CN102442967B - Dichloropropylene compound and application thereof - Google Patents

Abstract

The invention discloses a dichloropropene compound with a novel structure, as shown in general formula I: In the formula: Q is selected from Q ₁ , Q ₂ or Q ₃ as shown below: Among them: R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ can be the same or different, and are selected from H, fluorine, and chlorine respectively , bromine, iodine, CN, NO ₂ , C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy or C ₁ -C ₃ haloalkoxy; X is selected from O, S or NR ₁₃ ; R ₁₃ is selected from C ₁ -C ₃ alkyl, allyl or propargyl; n=1, 2, 3 or 4. Compound I of the general formula has excellent insecticidal activity and can be used for controlling insect pests.

Description

A kind of dichloropropene compound and its application

technical field

The invention belongs to the field of pesticides. It relates to a dichloropropene compound and its application.

Background technique

Since pests develop resistance to insecticides over a period of time, there is a continuing need to invent new and improved compounds and compositions having insecticidal activity.

WO9604228A1 discloses the following dichloropropene compounds (compound 213 in the patent, hereinafter code-named KC) and their insecticidal activity, and the lethality to Spodoptera litura reaches more than 80% at a concentration of 500ppm:

In the prior art, there is no disclosure of dichloropropene compounds containing (substituted) benzoheterocycles or substituted pyridine rings and substituted alkyl bridges as shown in the present invention and their insecticidal activity.

Contents of the invention

The object of the present invention is to provide a dichloropropene compound with novel structure and better insecticidal activity, which can be applied to the prevention and control of insect pests in agriculture, forestry or hygiene.

Technical scheme of the present invention is as follows:

The present invention provides a dichloropropene compound containing a (substituted) benzoheterocycle or a substituted pyridine ring and a substituted alkyl bridge, as shown in general formula I:

In the formula:

Q is selected from Q ₁ , Q ₂ or Q ₃ as shown below:

Among them: R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ can be the same or different, and are selected from H, fluorine, and chlorine respectively , bromine, iodine, CN, NO ₂ , C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy or C ₁ -C ₃ haloalkoxy;

X is selected from O, S or NR ₁₃ ; R ₁₃ is selected from C ₁ -C ₃ alkyl, allyl or propargyl;

n=1, 2, 3 or 4.

According to different selections of Q, the dichloropropene ether compounds of the present invention can be expressed as the following three structures:

Preferred compound among the present invention is, in general formula I:

Q is selected from Q ₁ , Q ₂ or Q ₃ ;

When Q is selected from _Q1 , _R1 , _R2 , _R3 , and _R4 are respectively selected from H, fluorine, chlorine, bromine, methyl or trifluoromethyl, but at least one of _R1 and _R2 is H , at least one of R ₃ and R ₄ is H; X is selected from O, S or NR ₁₃ , and R ₁₃ is selected from methyl;

When Q is selected from _Q2 , _R5 , _R6 , _R7 , and _R8 are respectively selected from H, fluorine, chlorine, bromine, methyl or trifluoromethyl, but at least one of _R5 and _R6 is H , at least one of R ₇ and R ₈ is H;

When Q is selected from Q ₃ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are respectively selected from H, fluorine, chlorine, bromine, methyl or trifluoromethyl;

n=1, 2 or 3.

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

Q is selected from Q ₁ , Q ₂ or Q ₃ ;

When Q is selected from Q ₁ , R ₁ , R ₂ , R ₃ , and R ₄ are respectively selected from H, chlorine or trifluoromethyl, but at least one of R ₁ and R ₂ is H, and R ₃ and R ₄ At least one is H; X is selected from O or S;

When Q is selected from Q ₂ , R ₅ , R ₆ , R ₇ , and R ₈ are respectively selected from H, chlorine or trifluoromethyl, but at least one of R ₅ and R ₆ is H, and among R ₇ and R ₈ at least one is H;

When Q is selected from Q ₃ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ are respectively selected from H, chlorine or trifluoromethyl;

n=1 or 2.

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

Q is selected from _Q1 or _Q2 ;

R ₁ , R ₅ , R ₈ are selected from H;

R ₂ and R ₃ are selected from H, chlorine or trifluoromethyl;

_R is selected from H or chlorine;

R ₆ and R ₇ are selected from H or trifluoromethyl;

n=1 or 2.

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

Q is selected from _Q1 ;

R ₁ , R ₃ , R ₄ are selected from H;

R ₂ is selected from trifluoromethyl;

n=2.

