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CN102952087B - Quinazoline ring contained ether compound and its use - Google Patents

Quinazoline ring contained ether compound and its use Download PDF

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CN102952087B
CN102952087B CN201110240653.3A CN201110240653A CN102952087B CN 102952087 B CN102952087 B CN 102952087B CN 201110240653 A CN201110240653 A CN 201110240653A CN 102952087 B CN102952087 B CN 102952087B
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gram
chloro
hydrogen
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CN102952087A (en
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李斌
吕亮
梁博
梁松军
常秀辉
谷旭林
关爱莹
朱党强
宋玉泉
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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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Abstract

The invention discloses a quinazoline ring contained ether compound. The structure of the ether compound is represented by general formula I shown in the specification, wherein R1 and R2 in the general formula I are respectively selected from hydrogen, halogens or Q, at least one of the R1 and the R2 is Q, and Q is defined in the specification; and R3, R4, R5 and R6 in the general formula I can be same or different and are respectively selected from hydrogen, halogens, a cyan group, a nitro group, C1-C3 alkyl groups, C1-C3 halogenated alkyl groups, C1-C3 alkyloxy groups or C1-C3 halogenated alkyloxy groups. The compound of the general formula I has an excellent insecticidal activity and can be used for controlling agricultural or forestal insect pests.

Description

A kind of ether compound containing quinazoline ring and uses thereof
Technical field
The invention belongs to field of pesticides, relate to a kind of ether compound containing quinazoline ring and uses thereof.
Background technology
Due to sterilant in use for some time, insect can produce resistance to it, therefore, need constantly invention novel or the compound of tool insecticidal activity that improves and composition.
Patent EP0326329A2 reports the quinazoline cyclic cpds shown in following general formula certain fungicidal activity, and wherein No. 29 (code name KC) compound is greater than 90% to the preventive effect of rice blast under 100ppm dosage.
In prior art, the ether compound containing quinazoline ring that the present invention relates to and insecticidal activity have no open.
Summary of the invention
The object of the present invention is to provide a kind of ether compound containing quinazoline ring of novel structure, it can be applicable to the control of insect pest in agricultural or forestry.
Technical scheme of the present invention is as follows:
An ether compound containing quinazoline ring, as shown in general formula I:
In formula:
R 1, R 2be selected from hydrogen, halogen or Q, but R 1or R 2in have at least a group to be Q; Described Q is selected from Q as follows 1, Q 2, Q 3, Q 4or Q 5:
R 3, R 4, R 5, R 6may be the same or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 3alkyl, C 1-C 3haloalkyl, C 1-C 3alkoxyl group or C 1-C 3halogenated alkoxy.
In the present invention, preferred compound is, R in general formula I 1or R 2be selected from Q, and:
Work as R 1when being selected from Q, R 2, R 3, R 4, R 5, R 6be selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, methyl or trifluoromethyl respectively, but wherein at least one is hydrogen; Or
Work as R 2when being selected from Q, R 1, R 3, R 4, R 5, R 6be selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, methyl or trifluoromethyl respectively, but wherein at least one is hydrogen.
In the present invention, preferred compound is, in general formula I further:
Work as R 1when being selected from Q, R 2, R 3, R 4, R 5, R 6be selected from hydrogen, chlorine or trifluoromethyl respectively, but wherein at least one is hydrogen;
Work as R 2when being selected from Q, R 1, R 3, R 4, R 5, R 6be selected from hydrogen, chlorine or trifluoromethyl respectively, but wherein at least one is hydrogen.
In the definition of the compound of Formula I provided above, collect term used and be generally defined as follows:
Alkyl refers to the group of straight or branched form, such as methyl, ethyl, n-propyl, sec.-propyl etc.Haloalkyl refers to the group that alkyl is optionally substituted with one or more halogen atoms, such as trifluoromethyl.Alkoxyl group refers to that alkyl end is connected with the group of Sauerstoffatom, such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy etc.Halogenated alkoxy refers to that alkyl is optionally substituted with one or more halogen atoms, and end is connected with the group of Sauerstoffatom, such as trifluoromethoxy.Halogen refers to fluorine, chlorine, bromine, iodine.
