CN107915718B - N-acyl alkyl benzoyl amide compound with insecticidal activity and application thereof - Google Patents

N-acyl alkyl benzoyl amide compound with insecticidal activity and application thereof Download PDF

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CN107915718B
CN107915718B CN201610880141.6A CN201610880141A CN107915718B CN 107915718 B CN107915718 B CN 107915718B CN 201610880141 A CN201610880141 A CN 201610880141A CN 107915718 B CN107915718 B CN 107915718B
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CN107915718A (en
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冯美丽
李宏举
胡志全
石欣欣
王林波
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Jiangsu Flag Chemical Industry Co ltd
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    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
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    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/84—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
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    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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    • 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
    • C07D401/14—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 three or more hetero rings

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Abstract

The invention discloses an N-acyl alkyl benzoyl amide compound with insecticidal activity and application thereof, and provides a derivative of the N-acyl alkyl benzoyl amide compound with a general formula I.

Description

N-acyl alkyl benzoyl amide compound with insecticidal activity and application thereof
Technical Field
The invention relates to the field of agricultural pesticides, in particular to an N-acyl alkyl benzoyl amide compound with insecticidal activity and application thereof.
Background
The problem of drug resistance of diseases, insects and weeds is always a problem which confuses plant protection workers, and chemical pesticides with unique action mechanisms are continuously sought for solving the problem. N-acyl alkyl benzoyl amide compounds developed by DuPont are novel compounds taking a ryanodine receptor as an action target, and represent evaluation results of the compound chlorantraniliprole (Rynaxypyr) such as comprehensive excellent insecticidal activity and field effect, low toxicity to mammals, good environmental compatibility and the like.
By summarizing the structure of a large number of reported N-acyl alkyl benzoyl amide compounds, the general formula of the compounds can be represented as follows: (formula 1-1) namely (A) a bridging moiety, (B) an amide moiety and (C) an amide moiety. Among them, the modification of the (C) amide moiety has been carried out more.
Figure GDA0001201969040000011
Structural general formula of 1-1N-acyl alkyl benzoyl amide compound
Patent ZL201410680448.2 discloses a pyrazole amide compound and its application, wherein the general formula of the compound is:
Figure GDA0001201969040000012
in the compound, when the substituent Q is
Figure GDA0001201969040000013
When the compound is used, the compound has certain insecticidal activity on pests such as diamondback moth and the like; however, it is known from the patent that the compound has better insecticidal effect at low concentration when applied to diamondback moth indoors; however, in the actual operation process, when the compound preparation is put into the field for application, the insecticidal effect is obviously poor, which is caused by the comprehensive combination of various factors such as field temperature, illumination, air flow and the like, although the patent discloses an analog test of related compounds in the field to obtain a certain insecticidal effect, the timeliness of the insecticidal activity of the compound is obviously short, the compound generally achieves the maximum effect within 3-7 days, and the insecticidal effect of the compound is reduced after more than 7 days.
In addition, the insecticidal effect of the composition in the patent compound is increased along with the increase of the concentration of the compound, but the synergy is not obvious, when the product is applied to mass agriculture for producing disinsection, a large amount of product is needed, and the use cost is greatly increased.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a derivative of N-acyl alkyl benzoyl amide compound which has long duration of drug effect and good environmental compatibility and is suitable for large-scale field disinsection.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a derivative of an N-acylalkylbenzoyl amide compound of the general formula I:
Figure GDA0001201969040000021
wherein R is1Is halogen or CN; r2Is C1-C8Alkyl or halogen;
R3is H or C1-C8An alkyl group; r4Is H or C1-C8An alkyl group;
R5selected from the following groups: OH, OH,
Figure GDA0001201969040000022
R5Wherein the substituent comprises R6，R7，X，R8And R9；
Substituent R6Selected from the following groups: h, H & HCl, or the following group C which may be substituted1-C8Alkyl radical, C3-C6Alkanyl radical, C3-C6Alkynyl radical, containing C1-C8Acyl of alkyl, containing C1-C8Acyl of alkoxy, containing C1-C8Acyl, acylamino, morpholinoyl of alkylamino, containing C1-C8A sulfonyl group of an alkyl group;
substituent R7Selected from the following groups: NH (NH)2，NH2HCl, or the following groups which may be substituted: c1-C8Alkyl radical, C3-C6Alkanyl radical, C3-C6Alkynyl radical, containing C1-C8Amide group of alkyl group, containing C1-C8Amide group of alkoxy group, containing C1-C8Amide group of alkylamino group, containing C1-C8Acylalkane of alkylamino radicalBase, containing C1-C8Alkyl sulfonamide, ureido, morpholinamide
The substituent X is CH or N;
substituent R8Selected from the following groups: h, or the following group C which may be substituted1-C8Alkyl radical, C3-C8Cycloalkyl or C3-C6A heterocycloalkyl group;
substituent R9Selected from the following groups: h, or the following group C which may be substituted1-C8Alkyl radical, C3-C8Cycloalkyl or C3-C6A heterocycloalkyl group;
substituent R8And R9Also includes both and R5C formed by N together2-C6The heterocyclic alkane of (1).
The substituent R of the invention6Or R7The substituted group in (1) is selected from halogen, C1-C4Alkyl radical, C1-C4Alkoxy or nitro.
R in the invention1Preferably Cl or CN.
R in the invention2Preferably CH3Or Cl.
