WO2006125337A1

WO2006125337A1 - α, β- AND, Ϝ-UNSATURATED CARBOXYLATES AND THE USE AS HERBICIDIDE THEREOF

Info

Publication number: WO2006125337A1
Application number: PCT/CN2005/000706
Authority: WO
Inventors: Bin Li; Hongfei Wu; Dongliang Cui; Dong Xiang; Liping Bai; Huazheng Yang
Original assignee: Sinochem Corporation; Shenyang Research Institute Of Chemical Industry
Priority date: 2005-05-23
Filing date: 2005-05-23
Publication date: 2006-11-30

Abstract

The present invention relates to α, β- and β, Ϝ-unsaturated carboxylates and the use as herbicide thereof. The said compounds are shown below as general formula (I, II). Wherein: R1 is selected from C1-C4alkyl; R2 is selected from H, C1C6alkyl, C3-C6alkenyl or C3-C6alkynyl; Q is selected from all kinds of aromatic ring groups which are optionally substituted; Chiral carbon atom indexed by asterisk is R or S configuration or mixtures of R and S configuration in different proportion. The present compounds have execellent herbicidal activities and better safety to crop.

Description

α, β and β . Y unsaturated carboxylic acid ester compounds and their use as herbicides

The invention belongs to the field of herbicides. Specifically, it is an oc, β and β, hydrazine-unsaturated carboxylic acid ester compound and its use as a herbicide. Background technique

Due to the succession and changes of weed populations and the emergence and rapid development of chemical pesticide resistance, people's awareness of ecological environmental protection has been continuously strengthened, chemical pesticide pollution, pesticides' understanding of non-target organisms, and pesticide ecological environment. The emphasis on the issue of the home is constantly improving. With the gradual reduction of the world's arable land, the growing population and the increasing demand for food, people are forced to rapidly develop agricultural production techniques, improve and improve farming systems, and continuously invent new and improved herbicidal compounds and compositions.

At present, certain α,β and β, Υ unsaturated carboxylic acid ester compounds have been reported as herbicides (EP149034A2, USP6251829 but α-substituted acid groups α, β and β, γ unsaturated carboxylic acids as shown in the present invention. The ester compound has not been disclosed.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an a-substituted acid group of α, β and β, γ-unsaturated carboxylic acid ester compounds which are novel in structure and safe for crops and their use as herbicides.

The technical solution of the present invention is as follows:

The present invention provides an α-substituted acid group α,β and β,γ-unsaturated carboxylic acid ester compounds, as shown by the general formula (1, II):

I II

among them:

Ri is selected from -C4 alkyl;

R _{2 is} selected from H, C _r C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl; Q is selected from one of the groups shown below -

Ql Q2 Q3 Q4 The chiral carbon atom of the * is a R or S configuration, or a mixture of R and S in different ratios. A more preferred compound of the invention is in the formula (1, Π):

Selected from -C ₄ alkyl;

R _{2 is} selected from H, CC ₆ fluorenyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

Q is selected from Ql, Q2, Q3, Q4 or Q5 _;

The chiral carbon atom of the standard * is in the R configuration.

Alternatively, a more preferred compound of the invention is in the formula (1, II):

Selected from methyl;

R _{2 is} selected from H, dC ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

Q is selected from Q1 ;

The chiral carbon atom of the standard * is in the R or S configuration, or a mixture of R and S in different ratios. Further preferred compounds of the invention are those of the formula (1, II):

Selected from methyl;

Selected from H, C _r C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

Q is selected from Q1 ;

The chiral carbon atom of the standard * is in the R configuration.

A more preferred compound of the invention has the following structural formula:

The chiral carbon atom of the standard * is in the R configuration. The fluorenyl group referred to in the formula (1, II) includes a linear or branched alkyl group; the alkenyl group means a group having 1 to 2 carbon-carbon double bonds in a straight-chain or branched form, for example, a propenyl group And allyl group; alkynyl group means a group having 1 to 2 carbon-carbon triple bonds in a straight-chain or branched form, for example, propynyl group, block propyl group and the like.