Compound of Formula I of the present invention can be prepared by the following method:
(X is selected from halogen, R 2little is halogen) (R 1for Q) (X is selected from halogen) (R 2for Q)
In formula, each group unless otherwise indicated defines ditto.
(X is selected from halogen to general formula I I, R 2for halogen) or general formula III (X is selected from halogen) with general formula Q-H compound in suitable solvent, under suitable alkali exists, temperature is react 0.5-48 hour obtained target compound I (R in the target compound I obtained by general formula I I under-10 DEG C to boiling point 1for Q, R in the target compound I obtained by general formula III 2for Q, other each group definition are the same).
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 comprises the hydrogen compound of basic metal as lithium, sodium or potassium as sodium hydride, basic metal if the oxyhydroxide of lithium, sodium or potassium is as sodium hydroxide, can also be alkali-metal carbonate as sodium carbonate, also can be that organic bases is as triethylamine, sodium tert-butoxide etc.
The preparation of Compounds of formula II is carried out with reference to the operation of following documents: ChemMedChem, 2009,4 (7): 1069-1074
The preparation of compound of formula III is carried out with reference to the operation of following documents: Chinese Journal of Chemistry, 2009,27 (2): 379-383.
The preparation of general formula Q-H compound is carried out with reference to the operation of following documents: chemistry world, 2006,47 (6): 366-370; CN1432555A; CN1860874A.
Table 1 lists the structure of partial Formula I and physical properties so that the present invention to be described, but does not limit the present invention.
Table 1
Part of compounds 1h NMR (300MHz, CDCl 3), δ (ppm) data are as follows:
Compound 1:2.39-2.43 (m, 2H), 4.23 (t, 2H), 4.58 (d, 2H), 4.80 (t, 2H), 6.11 (t, 1H), 6.82 (s, 2H), 7.44-7.49 (m, 1H), 7.82-7.88 (m, 3H), 9.23 (s, 1H).
Compound 2:2.35-2.43 (m, 2H), 4.21 (t, 2H), 4.56 (d, 2H), 4.78 (t, 2H), 6.10 (t, 1H), 6.80 (s, 2H), 7.71-7.80 (m, 3H), 9.15 (s, 1H).
Compound 3:2.37-2.41 (m, 2H), 4.21 (t, 2H), 4.56 (d, 2H), 4.78 (t, 2H), 6.10 (t, 1H), 6.82 (s, 2H), 7.41 (m, 1H), 7.77-7.86 (m, 2H), 9.19 (s, 1H).
Compound 4:2.42-2.46 (t, 2H), 4.21-4.25 (d, 2H), 4.57-4.60 (t, 2H), 4.86-4.90 (t, 2H), 6.09-6.13 (t, 1H), 6.83-6.85 (d, 2H), 7.37-7.42 (t, 1H), 7.78-7.80 (d, 1H), 7.91-7.94 (d, 1H), 9.25 (s, 1H).
Compound 5:2.39-2.43 (m, 2H), 4.20-4.22 (d, 2H), 4.56-4.58 (d, 2H), 4.82-4.85 (t, 2H), 6.11 (s, 1H), 6.82 (s, 2H), 7.95-7.98 (d, 2H), 8.17 (s, 1H), 9.33 (s, 1H).
Compound 6:2.40-2.44 (m, 2H), 4.22 (t, 2H), 4.59 (d, 2H), 4.80 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.65 (dd, 1H), 8.00 (d, 1H), 8.14 (s, 1H), 9.33 (s, 1H).