R in the invention3Preferably H or CH3，R4Preferably H or CH3。
R in the invention6Preferably H.HCl or the following groups which may be substituted: containing C1-C4Acyl of alkyl, containing C1-C4Acyl of alkoxy, containing C1-C4Acyl of alkylamino, morpholinyl, containing C1-C4A sulfonyl group of an alkyl group; the substituent is selected from halogen and C1-C4Alkyl or C1-C4Alkoxy radical
R in the invention6Preferably contains C1-C4Acyl of alkoxy, containing C1-C4Acyl of alkylamino; the substituent is selected from halogen and C1-C4Alkyl or C1-C4Alkoxy radical。
R in the invention6Preferably H, -H.HCl, tert-butoxyacyl, methanesulfonyl, morpholinyl, N-methylaminoacyl, N-dimethylaminoyl, acetyl or methoxyacyl.
Said R of the invention7Preferably NH2、NH2HCl or the following groups which may be substituted: containing C1-C4Amide group of alkyl group, containing C1-C4Amide group of alkoxy group, containing C1-C8Amide group of alkylamino group, containing C1-C8Acylamino methylene of alkylamino, ureido, containing C1-C8Alkyl sulfonamide, morpholine amide; the substituent is selected from halogen and C1-C4Alkyl or C1-C4Alkoxy radical
R in the invention7Preferably NH2、NH2HCl, 3-methylureido, acetamido, 3-dimethylureido, methanesulfonamido, methoxyamido, N-ethylaminoacylethylene, tert-butoxyamido.
Table 1 lists the structures of some of the compounds of formula I and their physical properties.
Figure GDA0001201969040000041
Table 2 structural and physical properties of part of compounds of formula I
Figure GDA0001201969040000042
Figure GDA0001201969040000051
Table 3 structural and physical properties of part of compounds of formula I
Figure GDA0001201969040000052
Figure GDA0001201969040000061
Table 4 structural and physical properties of the compounds of formula I
Figure GDA0001201969040000062
Figure GDA0001201969040000071
Figure GDA0001201969040000081
Process for the preparation of the partial compounds of the general formula I according to the invention1HNMR(DMSO-d6300MHz) data are as follows:
compounds 2-11.20 (m,2H),1.28(s,6H),1.39(s,9H),1.69(m,2H),2.15(s,3H),2.43(s,2H),2.87(m,2H),3.82(m,3H),7.28(d,1H),7.35(s,1H),7.45(d,1H),7.62(dd,1H),7.96(m,2H),8.17(dd,1H),8.48(dd,1H),10.26(s, 1H).
Compounds 2-21.28 (s,6H),1.38(m,2H),1.75(m,2H),2.10(s,3H),2.46(m,2H), 2.77-2.82 (m,5H),3.41(m,2H),3.68(m,1H),7.31(m,3H),7.56(m,1H),7.98(m,2H),8.11(d,1H),8.45(d,1H),10.27(s, 1H).
Compounds 2-31.52 (s,6H),1.93(d,2H),2.21(s,3H),2.51(s,2H),2.92(t,2H),3.12(m,1H),3.27(m,3H), 3.68-3.75 (m,8H),3.95(m,1H),5.72(d,1H),7.09(s,1H),7.23(s,1H),7.34(m,2H),7.41(dd,1H),7.87(d,1H),8.48(d,1H),10.22(s, 1H).
Compounds 2-41.42 (s,6H),1.68(ws,2H),1.81(m,2H),2.11(s,3H),2.41(s,2H),2.72(s,3H),2.82(m,2H),3.79(m,2H),3.82(ws,1H),4.56(ws,1H),5.94(d,1H),7.04(s,1H),7.17(s,1H),7.23(m,2H),7.33(dd,1H),7.78(d,1H),8.39(d,1H),10.17(s, 1H).
Compounds 2-51.42 (s,6H),1.68(ws,2H),1.81(m,2H),2.11(s,3H),2.41(s,2H),2.72(s,3H),2.82(m,2H),3.79(m,2H),3.82(ws,1H),4.56(ws,1H),5.94(d,1H),7.04(s,1H),7.17(s,1H),7.23(m,2H),7.33(dd,1H),7.78(d,1H),8.39(d,1H),10.17(s, 1H).
Compounds 2-61.50 (s,6H),1.70(s,2H), 1.88-1.99 (m,2H),2.09(s,3H),2.19(s,3H),2.49(s,2H),2.72(m,1H),3.17(m,1H),3.76(m,1H),3.99(m,1H),4.52(m,1H),5.94(ws,1H),7.13(s,1H),7.26(s,2H),7.30(s,1H),7.41(dd,1H),7.87(d,1H),8.47(d,1H),10.28(s, 1H).
Compounds 2-71.28 (s,6H),1.67(m,2H),2.10(s,3H),2.50(m,3H),2.91(ws,2H),3.34(s,1H),3.57(s,3H),3.81(m,3H),7.35(ws,3H),7.56(dd,1H),7.79(m,2H),8.12(d,1H),8.46(d,1H),10.36(s, 1H).
Compounds 2-81.29 (s,6H),1.60(m,2H),1.85(m,2H),1.96(s,1H),2.15(s,3H),2.49(s,2H),2.78(s,1H),2.94(m,2H),3.23(m,2H),3.84(m,1H),7.29(d,1H),7.41(s,1H),7.44(d,1H),7.63(dd,1H),7.94(s,1H),8.18(d,1H),8.24(d,1H),8.49(d,1H),10.35(s, 1H).
