CN1296366C - Dibenzocyclooctane carboxylic ether compounds with herbicidal activity - Google Patents

Abstract

The present invention relates to a dibenzo-1, 3-dioxa-cyclooctane-2-carboxylate compound with herbicidal activity, which is shown in a general formula (I). In the formula, n=1-8, R is selected from alkyl, or Q represents substituted or unsubstituted phenyl. The compound and the composition of the present invention can be used to effectively control various monocotyledonous weeds and dicotyledonous weeds before seedling emergence and after seedling emergence.

Description

Dibenzocyclooctyl carboxylate compounds with herbicidal activity

technical field

The present invention belongs to the field of herbicides.

Background technique

Because weeds develop resistance to herbicides or compositions thereof over time, there is a continuing need to invent new and improved herbicidal compounds and compositions. In addition, considering economical and environmental factors, it is also necessary to invent herbicides with different mechanisms of action from existing herbicides.

Certain dibenzo-1,3-dioxa-cyclooctane-2-carboxylate compounds have been used as medicine (J. Medicinal Chemistry, 15, 1273-1278 (1972)), herbicide (USP 4938790) There are reports. But the dicarboxylate ester compound as shown in the present invention has not been disclosed.

Contents of the invention

The invention provides a novel dibenzo-1,3-dioxa-cyclooctane-2-carboxylate compound.

As shown in general formula (I):

in:

n=1-8;

R is selected from (C ₁ -C ₄ ) alkyl groups, or substituent groups Q1, Q2 or Q3 as shown below:

Wherein: R ₁ is selected from H, halogen, CN or NO ₂ ;

R _is selected from H, halogen or phenoxy substituted by halogen or haloalkyl;

R ₃ is selected from H, halogen or (C ₁ -C ₄ ) alkyl;

R ₄ is selected from H or (C ₁ -C ₄ ) alkyl;

A is selected from H or halogen, or one of the groups shown below:

Wherein: R ₅ and R ₆ are selected from H, halogen, (C ₁ -C ₄ ) alkyl or halogenated (C ₁ -C ₄ ) alkyl;

R ₇ , R ₈ , R ₉ , R ₁₀ are selected from H, halogen, CN, NO ₂ , (C ₁ -C ₄ ) alkyl or halogenated (C ₁ -C ₄ ) alkyl; and stereoisomers thereof .

More preferred compound among the present invention is in general formula (I):

n=1-8;

R is selected from (C ₁ -C ₄ ) alkyl groups, or substituent groups Q1, Q2 or Q3 as shown below:

Wherein: R ₁ is selected from H or NO ₂ ;

R is selected from H or (2-chloro-4 _- trifluoromethyl)phenoxy;

_R is selected from H, chlorine or methyl;

_R is selected from H or methyl;

A is selected from H or chlorine, or one of the groups shown below:

Wherein: R ₅ and R ₆ are selected from H or chlorine;

R ₁₀ is selected from H, halogen, CN or NO ₂ ;

and its stereoisomers.

Further preferred compounds in the present invention are in general formula (I):

n=1-6;

R is selected from (C ₁ -C ₄ ) alkyl, or a substituent Q2 or Q3 as shown below:

Wherein: R ₃ is selected from H, chlorine or methyl;

_R is selected from H or methyl;

A is selected from H or chlorine, or one of the groups shown below:

Wherein: R _is selected from 2-chloro;

R ₆ is selected from 4-chloro;

R ₁₀ is selected from 6-chloro;

and its stereoisomers.

The alkyl group referred to in the general formula includes linear or branched chain alkyl groups. Haloalkyl refers to a group in which the alkyl group is substituted with one or more halogen atoms. Halogen refers to fluorine, chlorine, bromine, iodine.

General formula compound (I) of the present invention can be prepared by following method:

The preparation of compound (II) is referred to (J. Medicinal Chemistry, 15, 1273-1278 (1972)).

Compound (II) is dissolved with SOCl ₂ , oxalyl chloride or PCl ₃ in a suitable solvent such as chloroform, dichloromethane, carbon tetrachloride, n-hexane, benzene, toluene, ethyl acetate, THF or dioxane, and Under the condition of an organic base such as triethylamine, pyridine or DMF as a catalyst, the acid chloride (II-1) is prepared by reacting at a temperature ranging from -10°C to boiling point for 0.5-48 hours.