Compound 7:1.51 (d, 3H), 2.36 (m, 2H), 4.13 (d, 2H), 4.51 (d, 2H), 5.93 (m, 1H), 6.02 (t, 1H), 6.76 (s, 2H), 7.44 (t, 1H), 7.82 (t, 2H), 8.1 (d, 1H), 9.2 (s, 1H).
Compound 8:4.50 (d, 2H), 4.78 (d, 2H), 5.13 (d, 2H), 6.01-6.10 (m, 3H), 6.82 (s, 2H), 7.49 (t, 1H), 7.82 (t, 3H), 9.22 (s, 1H).
Compound 9:4.61 (d, 2H), 4.73 (d, 2H), 5.15 (d, 2H), 5.32 (s, 1H), 6.01-6.10 (m, 3H), 6.85 (s, 1H), 7.93 (m, 2H), 8.16 (s, 1H), 9.35 (s, 1H).
Compound 10:4.51 (d, 4H), 5.09 (d, 2H), 6.13 (t, 1H), 6.25 (m, 2H), 6.83 (s, 2H), 7.46 (m, 1H), 7.84 (d, 3H), 9.27 (s, 1H).
Compound 11:4.50 (d, 2H), 4.73 (s, 2H), 5.27 (s, 2H), 6.15 (t, 1H), 6.77 (s, 2H), 7.41-7.50 (m, 1H), 7.82 (t, 3H), 9.32 (s, 1H).
Compound 12:4.52 (d, 2H), 4.77 (d, 2H), 5.23 (d, 2H), 6.15 (t, 1H), 6.70 (s, 2H), 7.91-8.5 (m, 2H), 8.22 (s, 1H), 9.32 (s, 1H).
Compound 13:41-2.48 (m, 2H), 4.21 (t, 2H), 4.57 (d, 2H), 4.89 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.55-7.60 (m, 1H), 7.82-7.87 (m, 1H), 7.95 (d, 1H), 8.19 (dd, 1H), 8.82 (s, 1H).
Compound 14:37-2.41 (m, 2H), 4.21 (t, 2H), 4.56 (d, 2H), 4.78 (t, 2H), 6.10 (t, 1H), 6.82 (s, 2H), 7.41 (m, 1H), 7.77-7.86 (m, 2H), 9.19 (s, 1H).
Compound 15:37-2.46 (m, 2H), 4.19 (t, 2H), 4.58 (d, 2H), 4.88 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.51 (dd, 1H), 7.93 (d, 1H), 8.12 (d, 1H), 8.81 (s, 1H).
Compound 16:2.42-2.46 (m, 2H), 4.21 (t, 2H), 4.58 (d, 2H), 4.94 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 8.02-8.05 (m, 2H), 8.49 (s, 1H), 8.90 (s, 1H).
Compound 17:40-2.48 (m, 2H), 4.21 (t, 2H), 4.58 (d, 2H), 4.93 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.75 (d, 1H), 8.24 (s, 1H), 8.31 (d, 1H), 8.90 (s, 1H).
Compound 18:2.43-2.48 (m, 2H, CH2), 4.24 (t, 2H), 4.58 (d, 2H), 4.76 (t, 2H), 6.12 (t, 1H), 6.84 (s, 2H), 7.68 (d, 1H), 7.91 (d, 1H), 8.15 (d, 1H).
Compound 19:40-2.48 (m, 2H), 4.21 (t, 2H), 4.58 (d, 2H), 4.98 (t, 2H), 6.11 (t, 1H ,=CH), 6.84 (s, 2H), 7.67-7.72 (m, 1H), 7.91-7.96 (m, 1H), 8.08 (d, 1H), 8.25 (d, 1H).
Compound 20:1.53 (d, 3H), 2.35 (m, 2H), 4.12 (d, 2H), 4.53 (d, 2H), 5.94 (m, 1H), 6.08 (t, 1H), 6.72 (s, 2H), 7.55 (d, 1H), 7.72-7.93 (m, 2H), 8.10 (d, 1H), 8.81 (s, 1H).
