CN102388026B - Dichloropropene compounds and uses thereof - Google Patents

Dichloropropene compounds and uses thereof Download PDF

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CN102388026B
CN102388026B CN201080016114.5A CN201080016114A CN102388026B CN 102388026 B CN102388026 B CN 102388026B CN 201080016114 A CN201080016114 A CN 201080016114A CN 102388026 B CN102388026 B CN 102388026B
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ethyl acetate
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CN102388026A (en
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李斌
关爱莹
王军锋
秦玉坤
张弘
于海波
梁松军
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles

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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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Abstract

A dichloropropene compound represented by formula (I) and the uses thereof, wherein R1 or R2 is H, halo, C1-C3 alkyl or C1-C3 haloalkyl, with the proviso that R1 or R2 is H, and wherein n=0, 1, 2 or 3. The compound represented by formula (I) has insecticidal activity and is useful for the prevention and control of various insect pests.

Description

A kind of dichloropropylene compound and application thereof
Technical field
The invention belongs to field of pesticides, be specifically related to a kind of dichloropropylene compound and application thereof.
Background technology
Due to sterilant in use for some time, insect can produce resistance to it, therefore, need constantly invention novel with compound and composition improved tool insecticidal activity.Meanwhile, along with people are to growing needs and pay attention to day by days to environment protection such as agricultural and animal products, also need lower, the environment amenable new sterilant of use cost always.
In Chinese patent application CN1169147A, disclose the dichloropropylene compound and the insecticidal activity thereof that partly contain benzheterocycle group, for example, disclose the dichloropropylene compound KC that contains benzothiazole and contain benzoglyoxaline five-membered ring group 1, KC 2for preventing and treating the activity data of prodenia litura.
Figure GPA0000126723600000031
This patent emphasis discloses and has contained pyridyloxy, compound that insecticidal activity is higher, as compound K C 3(structure is as follows) can prevent and treat small cabbage moth under the concentration of 50ppm.Oneself is developed to commercialization sterilant this compound, general pyridalyl by name:
Figure GPA0000126723600000032
In the prior art, preparation and the insecticidal activity thereof containing the dichloropropylene compound of benzoxazoles oxygen base has no open.
Summary of the invention
The object of the present invention is to provide a kind of novel structure, the better dichloropropylene compound of insecticidal activity, it can be applicable to the control of insect pest in agricultural, forestry or health.
Technical scheme of the present invention is as follows:
The invention provides a kind of dichloropropylene compound, as shown in general formula I:
Figure GPA0000126723600000033
In formula:
R 1or R 2be selected from H, halogen, C 1-C 3alkyl or C 1-C 3haloalkyl, but R 1or R 2in have one for H;
N=0,1,2 or 3.
In the present invention, more preferably compound is, in general formula I:
R 1or R 2be selected from H, Cl, methyl, trifluoromethyl or seven fluorine sec.-propyls, but R 1or R 2in have one for H;
N=0,1 or 2.
In the present invention, further preferred compound is, in general formula I:
R 1be selected from trifluoromethyl;
R 2be selected from H;
N=1 or 2.
In the definition of the compound of Formula I providing, collect term General Definition used as follows above:
Alkyl refers to the group of straight or branched form, for example methyl, ethyl, n-propyl, sec.-propyl.Haloalkyl refers to straight or branched form, the group that for example methyl, ethyl, n-propyl, sec.-propyl are replaced by one or more halogen atoms, for example trifluoromethyl or seven fluorine sec.-propyls.Halogen refers to fluorine, chlorine, bromine, iodine.
Compound of Formula I of the present invention can be prepared by the following method, and except separately having and indicating, in reaction formula, each group definition is the same.
Figure GPA0000126723600000041
General formula I I compound with compound of formula III in suitable solvent, suitable alkali exist under, temperature for-10 ℃ to boiling spread, react and within 0.5-48 hour, make target compound I.
Suitable solvent is selected from methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, DMF or dimethyl sulfoxide (DMSO) etc.
Suitable alkali can be selected from basic metal if the hydrogen compound of lithium, sodium or potassium is as sodium hydride, or basic metal is if the oxyhydroxide of lithium, sodium or potassium is as sodium hydroxide, can also be selected from alkali-metal carbonate as sodium carbonate, also can be selected from organic bases as triethylamine, sodium tert-butoxide etc.