Compound (II-2) can be obtained by reacting acid chloride (II-1) with alkanediol (commercially available) in a suitable solvent at a temperature ranging from -10°C to boiling point for 0.5-48 hours. The solvent can be chloroform, methylene chloride, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetone, DMF, THF or dioxane, etc. Adding alkalis, such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, etc. is beneficial to the reaction.

Compound (I) is prepared by reacting compound (II-2) with acid chloride (RCOCl) in a suitable solvent at a temperature ranging from -10°C to boiling point for 0.5-48 hours. The solvent can be chloroform, methylene chloride, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetone, DMF, THF or dioxane, etc. Adding alkalis, such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, etc. is beneficial to the reaction.

Acid chloride (RCOCl) can be purchased from the market, or can be obtained from commercially available RCOOH according to the preparation method of acid chloride (II-1).

                Table 1: Some of the compounds of the present invention shown in general formula I

compound no R mp(°C) 123456789101112131415161718192021 123412341234111211234 CH ₃ CH ₃ CH ₃ CH ₃ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ Q1(R ₁ =R ₂ =H)Q1(R ₁ =R ₂ =H)Q1(R ₁ =R ₂ = H) Q1 (R ₁ = R ₂ = H) Q1 (R ₁ = NO ₂ , R ₂ = (2-Cl-4-CF ₃ ) phenoxy) Q2 (R ₃ = Cl, R ₄ = H , A=Cl) Q2(R ₃ =H, R ₄ =CH ₃ , A=A1(R ₅ =2-Cl, R ₆ =4-Cl)) Q2(R ₃ =H, R ₄ =CH ₃ , A=A1(R ₅ =2-Cl, R ₆ =4-Cl))Q2(R ₃ =H, R ₄ =CH ₃ , A=A4(R ₁₀ =6-Cl))Q3Q3Q3Q3 Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil

^{The 1} H NMR (Mercury 300 nuclear magnetic resonance instrument, CDCl ₃ ) data of some compounds in Table 1 are as follows:

Compound 1:

7.351-7.321(q, 2H), 7.198-7.048(m, 6H), 5.109(s, 1H), 4.638-4.596(d, 1H), 4.587-4.556(q, 2H), 4.450-4.419(q, 2H ), 3.508-3.466(d, 1H), 2.119(s, 3H)

Compound 2:

7.351-7.320(m, 2H), 7.193-7.047(m, 6H), 5.120(s, 1H), 4.636-4.595(d, 1H), 4.544-4.512(m, 2H), 4.275-4.244(m, 2H ), 3.879-3.847(m, 2H), 3.793-3.762(m, 2H), 3.509-3.466(d, 1H), 2.072(S, 3H)

Compound 3:

7.345-7.315(m, 2H), 7.183-7.044(m, 6H), 5.110(s, 1H), 4.633-4.590(d, 1H), 4.538-4.506(m, 2H), 4.230-4.198(m, 2H ), 3.880-3.847(m, 2H), 3.759-3.669(m, 6H), 3.503-3.461(d, 1H), 2.051(s, 3H)

Compound 4:

7.348-7.318(q, 2H), 7.192-7.047(m, 6H), 5.109(s, 1H), 4.634-4.592(d, 1H), 4.535-4.503(m, 2H), 4.217-4.186(m, 2H ), 3.877-3.845(m, 2H), 3.756-3.624(m, 10H), 3.504-3.462(d, 1H), 2.066(S, 3H)

Compound 5:

7.352-7.323(q, 2H), 7.256-7.047(m, 6H), 5.105(s, 1H), 4.638-4.592(d, 1H), 4.580-4.561(m, 2H), 4.453-4.430(m, 2H ), 3.508-3.466(d, 1H), 2.437-2.362(q, 2H), 1.190-1.139(t, 3H)

Compound 6:

7.350-7.319(m, 2H), 7.192-7.044(m, 6H), 5.118(s, 1H), 4.636-4.594(d, 1H), 4.540-4.508(q, 2H), 4.283-4.252(t, 2H ), 3.878-3.846(q, 2H), 3.793-3.762(t, 2H), 3.508-3.466(d, 1H), 2.366-2.315(q, 2H), 1.146-1.096(t, 3H)

Compound 7:

7.343-7.314(m, 2H), 7.188-7.043(m, 6H), 5.109(s, 1H), 4.632-4.590(d, 1H), 4.535-4.503(t, 2H), 4.239-4.207(t, 2H ), 3.877-3.845(t, 2H), 3.748-3.672(m, 6H), 3.502-3.460(d, 1H), 2.365-2.289(q, 2H), 1.254-1.019(t, 3H)

Compound 8:

7.347-7.317(q, 2H), 7.191-7.047(m, 6H), 5.109(s, 1H), 4.634-4.592(d, 1H), 4.534-4.502(m, 2H), 4.227-4.194(m, 2H ), 3.875-3.843(m, 2H), 3.748-3.631(m, 10H), 3.503-3.462(d, 1H), 2.384-2.309(q, 2H), 1.154-1.104(t, 3H)

Compound 9:

8.103-8.075(m, 1H), 7.551-7.538(m, 2H), 7.471-7.420(m, 2H), 7.335-7.314(m, 2H), 7.117-6.990(6H), 5.114(s, 1H), 4.734-4.683(4H), 4.627-4.584(d, 1H), 3.494-3.452(d, 1H)

Compound 10:

8.047-8.016(m, 2H), 7.566-7.471(m, 3H), 7.379-7.311(m, 2H), 7.135-7.021(m, 6H), 5.082(s, 1H), 4.618-4.576(d, 1H) ), 4.558-4.498(m, 4H), 3.931-3.896(m, 4H), 3.490-3.448(d, 1H)

Compound 11:

8.053-8.024(m, 1H), 7.563-7.512(m, 2H), 7.440-7.390(m, 2H), 7.335-7.305(q, 2H), 7.177-7.038(m, 6H), 5.097(s, 1H) ), 4.625-4.583(d, 1H), 4.514-4.458(m, 4H), 3.875-3.837(m, 4H), 3.755-3.743(m, 4H), 3.492-3.450(d, 1H)

Compound 12:

8.072-8.033(m, 1H), 7.575-7.501(m, 2H), 7.471-7.401(m, 2H), 7.385-7.334(q, 2H), 7.184-7.043(m, 6H), 5.101(s, 1H) ), 4.630-4.587(d, 1H), 4.517-4.441(m, 4H), 3.854-3.792(m, 4H), 3.723-3.664(m, 8H), 3.496-3.453(d, 1H)

Compound 15:

7.420-6.708(m, 15H), 5.083(s, 1H), 4.757-4.732(q, 1H), 4.595-4.552(d, 1H), 4.599-4.543(m, 4H), 3.489-3.446(d, 1H ), 1.673-1.639(3H)

Compound 16:

7.415-6.700(m, 15H), 5.081(s, 1H), 4.781-4.751(q, 1H), 4.594-4.551(d, 1H), 4.602-4.556(m, 8H), 3.484-3.441(d, 1H) ), 1.666-1.643(d, 3H)

Compound 17:

8.612(s, 1H), 8.043(s, 1H), 7.668-7.591(m, 3H), 7.317-6.940(m, 12H), 5.079(s, 1H), 4.849-4.826(q, 1H), 4.644- 4.601(d, 1H), 4.590-4.559(m, 4H), 3.471-3.428(d, 1H), 1.696-1.674(d, 3H)

Compound 18:

7.328-7.297(q, 4H), 7.094-7.065(m, 12H), 5.144(s, 2H), 4.73(s, 4H), 4.626-4.584(d, 2H), 3.487-3.445(d, 2H)

Compound 19:

7.317-7.286(q, 4H), 7.105-7.063(m, 12H), 5.108(s, 2H), 4.586-4.545(d, 2H), 4.562-4.529(t, 4H), 3.946-3.914(t, 4H) ), 3.466-3.423(d, 2H)

Compound 20:

7.340-7.309(q, 4H), 7.127-7.044(m, 12H), 5.123(s, 2H), 4.625-4.582(d, 2H), 4.554-4.521(t, 4H), 3.878-3.846(t, 4H ), 3.738-3.706(t, 4H), 3.501-3.458(d, 2H)

Compound 21:

7.335-7.305(q, 4H), 7.188-7.037(m, 12H), 5.095(s, 2H), 4.623-4.581(d, 2H), 4.505-4.473(q, 4H), 3.841-3.808(q, 4H ), 3.720-3.708 (m, 8H), 3.492-3.450 (d, 2H).