Compound 21:1.53 (t, 5H), 1.50-1.61 (m, 2H), 4.12 (d, 2H), 4.55 (d, 2H), 5.90 (m, 1H), 6.05 (t, 1H), 6.73 (s, 2H), 8.02 (d, 1H), 8.85 (s, 1H).
Compound 22:4.51 (d, 2H), 4.73 (d, 2H), 5.52 (d, 2H), 6.04 ~ 6.01 (m, 2H), 6.82 (s, 2H), 7.55 (t, 1H), 7.85 (t, 2H), 7.92 (t, 1H), 8.16 (d, 1H), 8.79 (s, 1H).
Compound 23:4.51 (d, 2H), 4.73 (d, 2H), 5.26 (d, 2H), 6.03 ~ 6.11 (m, 3H), 6.81 (s, 2H), 8.02 (m, 2H), 8.45 (s, 1H), 8.80 (s, 1H).
Compound 24:4.51 (d, 4H), 5.12 (d, 2H), 6.13 (t, 1H), 6.25 (d, 2H), 6.82 (s, 2H), 8.01 (d, 2H), 8.52 (s, 1H), 8.80 (s, 1H).
Compound 25:4.51 (d, 2H), 4.73 (s, 2H), 5.38 (s, 2H), 6.12 (t, 1H), 6.82 (s, 2H), 8.09 (m, 2H), 8.54 (s, 1H), 8.92 (s, 1H).
The ether compound that the present invention relates to quinazoline ring has high insecticidal activity.Therefore, the present invention also comprises compound of Formula I for controlling the purposes of agricultural or forestry insect pest.Specifically, technical scheme of the present invention also comprises the purposes of compound of Formula I for the preparation of insecticidal materials.
The present invention also comprises the insect-killing composition using compound of Formula I as active ingredient.In this insect-killing composition, the weight percentage of active ingredient is between 1-99%.Acceptable carrier in agricultural, forestry, health is also comprised in this insect-killing composition.
Composition of the present invention can the form of preparation be used.Compound of Formula I is dissolved or dispersed in carrier as active ingredient or is mixed with preparation to be easier to dispersion when using as desinsection.Such as: 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 suitable tensio-active agent can be added when needed.
The technical scheme that the present invention relates to also comprises the method for pest control: imposed on by insect-killing composition of the present invention on described insect or its growth medium.The comparatively suitable effective amount of usual selection is per hectare 10 grams to 1000 grams, and preferably having effective amount is per hectare 20 grams to 500 grams.
For some application, such as, one or more other sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator or fertilizer etc. agriculturally can be added in insect-killing composition of the present invention, additional advantage and effect can be produced thus.
Should it is clear that, in claim limited range of the present invention, can various conversion and change be carried out.
Embodiment
Following synthesis example, raw test-results of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthesis example
The preparation of example 1 compound 1
3-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group) the third-1-alcohol (0.69 gram, 2.00 mmole, embodiment 1,2,3 in synthetic method referenced patent CN1860874A), tetrahydrofuran (THF) (15mL), sodium hydride (0.14 gram, 4.00 mmoles), is stirred to bubble-free and releases, add 2-chloro-quinazoline (0.33 gram, 2.00 mmoles, synthetic method reference ChemMedChem, 2009,4 (7): 1069-1074), room temperature reaction spends the night.React complete, reaction solution drops in water (50mL), and with ethyl acetate (3 × 100mL) extraction, organic layer is respectively with saturated sodium bicarbonate, saturated nacl aqueous solution washing, and anhydrous magnesium sulfate drying, filter, concentrating under reduced pressure obtains resistates.Resistates is through column chromatography (leacheate: ethyl acetate: sherwood oil=1: 0.32 g of compound 1 of 1.5) purifying to obtain, yellow solid, yield 34%, fusing point: 85-87 DEG C.