Preparing with reference to the method for introducing in following document of general formula I I compound: J.Org.Chem.1996,61,3289-3297; Bioorganic & Medicinal Chemistry Letters17 (2007) 4689-4693; WO2009023844; Journal of Medicinal Chemistry, 2008,51 (5), 1482-1486.
The preparation of compound of formula III is referring to the method for describing in CN1860874A (embodiment 1,2,3).
Table 1 has been listed structure and the physical properties of part compound of Formula I.
Figure GPA0000126723600000051
Table 1
Compound R 1 R 2 n Outward appearance (fusing point (℃)
1 H Cl 0 Yellow solid (104-106)
2 H CF 3 0 Yellow oil
3 CF 3 H 0 Yellow solid (66-69)
4 H Cl 1 White solid (58-60)
5 Cl H 1 Yellow oil
6 CH 3 H 1 Yellow oil
7 H CF 3 1 Yellow oil
8 CF 3 H 1 Yellow oil
9 H Cl 2 White solid (63-65)
10 H CF 3 2 Yellow oil
11 CF 3 H 2 Yellow oil
12 H i-C 3F 7 1 Yellow oil
Part of compounds 1h NMR (300MHz, CDCl 3) data are as follows:
Compound 1:4.39-4.42 (m, 2H), 4.59 (d, 2H), 7.833 (d, 1H), 4.89-4.92 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.22-7.27 (m, 1H), 7.8-7.41 (m, 2H).
Compound 2:4.40-4.43 (m, 2H), 4.59 (d, 2H), 7.833 (d, 1H), 4.93-4.96 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.56 (s, 2H), 7.65 (s, 1H).
Compound 3:4.40-4.43 (m, 2H), 4.58 (d, 2H), 7.833 (d, 1H), 4.92-4.95 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.47-7.48 (m, 2H), 7.75 (s, 1H).
Compound 4:2.34-2.42 (m, 2H), 4.14 (t, 2H), 4.58 (d, 2H), 4.87 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.21-7.26 (m, 2H), 7.38-7.41 (m, 1H).
Compound 5:2.36-2.40 (m, 2H), 4.14 (t, 2H), 4.58 (d, 2H), 4.88 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.15 (dd, 1H), 7.25-7.28 (m, 1H), 7.47 (d, 1H).
Compound 6:2.35-2.39 (m, 2H), 2.42 (s, 3H), 4.14 (t, 2H), 4.56 (d, 2H), 4.85 (t, 2H), 6.10 (t, 1H), 6.82 (s, 2H), 7.25 (d, 2H), 7.15 (dd, 1H), 7.28-7.29 (m, 2H).
Compound 7:2.37-2.42 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.92 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.55-7.56 (m, 2H), 7.62 (d, 1H).
Compound 8:2.35-2.41 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.91 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.42-7.46 (m, 2H), 7.76 (s, 1H).
Compound 9:1.99-2.06 (m, 2H), 2.17-2.21 (m, 2H), 4.03 (t, 2H), 4.58 (d, 2H), 4.67 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 6.85-7.26 (m, 1H), 7.37-7.40 (m, 1H).
Compound 10:2.00-2.05 (m, 2H), 2.19-2.23 (m, 2H), 4.03 (t, 2H), 4.58 (d, 2H), 4.71 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.54 (d, 2H), 7.62 (s, 1H).
Compound 11:2.02-2.05 (m, 2H), 2.18-2.21 (m, 2H), 4.04 (t, 2H), 4.58 (d, 2H), 4.71 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.44-7.46 (m, 2H), 7.74-7.75 (m, 1H).
Compound 12:2.38-2.42 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.59 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.50-7.61 (m, 2H), 7.63 (d, 1H).
Through a large amount of research and test, the present invention successfully prepares containing the dichloropropylene compound of benzoxazoles oxygen groups and confirms that this compounds has excellent insecticidal activity.Further, in further investigation process, contriver have been surprisingly found that: in the benzoxazoles ring of compound of Formula I, introduce substituting group more favourable than introducing substituting group on 6-position on 5-position.With the Compound Phase ratio of greater activity in prior art, under identical preventive effect, the using dosage of the compounds of this invention is lower, general low more than one times, has beyond thought high insecticidal activity.Therefore, the present invention also comprises that compound of Formula I can be used for controlling the purposes of insect pest.
