CN104650036A - 6-substituented phenyl quinazolinone compound and use thereof - Google Patents

6-substituented phenyl quinazolinone compound and use thereof Download PDF

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CN104650036A
CN104650036A CN201310606462.3A CN201310606462A CN104650036A CN 104650036 A CN104650036 A CN 104650036A CN 201310606462 A CN201310606462 A CN 201310606462A CN 104650036 A CN104650036 A CN 104650036A
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compound
hydrogen
pyridine
general formula
formula
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CN104650036B (en
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李斌
王刚
范晓溪
施学庚
李轲轲
于海波
吕亮
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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
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

Abstract

The invention discloses a 6-substituented phenyl quinazolinone compound with a novel structure. The 6-substituented phenyl quinazolinone compound is represented by a general formula I shown in the specification, wherein L is selected from L1 or L2, L1 is a formula shown in the specification, and L2 is a formula shown in the specification; R1 is selected from hydrogen, C1-C6 alkyl carbonyl or C1-C6 alkoxy carbonyl; R2 is selected from hydrogen or halogen; R3 is selected from hydrogen or halogen; R2 and R3 are not simultaneously hydrogen. The compound of the general formula I has excellent insecticidal activity, can be applied to pest control and can be particularly applied to aphid control.

Description

6-substituted-phenyl quianzolinones and uses thereof
Technical field
The invention belongs to agricultural insecticide field, relate to a kind of 6-substituted-phenyl quianzolinones and uses thereof.
Background technology
Due to sterilant in use for some time, insect can produce resistance to it, therefore, need constantly invention novel with the compound with insecticidal activity improved and composition.
Some 6-substituted-phenyl quianzolinones with insecticidal activity has been reported.WO2013075645A1 reports 6 position trifluoromethyl substituted-phenyl quianzolinones KC 1(in patent compound 7) and KC 2it is active that (in patent compound 102) has good killing aphis.But the preventive effect under low dosage is unsatisfactory.
The substituent phenylquinazoline ketone compounds of illustrated 6-has no open.
Summary of the invention
The object of the present invention is to provide the Compound Phase ratio with prior art, the quianzolinones that insecticidal activity is significantly improved.To developing a kind of sterilant of novel structure, use it for the control of insect pest.
Technical scheme of the present invention is as follows:
A kind of 6-substituted-phenyl quianzolinones, compound as shown in general formula I, or the salt of compound shown in general formula I, wherein general formula I is as follows:
In general formula I:
L is selected from L 1or L 2:
L 1= 、L 2=
R 1be selected from hydrogen, C 1-C 6alkyl-carbonyl or C 1-C 6alkoxy carbonyl;
R 2be selected from hydrogen or halogen;
R 3be selected from hydrogen or halogen;
Wherein R 2and R 3be asynchronously hydrogen.
In the present invention, comparatively preferred compound is, compound as shown in general formula I, or the salt of compound shown in general formula I, and wherein general formula I is as follows:
In general formula I:
L is selected from L 1or L 2:
L 1= 、L 2=
R 1be selected from hydrogen, C 1-C 4alkyl-carbonyl or C 1-C 4alkoxy carbonyl;
R 2be selected from hydrogen, fluorine, chlorine, bromine or iodine;
R 3be selected from hydrogen, fluorine, chlorine, bromine or iodine;
Wherein R 2and R 3be asynchronously hydrogen.
The hydrochloride of compound of Formula I, vitriol, nitrate, supercarbonate, carbonate, phosphoric acid salt, formate, acetate, trifluoroacetate, benzene sulfonate, tosilate, metilsulfate, benzoate, Citrate trianion, malate, tartrate, maleate, succinate, ascorbate salt or oxalate.
In the present invention, preferred compound is, in general formula I further:
L is selected from L 1or L 2:
L 1= 、L 2=
R 1be selected from hydrogen, C 1-C 4alkyl-carbonyl or C 1-C 4alkoxy carbonyl;
R 2be selected from hydrogen, fluorine, chlorine or bromine;
R 3be selected from hydrogen, fluorine, chlorine or bromine;
Wherein R 2and R 3be asynchronously hydrogen.