The preparation of example 2 compound 3
3-(the chloro-4-of 2,6-bis-(the chloro-allyloxy of 3,3-bis-) phenoxy group) the third-1-alcohol (0.50 gram is added in reaction flask, 1.44 mmoles), tetrahydrofuran (THF) (15mL), sodium hydride (0.10 gram, 2.88 mmoles), be stirred to bubble-free and release, add 2,7-dichloroquinazoline (0.28 gram, 1.44 mmoles, synthetic method reference ChemMedChem, 2009,4 (7): 1069-1074), room temperature reaction spends the night.React complete, reaction solution drops in water (50mL), and with ethyl acetate (3 × 100mL) extraction, organic layer is respectively with saturated sodium bicarbonate, saturated nacl aqueous solution washing, and anhydrous magnesium sulfate drying, filter, concentrating under reduced pressure obtains resistates.Resistates is through column chromatography (leacheate: ethyl acetate: sherwood oil=1: 0.28 g of compound 3 of 1.5) purifying to obtain, white solid, yield 38%, fusing point: 96-98 DEG C
The preparation of example 3 compound 7
2-methyl-3-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-1-alcohol (0.43 gram, 1.2 mmole, embodiment 1 in synthetic method referenced patent CN1860874A, 2, 3), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.60 gram, 2.4 mmoles), stir after 1 hour, add 2-chloro-quinazoline (0.20 gram, 1.2 mmoles), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, with (3 × 100mL) extraction into ethyl acetate, organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 10) obtain 0.15 g of compound 7, yellow oil, yield 25%.
The preparation of example 5 compound 8
(Z)-4-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-2-butylene-1-alcohol (0.43 gram, 1.2 mmole, embodiment 1 in synthetic method referenced patent CN1432555A, 2), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.60 gram, 2.4 mmoles), stir after 1 hour, add 2-chloro-quinazoline (0.20 gram, 1.2 mmoles), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 20) obtain 0.35 g of compound 8, white solid, yield 60%, fusing point: 111-113 DEG C.
The preparation of example 6 compound 9
(Z)-4-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-2-butylene-1-alcohol (0.35 gram, 0.9 mmole, embodiment 1 in synthetic method referenced patent CN1432555A, 2), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.48 gram, 1.6 mmoles), stir after 1 hour, add 2-chloro-7-trifluoromethyl quinazoline (0.07 gram, 1.6 mmole, synthetic method is with reference to ChemMedChem, 2009, 4 (7): 1069-10743), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 20) obtain 0.15 g of compound 9, white solid, yield 34%, fusing point: 88-90 DEG C.
The preparation of example 7 compound 10
(E)-4-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-2-butylene-1-alcohol (0.43 gram, 1.2 mmole, embodiment 1 in synthetic method referenced patent CN1432555A, 2), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.60 gram, 2.4 mmoles), stir after 1 hour, add 2-chloro-quinazoline (0.20 gram, 1.2 mmoles), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 20) obtain 0.18 g of compound 10, white solid, yield 30.8%, fusing point: 105-107 DEG C.
The preparation of example 8 compound 11
4-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-2-butyne-1-alcohol (0.43 gram, 1.2 mmole, synthetic method is with reference to J.Org.Chem.1996, 61, 3294), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.60 gram, 2.4 mmoles), stir after 1 hour, add 2-chloro-quinazoline (0.20 gram, 1.2 mmoles), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 10) obtain 0.12 g of compound 11, white solid, yield 20%, fusing point: 107-109 DEG C.
The preparation of example 9 compound 12
4-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-2-butyne-1-alcohol (0.35 gram, 0.9 mmole), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.04 gram, 1.6 mmoles), stir after 1 hour, add 2-chloro-7-trifluoromethyl quinazoline (0.19 gram, 0.81 mmole), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 20) obtain 0.17 g of compound 12, oyster white oily matter, yield 38%.