The present invention also comprises usings the insect-killing composition of compound of Formula I as active ingredient.In this insect-killing composition, the weight percentage of active ingredient is between 1-99%.In this insect-killing composition, also comprise acceptable carrier in agricultural, forestry, health.
Composition of the present invention can preparation form use.Compound of Formula I is easier to as solubilization of active ingredient or when being scattered in carrier or being mixed with preparation to using as sterilant disperse.For example: these chemicals can be made into wettable powder or missible oil.In these compositions, at least add a kind of liquid or solid carrier, and can add suitable tensio-active agent when needed.
Technical scheme of the present invention also comprises the method for pest control: insect-killing composition of the present invention is imposed on described insect or its growth medium.Conventionally the comparatively suitable significant quantity of selecting is 10 grams to 1000 grams of per hectares, and preferably significant quantity is 20 grams to 500 grams of per hectares.
For some application, such as can add one or more other sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator or fertilizer etc. in insect-killing composition of the present invention in agricultural, can produce additional advantage and effect thus.
Should be clear and definite, in claim limited range of the present invention, can carry out various conversion and change.
Embodiment
Following synthetic example, the raw test-results of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthetic example
The preparation of example 1 compound 7
(1) the chloro-6-trifluoromethyl of 2-benzo oxazole is synthetic
(a) 2-nitro-5-trifloro methyl phenol is synthetic
Figure GPA0000126723600000071
In reaction flask, add (20.00 grams of m-trifluoromethyl phenols, 123 mmoles, commercially available), then drip wherein 60% the salpeter solution (formulated with 11.60 grams of nitrosonitric acids and 7.40 grams of water) preparing in advance, finish, reaction mixture was in room temperature reaction 24 hours.Afterwards, reaction solution is washed till neutrality with saturated sodium bicarbonate liquid, by ethyl acetate (3 * 800 milliliters), extract, saturated aqueous common salt for organic layer (3 * 400 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:100), obtain 5.00 grams of yellow oils, yield 20% of purifying.
1H?NMR(300MHz，CDCl 3)：7.24(dd，3H)，7.46(s，1H)，8.24(d，1H)，10.60(d，1H)。
(b) 2-amino-5-trifloro methyl phenol is synthetic
In reaction flask, add 2-nitro-5-trifloro methyl phenol (5.00 grams, 24.2 mmoles), Glacial acetic acid (60 milliliters), reaction solution is slowly warming up to 50 ℃, then add (5.41 grams of iron powders in batches, 96.6 mmoles), finish, reaction solution is warming up to 70 ℃ of reactions 2 hours.Afterwards, in reaction solution impouring water (200 milliliters), by ethyl acetate (3 * 400 milliliters), extract, saturated aqueous common salt for organic layer (3 * 200 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:2), obtain 2.69 grams of yellow solids, yield 63% of purifying.
1H?NMR(300MHz，CDCl 3)：6.74(d，1H)，6.94(s，1H)，7.05(d，1H)。
(c) 2-sulfydryl-6-trifluoromethyl-benzoxazoles is synthetic
Figure GPA0000126723600000073
In reaction flask, add successively potassium hydroxide (25.70 grams, 459 mmoles), ethanol (250 milliliters), water (100 milliliters), stir in downhill reaction liquid and drip CS 2(19.16 grams, 252 mmoles), finish, and continue to stir 15 minutes, then add 2-amino-5-trifloro methyl phenol (40.50 grams, 229 mmoles) in reaction solution, and reaction solution is slowly warming up to backflow.After 4 hours, reaction solution uses dilute hydrochloric acid adjust pH to approximately 4, in reaction solution impouring water (200 milliliters), by ethyl acetate (3 * 800 milliliters), extract, saturated aqueous common salt for organic layer (3 * 200 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:5) of purifying, obtain 24.09 grams of yellow solids, yield 48%.Fusing point: 194～196 ℃.