In the definition of the general formula compound I provided above, collect term used and be generally defined as follows:
Alkyl refers to straight or branched form, the groups such as such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, tertiary butyl, n-pentyl, isopentyl, n-hexyl.Haloalkyl refers to the group that alkyl is optionally substituted with one or more halogen atoms.Alkoxyl group refers to that alkyl end is connected with the group of Sauerstoffatom, such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, tert-butoxy etc.Halogenated alkoxy refers to the group that alkoxyl group is optionally substituted with one or more halogen atoms.
The preparation method of general formula compound I of the present invention is as follows:
R 1for H, L are L 1the structure of compound of Formula I of the present invention such as formula shown in I-A, can prepare by the following method:
General formula compound II and pyridylaldehyde are in suitable solvent, and temperature is react 0.5-48 hour obtained general formula compound I-A under room temperature to boiling point.
Suitable solvent is selected from methylene dichloride, chloroform, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, ethanol, methyl alcohol, DMF or dimethyl sulfoxide (DMSO) etc.
Add suitable acid favourable to reaction, suitable acid is selected from mineral acid (such as sulfuric acid, hydrochloric acid) or organic acid (such as acetic acid, tosic acid etc.).
General formula compound II preparation method is as follows:
General formula compound III(preparation method is see US20040082586; J.Org.Chem.60,7508-7510,1995; Tetrahedron Lett.52,6489 – 6491,2011; Tetra.66,3207-3213,2010) with hydrazine hydrate in suitable solvent, temperature is react 0.5-48 hour obtained general formula compound II under room temperature to boiling point.
Suitable solvent is selected from methylene dichloride, chloroform, toluene, acetonitrile, tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, DMF, dimethyl sulfoxide (DMSO) or HMPA etc.
R can be prepared by above-mentioned general formula I-A compound 1it is not other general formula Is-B compound of H.Reaction formula is as follows:
In formula: LG represents suitable leavings group, as chlorine atom, bromine atoms or acyloxy etc.
General formula I-A compound and compound of Formula IV (as carboxylic acid halides or acid anhydrides etc.) in suitable solvent, temperature reacts 0.5-48 hour obtained general formula I-B compound under-10 DEG C to boiling point.
Suitable solvent is selected from methylene dichloride, chloroform, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, DMF, dimethyl sulfoxide (DMSO) or HMPA etc.
Add suitable alkaloids favourable to reaction.Suitable alkali is selected from organic bases as triethylamine, DMA, pyridine, sodium methylate, sodium ethylate, sodium tert-butoxide or potassium tert.-butoxide etc., or mineral alkali is as sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood or sodium hydride etc.
General formula compound I-C of the present invention can by general formula compound I-B conventionally hydrogenating reduction obtain.Preparation method is as follows, in reaction formula unless otherwise indicated outer, each group definition is the same.
General formula compound I-B in suitable solvent, temperature be room temperature under boiling point, reaction 0.5-48 hour, passes into hydrogen (hydrogen pressure is 1-100 normal atmosphere) catalytic reduction and obtains general formula compound I-C.
Suitable solvent is selected from methylene dichloride, chloroform, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, DMF, dimethyl sulfoxide (DMSO) or HMPA etc.
Catalyzer is selected from palladium carbon, palladium dioxide, Raney Ni etc.
Table 1 lists structure and the physico-chemical property of partial Formula I.