Or, a further preferred compound in the present invention is, in general formula I:

Q is selected from _Q2 ;

R ₅ , R ₆ , R ₈ are selected from H;

R ₇ is selected from trifluoromethyl;

n=2.

In the definitions of the compounds of general formula I given above, the collectively used terms are generally defined as follows:

Alkyl refers to straight chain or branched chain forms, eg methyl, ethyl, n-propyl, isopropyl groups. Haloalkyl refers to groups in which the alkyl group is substituted with one or more halogen atoms, eg trifluoromethyl. Alkoxy refers to a group with an oxygen atom attached to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy and the like. Haloalkoxy means that the alkyl group is substituted by one or more halogen atoms, and the terminal is connected with an oxygen atom, such as trifluoromethoxy. The halogen atom refers to fluorine, chlorine, bromine, and iodine.

The compound of general formula I of the present invention can be prepared by the following method, unless otherwise noted, the definition of each group in the reaction formula is the same as before.

When Q=Q ₁ :

The compounds of general formula II, IV and V are respectively reacted with the compound of general formula III (in the formula: n=1, 2, 3 or 4) in a suitable solvent and in the presence of a suitable base at a temperature of -10°C to the boiling point for 0.5 - 48 hours to obtain target compounds I-1, I-2 and I-3.

Suitable solvents are selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethylmethylene Sulfone etc.

Suitable bases include alkali metals such as lithium, sodium or potassium hydrogen compounds such as sodium hydride, alkali metals such as lithium, sodium or potassium hydroxides such as sodium hydroxide, alkali metal carbonates such as sodium carbonate, and It can be an organic base such as triethylamine, sodium tert-butoxide, etc.

When X=O, the preparation of the compound of general formula II is carried out with reference to the operations of the following documents: J.Org.Chem.1996, 61, 3289-3297; Bioorganic & Medicinal Chemistry Letters 17 (2007) 4689-4693.

When X=S, the preparation of the compound of general formula II is carried out with reference to the operations of the following documents: J.Am.Chem.Soc.1927, 49, 1748-1758; ARKIVOC 2008(xiv)109-114.

When X=NR ₁₃ , the compound of general formula II can be prepared by referring to the method provided by CN1425665A (Example 5, 7).

The preparation of the compound of general formula III is carried out with reference to the operation of the following literature: Chemical World, 6, 366-370: 2006; CN1432555A.

The preparation of the compound of general formula IV is carried out with reference to the operation of the following documents: Journal of Medicinal Chemistry, 24 (1), 93-101; 1981; Journal of Medicinal Chemistry, 44 (11), 1785-1776; 2001.

The substituted pyridines represented by the general formula V are all commercially available.

Tables 1 to 3 list the structures and physical properties of some compounds of general formula I.

The structure and physical property of the compound of general formula I-1 of table 1 part

compound R ₁ R ₂ R ₃ R ₄ x n Appearance (melting point (°C)) 1 h h h h o 1 yellow oil 1a h h h h o 2 yellow oil 2 h Cl h h o 1 yellow oil 3 h CF ₃ h h o 1 yellow oil 3a h CF ₃ h h o 2 yellow oil 4 h h Cl h o 1 yellow oil 5 h h CF ₃ h o 1 yellow oil 6 h CF ₃ h Cl o 2 yellow oil 7 h Cl h h S 1 yellow oil

Structure and physical properties of the general formula I-2 compound of table 2

compound R ₅ R ₆ R ₇ R ₈ n Appearance (melting point (°C)) 8 h h CF ₃ h 1 yellow oil 9 h h CF ₃ h 2 Yellow solid (94-96) 10 h CF ₃ h h 1 yellow oil 11 h CF ₃ h h 2 Yellow solid (87-89)

Structure and physical properties of the general formula I-3 compound of table 3 part

compound R ₉ R ₁₀ R ₁₁ R ₁₂ n Appearance (melting point (°C)) 12 Cl h Cl Cl 1 yellow oil

The ¹ H NMR (300MHz, CDCl ₃ ) data of some compounds are as follows:

Compound 1: 1.47(d, 3H), 4.24(t, 2H), 4.57(d, 2H), 5.52-5.56(m, 1H), 6.12(t, 1H), 6.81(s, 2H), 7.17-7.27 (m, 2H), 7.36(d, 1H), 7.49(d, 1H).

Compound 1a: 1.62 (d, 3H), 2.20-2.40 (m, 2H), 4.16 (t, 2H), 4.12 (t, 1H), 4.58 (d, 2H), 5.52-5.56 (m, 1H), 6.10 (t, 1H), 6.82 (s, 2H), 7.15-7.27 (m, 2H), 7.35 (d, 1H), 7.50 (d, 1H).