The preparation of example 10 compound 14
3-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group) the third-1-alcohol (0.50 gram, 1.44 mmole), tetrahydrofuran (THF) (15mL), sodium hydride (0.70 gram, 2.88 mmoles), be stirred to bubble-free and release, add 4,6-dichloroquinazoline (0.28 gram, 1.44 mmoles, synthetic method ginseng Chinese Journal of Chemistry, 2009,27 (2): 379-383), room temperature reaction spends the night.React complete, reaction solution drops in water (50mL), and with ethyl acetate (3 × 100mL) extraction, organic layer uses saturated sodium bicarbonate respectively, and saturated nacl aqueous solution washs, anhydrous magnesium sulfate drying, and filter, concentrating under reduced pressure obtains resistates.Resistates is through column chromatography (leacheate: ethyl acetate: sherwood oil=1: 0.34 g of compound 14 of 1.5) purifying to obtain, white solid, yield 45%, fusing point: 93-95 DEG C.
The preparation of example 11 compound 17
3-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group) the third-1-alcohol (0.50 gram, 1.44 mmole), tetrahydrofuran (THF) (15mL), sodium hydride (0.05 gram, 2.16 mmole), be stirred to bubble-free release, add 4-chloro-7-trifluoromethyl quinazoline (0.33 gram, 1.44 mmoles, synthetic method ginseng Chinese Journal of Chemistry, 2009,27 (2): 379-383), room temperature reaction spends the night.React complete, reaction solution drops in water (50mL), extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate (50mL) respectively, saturated nacl aqueous solution (50mL) washs, anhydrous magnesium sulfate drying, filter, concentrating under reduced pressure obtains resistates.Resistates is through column chromatography (leacheate: ethyl acetate: sherwood oil=1: 0.30 g of compound 17 of 1.5) purifying to obtain, yellow oil, yield 38%.
The preparation of example 12 compound 20
2-methyl-3-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-1-alcohol (0.20 gram, 0.56 mmole), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.03 gram, 1.0 mmoles), stir after 1 hour, add 4-chloro-quinazoline (0.10 gram, 0.56 mmole, synthetic method ginseng Chinese Journal of Chemistry, 2009, 27 (2): 379-383), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, with (3 × 100mL) extraction into ethyl acetate, organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 10) obtain 0.17 g of compound 20, yellow oil, yield 62%.
The preparation of example 13 compound 23
(Z)-4-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-2-butylene-1-alcohol (0.30 gram, 0.85 mmole), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.40 gram, 1.7 mmoles), stir after 1 hour, add 4-chloro-6-trifluoromethyl quinazoline (0.20 gram, 0.85 mmole, synthetic method ginseng ChineseJournal of Chemistry, 2009, 27 (2): 379-383), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 10) obtain 0.24 g of compound 23, white solid, yield 51%, fusing point: 108-110 DEG C.
The preparation of example 14 compound 24
(E)-4-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-2-butylene-1-alcohol (0.30 gram, 0.85 mmole), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.40 gram, 1.7 mmoles), stir after 1 hour, add 4-chloro-6-trifluoromethyl quinazoline (0.20 gram, 0.85 mmole), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 10) obtain 0.23 g of compound 24, yellow solid, yield 48%, fusing point: 64-66 DEG C.
The preparation of example 15 compound 25
4-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group)-2-butyne-1-alcohol (0.30 gram, 0.85 mmole), tetrahydrofuran (THF) 5 milliliters, stirred at ambient temperature is to dissolving, add sodium hydride (0.40 gram, 1.6 mmoles), stir after 1 hour, add 4-chloro-6-trifluoromethyl quinazoline (0.14 gram, 0.85 mmole), reaction is continued after 11 hours under room temperature, by in reaction solution impouring 50 ml water, extract by ethyl acetate (3 × 100mL), organic layer uses saturated sodium bicarbonate aqueous solution respectively, saturated common salt water washing, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 10) obtain 0.20 g of compound 25, colorless oil, yield 42%.
