mu inhibition rate (%) 52.93 74.72 88.34 100 100 100g (ai) / mu inhibition rate (%) 54.24 75.08 40.42 100 100

VD

Chemical lg (ai) / mu inhibition rate (%) 48.10 63.71 40.42 100 100 people

in 10g (ai) / mu inhibition rate (%) 84.31 74.50 64.13 100 100 objects 100g (ai) / mu inhibition rate (%) 82.31 96.68 97.11 100 100 l

Inhibition rate of lg (ai) / mu (%) 50.23, 61.32 32.49 100 100

10g (ai) / mu inhibition rate (%) 65.41 79.38 68.55 100 100 objects 100g (ai) / mu inhibition rate (%) 80.88 92.99 91.32 100 100

IX

Chemical lg (ai) / mu inhibition rate (%) 45.83 50.92 46.13 100 100

10g (ai) / mu inhibition rate (%) 60.49 71.00 73.20 100 100 objects 100g (ai) / mu inhibition rate (%) 85.78 89.34 88.56 100 100

The data of XII preliminary screening experiments show that the twelve compounds of the present invention all have high herbicidal activity, and their control effect on broadleaf is better than that of grasses. Weak differences are evident at low concentrations of lgai / mu, which proves that It has high selectivity. Based on this experiment, broadleaf grass is selected for re-screening.

Rescreening data sheet:

Inhibition rate of weed fresh weight by different dosages (15 days after treatment) Index Zinnia (%) Ramie (%) Yarrow (%)

0.25g (ai) / mu 96.17 72.50 59.94

KIH9201 0.5g (ai) / mu 95.72 78.14 86.17 lg (ai) / mu 95.33 83.28 89.11

2g (ai) / mu 95.74 73.69 76.52

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££ 'ί \ ZVOL ζζτς 単 / (/ 00Z l3 / 13d o / sooz OAV 0.25g (ai) / mu 84.46 75.07 24.43 0.5g (ai) / mu 88.29 74.68 60.51

1 g (ai) / mu 97.15 76.16 25.76 2 g (ai) / mu 93.77 73.59 49.91

VI 4 g (ai) / mu 97.84 77.15 88.73

0.25g (ai) / mu 87.58 72.40 33.52 0.5g (ai) / mu 97.09 78.24 27.08

1 g (ai) / mu 96.48 80.32 61.65 2 g (ai) / mu 94.58 80.22 71.40 νπ 4 g (ai) / mu 96.31-73.79 88.45

0.25g (ai) / mu 69.34 64.49 36.79 0.5g (ai) / mu 90.23 73.98 65.37

1 g (ai) / mu 95.44 78.45 85.34 2 g (ai) / mu 96.79 76.37 88.29

VDl 4 g (ai) / mu 96.23 79.72 93.35

0.25g (ai) / mu 60.73 70.39 56.31 0.5g (ai) / mu 89.25 75.61 45.29

1 g (ai) / mu 91.39 79.83 65.98 2 g (ai) / mu 93.77 80.25 73.66

IX 4 g (ai) / mu 99.20 84.96 88.37

0.25g (ai) / mu. 80.25 73.38 37.76 0.5g (ai) / mu 95.36 76.42 65.19

1 g (ai) / mu 94.49 75.93 70.38 2 g (ai) / mu 97.35 79.40 81.26

X 4 g (ai) / mu 98.20 78.95 90.67 0.25g (ai) / mu 75.39 78.34 66.32 0.5g (ai) / mu 90.22 82.98 80.46

1 g (ai) / mu 95.74 93.20 86.77 2 g (ai) / mu 95.38 96.78 87.98

XI 4 g (ai) / mu 97.25 94.77 96.00 It can be seen from the re-screening data:

Compounds V, VI, VII,, IX, X, and XI can effectively inhibit the growth of zinnia, ramie, and amaranth at a dose of 1 gai / mu, and are super efficient herbicides.

[detailed description]

Five examples are given below to further illustrate the present invention.

Example one

Synthesis of compound I

In a 1000 ml four-necked flask, put 81 g of 4-chloro-2-fluoro-5 (2-methyl-2-propenyl) oxyphenylcarbamate (99.3% 0.28ml), 40% hydroxide 60 grams of sodium solution (0.6 ral) and 300 ml of ethanol were stirred and heated to reflux for 3 hours, and then neutralized with dilute hydrochloric acid to pH = 5-6, and distilled to remove ethanol. The residue in the kettle was extracted with 200 ml of dichloromethane, and the aqueous layer was separated to obtain a solution of 4-chloro-2-fluoro-5 (2-methyl-2-propenyl) aniline in dichloromethane. Into this solution was added 37.3 g (95%, 0.31 ml) of thiophosgene, 62.6 g (0.62 ml) of triethylamine, and the reaction was carried out at low temperature for 30 minutes. After the reaction, the organic phase was washed three times with 150 ml of water. 7 克 Add hexahydropyridazine 27g (0. 31ml) supplemented with 100ml dichloroformamidine, react at room temperature for 30 minutes, and then add pyridine 45.3 g (0.62ml) to this solution, and solid phosgene 30.7 g (0. 31ml), react at low temperature for 30 minutes, wash with 150ml water three times after the reaction is completed, desolvate the organic phase, obtain the product compound I after cooling, dry constant weight 64 grams, light yellow powder, purity 97.4%, yield 61.9%, melting point 98-99 ° C, structure confirmed by H-band R.