Compounds 2-101.16 (m,2H),1.39(m,2H),2.14(s,3H), 2.24-2.28 (m,2H),2.81(m,5H),3.08(m,2H),3.36(m,2H),3.66(ws,1H),7.32(s,1H),7.36(s,1H),7.45(s,1H),7.58(dd,1H),7.85(d,1H),8.14(d,1H),8.32(t,1H),8.47(d,1H),10.22(s, 1H).
Compounds 2-111.39 (m,2H),1.85(m,2H),2.20(s,3H),2.87(t,2H),3.23(m,7H), 3.66-3.72 (m,8H),3.97(m,3H),6.03(d,1H),7.13(s,1H),7.21(s,1H),7.27(m,1H),7.39(m,1H),7.86(d,1H),8.44(s,1H),10.02(s,1H),10.23(s, 1H).
Compounds 2-131.23 (m,2H),1.82(m,2H),2.20(s,3H),2.40(m,2H),2.75(d,3H),2.84(m,2H),3.64(m,2H),3.82(m,3H),4.52(m,1H),5.94(d,1H),7.06(s,1H), 7.26-7.27 (m,3H),7.39(dd,1H),7.86(d,1H),8.44(d,1H),8.39(d,1H),10.23(s, 1H).
Compounds 2-141.28 (m,2H),1.72(m,1H),1.76(m,1H),2.08(s,3H),2.20(s,3H),2.39(m,2H),2.70(m,1H),3.15(m,1H),3.64(m,2H),3.76(m,1H),3.96(m,1H),4.51(m,1H),5.94(m,1H),7.06(s,1H),7.15(t,1H),7.28(m,2H),7.39(dd,1H),7.86(d,1H),8.42(d,1H),10.11(s, 1H).
Compounds 2-151.26 (m,2H),1.86(m,2H),2.19(s,3H),2.38(m,2H),2.88(t,2H),3.64(m,2H),3.68(s,3H),3.91(m,1H),4.06(m,1H),5.75(d,1H),7.08(s,1H),7.14(t,1H),7.26(m,2H),7.38(dd,1H),7.85(d,1H),8.44(d,1H),10.19(s, 1H).
Compounds 3-20.83 (m,1H),1.18(m,3H),1.32(d,6H),1.69(m,2H),2.09(s,3H),2.73(m,3H),3.08(m,1H),3.59(m,1H),3.85(d,1H),4.20(d,1H),7.46(s,1H),7.60(dd,1H),7.85(s,1H),7.93(s,1H),8.00(s,3H),8.14-8.17(m,2H),8.47(d,1H),10.48(s, 1H).
Compounds 3-31.32 (m,8H),1.79(m,5H),2.15(s,3H),2.74(m,3H),3.11(m,1H),3.76(m,1H),3.90(m,1H),4.25(m,1H),7.29(s,1H),7.36(s,1H),7.44(s,1H),7.62(dd,1H),7.81(d,1H),7.96(s,1H),8.16(d,1H),8.49(s,1H),10.23(s, 1H).
Compounds 3-51.30 (m,8H),1.77(m,2H),2.09(s,3H),2.73(m,3H),2.88(m,3H),3.09(m,1H),3.35(m,1H),3.83(d,1H),4.18(d,1H),7.34(s,1H),7.31(ws,3H),7.57(dd,1H),7.95(w,1H),8.10(d,1H),8.45(d,1H),10.25(s, 1H).
Compounds 3-71.06 (t,3H),1.32(s,6H),2.16(s,3H),2.48(s,2H),2.78-3.19(m,8H),3.90(m,2H),4.04(m,1H),4.45(m,1H),7.28(s,1H),7.40(s,1H),7.46(s,1H),7.63(dd,1H),7.92(s,1H),8.18(d,1H),8.49(d,1H),8.58(m,1H),10.25(s, 1H).
Compounds 3-81.20 (m,2H),1.31(s,6H),1.38(s,9H),1.72(m,2H),2.15(s,3H),2.50(s,2H),2.67(m,1H),3.06(m,1H),3.47(m,1H),3.90(m,1H),4.26(m,1H),6.90(d,1H),7.30(d,1H),7.37(s,1H),7.45(d,1H),7.62(dd,1H),7.97(s,1H),8.18(dd,1H),8.49(dd,1H),10.24(s, 1H).
Compounds 3-91.37 (m,2H),1.92(m,2H),2.16(s,3H),2.45(t,2H),2.60(t,1H),3.01(t,1H),3.31(m,2H),3.72(m,1H),4.37(m,1H),7.34(d,1H),7.48(s,2H),7.63(dd,1H),8.10(ws,1H),8.18(d,1H),8.39(t,1H),8.50(d,1H),10.39(s, 1H).
Compounds 3-111.17 (m,2H),1.74(m,2H),2.16(s,3H),2.44(t,2H),2.53(d,3H),2.73(t,1H),3.04(t,1H),3.32(m,2H),3.62(m,2H),4.16(d,1H),5.64(q,1H),5.87(d,1H),7.39(s,1H),7.43(d,1H),7.48(d,1H),7.62(dd,1H),8.18(d,1H),8.28(t,1H),8.49(d,1H),10.26(s, 1H).
Compounds 3-121.27 (m,2H),1.73(m,2H),2.16(s,3H),2.46(t,2H),2.59(m,1H),2.76(s,6H),2.99(m,1H),3.30(m,2H),3.66-3.71(m,2H),4.30(m,1H),5.98(d,1H),7.35(s,1H),7.39(s,1H),7.48(s,1H),7.62(dd,1H),8.18(d,1H),8.29(t,1H),8.49(d,1H),10.27(s, 1H).