Compound 2: 1.65(d, 3H), 4.23(t, 2H), 4.57(d, 2H), 5.50-5.60(m, 1H), 6.10(t, 1H), 6.83(s, 2H), 7.16(d , 1H), 7.28(s, 1H), 7.46(s, 1H).

Compound 3: 1.67(d, 3H), 4.24(t, 2H), 4.57(d, 2H), 5.50-5.60(m, 1H), 6.10(t, 1H), 6.83(s, 2H), 7.45-7.47 (m, 2H), 7.75 (s, 1H).

Compound 3a: 1.64 (d, 3H), 2.28-2.32 (m, 2H), 4.10-4.13 (m, 3H), 4.56 (d, 2H), 6.10 (t, 1H), 6.81 (s, 2H), 7.26 (dd, 1H), 7.40-7.50 (m, 2H), 7.76 (s, 1H).

Compound 4: 1.63(d, 3H), 4.23(t, 2H), 4.57(d, 2H), 5.50-5.53(m, 1H), 6.10(t, 1H), 6.83(s, 2H), 7.23(dd , 1H), 7.37-7.39 (m, 2H).

Compound 5: 1.67(d, 3H), 4.24(t, 2H), 4.57(d, 2H), 5.50-5.53(m, 1H), 6.10(t, 1H), 6.82(s, 2H), 7.54-7.63 (m, 3H).

Compound 6: 1.64(d, 3H), 2.28-2.32(m, 2H), 4.11(t, 2H), 4.12(t, 1H), 4.56(d, 2H), 5.50-5.50(m, 1H), 6.10 (t, 1H), 6.821 (s, 2H), 7.47 (d, 1H), 7.65 (d, 1H).

Compound 7: 1.63(d, 3H), 4.24(t, 2H), 4.57(d, 2H), 5.50-5.60(m, 1H), 6.10(t, 1H), 6.83(s, 2H), 7.20(dd , 1H), 7.54(d, 1H), 7.66(d, 1H).

Compound 8: 1.62(d, 3H), 4.25(t, 2H), 4.56(d, 2H), 5.70-5.90(m, 1H), 6.10(t, 1H), 6.82(s, 2H), 7.86-7.90 (m, 2H), 8.31 (s, 1H), 8.55 (s, 1H).

Compound 9: 1.55(d, 3H), 2.29-2.30(m, 2H), 4.12(t, 2H), 4.54(d, 2H), 5.81-5.90(m, 1H), 6.09(t, 1H), 6.78 (s, 2H), 7.84-7.94 (m, 2H), 8.31 (s, 1H), 8.52 (s, 1H).

Compound 10: 1.62(d, 3H), 4.25(t, 2H), 4.56(d, 2H), 5.80-5.82(m, 1H), 6.10(t, 1H), 6.81(s, 2H), 7.74(d , 1H), 8.12(s, 2H), 8.60(s, 1H).

Compound 11: 1.55 (d, 3H), 2.29-2.31 (m, 2H), 4.12 (t, 2H), 4.55 (d, 2H), 5.70-5.90 (m, 1H), 6.09 (t, 1H), 6.79 (s, 2H), 7.75 (dd, 1H), 8.11-8.15 (d, 2H), 8.53 (s, 1H).

Compound 12: 1.54(d, 3H), 4.12(t, 2H), 4.57(d, 2H), 5.50-5.70(m, 1H), 6.10(t, 1H), 6.82(s, 2H), 7.70(s , 1H).

Compared with known dichloropropene compounds, the dichloropropene compounds represented by the general formula I of the present invention have unexpectedly high insecticidal activity. Therefore, the present invention also includes the use of compounds of general formula I for controlling pests.

The present invention also includes the pesticidal composition with the compound of general formula I as an active ingredient. The weight percent content of the active components in the insecticidal composition is between 1-99%. The pesticidal composition also includes agricultural, forestry, and hygienic acceptable carriers.

The compositions of the invention may be administered in the form of formulations. The compound of general formula I is dissolved or dispersed in the carrier as an active ingredient or formulated into a preparation so that it is easier to disperse when used as an insecticide. For example: These chemicals can be formulated as wettable powders or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant may be added.

The technical solution of the present invention also includes a method for controlling pests: applying the pesticidal composition of the present invention to the pests or their growth medium. Usually, the more suitable effective dose is 10 grams to 1000 grams per hectare, and the preferred effective dose is 20 grams to 500 grams per hectare.