The structure of table 1 partial Formula I and physico-chemical property
Part of compounds 1h NMR (300MHz, DMSO) data are as follows:
Compound 1:5.02 (s, 2H, NCH 2), 7.00 (d, 1H, J=7.8Hz, Ph-H), 7.32 ~ 7.36 (m, 1H, Ph-H), 7.32 ~ 7.36 (m, 1H, Pyridine-H), 7.56 ~ 7.63 (m, 2H, Ph-H), 7.74 ~ 7.76 (m, 1H, Ph-H), 7.88 (s, 1H, Ph-H), 8.12 ~ 8.14 (m, 1H, Pyridine-H), 8.29 (d, 1H, J=8.4Hz, Pyridine-H), 8.62 (d, 1H, J=3.6Hz, Pyridine-H), 8.93 (s, 1H, N=CH), 10.13 (s, 1H, NH)
Compound 2:5.00 (s, 2H, NCH 2), 6.98 ~ 7.14 (m, 2H, Ph-H), 7.30 ~ 7.35 (m, 1H, Pyridine-H), 7.42 ~ 7.47 (m, 1H, Ph-H), 7.63 (s, 1H, Ph-H), 7.89 (s, 1H, Ph-H), 8.09 (s, 1H, Pyridine-H), 8.17 (d, 1H, J=7.5Hz, Pyridine-H), 8.54 (d, 1H, J=4.2Hz, Pyridine-H), 8.86 (s, 1H, N=CH), 10.11 (s, 1H, NH)
Compound 4:2.53 (s, 3H, CH 3), 5.08 (s, 2H, NCH 2), 7.46 ~ 7.53 (m, 2H, Ph-H), 7.46 ~ 7.53 (m, 1H, Pyridine-H), 7.65 ~ 7.68 (m, 1H, Ph-H), 7.77 ~ 7.83 (m, 2H, Ph-H), 7.92 (s, 1H, Ph-H), 8.17 (d, 1H, J=8.1Hz, Pyridine-H), 8.60 ~ 8.63 (m, 1H, Pyridine-H), 8.60 ~ 8.63 (m, 1H, N=CH), 8.89 (s, 1H, Pyridine-H)
Compound 9:2.67 (s, 3H, CH 3), 4.94 (s, 2H, NCH 2), 7.20 ~ 7.32 (m, 1H, Ph-H), 7.36 ~ 7.49 (m, 2H, Ph-H), 7.36 ~ 7.49 (m, 1H, Pyridine-H), 7.69 ~ 7.77 (m, 1H, Ph-H), 7.92 ~ 7.99 (m, 1H, Ph-H), 8.16 ~ 8.19 (m, 1H, Pyridine-H), 8.65 (m, 1H, N=CH), 8.88 (d, 1H, J=1.5Hz, Pyridine-H), 8.99 (d, 1H, J=2.7Hz, Pyridine-H)
Compound 22:1.28 (t, 3H, CH 2cH 3), 3.03 (q, 2H, CH 2cH 3), 4.94 (s, 2H, NCH 2), 7.27 ~ 7.40 (m, 1H, Ph-H), 7.27 ~ 7.40 (m, 1H, Pyridine-H), 7.45 ~ 7.48 (m, 2H, Ph-H), 7.58 ~ 7.61 (m, 1H, Ph-H), 7.76 (s, 1H, Ph-H), 7.91 ~ 7.94 (m, 1H, Ph-H), 8.17 (d, 1H, J=8.4Hz, Pyridine-H), 8.64 ~ 8.66 (m, 1H, Pyridine-H), 8.89 (s, 1H, N=CH), 9.00 (s, 1H, Pyridine-H)