1H?NMR(300MHz，CDCl 3)：7.30(d，1H)，7.58-7.62(m，2H)，10.84(s，1H)。
(d) the chloro-6-trifluoromethyl of 2-benzo oxazole is synthetic
Figure GPA0000126723600000081
In reaction flask, add successively 2-sulfydryl-6-trifluoromethyl benzo oxazole (1.20 grams, 5.5 mmoles), 15 milliliters of sulfur oxychlorides, 2 of DMFs, be slowly warming up to 70 ℃.React after 2 hours, remove sulfur oxychloride under reduced pressure, reaction solution adds water (50 milliliters), with the extraction of ethyl acetate (3 * 150) milliliter, saturated sodium bicarbonate solution for organic layer (3 * 50 milliliters), saturated aqueous common salt (3 * 50 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:100), obtain 1.01 grams of yellow solids, yield 83% of purifying.Fusing point: 245～247 ℃.
1H?NMR(300MHz，CDCl 3)：7.65-7.68(m，2H)，7.80(d，1H)。
(2) compound 7 is synthetic
In reaction flask, add 3-(2, the chloro-4-of 6-bis-(the chloro-allyloxy of 3,3-bis-) phenoxy group) third-1-alcohol (0.35 gram, 1.0 mmoles, in synthetic method referenced patent CN1860874A, embodiment 1,2,3), tetrahydrofuran (THF) (5 milliliters), under room temperature, be stirred to dissolving, add 60% sodium hydride (0.08 gram, 2 mmoles), stir after 2 hours, add the chloro-6-trifluoromethyl of 2-benzo oxazole (0.22 gram, 1.0 mmoles), under room temperature, continue reaction 5 hours.Afterwards, by in reaction solution impouring water (50 milliliters), with ethyl acetate (3 * 150 milliliters) extraction, organic layer is used respectively saturated sodium bicarbonate aqueous solution (3 * 50 milliliters), saturated aqueous common salt (3 * 50 milliliters) washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:20) obtain 0.27 gram of colorless oil, yield 52% of purifying.
The preparation of example 2 compounds 8
(1) the chloro-5-trifluoromethyl of 2-benzo oxazole is synthetic
(a) 2-nitro-4-trifloro methyl phenol is synthetic
Figure GPA0000126723600000083
In reaction flask, add (29.60 grams of the trimethyl carbinols, 400 mmoles), dimethyl sulfoxide (DMSO) (250 milliliters), add wherein again (30.24 grams, potassium hydroxide, 540 mmoles), reaction mixture is heated to 100 ℃, wherein drip again afterwards the chloro-2-nitro-4-of 1-phenylfluoroform (22.50 grams, 100 mmoles, commercially available).Finish, continue insulation reaction after 2 hours.Reaction solution is chilled to after room temperature, in impouring water (500 milliliters), with dilute hydrochloric acid adjust pH to approximately 4, by ethyl acetate (3 * 1000 milliliters), extract, saturated aqueous common salt for organic layer (3 * 500 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:5) of purifying, obtain 11.20 grams of yellow oils, yield 54%.
1H?NMR(300MHz，CDCl 3)：7.31(d，1H)，7.82(dd，1H)，8.42(d，1H)，10.80(s，1H)。
(b) 2-amino-4-trifloro methyl phenol is synthetic
Figure GPA0000126723600000091
In reaction flask, add 2-nitro-4-trifloro methyl phenol (4.60 grams, 22.2 mmoles), acetic acid (100 milliliters), reaction solution is slowly warming up to 50 ℃, then add (4.98 grams of iron powders in batches, 88.9 mmoles), finish, reaction solution is warming up to 70 ℃ of reactions 2 hours.Afterwards, in reaction solution impouring water (200 milliliters), by ethyl acetate (3 * 400 milliliters), extract, saturated aqueous common salt for organic layer (3 * 200 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:5), obtain 3.19 grams of yellow solids, yield 82% of purifying.Fusing point: 139～141 ℃.