The compound of the general formula (I) of the present invention has herbicidal activity and can effectively control monocot and dicotyledonous weeds when used before and after emergence. Compared with the compounds in the prior art, it has a wider spectrum of herbicidal activity, especially unexpectedly high activity on monocotyledonous weeds.

The present invention also includes herbicidal compositions containing the compound of general formula (I) as an active ingredient. The weight percent content of the active components in the herbicidal composition is between 0.1-99%. The herbicidal composition also includes an agriculturally acceptable carrier.

Another embodiment of the present invention is a method of controlling weeds, the method comprising applying the herbicidal composition of the present invention to said weeds or the locus of said weeds or the surface of the growing medium of said weeds. Usually, the more suitable effective dose is 100 grams to 5000 grams per hectare, and the preferred effective dose is 200 grams to 3000 grams per hectare.

The compounds of the invention can be applied to the soil or foliage in the form of formulations. Such compounds are usually dissolved in a carrier or formulated to facilitate dispersion for use as herbicides. For example: These chemicals can be made into wettable powders or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is incorporated, and when necessary, suitable surfactants may be incorporated.

For some applications, one or more other herbicides may be added to the herbicidal compositions of the present invention, thereby producing additional advantages and effects.

The compounds of the present invention can be used alone or in combination with other known insecticides, fungicides, herbicides, plant growth regulators or fertilizers.

It should be understood that various changes and modifications can be made within the scope of the present invention defined by the claims.

Detailed ways

The following examples, bioassay results and tables can be used to further illustrate the present invention, but are not meant to limit the present invention.

synthetic example

Synthesis of Compound 9 in Table 1:

Drop into II (7.5 grams, 0.0335mol), dichloromethane (70ml), oxalyl chloride (6.4 grams, 0.0503mol) in the reaction bottle of 150ml, absorb tail gas with lye, react at room temperature for 30 minutes, add 2 drops of DMF, and A large amount of gas was released, and the reaction was stopped after 2 hours. The reaction liquid was concentrated under reduced pressure to obtain 5.6 g of oily substance II-1.

Add II-1 (1.0 grams, 0.00365mol) and 10ml of dichloromethane in a 50ml reaction flask, add ethylene glycol (2.2 grams, 0.0365mol) after stirring, triethylamine (0.44 grams, 0.00365mol), room temperature React for 2 hours. Pour the reaction solution into a 250ml separatory funnel, add 100ml ethyl acetate, 50ml water, separate layers, wash the ethyl acetate layer with 50ml saturated aqueous sodium bicarbonate solution, 50ml saturated aqueous sodium chloride solution, and dry over anhydrous magnesium sulfate. Concentrate and separate by silica gel column chromatography with a developing solvent of ethyl acetate:petroleum ether=1:2 to obtain 0.35 g of oily substance II-2.

Add II-2 (0.5 g, 0.00167 mol) and 10 ml of dichloromethane into a 50 ml reaction flask, add benzoyl chloride (0.28 g, 0.00192 mol) and triethylamine (0.20 g, 0.00192 mol) after stirring evenly, at room temperature React for 2 hours. Pour the reaction solution into a 250ml separatory funnel, add 100ml ethyl acetate, 50ml water, separate layers, wash the ethyl acetate layer with 50ml saturated aqueous sodium bicarbonate solution, 50ml saturated aqueous sodium chloride solution, and dry over anhydrous magnesium sulfate. Concentrate and separate by silica gel column chromatography with a developing solvent of ethyl acetate:petroleum ether=1:2 to obtain 0.30 g of an oily compound 9.

Other compounds in Table 1 can be prepared by similar methods above.

Biotest example

Pre-emergence test: after sowing, the test compound is sprayed on the soil surface, placed in the greenhouse after treatment, and then watered; post-emergence test, the seeds germinate and grow for 10-21 days, so that the test material has a series of growth stages before treatment , and then select the test materials with the same size and growth stage, and process them. After the treatment, they are placed in the greenhouse and watered. Samples not treated with compounds were used as controls. The test materials were dicotyledonous weeds zinnia, velvetleaf and cassia; monocotyledonous weeds barnyardgrass, dogtail and crabgrass.