Compounds 3-131.29 (m,2H),1.83(m,2H),2.16(s,3H),2.44(t,2H),2.74(t,1H),2.94(s,3H),3.05(t,1H),3.30(m,2H),3.37(m,1H),3.64(d,1H),4.18(d,1H),7.18(d,1H),7.34(s,1H),7.39(s,1H),7.48(s,1H),7.62(dd,1H),8.17(d,1H),8.28(t,1H),8.49(t,1H),10.28(s, 1H).
Compounds 3-141.25 (m,2H),1.74(m,2H),2.16(s,3H),2.44(t,2H),2.71(t,1H),3.03(s,2H),3.30(s,2H),3.52(s,4H),3.65(d,1H),4.19(d,1H),7.21(d,1H),7.34(d,1H),7.39(s,1H),7.48(s,1H),7.62(dd,1H),8.17(d,1H),8.28(t,1H),8.49(dd,1H),10.26(s, 1H).
Compounds 3-161.22 (m,2H),1.38(s,9H),1.67(m,2H),2.16(s,3H),2.43(t,2H),2.66(t,1H),3.00(t,1H),3.35(ws,2H),3.45(ws,1H),3.65(d,1H),4.21(d,1H),6.89(d,1H),7.34(s,1H),7.39(s,1H),7.48(s,1H),7.62(dd,1H),8.17(d,1H),8.27(t,1H),8.49(t,1H),10.26(s, 1H).
Compounds 4-11.49 (s,6H),2.17(s,3H),2.50(s,2H),2.79(d,3H),5.74(m,1H),7.09(s,1H),7.24(s,1H),7.32(s,2H),7.37(dd,1H),7.84(d,1H),8.45(d,1H),10.26(s, 1H).
Compounds 4-22.16 (s,3H),2.23(t,2H),2.54(d,3H),3.30(m,2H),7.33(d,1H),7.39(s,1H),7.47(d,1H),7.61(dd,1H),7.71(s,1H),8.16(d,1H),8.36(s,1H),8.49(d,1H),10.26(s, 1H).
Compounds 4-31.52 (s,6H),2.17(s,3H),2.67(s,2H),2.98(s,3H),3.07(s,3H),7.07(s,1H),7.23(d,1H),7.37(m,2H),7.81(dd,1H),7.85(d,1H),8.45(dd,1H),10.34(s, 1H).
Compounds 4-42.16 (s,3H),2.43(t,2H),2.80(s,3H),2.88(s,3H),3.31(t,2H),7.34(d,1H),7.39(s,1H),7.47(d,1H),7.61(dd,1H),8.16(d,1H),8.23(t,1H),8.49(d,1H),10.25(s, 1H).
Compounds 4-181.46 (m,1H),1.78(m,3H),2.15(s,3H),2.27(m,2H),3.12(m,2H),3.30(m,2H),3.59(m,1H),3.73(m,1H),3.81(m,1H),7.33(s,1H),7.39(s,1H),7.47(s,1H),7.60(dd,1H),7.96(t,1H),8.16(d,1H),8.34(t,1H),8.49(d,1H),10.26(s, 1H).
Compounds 4-191.28 (s,6H),1.71(m,1H),1.92(m,1H),2.15(s,3H),2.46(s,2H),3.44(m,1H),3.75(m,3H),4.22(m,1H),7.29(s,1H),7.35(s,1H),7.44(s,1H),7.62(dd,1H),7.95(s,1H),8.16(d,1H),8.22(d,1H),8.49(d,1H),10.25(s, 1H).
Compounds 4-201.71 (m,1H),2.05(m,1H),2.11(s,3H),2.25(t,2H),3.30(m,2H),3.44(m,1H),3.71(m,3H),4.22(m,1H),7.33(d,1H),7.39(s,1H),7.48(d,1H),7.61(dd,1H),8.15(m,2H),8.38(t,1H),8.49(d,1H),10.27(s, 1H).
Compounds 4-211.29 (s,6H),1.51(m,1H),1.89(m,1H),2.16(s,3H),2.31(m,1H),2.47(m,2H),3.04(m,2H),3.38(m,1H),3.63(m,3H),7.29(s,1H),7.35(s,1H),7.44(s,1H),7.62(dd,1H),7.98(s,1H),8.09(t,1H),8.18(d,1H),8.48(d,1H),10.25(s, 1H).
Compounds 4-221.5 (m,1H),1.88(m,1H),2.16(s,3H),2.24-2.34(m,3H),2.50(t,2H),3.03(m,2H),3.30(m,1H),3.54-3.72(m,3H),7.33(d,1H),7.39(s,1H),7.48(d,1H),7.61(dd,1H),7.97(t,1H),8.17(dd,1H),8.38(t,1H),8.49(dd,1H),10.27(s, 1H).
Compounds 4-230.48 (m,2H),0.79(m,2H),1.52(s,6H),2.17(s,3H),2.45(s,2H),2.71(m,1H),5.87(d,1H),7.11(s,1H),7.23(m,2H),7.37(m,2H),7.84(d,1H),8.45(d,1H),10.17(s, 1H).
Compounds 4-240.38 (m,2H),0.58(m,2H),2.17(s,3H),2.22(t,2H),2.61(m,1H),3.30(m,2H),7.33(d,1H),7.40(s,1H),7.50(d,1H),7.62(dd,1H),7.93(d,1H),8.18(dd,1H),8.39(t,1H),8.50(dd,1H),10.28(s, 1H).