For some applications, for example, in agriculture, one or more other bactericides, insecticides, herbicides, plant growth regulators or fertilizers, etc. can be added to the pesticidal composition of the present invention, thereby producing additional advantages and effects.

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 synthesis examples and biological activity measurement examples can be used to further illustrate the present invention, but are not meant to limit the present invention.

synthetic example

The preparation of example 1 compound 2

Add 3-(2,6-dichloro-4-(3,3-dichloro-allyloxy)phenoxy)propan-2-alcohol (0.50 g, 1.44 mmoles, synthetic method reference chemical World, 2006, 6, 366), tetrahydrofuran (10 ml), stirred at room temperature until dissolved, added 70% sodium hydride (0.10 g, 2.88 mmol), after stirring for 2 hours, added 2,5-dichlorobenzo Oxazole (0.27 g, 1.44 mmol, refer to J. Org. Chem. 1996, 61, 3294 for the synthesis method). After continuing to react at room temperature for 5 hours, the reaction solution was poured into water (50 ml), extracted with ethyl acetate (3×100 ml), and the organic layer was washed with saturated aqueous sodium bicarbonate (3×50 ml) and saturated brine, respectively. (3×50 ml) was washed, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluent: ethyl acetate: petroleum ether = 1:50) to obtain 0.32 g of compound 2, appearance: colorless oil. Yield 35%.

The preparation of example 2 compound 3a

Add 3-(2,6-dichloro-4-(3,3-dichloro-allyloxy)phenoxy)butan-2-ol (0.50 g, 1.44 mmol) into the reaction flask, the synthesis method refers to the patent Example 1, 2) in CN1432555A, tetrahydrofuran (10 ml), stirred at room temperature until dissolved, added 70% sodium hydride (0.10 g, 2.88 mmol), stirred for 2 hours, added 2-chloro-5-trifluoro Tolylbenzoxazole (0.31 gram, 1.44 mmol, synthetic method is with reference to J.Org.Chem.1996,61,3294), after continuing to react at room temperature for 5 hours, the reaction solution was poured into water (50 milliliters), and used Extracted with ethyl acetate (3×100 mL), the organic layer was washed with saturated aqueous sodium bicarbonate (3×50 mL) and saturated brine (3×50 mL), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluent: ethyl acetate: petroleum ether = 1:100) to obtain 0.2 g of compound 3a, appearance: colorless oil. Yield 22%.

The preparation of example 3 compound 9

Add 3-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)butan-2-ol (0.50 g, 1.44 mmol), tetrahydrofuran (10 ml ), stirred at room temperature until dissolved, and added 70% sodium hydride (0.10 g, 2.88 mmol). After stirring for 2 hours, add 2-chloro-6-trifluoromethylquinoxaline (0.32 g, 1.44 mmol, the synthesis method refers to J.Med.Chem.1981, 24 (1), 93), and continue the reaction at room temperature 6 hours. Afterwards, the reaction solution was poured into water (50 ml), extracted with ethyl acetate (3×150 ml), and the organic layer was washed with saturated aqueous sodium bicarbonate (3×50 ml) and saturated brine (3×50 ml) respectively. After washing, drying over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluent: ethyl acetate: petroleum ether = 1:100) to obtain 0.30 g of compound 9, appearance: yellow solid. Yield 31%.

The preparation of example 4 compound 12

Add 3-(2,6-dichloro-4-(3,3-dichloro-allyloxy)phenoxy)propan-2-ol (0.50 g, 1.44 mmol), tetrahydrofuran (10 mL), stirred at room temperature until dissolved, added 70% sodium hydride (0.10 g, 2.88 mmol), stirred for 2 hours, added 2,3,5,6-tetrachloropyridine (0.30 g, 1.44 mmol, After continuing to react at room temperature for 10 hours, the reaction solution was poured into water (50 ml), extracted with ethyl acetate (3×100 ml), and the organic layer was washed with saturated aqueous sodium bicarbonate (3×50 ml), Wash with saturated brine (3×50 ml), dry over anhydrous magnesium sulfate, and evaporate the solvent under reduced pressure. The residue was purified by column chromatography (eluent: ethyl acetate: petroleum ether = 1:500) to obtain 0.05 g of compound 12, appearance: colorless oil. Yield 7%.

Other compounds of general formula I of the present invention can be prepared by referring to the above-mentioned methods.

Examples of biological activity assays

The mensuration of example 5 insecticidal activity

According to the solubility of the compound to be tested, dissolve the original drug with acetone or dimethyl sulfoxide, and then use 1‰ Tween 80 solution to prepare 50 ml of the test solution with the required concentration, acetone or dimethyl sulfoxide in the total solution The content does not exceed 10%.