(c) 2-sulfydryl-5-trifluoromethyl-benzoxazoles is synthetic
Figure GPA0000126723600000092
In reaction flask, add successively potassium hydroxide (25.62 grams, 457 mmoles), ethanol (250 milliliters), water (100 milliliters), stir in downhill reaction liquid and drip CS 2(19.13 grams, 251 mmoles), finish, and continue to stir 15 minutes, then add 2-amino-4-trifloro methyl phenol (40.50 grams, 229 mmoles) in reaction solution, and reaction solution is slowly warming up to backflow.After 4 hours, reaction solution uses dilute hydrochloric acid adjust pH to approximately 4.In reaction solution impouring water (500 milliliters), by ethyl acetate (3 * 1000 milliliters), extract, concentrated after saturated aqueous common salt for organic layer (3 * 500 milliliters) washing anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:5) of purifying, obtain 18.75 grams of yellow solids, yield 30%.Fusing point: 181～183 ℃.
1H?NMR(300MHz，CDCl 3)：7.45-7.50(m，2H)，7.57(d，1H)，11.21(s，1H)。
(d) the chloro-5-trifluoromethyl-benzoxazoles of 2-is synthetic
In reaction flask, add successively 2 of 2-sulfydryl-5-trifluoromethyl benzo oxazoles (2.70 grams, 12.3 mmoles), sulfur oxychloride (20 milliliters), DMF, reaction solution is slowly warming up to 70 ℃.After 2 hours, remove sulfur oxychloride under reduced pressure, reaction solution adds water (100 milliliters), with ethyl acetate (3 * 300 milliliters) extraction, saturated sodium bicarbonate solution for organic layer (3 * 100 milliliters), saturated aqueous common salt (3 * 100 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:100), obtain 1.40 grams of yellow solids, yield 51% of purifying.Fusing point: 176～178 ℃.
1H?NMR(300MHz，CDCl 3)：7.61-7.66(m，2H)，7.97(s，1H)。
(2) compound 8 is synthetic
In reaction flask, add 3-(2, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group) third-1-alcohol (0.35 gram, 1.0 mmoles), tetrahydrofuran (THF) (5 milliliters), be stirred to dissolving under room temperature, add (0.08 gram of 60% sodium hydride, 2 mmoles), stir after 2 hours, add (0.22 gram of the chloro-5-trifluoromethyl of 2-benzo oxazole, 1.0 mmoles), under room temperature, continue reaction 5 hours.Afterwards, by in reaction solution impouring water (50 milliliters), with ethyl acetate (3 * 150 milliliters) extraction, organic layer is used respectively saturated sodium bicarbonate aqueous solution (3 * 50 milliliters), saturated aqueous common salt (3 * 50 milliliters) washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:20) obtain 0.18 gram of colorless oil, yield 35% of purifying.
The preparation of example 3 compounds 11
Figure GPA0000126723600000101
In reaction flask, add 4-(2, the chloro-4-of 6-bis-(the chloro-allyloxy of 3,3-bis-) phenoxy group) fourth-1-alcohol (0.36 gram, 1.0 mmoles, in synthetic method referenced patent CN1860874A, embodiment 1,2,3), tetrahydrofuran (THF) (5 milliliters), under room temperature, be stirred to dissolving, add 60% sodium hydride (0.08 gram, 2 mmoles), stir after 2 hours, add the chloro-5-trifluoromethyl of 2-benzo oxazole (0.22 gram, 1.0 mmoles), under room temperature, continue reaction 5 hours.Afterwards, by in reaction solution impouring water (50 milliliters), with ethyl acetate (3 * 150 milliliters) extraction, organic layer is used respectively saturated sodium bicarbonate aqueous solution (3 * 50 milliliters), saturated aqueous common salt (3 * 50 milliliters) washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:20) obtain 0.11 gram of yellow oil, yield 20% of purifying.
The preparation of example 4 compounds 12
(1) the chloro-6-sevoflurane isopropyl of 2-oxazole is synthetic
(a) 2-amino-5-sevoflurane isopropyl phenol is synthetic
Figure GPA0000126723600000102
In reaction flask, add successively each 200 milliliters of 2-hydroxyl phenol (10.00 grams, 91 mmoles, commercially available), water and ether, seven fluorine isopropyl iodides (35.52 grams, 120 mmoles, commercially available), Na 2s 2o 4(20.88 grams, 120 mmoles), NaHCO 3(10.08 grams, 120 mmoles), (n-Bu) 4nHSO 4(2.70 grams, 10.0 mmoles).Reaction mixture room temperature reaction spends the night.By in reaction solution impouring water (300 milliliters), by ethyl acetate (3 * 600 milliliters), extract, 1mol/L hydrochloric acid (3 * 300 milliliters), 5% sodium carbonate solution (3 * 300 milliliters), saturated aqueous common salt (3 * 300 milliliters) washing for organic layer, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:10) of purifying, obtain 10.0 grams of yellow solids, yield 40%.Fusing point: 142～144 ℃.