Compounds 4-251.40 (m,2H),1.50(s,6H),1.85(m,2H),2.22(s,3H),2.48(s,2H),3.47(t,2H),3.92-3.95(m,3H),5.67(d,1H),7.08(s,1H),7.24(s,1H),7.31(s,2H),7.37(dd,1H),7.84(d,1H),8.45(d,1H),10.19(s, 1H).
Compounds 4-271.53 (s,6H),1.89-1.99(m,4H),2.17(s,3H),2.61(s,2H),3.49(m,4H),7.08(s,1H),7.24(s,1H),7.34-7.39(m,2H),7.83(d,1H),7.92(s,1H),8.45(d,1H),10.39(s, 1H).
Compounds 4-281.74-1.89 (m,4H),2.17(s,3H),2.39(t,2H),3.25-3.33(m,6H),7.35(d,1H),7.40(s,1H),7.49(d,1H),7.62(dd,1H),8.18(dd,1H),8.51(dd,1H),10.28(s, 1H).
Compounds 4-291.50 (s,6H),2.17(s,3H),2.30(t,2H),2.38(s,2H),4.08(t,2H),4.20(t,2H),7.08(s,1H),7.23(s,2H),7.38(m,2H),7.68(s,1H),7.83(d,1H),8.46(s,1H),10.33(s, 1H).
Compounds 4-302.16 (m,6H),3.29(t,2H),3.82(t,2H),4.00(t,2H),7.33(d,1H),7.39(s,1H),7.49(d,1H),7.62(dd,1H),8.18(d,1H),8.33(t,1H),8.50(s,1H),10.28(s, 1H).
Compounds 4-311.53 (s,6H),2.17(s,3H),2.69(s,2H),3.53(s,2H),3.67(s,6H),7.05(s,1H),7.24(s,1H),7.37(m,2H),7.56(s,1H),7.84(d,1H),8.46(d,1H),10.27(s, 1H).
Compounds 4-322.16 (s,3H),2.43(s,2H),3.36(m,4H),3.43(m,2H),3.53(s,4H),7.34(d,1H),7.39(s,1H),7.49(d,1H),7.62(dd,1H),8.20(dd,1H),8.30(t,1H),8.50(d,1H),10.27(s, 1H).
Compounds 4-371.29 (s,6H),2.44(s,2H),6.99(s,1H),7.39(d,2H),7.48(d,1H),7.62(dd,1H),7.79(s,1H),8.06(ws,1H),8.17(d,1H),8.49(d,1H),10.50(s, 1H).
The N-acyl alkyl benzoyl amide compound derivative represented by the general formula I or pharmaceutically acceptable salt thereof can be used for preparing pesticides, particularly agricultural pesticides used as active ingredients for controlling various harmful insects such as agricultural harmful insects, stored grain harmful insects, sanitary harmful insects, nematodes and the like which are harmful to rice, fruit trees, vegetables, other crops, flowers, ornamental plants and the like, and have remarkable pesticidal effects on lepidoptera pests such as cotton bollworms, beet armyworms, diamond back moths, cabbage caterpillars, rice leaf rollers, chilo suppressalis and the like, homoptera pests such as leafhoppers, plant hoppers, aphids, whiteflies and the like, diptera pests such as houseflies, leaf miners, mosquitoes and the like, orthoptera pests, coleoptera pests and the like. The compounds of the present invention are therefore useful as pesticides for protecting plants in agriculture, horticulture, and the like. Of course, the pests which the compounds of the invention can control are not limited to the above exemplified ranges. The o-methylaminobenzamide derivative or the pharmaceutically acceptable salt thereof is used as an active component, and an agriculturally acceptable carrier can be prepared into an insecticidal composition, wherein the weight percentage of the active component in the composition is 0.1-99.5%.
The agronomic pesticides of this invention are generally formulated into conventional formulations according to conventional methods for the preparation of agricultural chemicals.
That is, the N-acylalkylbenzoyl amide type compound derivative represented by I or a salt thereof and optionally an auxiliary agent are blended in an appropriate ratio with a suitable inert carrier to prepare a suitable dosage form such as suspension, emulsifiable concentrate, soluble concentrate, wettable powder, granule, powder, tablet, pack and the like by dissolving, dispersing, suspending, mixing, impregnating, adsorbing or adhering.
Inert carriers useful in the present invention may be either solid or liquid. As raw materials which can be used as solid carriers, there can be exemplified soybean powder, cereal flour, wood flour, bark powder, sawdust, tobacco stalk powder, walnut shell flour, bran, cellulose powder, vegetable extraction residues, synthetic polymer or resin powder, clay (e.g., kaolin, bentonite and acid clay), talc (e.g., talc and pyrophyllite), silica powder or flakes (e.g., diatomaceous earth, silica sand, mica and white carbon (synthetic highly dispersible silicic acid, also known as finely divided hydrated silica or hydrated silicic acid, some commercially available products containing calcium silicate as a main component), activated carbon, sulfur powder, pumice, calcined diatomaceous earth, ground bricks, fly ash, sand, calcium carbonate, calcium phosphate and other inorganic or mineral powders, plastic carriers (e.g., polyethylene, polypropylene and polyvinylidene chloride), chemical fertilizers (e.g., ammonium sulfate, calcium phosphate and other inorganic or mineral powders), calcined diatomaceous earth, ground bricks, fly ash, calcium carbonate, calcium phosphate and other inorganic or mineral powders, plastic carriers (e., Ammonium phosphate, ammonium nitrate, urea, ammonium chloride) and compost. These carriers may be used alone or as a mixture.