The compound of the formula (Ι, Π) of the present invention can be produced by the following method:

III III- 1 ΙΙΙ-2

II 1-2

II The raw material (ΠΙ, commercially available) is dissolved in a suitable solvent and added to an alkaline aqueous solution at a temperature of -10 ° C to the boiling point for 0.5-48 hours, and then acidified with hydrochloric acid or sulfuric acid. The intermediate acid is the compound (111-1). Suitable solvents are selected from the group consisting of chloroform, dichloromethane, carbon tetrachloride, n-hexane, benzene, toluene, ethyl acetate, THF or dioxane, etc.; suitable bases are selected from sodium hydroxide, potassium hydroxide, sodium carbonate , potassium carbonate or sodium hydrogencarbonate.

The intermediate acid (ΠΙ-1) is dissolved in a suitable solvent with S0C1 ₂ , oxalyl chloride or PC1 ₃ such as chloroform, dichloromethane, carbon tetrachloride, n-hexane, benzene, toluene, ethyl acetate, THF or dioxane. In the six-ring and the like, an organic acid such as triethylamine, pyridine or DMF is used as a catalyst, and the reaction is carried out at a temperature of from -10 ° C to the boiling point for 0.5 to 48 hours to prepare an intermediate acid chloride (ΠΙ-2).

Intermediate acid chloride (ΠΙ-2) with 3-methyl-2-oxobutyrate (commercially available from '), in a suitable solvent, temperature between -10 ° C and boiling point between 0.5-48 The product (1) was obtained in an hour. The solvent is selected from the group consisting of chloroform and dichloro Formamidine, carbon tetrachloride, hexanyl, benzene, toluene, ethyl acetate, acetone, DMF, THF or dioxane; adding alkalis such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide Sodium carbonate, potassium carbonate, sodium hydrogencarbonate, etc. are advantageous for the reaction.

The product (11) can be obtained by reacting an intermediate acid chloride (?-2) with 2-hydroxy-3-methyl-3-butenoate (commercially available). The reaction conditions and the choice of solvent and base are directed to the preparation of the product (1).

Table 1: Part of the compound of the invention as shown in Formula I

(The chiral carbon atom of the standard * is the R configuration)

Compound Q Ri Physical Properties [a] _D ²⁵ (c=l, Acetone)

1 Q1 methyl ethyl yellowish oil +7.98°

3 Q2 methyl ethyl yellowish oil +10.75°

5 ' Q5 methyl ethyl yellowish oil +6.66°

Table 2: Compounds of the invention partially as shown in Formula II

(The chiral carbon atom of the standard * is the R configuration)

Compound Q Ri Physical Properties [ ] _D ²⁵ (c=l, Acetone)

2 Q1 methyl ethyl yellowish oil +18.84°

4 Q2 methyl ethyl yellowish oil +24.62°

6 Q5 , methyl ethyl yellow oil +20.33 ° The 1H NMR (CDC1 ₃ , 300 MHz) data for some of the compounds in the table are as follows:

Compound 1: 8.675 (s, 1H), 8.049 (d, 1H), 7.634 (d, 1H), 7.602 (dd, IH), 7.21-7.17 (m, 2H), 7.06-7.02 (m, 2H), 4.956 (q, IH), 4.202 (q, 2H), 2.220 (d, 3H), 1.788 (d, 3H), 1.709 (d, 3H), 1.261 (t, 3H);

Compound 2: 8.661 (s, IH), 8.028 (d, 1H), 7.666 (d, IH), 7.583 (dd, H), 7.20-7.17 (m, 2H), 7.02-6.98 (m, 2H), 5.48 -5.46 (m, IH), 5.23-5.20 (m, IH), 5.15-5.13 (m, IH), 4.92-4.88 (m, IH), 4.28-4.15 (m, 2H), 1.81-1.80 (m, 3H), 1.76-1.70 (m, 3H), 1.268 (t, 3H);

Compound 3: 7.46-7.18 (m, 5H), 7.05-7.01 (m, 2H), 4.926 (q, IH), 4.196 (q, 2H), 2.208 (s, 3H), 1.766 (d, 3H), 1.701 (s, 3H), 1.261 (t, 3H);

Compound 4: 7.44-7.39 (m, 2H), 7.35-7.29 (m, 2H), 7.27-7.22 (m, IH), 7.02-6.97 (m,

2H), 5.46-5.44 (m, IH), 5.22-5.19 (m, ' IH), 5.15-5.12 (m, 1H), 4.88-4.85 (m, IH), 4.28-4.19 (m, 2H), 1.80 -1.79 (m, 3H), 1.74-1.68 (m, 3H), 1.269 (t, 3H) Compound 5: 8.242 (d, IH), 7.967 (d, IH), 7.11-7.08 (m, 2H), 7.03-7.00 (m, 2H), 4.926 (q, IH), 4.196 (q, 2H), 2.209 (s, 3H), 1.767 (d, 3H), 1.688 (s, 3H), 1.261 (t, 3H);

Compound 6: 8.250 (d, IH), 7.962 (d, IH), 7.10-7.06 (m, 2H), 7.00-6.96 (m, 2H), 5.46-5.44 (m, IH), 5.22-5.18 (m, IH), 5.15-5.12 (m, IH), 4.89-4.85 (m, IH), 4.26-4.18 (m, 2H), 1.189 (s, 3H), 1.74-1.69 (m, 3H), 1.269 (t, 3H).