Compound 27:1.21 (t, 3H, CH 2cH 3), 2.93 (q, 2H, CH 2cH 3), 5.08 (s, 2H, NCH 2), 7.47 ~ 7.51 (m, 2H, Ph-H), 7.74 (s, 1H, Pyridine-H), 7.79 ~ 7.82 (m, 2H, Ph-H), 8.00 ~ 8.09 (m, 1H, Ph-H), 8.16 ~ 8.19 (m, 1H, Pyridine-H), 8.61 ~ 8.62 (m, 1H, Pyridine-H), 8.61 ~ 8.62 (m, 1H, N=CH), 8.90 (s, 1H, Pyridine-H)
Compound 31:0.96 (t, 3H, CH 2cH 3), 1.66 ~ 1.73 (m, 2H, CH 2cH 3), 2.90 (t, 2H, COCH 2), 5.08 (s, 2H, NCH 2), 7.45 ~ 7.49 (m, 3H, Ph-H), 7.45 ~ 7.49 (m, 1H, Pyridine-H), 7.64 ~ 7.90 (m, 3H, Ph-H), 8.18 (d, 1H, J=7.8Hz, Ph-H), 8.61 (d, 1H, J=4.8Hz, Pyridine-H), 8.65 (s, 1H, N=CH), 8.90 (s, 1H, Pyridine-H)
Compound 36:0.98 (t, 3H, CH 2cH 3), 1.67 ~ 1.78 (m, 2H, CH 2cH 3), 2.99 (t, 2H, COCH 2), 4.93 (s, 2H, NCH 2), 7.20 ~ 7.49 (m, 2H, Ph-H), 7.20 ~ 7.49 (m, 1H, Pyridine-H), 7.69 ~ 7.76 (m, 2H, Ph-H), 7.92 ~ 7.98 (m, 1H, Ph-H), 8.18 ~ 8.20 (m, 1H, Pyridine-H), 8.65 (d, 1H, J=4.8Hz, Pyridine-H), 8.89 (s, 1H, N=CH), 8.99 (s, 1H, Pyridine-H)
Compound 45:1.08 ~ 1.26 (m, 6H, CH (CH 3) 2), 3.51 ~ 3.55 (m, 1H, CH (CH 3) 2), 5.09 (s, 2H, NCH 2), 7.25 ~ 7.34 (m, 1H, Ph-H), 7.46 ~ 7.53 (m, 1H, Pyridine-H), 7.46 ~ 7.53 (m, 1H, Ph-H), 7.66 (s, 1H, Ph-H), 7.82 ~ 7.95 (m, 2H, Ph-H), 8.19 (d, 1H, J=5.7Hz, Pyridine-H), 8.60 (s, 1H, N=CH), 8.70 (s, 1H, J=4.2Hz, Pyridine-H), 8.90 (s, 1H, Pyridine-H)
Compound 94:2.53 (s, 3H, CH 3), 4.01 (d, 2H, J=3.9Hz, NHCH 2), 4.42 (s, 2H, NCH 2), 6.19 (t, 1H, NHCH 2), 7.18 ~ 7.29 (m, 1H, Ph-H), 7.25 ~ 7.36 (m, 1H, Ph-H), 7.36 ~ 7.39 (m, 1H, Pyridine-H), 7.67 ~ 7.82 (m, 3H, Ph-H), 7.67 ~ 7.82 (m, 1H, Pyridine-H), 7.84 (s, 1H, Ph-H), 8.39 (m, 1H, Pyridine-H), 8.42 (s, 1H, Pyridine-H).