Materials which can be used as liquid carriers are selected from those which are soluble in themselves or, although not soluble, are capable of dispersing the active ingredient compound with the aid of auxiliaries. Common liquid carriers, such as water; organic solvents such as toluene, xylene, cyclohexane, methanol, butanol, ethylene glycol, acetone, dimethylformamide, diethyl ether, dimethyl sulfoxide, animal and vegetable oils and fatty acids; commonly used surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants; other adjuvants, such as wetting agents, thickeners, and the like.
When the compound of the present invention represented by the general formula I or a salt thereof is used as an active ingredient in an insecticide, the content in the insecticide may be selected from the range of 0.1% to 99.5%, and an appropriate content of the active ingredient may be determined according to the formulation form and the application method. In general, the aqueous emulsion contains 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably 10% to 40%; the microemulsion contains 5% to 50% of active ingredients, preferably 10% to 30%; the emulsifiable concentrates contain 1% to 90% of active ingredient, preferably 10% to 80%.
For example, the aqueous emulsion or microemulsion may be prepared by uniformly mixing the compound of the present invention as an active ingredient with an auxiliary agent such as a solvent or a surfactant, and may be diluted with water to a predetermined concentration when used. The wettable powder can be prepared by mixing and pulverizing the compound of the present invention as an active ingredient, a solid carrier, a surfactant, and the like, and can be diluted with water for use. Of course, the method of processing the formulation is in no way limited to the above. Those skilled in the art can select an appropriate method according to the active ingredient and the purpose of use, etc.
The insecticide of the present invention may contain, in addition to the compound represented by the general formula I as an active ingredient, any suitable active ingredient such as other insecticides, acaricides, fungicides, insect growth regulators, plant growth regulators and soil conditioners.
For the use of the insecticide of the present invention, a commonly used application method such as stem and leaf spraying, water surface application, soil treatment, seed treatment, and the like can be selected. For example, when spray from stems and leaves is employed, an aqueous emulsion, microemulsion or emulsifiable concentrate of the compound represented by formula I as the active ingredient may be used in a concentration range of 1 to 1000ppm, preferably in a concentration range of 1 to 500 ppm.
The invention has the advantages that: the invention adjusts the structure of the derivative of the N-acyl alkyl benzoyl amide compound in the prior art, and aims at the defects of the compound in the prior art in the application process, the invention discovers the derivative of the N-acyl alkyl benzoyl amide compound which has long duration of drug effect, good synergy and good stability of the compound, is suitable for large-batch agricultural production and has low cost of batch application.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Unless otherwise indicated, the following terms used in the specification and claims have the meanings discussed below:
"alkyl" means a saturated aliphatic group of 1 to 20 carbon atoms, including straight and branched chain groups (a numerical range referred to herein, e.g., "1 to 20", means that the group, in this case alkyl, may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms). Alkyl groups having 1 to 4 carbon atoms are referred to as lower alkyl groups. When a lower alkyl group has no substituent, it is referred to as unsubstituted lower alkyl. More preferably, the alkyl group is a medium size alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl, and the like. Preferably, the alkyl group is a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, or the like.
"alkanyl" refers to an unsaturated aliphatic radical of 2 to 20 carbon atoms containing at least one carbon-carbon double bond, C ═ C, including straight and branched chain radicals (a range of numbers referred to in this application, e.g., "2 to 20", refers to the radical, which in this case may contain 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms). Alkylenyl groups containing 2 to 6 carbon atoms are referred to as lower alkanyl groups. When the lower alkenyl group has no substituent, it is referred to as unsubstituted lower alkenyl. More preferably, the alkanyl group is a medium size alkyl group having 3 to 6 carbon atoms.
"alkynyl" means an unsaturated aliphatic hydrocarbon group of 2 to 20 carbon atoms containing at least one carbon C.ident.C, including straight and branched chain groups (reference to a range of numbers in this application, e.g., "1 to 20", means that the group, in this case, may contain 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms). Alkynyl groups having 2 to 6 carbon atoms are referred to as lower alkynyl groups. When the lower alkynyl group has no substituent, it is referred to as an unsubstituted lower alkynyl group. More preferably, the alkynyl group is a medium size alkynyl group having 3 to 6 carbon atoms.
"acyl" represents a- (C ═ O) -group or a- (C ═ O) H group.
"(C1-C8 alkyl) acyl" represents an acyl group having a C1-C8 alkyl group as a substituent, wherein "C1-C8" represents that the number of carbon atoms in the alkyl substituent is 1 to 8, for example, acetyl, n-propionyl, isopropionyl, n-butyryl and the like.
"(C1-C8 alkoxy) acyl" represents an acyl group having a substituent C1-C8 alkoxy group, such as methoxyacyl group, ethoxyacyl group, n-propoxycarbonyl group, isopropoxyacyl group, n-butoxyacyl group, t-butoxyacyl group, etc.
"alkoxy" means an "alkyl-O-" group in which alkyl is as defined above.
"alkylamino" refers to an amino group having one or two alkyl substituents, such as an "alkyl-NH-" or "(alkyl) 2N-" group, wherein alkyl is as defined above.
"(C1-C8 alkylamino) acyl," refers to acyl having C1-C8 alkylamino substituents.
"amido" means an "H (C ═ O) -NH-" group.
"Morpholinoyl" means
Figure GDA0001201969040000141
A group. "sulfonyl" represents an "-S (═ O) 2-" group.
"(C1-C8 alkyl) sulfonyl" represents a "sulfonyl with C1-C8 alkyl substituents" group.
"acylalkyl" denotes a "- (C ═ O) -alkyl-" or "H (C ═ O) -alkyl-" group. Wherein alkyl is as defined above, alkyl in this group is preferably lower alkyl, especially methylene or ethylene.