1H?NMR(300MHz，CDCl 3)：3.84(d，3H)，7.39(d，1H)，7.57(d，1H)，7.97(d，1H)。
(b) 6-sevoflurane isopropyl oxazole-2-ketone is synthetic
Figure GPA0000126723600000111
In reaction flask, add successively (5.00 grams, 2-amino-5-sevoflurane isopropyl phenol, 18.0 mmoles), methylene dichloride (50 milliliters), under stirring, add (2.67 grams of solid phosgenes, 9.0 mmole, commercially available), then in reaction mixture, drip triethylamine (3.65 grams, 36.1 mmoles).Room temperature reaction spends the night.By in reaction solution impouring water (200 milliliters), with methylene dichloride (3 * 400 milliliters), extract, saturated sodium bicarbonate solution for organic layer (3 * 200 milliliters), saturated nacl aqueous solution (3 * 200 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:10), obtain 4.00 grams of yellow solids, yield 74% of purifying.Fusing point: 162～164 ℃.
1H?NMR(300MHz，CDCl 3)：7.22(d，1H)，7.47(d，2H)，9.06(s，1H)。
(c) 2-sulfydryl 6-sevoflurane isopropyl oxazole is synthetic
Figure GPA0000126723600000112
In reaction flask, add successively 6-sevoflurane isopropyl oxazole-2-ketone (4.00 grams, 13.2 mmoles), toluene (100 milliliters), be stirred to dissolving, then add lawesson reagent wherein (8.00 grams, 19.8 mmoles, commercially available).Reaction mixture is warming up to backflow, react after 15 hours, reaction solution is chilled to room temperature, in impouring water (200 milliliters), with toluene (3 * 400 milliliters) extraction, saturated sodium bicarbonate for organic layer (3 * 200 milliliters) solution, saturated nacl aqueous solution (3 * 200 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:15) of purifying, obtain 1.60 grams of white solids, yield 38%.Fusing point: 168～170 ℃.
1H?NMR(300MHz，CDCl 3)：7.35(d，1H)，7.57(d，1H)，7.63(s，1H)，11.10(s，1H)。
(d) the chloro-6-sevoflurane isopropyl of 2-oxazole is synthetic
Figure GPA0000126723600000113
In reaction flask, add successively 2 of 6-sevoflurane isopropyl oxazole-2-thioketones (1.00 grams, 3.1 mmoles), sulfur oxychloride (15 milliliters), DMFs, reaction solution is slowly warming up to 70 ℃.After 2 hours, remove sulfur oxychloride under reduced pressure, reaction solution adds water (100 milliliters), with ethyl acetate (3 * 100 milliliters) extraction, saturated sodium bicarbonate solution for organic layer (3 * 100 milliliters), saturated aqueous common salt (3 * 100 milliliters) washing, concentrated after anhydrous magnesium sulfate drying, resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:100), obtain 0.40 gram of yellow oil, yield 42% of purifying.
1H?NMR(300MHz，CDCl 3)：7.66(d，1H)，7.83(t，2H)。
(2) compound 12 is synthetic
In reaction flask, add (0.43 gram of 3-(the chloro-4-of 2,6-bis-(the chloro-allyloxy of 3,3-bis-) phenoxy group) third-1-alcohol, 1.1 mmoles), tetrahydrofuran (THF) (10 milliliters), under room temperature, be stirred to dissolving, add 60% sodium hydride (0.09 gram, 2 mmoles).Stir after 2 hours, add the chloro-6-sevoflurane isopropyl of 2-oxazole (0.36 gram, 1.1 mmoles), under room temperature, continue reaction 5 hours.Afterwards, by in reaction solution impouring water (50 milliliters), with ethyl acetate (3 * 150 milliliters) extraction, organic layer is used respectively saturated sodium bicarbonate aqueous solution (3 * 50 milliliters), saturated aqueous common salt (3 * 50 milliliters) washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by the column chromatography (leacheate: ethyl acetate: sherwood oil=1:100) obtain 0.38 gram of colorless oil of purifying.Yield 48%.