Compound 99:2.44 (s, 3H, CH 3), 4.00 (d, 2H, J=5.1Hz, NHCH 2), 4.37 (s, 2H, CH 2n), 6.19 (t, 1H, NHCH 2), 7.14 (s, 1H, Ph-H), 7.18 ~ 7.26 (m, 1H, Ph-H), 7.37 ~ 7.40 (m, 1H, Pyridine-H), 7.64 ~ 7.73 (m, 2H, Ph-H), 7.64 ~ 7.73 (m, 1H, Pyridine-H), 7.99 (s, 1H, Ph-H), 8.35 ~ 8.41 (m, 2H, Pyridine-H)
Compound 112:1.12 (t, 3H, CH 2cH 3), 2.82 (q, 2H, CH 2cH 3), 4.02 (d, 2H, J=4.5Hz, NHCH 2), 4.41 (s, 2H, NCH 2), 6.13 (t, 1H, NHCH 2), 7.19 (s, 1H, Ph-H), 7.20 ~ 7.24 (m, 1H, Ph-H), 7.36 ~ 7.39 (m, 1H, Pyridine-H), 7.60 ~ 7.76 (m, 3H, Ph-H), 7.60 ~ 7.76 (m, 1H, Pyridine-H), 7.84 (s, 1H, Ph-H), 8.38 ~ 8.40 (dd, 1H, J 1=1.5Hz, J 2=4.8Hz, Pyridine-H), 8.43 (s, 1H, Pyridine-H)
Compound 117:1.13 (t, 3H, CH 2cH 3), 2.83 (q, 2H, CH 2cH 3), 4.00 (d, 2H, J=4.2Hz, NHCH 2), 4.38 (s, 2H, CH 2n), 6.14 (t, 1H, NHCH 2), 7.14 ~ 7.15 (m, 1H, Ph-H), 7.19 ~ 7.25 (m, 1H, Ph-H), 7.37 ~ 7.40 (m, 1H, Pyridine-H), 7.65 ~ 7.97 (m, 3H, Ph-H), 7.65 ~ 7.97 (m, 1H, Pyridine-H), 8.37 ~ 8.39 (m, 1H, Pyridine-H), 8.47 ~ 8.48 (m, 1H, Pyridine-H)
Compound 121:0.95 (t, 3H, CH 2cH 3), 1.60 ~ 1.68 (m, 2H, CH 2cH 3), 2.76 (t, 2H, COCH 2), 4.02 (d, 2H, J=4.8Hz, NHCH 2), 4.42 (s, 2H, NCH 2), 6.18 (t, 1H, NHCH 2), 7.21 (s, 1H, Ph-H), 7.23 ~ 7.25 (m, 1H, Ph-H), 7.36 ~ 7.40 (m, 1H, Pyridine-H), 7.64 ~ 7.78 (m, 3H, Ph-H), 7.64 ~ 7.78 (m, 1H, Pyridine-H), 7.87 (s, 1H, Ph-H), 8.40 (dd, 1H, J 1=1.5Hz, J 2=3.3Hz, Pyridine-H), 8.44 (s, 1H, Pyridine-H)
Compound 126:0.95 (t, 3H, CH 2cH 3), 1.60 ~ 1.65 (m, 2H, CH 2cH 3), 2.77 (t, 2H, CH 2cO), 4.00 (d, 2H, J=4.8Hz, NHCH 2), 4.38 (s, 2H, CH 2n), 6.22 (t, 1H, NHCH 2), 7.17 ~ 7.28 (m, 2H, Ph-H), 7.33 ~ 7.42 (m, 1H, Pyridine-H), 7.68 ~ 7.77 (m, 1H, Pyridine-H), 7.68 ~ 7.77 (m, 2H, Ph-H), 7.92 (s, 1H, Ph-H), 8.37 ~ 8.39 (m, 1H, Pyridine-H), 8.48 (s, 1H, Pyridine-H)
Compound 135:1.20 (t, 6H, CH (CH 3) 2), 3.47 (m, 1H, CH (CH 3) 2), 4.02 (d, 2H, J=3.9Hz, NHCH 2), 4.38 (s, 2H, CH 2n), 6.15 (t, 1H, NHCH 2), 7.12 (s, 1H, Ph-H), 7.21 ~ 7.25 (m, 1H, Pyridine-H), 7.36 ~ 7.39 (m, 1H, Ph-H), 7.64 ~ 7.77 (m, 3H, Ph-H), 7.90 (s, 1H, Pyridine-H), 8.37 (a, 1H, Pyridine-H), 8.39 (s, 1H, Pyridine-H)
General formula compound I of the present invention has high insecticidal activity.To insect as black bean aphid has good control effects.Therefore, the present invention also comprises general formula compound I for controlling the purposes of insect pest; Especially, compound of the present invention is preferred for the purposes controlling aphid such as black bean aphid insect pest.
The present invention also comprises the insect-killing composition using general formula compound 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.
Technical scheme of the present invention 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.