"sulfonamide" refers to an amine group having one or two sulfonyl substituents, e.g., a sulfonyl group.
"halogen" means a fluorine, chlorine, bromine or iodine group.
A typical preparation method of the present invention is as follows, but it is by no means intended to limit the scope of the present invention in any way; compounds of general formula I may be prepared by reaction of formulas 1-6, wherein the substituents are as previously defined unless otherwise indicated.
1) When R is5When represents-OH, compound I of general formula I can be prepared by reaction of formula 1:
reaction formula 1:
Figure GDA0001201969040000142
and (3) reacting the III and the II in a proper solvent at the temperature of between 20 ℃ below zero and the boiling point for 0.5 to 48 hours under the alkaline condition to obtain the target compound (I-1).
As the base usable in this reaction, there may be mentioned organic bases such as pyridine, triethylamine, 4-dimethylaminopyridine or N-methylmorpholine and the like, and inorganic bases such as potassium carbonate, sodium hydroxide and the like. The amount of the base to be used may be appropriately selected within a range of from 1mol to an excess mol per mol of the compound of the formula III or the compound of the formula II.
Suitable solvents are selected from the group consisting of halogenated alkanes, acetone, benzene, toluene, ethyl acetate, acetonitrile, propionitrile, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or the like. The synthesis of starting material III is carried out by known methods, for example as described in CN 1541063A.
After completion of the reaction, the reaction mixture containing the desired product is subjected to a separation treatment according to a usual method, and if necessary, purified by recrystallization, column chromatography, or the like, whereby the desired product can be obtained.
2) When R is5Represents
Figure GDA0001201969040000151
When compounds of general formula I can be prepared by reaction scheme 2-1 or reaction scheme 2-2:
reaction formula 2-1:
Figure GDA0001201969040000152
wherein R is6Represents optionally substituted C1-C3Alkyl, C which may be substituted3-C6Alkanyl, optionally substituted C3-C6Alkynyl, optionally substituted alkoxyacyl;
in the presence of an inert solvent and a condensing agent, the general formula compound I-1 and the general formula compound IV are condensed to obtain the derivative of the general formula I-2.
The inert solvent used in the reaction may be any solvent as long as it does not hinder the reaction from proceeding. Such as tetrahydrofuran, diethyl ether, dioxane, chloroform, dichloromethane, dichloroethane, and the like.
As the condensing agent used in this reaction, any condensing agent can be used as long as it is used in general amide synthesis. The condensing agent may be selected from the group consisting of Mukaiyama agents (e.g., 2-chloro-N-methylpyridine)
Figure GDA0001201969040000153
Iodide), 1, 3-Dicyclohexylcarbodiimide (DCC), Carbonyldiimidazole (CDI) and diethyl phosphorocyanide (DEPC), 2- (7-azobenzotriazol) -N, N' -tetramethyluronium Hexafluorophosphate (HATU). The amount of the condensation agent to be used may be appropriately selected in the range of 1mol to an excess number of moles.
As the base usable in this reaction, there may be mentioned organic bases such as pyridine, triethylamine, 4-dimethylaminopyridine or N-methylmorpholine and the like, and inorganic bases such as potassium carbonate, sodium hydroxide and the like. The amount of the base to be used may be appropriately selected within a range of from 1mol to an excessive number of moles per mole of the compound of the formula VI or the compound of the formula I-1.
As far as the reaction temperature is concerned, the reaction may be carried out at from-10 ℃ to the reflux temperature of the suitable solvent used. The reaction time varies depending on the scale or temperature of the reaction, and is appropriately determined generally within a range of several minutes to 48 hours.
After completion of the reaction, the reaction mixture containing the desired product is subjected to a separation treatment according to a usual method, and if necessary, purified by recrystallization, column chromatography, or the like, whereby the desired product can be obtained.
Reaction formula 2-2:
Figure GDA0001201969040000161
the I-1 and a halogenating agent react for 0.5 to 24 hours in a solvent-free or proper solvent at the temperature of between 20 ℃ below zero and the boiling point to obtain a target compound I-1'. The halogenating agent is selected from thionyl chloride, oxalic acid, light fixing, diphosgene, phosgene, phosphorus trichloride or phosphorus oxychloride and the like. Suitable solvents are selected from the group consisting of halogenated alkanes, acetone, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane, and the like.
Under the alkaline condition, in a polar or non-polar aprotic solvent and at a proper temperature, the compound I-1' reacts with the compound (IV) to obtain the compound (I-2) with the general formula. Wherein: the alkali is alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate or organic alkali; the polar or non-polar aprotic solvent is halogenated alkane, benzene, toluene, amides and nitrile solvents. The alkali metal hydroxide is sodium hydroxide or potassium hydroxide, the alkali metal carbonate is sodium carbonate or potassium carbonate, the alkali metal bicarbonate is sodium bicarbonate or potassium bicarbonate, and the organic base is pyridine, triethylamine, 4-dimethylaminopyridine or N-methylmorpholine; the amide solvent is N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone; the nitrile solvent is acetonitrile or propionitrile. The above-mentioned suitable temperature is-10 to 30 ℃ and preferably-5 to 0 ℃.