The formula of the present invention (1, ID compound has herbicidal activity and can be used for controlling a variety of weeds in agriculture. For example, the use of post-emergence can effectively control monocotyledonous weeds.

The present invention also includes a herbicidal composition having a compound of the formula (1, II) as an active ingredient. The herbicidal composition has a weight percentage of the active ingredient of from 1 to 99%. Also included in the herbicidal composition is an agriculturally acceptable carrier.

The herbicidal compositions of the invention can be administered in a variety of formulations. The compound of the present invention is usually dissolved or dispersed in a carrier to prepare a preparation to be more easily dispersed as a herbicide. For example, these chemicals can be made into wettable powders or emulsifiable concentrates and the like. Thus, in these compositions, at least one liquid or solid carrier is added and it is usually necessary to add a suitable surfactant.

The present invention also provides a method of controlling weeds comprising applying a herbicidally effective amount of the herbicidal composition of the present invention to the surface of the weeds or the weed growing or the surface of the growth medium thereof. Preferably, the effective dose is from 1 to 1000 grams per hectare, and the preferred effective dose is from 10 to 500 grams per hectare. For some applications, one or more additional herbicides may be added to the herbicidal compositions of the present invention, thereby providing additional advantages and benefits.

The compound of the present invention may be used alone or in combination with other known insecticides, bactericides, plant growth regulators or fertilizers.

The α-substituted acid groups of the present invention, α, β and β, oxime unsaturated carboxylic acid ester compounds not only have excellent herbicidal activity, but are also more safe for crops than the compounds disclosed in the prior art. In particular, the safety of gramineous crops has an unexpectedly satisfactory effect.

It is to be understood that various changes and modifications may be made within the scope of the appended claims. detailed description

The following examples and biotest results can be used to further illustrate the invention, but are not meant to limit the invention. Synthesis example

Example 1 Synthesis of Compound 1:

Into a 500 ml reaction flask, quizalofop-p-ethyl (30.00 g, 80.40 mmol, purchased from Jiangsu Fengshan Group Co., Ltd., the chiral carbon atom of the standard * is the R configuration, the same below) and 80 ml of tetrahydrofuran were stirred. To a total solution, a solution of sodium hydroxide (3.26 g, 80.68 mmol) and water (80 ml) was added, and the mixture was stirred at room temperature for 5 hours, the reaction was quenched, extracted with ethyl acetate (100 ml), and the aqueous phase was acidified with concentrated hydrochloric acid. After filtration, the filter cake was dried to give a white solid, which was 25.00 g.

Add the above intermediate acid (20.00 g, 58.00 mmol) and 150 ml of dichloromethane to a 250 ml reaction flask, slowly add oxalyl chloride (11.00 g, 85.74 mmol) with stirring, add 3 drops of DMF, stir at room temperature. After reacting for 4 hours, dichloromethane and excess oxalyl chloride were removed under reduced pressure to give 23.00 g of a yellow liquid, intermediate acid chloride.

Compound 1 To a 50 ml reaction flask was added ethyl 3-methyl-2-oxobutanoate (0.47 g, 3.16 mmol), triethylamine (0.35 g, 3.43 mmol) and 5 mL of dichloromethane. A solution of the above intermediate acid chloride (1.25 g, 3.40 mmol) and 10 ml of dichloromethane was added dropwise under ice-water bath, and the mixture was added dropwise over about half an hour, and reacted at room temperature for 5 hours. Thereafter, 100 ml was added to the reaction mixture. Ethyl acetate and 20 ml of water were separated, and the ethyl acetate layer was washed twice with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride (20 ml), dried over anhydrous magnesium sulfate. (ethyl acetate/petroleum ether = 1/10) gave 1.28 g of pale yellow oil as Compound 1.