Other compound of Formula I of the present invention can be synthetic with reference to aforesaid method.
Biological activity determination example
The mensuration of example 5 insecticidal activities
According to the solvability of testing compound, with acetone or methyl-sulphoxide, dissolve former medicine, then with 1 ‰ tween 80 solution preparation, become 50 milliliters of the liquid to be measured of desired concn, acetone or the methyl-sulphoxide content in total solution is no more than 10%.
Example 5.1 kills the mensuration of small cabbage moth activity
Cabbage leaves is broken into the leaf dish of 1 centimetre of diameter with punch tool, with Airbrush spraying, process, certain density test compounds is sprayed at every leaf dish pros and cons, and spouting liquid is 0.5 milliliter, 8 examination worms (3 age) of every processing access after drying in the shade, every processing repeats for 3 times.After processing, put into 24 ℃, the indoor cultivation of relative humidity 60%～70%, unglazed photograph, 72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
Part is known compound K C for the compound trying and oneself 1, KC 2and KC 3(pyridalyl) (be respectively compound No. 40, No. 39, No. 36) in CN1169147A carried out killing the replicate(determination) of small cabbage moth activity.Test-results is in Table 2.
Table 2: kill small cabbage moth activity (mortality ratio, %)
Figure GPA0000126723600000121
Note *: "--" representative is not surveyed.
The mensuration of example 5.2 killing beet noctuids activity
Cabbage leaves is broken into the leaf dish of 1 centimetre of diameter with punch tool, with Airbrush spraying, process, certain density test compounds is sprayed at every leaf dish pros and cons, and spouting liquid is 0.5 milliliter, 8 examination worms (3 age) of every processing access after drying in the shade, every processing repeats for 3 times.After processing, put into 24 ℃, the indoor cultivation of relative humidity 60%～70%, unglazed photograph, 96 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
Part is known compound K C for compound and oneself of greater activity of examination 3(pyridalyl) carried out the replicate(determination) of killing beet noctuids activity.Test-results is in Table 3.
Table 3: killing beet noctuids activity (mortality ratio, %)
Figure GPA0000126723600000131
Example 5.3 kills the mensuration of tea geometrid activity
Adopt leaf dipping method, the fresh tea tip is flooded and naturally dried afterwards for 10 seconds in liquid, put into assay flask, every bottle of 5 tea tips.In 20 access assay flasks of picking tea geometrid 2 instar larvae of the same size, every processing repeats for 4 times.In illumination box, (24 ± 0.5 ℃, photoperiod L:D=12:12) are cultivated, and 120 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.The compounds of this invention 8,11 and oneself know compound K C 3(pyridalyl) carry out the result of parallel comparison as follows:
Table 4: kill tea geometrid activity (mortality ratio, %)
Figure GPA0000126723600000132

Claims (4)

1. a dichloropropylene compound, as shown in general formula I:
Figure FSB0000115029580000011
In formula:
R 1be selected from trifluoromethyl;
R 2be selected from H;
n＝2。
2. a purposes of controlling tea geometrid according to compound of Formula I claimed in claim 1.
3. kill a tea geometrid composition, containing compound shown in general formula I as claimed in claim 1 is acceptable carrier in active ingredient and agricultural, forestry or health, and in composition, the weight percentage of active ingredient is 1-99%.
4. a method of controlling tea geometrid, is characterized in that: the effective dose by composition claimed in claim 3 with 10 grams to 1000 grams of per hectares imposes on the tea geometrid of needs control or the medium of its growth.
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CN1187809A (en) * 1995-04-18 1998-07-15 住友化学工业株式会社 Dihalopropene compounds, insecticides containing them as active ingredients, and intermediates for their production
CN1860874A (en) * 2006-05-16 2006-11-15 王正权 Dichloropropylene type pesticide

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CN1187809A (en) * 1995-04-18 1998-07-15 住友化学工业株式会社 Dihalopropene compounds, insecticides containing them as active ingredients, and intermediates for their production
CN1860874A (en) * 2006-05-16 2006-11-15 王正权 Dichloropropylene type pesticide

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