(1), the mensuration of activity of killing Plutella xylostella

The cabbage leaves are punched into leaf discs with a diameter of 3 cm, sprayed with an Airbrush, and a certain concentration of the test compound liquid is sprayed on the front and back of each leaf disc, and the spray volume is 0.5 milliliters. Blank control, each treatment repeated 3 times. After drying in the shade, 8 test insects (3 instars) were inoculated into each treatment. After treatment, put them into a room with 24°C, 60%-70% relative humidity and no light for indoor cultivation. After 72 hours, investigate the number of surviving insects and calculate the mortality rate.

Among some tested compounds, the following compounds have better control effects on diamondback moth at a concentration of 100 ppm, and the mortality rate is above 90%: 3a, 9.

According to the above method, the compounds 3a and 9 and the known compound KC (compound 213 in WO9604228A1) were selected to measure the activity of killing Plutella xylostella. The test results are shown in Table 4.

Table 4 Plutella xylostella activity (death rate, %)

(2), the assay of killing beet armyworm activity

The artificial feed film method was adopted. Take a 24-well plate and add 1 ml of prepared artificial feed to each well. After the feed cools down, use a continuous sampler to add the prepared medicinal solution in the order from low dose to high dose according to the test design, and shake it gently to make it A uniform drug film was formed on the surface of the feed, and after natural drying in the shade, neat and healthy test insects were inserted, with one insect per hole, a total of 48 insects per treatment. In addition, clean water treatment was set as the blank control. After treatment, put them into a room with 24°C, 60%-70% relative humidity and no light for indoor cultivation. After 72 hours, investigate the number of surviving insects and calculate the mortality rate.

Among some tested compounds, the following compounds had better control effects on beet armyworm at a concentration of 600ppm, and the mortality rate was 100%: 2, 3, 3a, 7, 8, and 9.

According to the above method, compounds 3a and 9 and the known compound KC (compound 213 in WO9604228A1) were selected to measure the activity against beet armyworm. The test results are shown in Table 5.

Table 5 activity against beet armyworm (death rate, %)

(3), Determination of armyworm activity

Cut the corn leaves into 4-5 cm long sections, spray them with Airbrush, spray a certain concentration of the test compound liquid on the front and back of each leaf, the spray volume is 0.5 ml, and set the water treatment as a blank control, each treatment 3 repetitions. After drying in the shade, 8 test insects (3 instars) were inoculated into each treatment. After treatment, put them into a room with 24°C, 60%-70% relative humidity and no light for indoor cultivation. After 72 hours, investigate the number of surviving insects and calculate the mortality rate.

Among some tested compounds, the following compounds have better control effect on armyworm at a concentration of 600ppm, and the mortality rate is 100%: 1, 1a, 2, 3, 4, 5, 6, 7, 8, 10.

According to the above method, compounds 3a and 9 were selected and the known compound KC (compound 213 in WO9604228A1) was selected to measure the armyworm killing activity. The test results are shown in Table 6.

Table 6 Armycidal activity (application concentration: 10ppm)

compound Insecticidal activity (mortality, %) 3a 70 9 70 KC 0

Claims (6)

1. A dichloropropene compound, as shown in general formula I:

In the formula: Q is selected from _Q1 or _Q2 as shown below:

in: Q is selected from _Q1 or _Q2 ; X is selected from O; R ₁ , R ₅ , R ₈ are selected from H; R ₂ and R ₃ are selected from H, chlorine or trifluoromethyl; _R is selected from H or chlorine; R ₆ and R ₇ are selected from H or trifluoromethyl; n=1 or 2. 2. according to the described compound of claim 1, it is characterized in that, following compound in general formula I: Q is selected from _Q1 ; R ₁ , R ₃ , R ₄ are selected from H; R ₂ is selected from trifluoromethyl; n=2. 3. according to the described compound of claim 1, it is characterized in that, the following compound in general formula I: Q is selected from Q ₂ ; R ₅ , R ₆ , R ₈ are selected from H; R ₇ is selected from trifluoromethyl; n=2. 4. A use of the compound of general formula I according to claim 1 to control agricultural or forestry pests. 5. A pesticidal composition, containing the general formula I compound as claimed in claim 1 as an active component and an agricultural or forestry acceptable carrier, the weight percentage of the active component in the composition is 1-99 %. 6. A method for controlling agricultural or forestry pests, characterized in that: the composition according to claim 5 is applied to the pests to be controlled or the growth medium thereof at an effective dose of 10 grams to 1000 grams per hectare.