Composition of the present invention can the form of preparation be used on insect or its growth medium.General formula compound I is dissolved or dispersed in carrier as active ingredient or is mixed with preparation to be easier to dispersion when using as sterilant.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.
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 synthetic example, 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 embodiment 1, compound 2,9,27,36,99,117,126
(1), the chloro-4-(trifluoromethyl of 3-amino-6-(2,6-bis-) phenyl) synthesis of-3,4-dihydroquinazoline-2 (1H)-one
2-chloromethyl-4-(2 is added successively, the chloro-4-(trifluoromethyl of 6-bis-in reaction flask) phenyl) N-phenylurethane (4.00 grams, 9.38 mmoles, reference US20040082586; J.Org.Chem.60,7508-7510,1995; Tetrahedron Lett.52,6489 – 6491,2011; Tetra.66,3207-3213,2010 obtain), ethanol (50 milliliters) and hydrazine hydrate (4.42 grams, 75.04 mmoles), reaction solution is heated to backflow.Reaction solution, after 3 hours, is down to room temperature by back flow reaction, and adularescent solid is separated out, and solid collected by filtration, use ethanol (10 milliliters) washing gained white solid, obtain white solid 2.45 grams, yield 69.44% after drying.
(2), the preparation of compound 2
3-amino-6-(2 is added successively in reaction flask, the chloro-4-(trifluoromethyl of 6-bis-) phenyl)-3,4-dihydroquinazoline-2 (1H)-one (1.50 grams, 3.99 mmoles), ethanol (30 milliliters), (0.56 gram, cigarette aldehyde, 5.19 mmole), the vitriol oil 1, reaction solution is warming up to backflow.Reaction solution, after 2 hours, is down to room temperature by back flow reaction, has a large amount of solid to separate out, solid collected by filtration, with ethanol (10 milliliters) washing gained solid, obtains white solid 1.23 grams, yield 66.26% after drying.
(3), the preparation of compound 9
In reaction flask, add compound 2(0.33 gram successively, 0.71 mmole), DMF(20 milliliter), stirring at room temperature is entirely molten to solid.Add sodium hydride (0.11 gram, 2.84 mmoles) again, have bubble to produce, be stirred to after bubble-free produces and add diacetyl oxide (0.34 gram, 2.84 mmoles).Room temperature reaction is after 2 hours, water (40 milliliters) is added in reaction solution, extract by ethyl acetate (150 milliliters), organic layer is after saturated aqueous common salt (50 milliliters) washing, anhydrous magnesium sulfate drying, concetrated under reduced pressure, resistates, through chromatography over CC (leacheate is PE: acetone=2:1), obtains white solid 0.18 gram, yield 48.63%.
(4), the preparation of compound 27
In reaction flask, add compound 2(0.44 gram successively, 0.95 mmole), DMF(20 milliliter), stirring at room temperature is entirely molten to solid.Add sodium hydride (0.15 gram, 3.80 mmoles) again, have bubble to produce, be stirred to after bubble-free produces and add propionic anhydride (0.58 gram, 3.80 mmoles).Room temperature reaction is after 2 hours, water (40 milliliters) is added in reaction solution, extract by ethyl acetate (150 milliliters), organic layer is after saturated aqueous common salt (50 milliliters) washing, anhydrous magnesium sulfate drying, concetrated under reduced pressure, resistates, through chromatography over CC (leacheate is PE: acetone=2:1), obtains pale yellow oily liquid body 0.20 gram, yield 40.38%.
(5), the preparation of compound 36
In reaction flask, add compound 2(0.33 gram successively, 0.71 mmole), DMF(20 milliliter), stirring at room temperature is entirely molten to solid.Add sodium hydride (0.11 gram, 2.84 mmoles) again, have bubble to produce, be stirred to after bubble-free produces and add butyryl oxide (0.53 gram, 2.84 mmoles).Room temperature reaction is after 2 hours, water (40 milliliters) is added in reaction solution, extract by ethyl acetate (150 milliliters), organic layer is after saturated aqueous common salt (50 milliliters) washing, anhydrous magnesium sulfate drying, concetrated under reduced pressure, resistates, through chromatography over CC (leacheate is PE: acetone=2:1), obtains pale yellow oily liquid body 0.19 gram, yield 49.99%.