Dissolve the original drug with acetone, add it into a certain amount of water containing surfactant according to the designed dosage, and prepare a certain concentration of the preparation. Spray with a mobile belt sprayer. The test material is placed on the rolling belt in the spray cabinet, and the nozzle is moved over the upper part of the test material to spray the agent on the test material in the form of fan spraying. The nozzle is the same as that on the usual field sprayer. Roll the test material out of the cabinet and place it in a drying oven to dry.

The spray-dried samples were placed in the greenhouse. The pre-emergence test was sprayed with water from the top, and the post-emergence test was irrigated with water from the bottom and kept for 48 hours so that the water did not touch the leaves.

Surveys were performed 4 weeks after treatment. The inhibition rate is the total effect of various damages such as chlorosis, dead spot, growth retardation or burning of leaf corners, and the result is obtained after comparing with the blank control. Some test results are shown in Table 2.

                                                

[Pre-emergence (2250 g/ha)/post-emergence (2250 g/ha)] compound Zinnia Abutilon Cassia barnyard grass dog tail crabgrass Seedling Emergence Seedling Emergence Seedling Emergence Seedling Emergence Seedling Emergence Seedling Emergence 13* -** - - 80 - - - 80 - - - - 14* - - - 80 - - - 40 - - - - 15 95 100 90 70 80 65 80 30 80 30 100 25 16 60 100 80 20 75 50 80 20 95 30 90 40 17 - - 0 30 0 30 100 40 - - 100 65 18 90 100 70 10 80 60 70 40 75 20 70 40 20 - - 0 100 10 40 40 45 - - 75 15 twenty two - - 0 100 0 50 10 20 - - 0 0

*: The dosage is 1200 g/ha

**: "-" means not tested.

Compound 22 is a compound in U.S. Patent (USP 4938790), and its structural formula is as follows:

Claims (6)

1. A dibenzo-1,3-dioxa-cyclooctane-2-carboxylate compound, as shown in general formula (I):

in: n=1-8; R is selected from (C ₁ -C ₄ ) alkyl groups, or substituent groups Q1, Q2 or Q3 as shown below:

Wherein: R ₁ is selected from H, halogen, CN or NO ₂ ; R _is selected from H, halogen or phenoxy substituted by halogen or haloalkyl; R ₃ is selected from H, halogen or (C ₁ -C ₄ ) alkyl; R ₄ is selected from H or (C ₁ -C ₄ ) alkyl; A is selected from H or halogen, or one of the groups shown below: Wherein: R ₅ and R ₆ are selected from H, halogen, (C ₁ -C ₄ ) alkyl or halogenated (C ₁ -C ₄ ) alkyl; R ₇ , R ₈ , R ₉ , R ₁₀ are selected from H, halogen, CN, NO ₂ , (C ₁ -C ₄ ) alkyl or halo (C ₁ -C ₄ ) alkyl; and its stereoisomers. 2. The compound according to claim 1, in the general formula (I): n=1-8; R is selected from (C ₁ -C ₄ ) alkyl groups, or substituent groups Q1, Q2 or Q3 as shown below: Wherein: R ₁ is selected from H or NO ₂ ; R is selected from H or (2-chloro-4 _- trifluoromethyl)phenoxy; _R is selected from H, chlorine or methyl; _R is selected from H or methyl; A is selected from H or chlorine, or one of the groups shown below: Wherein: R ₅ and R ₆ are selected from H or chlorine; R ₁₀ is selected from H, halogen, CN or NO ₂ ; and its stereoisomers. 3. The compound according to claim 2, in the general formula (I): n=1-6; R is selected from (C ₁ -C ₄ ) alkyl, or a substituent Q2 or Q3 as shown below:

Wherein: R ₃ is selected from H, chlorine or methyl; _R is selected from H or methyl; A is selected from H or chlorine, or one of the groups shown below: Wherein: R _is selected from 2-chloro; R ₆ is selected from 4-chloro; R ₁₀ is selected from 6-chloro; and its stereoisomers. 4. A herbicidal composition, characterized in that: the composition contains the compound of general formula (I) according to claim 1 as an active component and an agriculturally acceptable carrier, wherein the weight content of the active component is 0.1- 99%. 5. Use of the compound or its composition according to claim 1 for controlling monocotyledonous weeds. 6. A method for controlling weeds, characterized in that the method comprises applying a herbicidally effective amount of the herbicidal composition as claimed in claim 4 to the weeds or the growth medium or site of the weeds.