Example two

Synthesis of compound II

In a 250ml four-necked flask was added 100ml of ethanol, 2-chloro-4-fluoro_5-acetylacetylaminophenyl_N, N-diethylsulfonamide 7.0 g (90.5%, 0.02ml), 8.4 g of sodium hydroxide (40% aqueous solution, 0.084 ml) was heated under reflux for three hours, and the reaction was completely neutralized with dilute hydrochloric acid. The ethanol was removed under normal pressure. The residue in the kettle was extracted with 60 ml of dichloromethane to obtain 5-amino-2. -Chloro-4- 2oxyphenyl-N, N-diacetaldehyde sulfonamide in dichloromethane. To this solution was added thiophosgene 2.4 g (95%, 0.02 ml), triethylamine. 4.0 g (0.04 ml) was reacted for 30 minutes, washed three times with water, To the organic phase, 4.1 g of hexahydropyridazine was added, and the mixture was reacted at room temperature for 30 minutes. Then pyridine, solid phosgene, and low temperature reaction were added for 30 minutes, washed three times with 100 ml of water, and the organic phase was dissolved to obtain compound II, which was subjected to column chromatography ( Ethyl acetate: n-hexane 垸 = 1: 1) Purification yielded 2.5 g of pale yellow crystals with a purity of 99.7%, yield 28.7%, melting point

The structure of 109-lire was confirmed by H-NMR.

Example three

Synthesis of Compound III-Put 250ml of dichloromethane, 250ml of 4-amino-7-chloro-5-fluoro-2. 2-dimethylbenzofuran (85%, 0.1ml) in a 250ml four-neck flask , Thiophosgene 13.8 g (0.12 ml), triethylamine 24.4 g (0.24 ml), react at low temperature for 30 minutes, wash three times with 100 ml water, and add hexahydropyridazine 20. 6 g ( 50%, 0.12 ml), react at room temperature for 30 minutes, and then add 29.2 g of pyridine (0.4 ml), solid phosgene 29.7 g (0.3 ml), react at low temperature for 30 minutes, wash three times with 100 ml water , The organic phase was desolvated to obtain compound III, which was recrystallized in 100 ml of ethanol to obtain 20 g of earthy yellow powdery solid with a content of 99.9%, a yield of 55.9%, a melting point of 152-156 ° C, and a structure of H — Just R confirmed correct.

Example 4

Synthesis of compound IX

8 克， Into a 250ml four-necked flask, put 5 g of 4-chloro-2-fluoro-5- (2-propenyloxy) aniline, 40 g of dichloromethane, 4 g of thiophosgene, and 4.8 g of triethylamine. The reaction was allowed to proceed at a low temperature for 30 minutes, and then washed three times with 100 ml of water. To the organic phase, 4.5 g of hexahydropyridazine was added. After reacting at room temperature for 30 minutes, 6.1 g of pyridine and 4.6 g of thiophosgene were added to the solution. 30 minutes, washed three times with 100 ml of water, the organic phase was dissolved, and 11 g of kettle residue was obtained, and purified by column chromatography (ethyl acetate: n-hexane = 1: 1) to obtain product compound IX, melting point I, structure H— Just confirm that R is correct.

Example 5

Synthesis of compound XII

In a 250ml four-necked flask, put 5.9 g of 5-amino-2-chloro-4-fluorophenylthioacetic acid methyl ester, 40 g of dichloromethane, 4 g of thiophosgene, and 4.8 g of triethylamine. The reaction was carried out at low temperature for 30 minutes, and then washed three times with 100 ml of water. 3.5 g of hexahydropyridazine was added to the organic phase and reacted at room temperature for 30 minutes, then 6.1 g of pyridine, 5 g of chloroacetyl chloride, and 30 minutes of reaction at low temperature were used. Wash three times with ml of water, desolvate the organic phase to obtain 8 g of kettle residue, and purify by column chromatography (ethyl acetate: toluene: n-hexane = 1: 4: 1) to obtain the product compound XΠ, melting point 128--129 ° C , Structure H—Rigidity is correct.

Claims

Rights request

1. 'A super-efficient herbicide with substituted phenyl heterocycles, which is characterized in that: the molecular structure of the herbicide is connected to the fused heterocycle at position 1 on the benzene ring, and the positions 2 and 4 are respectively fluorine atoms and chlorine atoms And ethoxy groups, the 5-position on the benzene ring is methallyloxy, N, N—diethylsulfonyl, N, N—dimethylsulfonylfuranyl, methoxycarbonyl, chlorine Substituted vinyl, methoxycarbonylmethylthio, and allyl to obtain twelve super-efficient and low-toxic herbicides.

(I) (II) (III)

(X) (XI) (XII)