(6), the preparation of compound 99
In reaction flask, add compound 9(0.10 gram successively, 0.20 mmole), DMF(10 milliliter), stirring at room temperature is entirely molten to solid.Add palladium carbon (0.04 gram, 0.04 mmole) and 1 formic acid again, pass into N 2h is passed into after 30min 2.Stirring at room temperature is after 2 hours, water (40 milliliters) is added in reaction solution, extract by ethyl acetate (150 milliliters), organic layer is after saturated aqueous common salt (50 milliliters) washing, anhydrous magnesium sulfate drying, concetrated under reduced pressure, resistates, through chromatography over CC (leacheate is PE: acetone=2:1), obtains white solid 0.03 gram, yield 25.40%.
(7), the preparation of compound 117
In reaction flask, add compound 27(0.44 gram successively, 0.84 mmole), DMF(20 milliliter), stirring at room temperature is entirely molten to solid.Add palladium carbon (0.20 gram, 0.19 mmole) and 1 formic acid again, pass into N 2h is passed into after 30min 2.Stirring at room temperature is after 2 hours, water (40 milliliters) is added in reaction solution, extract by ethyl acetate (150 milliliters), organic layer is after saturated aqueous common salt (50 milliliters) washing, anhydrous magnesium sulfate drying, concetrated under reduced pressure, resistates, through chromatography over CC (leacheate is PE: acetone=2:1), obtains white solid 0.17 gram, yield 38.67%.
(8), the preparation of compound 126
In reaction flask, add compound 36(0.15 gram successively, 0.28 mmole), DMF(20 milliliter), stirring at room temperature is entirely molten to solid.Add palladium carbon (0.06 gram, 0.06 mmole) and 1 formic acid again, pass into N 2h is passed into after 30 minutes 2.Stirring at room temperature is after 2 hours, water (40 milliliters) is added in reaction solution, extract by ethyl acetate (150 milliliters), organic layer is after saturated aqueous common salt (50 milliliters) washing, anhydrous magnesium sulfate drying, concetrated under reduced pressure, resistates, through chromatography over CC (leacheate is PE: acetone=2:1), obtains white solid 0.08 gram, yield 49.41%.
Raw survey example
Example 2, kill the insecticidal activity assay of black bean aphid
Female one-tenth aphid shiny black to robust growth, body colour was provoked gently with moistening writing brush end in first 3 days in process, receive on the high broad bean seedling of 2cm, every strain 4-5 head, if give birth to after aphid 30-40 head (24h) until female one-tenth aphid, remove into aphid, if can for 3 age in days aphids of examination after 2 days.
If the broad bean seedling of tool aphid is cut from basal part of stem during process, in the liquid diluted, fully infiltrate 5s, remove unnecessary liquid, be inserted on moist sponge moisturizing dish, by lens on the broad bean seedling cover of process, with the gauze that bungee is fixing on lens upper opening place cover.Moisturizing dish is moved to standard sight indoor (23-25 DEG C, 40-60%R.H., L/D are 13h:11h), viewing duration then adds appropriate tap water to keep the strong of base of leaf if needed on the sponge of moisturizing dish.
Under 10ppm test concentrations, the preventive effect of compound 1,2,4,9,22,27,31,36,94,112,117,121 pairs of black bean aphids is more than 80%.
According to the method described above, by the compounds of this invention 4,22 and 117 and known compound KC 1(in CN103130771A No. 7, compound) and KC 2(in CN103130771A No. 102, compound) has carried out the replicate(determination) of killing black bean aphid activity, and test-results is in table 2.