Example 2 Synthesis of Compound 2:

Compound 2 To a 50 ml reaction vial was added 2-hydroxy-3-methyl-3-butenoate (0.50 g, 3.30 mmol), triethylamine (0.35 g, 3.43 mmol) and 5 mL of dichloro In the formazan solution, a solution of the intermediate acid chloride (1.26 g, 3.43 mmol, prepared in Example 1-2) and 10 ml of dichloromethane was added dropwise to the ice bath, and the reaction was completed in about half an hour. After 5 hours, 100 ml of ethyl acetate and 20 ml of water were added to the reaction mixture, and the mixture was evaporated. The mixture was evaporated under reduced pressure.

Other compounds in Tables 1 and 2 can be obtained by a similar method as above.

Biometric example

After the original medicinal acetone is dissolved, 1% is used according to the test requirements. The Tween 80 is allowed to stand in tap water to prepare a test solution of the desired concentration. Spray treatment was carried out using a crawler crop sprayer (designed and manufactured by Engineering Research Ltd., UK) (spray pressure 1.95 kg/cm ² , spray volume 50 ml/m ² , crawler speed 30 cm/s, nozzle nozzle fan). In the post-emergence test, quantitative seeds of grass weeds (Herb, foxtail, and crabgrass) and crops (rice, wheat, corn, soybean) were separately planted in culture rafts with a cross-sectional area of 100 cm ² , and the soil was covered with lcm after sowing. Repressed, drenched in the greenhouse Conventional method of cultivation. When the grass weeds grow to 1.5 leaf stage, rice, wheat, corn and soybean 2-3 leaf stage, the test materials with uniform growth are selected for post-emergence stem and leaf spray treatment to 1%. Tween 80 was placed in tap water treatment as a control. After the sample is treated, put it in a dry and ventilated place. After the liquid is naturally dried, it is placed in the greenhouse and managed according to the conventional method. The method of watering from the bottom is used within 48 hours after the treatment to avoid the liquid being washed away. Visual inspection was conducted 4 weeks after the treatment, and the inhibition rate was various degrees of damage compared with the control, including killing, chlorosis, blight, distortion, deformity, growth inhibition, or leaf burning. Some test results are shown in Table 3.

Table 3: Herbicidal activity of compounds of partial formulae I and II

(post-emergence, 40 g active ingredient / hectare, inhibition rate %)

Compound 2 was selected for expanded herbicidal spectrum and crop safety tests. The control agent was refined quizalofop-p-ethyl and purchased from Jiangsu Fengshan Group Co., Ltd. Some results are shown in Table 4.

Table 4: Comparison of herbicidal activity and crop safety of compound 2 with quinoline

(post-emergence, 40 g active ingredient / hectare, inhibition rate %)

Note 1: Indicates no collar

Claims

Claim

1. An α-substituted acid group α,β and β, an oxime unsaturated carboxylic acid ester compound, as shown in the formula (1, 11):

II

Ri is selected from Ci-C ₄ alkyl;

R _{2 is} selected from H, CC ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

Q is selected from one of the groups shown below:

The chiral carbon atom of the standard * is in the R or S configuration, or a mixture of different ratios of R and S.

The compound according to claim 1, wherein, in the formula (1, 11):

Selected from -C ₄ thiol;

Selected from H, -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

Q is selected from Ql, Q2, Q3, Q4 or Q5;

The chiral carbon atom of the standard * is in the R configuration.

The compound according to claim 1, wherein, in the formula (1, 11):

Ri is selected from methyl;

R _{2 is} selected from H, -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

Q is selected from Q1;

The chiral carbon atom of the standard * is in the R or S configuration, or a mixture of R and S in different ratios.

The compound according to claim 3, wherein, in the formula (1, 11): Ri is selected from methyl; '

R _{2 is} selected from H, QC ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

Q is selected from Ql;

The chiral carbon atom of the standard * is in the R configuration.

The compound according to claim 4, which is selected from the group consisting of -

The chiral carbon atom of the standard * is in the R configuration.

6. Use of a compound of claim 1 for controlling monocotyledonous weeds.

A herbicidal composition comprising a compound according to claim 1 and an agriculturally acceptable carrier, wherein the active ingredient is present in the composition in an amount of from 1 to 99% by weight.

8. A method of controlling weeds in a herbicidal composition according to claim 7, characterized by: applying a herbicidally effective amount to the growth medium or site of weeds or weeds as claimed in claim 7 Herbicidal composition.