Biological activity determination example
The mensuration of example 16 insecticidal activity
According to the solvability of testing compound, dissolve former medicine with acetone or methyl-sulphoxide, then become the liquid to be measured 50 milliliters of desired concn with the tween 80 solution preparation of 1 ‰, acetone or the content of methyl-sulphoxide in total solution are no more than 10%.
(1) mensuration of small cabbage moth activity, is killed
Cabbage leaves punch tool is broken into the leaf dish of diameter 3 centimetres, with Airbrush spraying process, sprayed at every leaf dish pros and cons by certain density test compound liquid, spouting liquid is 0.5 milliliter, separately establishes clear water to be treated to blank, often processes 3 times and repeats.Access 8 examination worm (3 age) is often processed after drying in the shade.Put into after process 24 DEG C, relative humidity 60% ~ 70%, unglazed photograph indoor cultivation, 72 hours " Invest, Then Investigate "s survival borer population, calculates mortality ratio.
In the compound of part for examination, following compounds is better to the prevention effect of small cabbage moth when concentration is 600ppm, and mortality ratio is 100%:13,16,17.
In the compound of part for examination, following compounds is better to the prevention effect of small cabbage moth when concentration is 100ppm, and mortality ratio is 100%:17.
In the compound of part for examination, following compounds is better to the prevention effect of small cabbage moth when concentration is 40ppm, and mortality ratio is 100%:17.
(2), the mensuration of mythimna separate
Maize leaf is cut into 4-5 cm long segment, with Airbrush spraying process, sprayed in every leave dual sides by certain density test compound liquid, spouting liquid is 0.5 milliliter, separately establishes clear water to be treated to blank, often processes 3 times and repeats.Access 8 examination worm (3 age) is often processed after drying in the shade.Put into after process 24 DEG C, relative humidity 60% ~ 70%, unglazed photograph indoor cultivation, 72 hours " Invest, Then Investigate "s survival borer population, calculates mortality ratio.
In the compound of part for examination, following compounds is better to the prevention effect of mythimna separata when concentration is 600ppm, and mortality ratio is 100%:1,13,16,17.
In the compound of part for examination, following compounds is better to the prevention effect of mythimna separata when concentration is 100ppm, and mortality ratio is 100%:17.
In the compound of part for examination, following compounds is better to the prevention effect of mythimna separata when concentration is 10ppm, and mortality ratio is greater than 80%:17.

Claims (6)

1. the ether compound containing quinazoline ring, as shown in general formula I:
In formula:
R 1be selected from hydrogen, R 2be selected from Q, described Q is selected from Q as follows 1:
R 3, R 4, R 5, R 6may be the same or different, be selected from hydrogen, halogen, C respectively 1-C 3alkyl, C 1-C 3haloalkyl.
2. according to compound according to claim 1, it is characterized in that: in general formula I
R 1be selected from hydrogen, R 2be selected from Q, R 3, R 4, R 5, R 6be selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl or trifluoromethyl respectively, but wherein at least one is hydrogen.
3., according to compound according to claim 2, it is characterized in that following compound:
。
4. one kind according to compound of Formula I according to claim 1 for controlling the purposes of insect pest in agricultural or forestry.
5. an insect-killing composition, containing, for example compound of Formula I according to claim 1 as acceptable carrier in active ingredient and agricultural or forestry, is 1-99% as the compound of Formula I weight percentage of active ingredient in composition.
6. control a method for insect pest, it is characterized in that: composition according to claim 5 is imposed on the insect of needs control or the medium of its growth with the effective dose of per hectare 10 grams to 1000 grams.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1031263C (en) * 1988-01-29 1996-03-13 伊莱利利公司 Quinoline, quinazoline, and cinnoline
CN101337940A (en) * 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1031263C (en) * 1988-01-29 1996-03-13 伊莱利利公司 Quinoline, quinazoline, and cinnoline
CN101337940A (en) * 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity

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