Table 2: kill black bean aphid activity data (mortality ratio, %)

Claims (7)

1. a 6-substituted-phenyl quianzolinones, as shown in general formula I:
In general formula I:
L is selected from L 1or L 2:
L 1= 、L 2=
R 1be selected from hydrogen, C 1-C 6alkyl-carbonyl or C 1-C 6alkoxy carbonyl;
R 2be selected from hydrogen or halogen;
R 3be selected from hydrogen or halogen;
Wherein R 2and R 3be asynchronously hydrogen.
Or the salt of compound of Formula I.
2. according to compound according to claim 1, it is characterized in that, in general formula I:
L is selected from L 1or L 2:
L 1= 、L 2=
R 1be selected from hydrogen, C 1-C 4alkyl-carbonyl or C 1-C 4alkoxy carbonyl;
R 2be selected from hydrogen, fluorine, chlorine, bromine or iodine;
R 3be selected from hydrogen, fluorine, chlorine, bromine or iodine;
Wherein R 2and R 3be asynchronously hydrogen.
Or the hydrochloride of compound of Formula I, vitriol, nitrate, supercarbonate, carbonate, phosphoric acid salt, formate, acetate, trifluoroacetate, benzene sulfonate, tosilate, metilsulfate, benzoate, Citrate trianion, malate, tartrate, maleate, succinate, ascorbate salt or oxalate.
3. according to compound according to claim 2, it is characterized in that, in general formula I:
L is selected from L 1or L 2:
L 1= 、L 2=
R 1be selected from hydrogen, C 1-C 4alkyl-carbonyl or C 1-C 4alkoxy carbonyl;
R 2be selected from hydrogen, fluorine, chlorine or bromine;
R 3be selected from hydrogen, fluorine, chlorine or bromine;
Wherein R 2and R 3be asynchronously hydrogen.
4. one kind according to compound of Formula I according to claim 1 for controlling the purposes of insect pest.
5. one kind according to compound of Formula I according to claim 1 for controlling the purposes of aphid.
6. an insect-killing composition, containing, for example the compound shown in general formula I according to claim 1 as active ingredient and agriculturally acceptable carrier, in composition, the weight percentage of active ingredient is 1-99%.
7. control a method for insect pest, it is characterized in that: composition according to claim 6 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.
CN201310606462.3A 2013-11-25 2013-11-25 6 substituted-phenyl quianzolinones and application thereof Active CN104650036B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105566232A (en) * 2016-03-07 2016-05-11 贵州省果树科学研究所 Compound for preventing and curing aphid disease of pitaya and composition containing compound
CN105669524A (en) * 2016-03-07 2016-06-15 贵州省果树科学研究所 Compound for controlling dragon fruit anthracnose and composition using compound

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1302801A (en) * 1999-11-02 2001-07-11 日本农药株式会社 Substituted aminoquinazolone (thio-ketone) derivative or its salt, its intermediate and pest controlling agent and its application method
CN103130771A (en) * 2011-11-25 2013-06-05 中国中化股份有限公司 6-substituted phenyl quinazoline ketone compound and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1302801A (en) * 1999-11-02 2001-07-11 日本农药株式会社 Substituted aminoquinazolone (thio-ketone) derivative or its salt, its intermediate and pest controlling agent and its application method
CN103130771A (en) * 2011-11-25 2013-06-05 中国中化股份有限公司 6-substituted phenyl quinazoline ketone compound and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105566232A (en) * 2016-03-07 2016-05-11 贵州省果树科学研究所 Compound for preventing and curing aphid disease of pitaya and composition containing compound
CN105669524A (en) * 2016-03-07 2016-06-15 贵州省果树科学研究所 Compound for controlling dragon fruit anthracnose and composition using compound
CN105669524B (en) * 2016-03-07 2018-05-22 贵州高山农业技术服务有限责任公司 It is a kind of prevent dragon fruit anthracnose compound and apply its composition
CN105566232B (en) * 2016-03-07 2018-07-17 贵州大学 It is a kind of prevention dragon fruit aphid disease compound and apply its composition

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