3) When R is6Represents H.HCl or (C) which may be substituted1-C8) Alkanoyl group, aminoacyl group which may be substituted, morpholinoyl group which may be substituted, (C)1-C8) For alkylsulfonyl, the preparation is carried out using equation 3:
reaction formula 3:
Figure GDA0001201969040000162
the I-2 and acid react for 0.5 to 48 hours in a solvent-free or proper solvent at the temperature of between 20 ℃ below zero and the boiling point to obtain a target compound I-3. The acid is selected from inorganic acid such as hydrochloric acid, concentrated sulfuric acid, etc.; organic acids such as trifluoroacetic acid, p-toluenesulfonic acid and the like. Suitable solvents are selected from the group consisting of halogenated alkanes, acetone, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane, and the like. The synthetic route of the raw material (I-2) is shown in a reaction formula 2-1 or a reaction formula 2-2.
The compound (I-3) is reacted with an acylating agent (V) under basic conditions in a polar or nonpolar aprotic solvent at an appropriate temperature to obtain a compound of the general formula (I-4). Wherein: the alkali is alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate or organic alkali; the polar or non-polar aprotic solvent is halogenated alkane, benzene, toluene, amides and nitrile solvents. The alkali metal hydroxide is sodium hydroxide or potassium hydroxide, the alkali metal carbonate is sodium carbonate or potassium carbonate, the alkali metal bicarbonate is sodium bicarbonate or potassium bicarbonate, and the organic base is pyridine, triethylamine, 4-dimethylaminopyridine or N-methylmorpholine; the amide solvent is N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone; the nitrile solvent is acetonitrile or propionitrile. Wherein the acylating agent (V) is R6-O-、R6-Cl or R6-Br. The above-mentioned suitable temperature is-10 to 30 ℃ and preferably-5 to 0 ℃.
4) When R is5Represents
Figure GDA0001201969040000171
When compounds of general formula I can be prepared by reaction scheme 4-1 or reaction scheme 4-2:
reaction formula 4-1:
Figure GDA0001201969040000172
reaction formula 4-2:
Figure GDA0001201969040000173
R7represents optionally substituted C1-C3Alkyl, C which may be substituted3-C6Alkanyl, optionally substituted C3-C6Alkynyl group, optionally substituted (C)1-C8) An alkyl group, an alkoxyamide group which may be substituted; x represents C-H or N.
The reaction conditions of the reaction formula 4-1 refer to the reaction conditions of the reaction formula 2-1.
The reaction conditions of the reaction formula 4-2 refer to the reaction conditions of the reaction formula 2-2.
5) When R is7Represents H.HCl or an alkylamide group which may be substituted, (C)1-C8) Alkylsulfonylamido, aminoamido which may be substituted, morpholinoyl which may be substituted; when X represents N, the compound is prepared by using the reaction formula 5:
reaction formula 5:
Figure GDA0001201969040000181
the synthesis conditions of (I-7) were referred to the reaction conditions of reaction scheme 3. The synthetic route of the raw material I-5 is shown in a reaction formula 2-1 or a reaction formula 2-2.
6) When R is5Represents
Figure GDA0001201969040000182
When the compound of the general formula I is prepared by the reaction formula 6-1 or the reaction formula 6-2:
reaction formula 6-1:
Figure GDA0001201969040000183
reaction formula 6-2:
Figure GDA0001201969040000184
R8or R9Represents H, substituted C1-C8Alkyl radical, C3-C8Cycloalkyl or C3-C6Heterocycloalkyl radical, R8And R9May be the same or different; or R8And R9Together with the nitrogen to which they are attached to form C2-C6The heterocyclic alkane of (1).
The reaction conditions of the reaction formula 6-1 refer to the reaction conditions of the reaction formula 2-1.
The reaction conditions of the reaction formula 6-2 refer to the reaction conditions of the reaction formula 2-2.
Test examples of insecticides containing the compound of the present invention as an active ingredient will be described below. However, the embodiments of the present invention are not limited to the following.
Test example 1: the insecticidal effect on diamondback moths is achieved;
selecting 3-instar larvae, and testing the insecticidal effect by a leaf soaking feeding method. The compounds of the examples of the present invention were each formulated into an insecticide according to the compositional means of formulation example 3. Diluting the obtained pesticide emulsifiable concentrate with purified water, and uniformly mixing to obtain a liquid medicine with the required concentration. Selecting bracteal herbs, cleaning and drying, making into leaf disks by using a puncher, soaking in the liquid medicine for 10 seconds, taking out, naturally drying, and then putting into a culture dish. And inoculating 10 larvae of plutella xylostella of 3 rd instar into each dish, repeating for 3 times, investigating the number of dead insects of 1d, 2d and 3d, counting the death rate, and evaluating the insecticidal effect.
Among some tested compounds, the following compounds have good control effect on diamondback moth when the concentration is 20ppm, and the death rate is more than 80 percent: 1-6, 1-8, 2-1, 2-2, 2-4, 2-6, 2-10, 2-12, 2-13-2-16, 2-18, 2-21, 3-1, 3-8, 3-13, 3-16, 4-1-4-6, 4-9-4-12, 4-14, 4-17-4-30 and 4-32-4-40.
Test example 2: determining the toxicity baseline of the diamondback moth;
the toxicity baseline measurement of the compound in the patent and a known compound KC1 (compound 1.4 in CN 2014106804482) on the plutella xylostella is carried out; the structural formula of KC1 is as follows:
Figure GDA0001201969040000191
six concentrations were selected: toxicity baseline measurements were made at 2ppm, 1ppm, 0.5ppm, 0.1ppm, 0.05ppm and 0.01ppm for plutella xylostella in the same manner as in test example 1, and the regression of toxicity for some of the compounds is shown in the following table:
medicament Time Regression of virulence r
2-2 72h y＝5.8615+2.1333x 0.929
4-3 72h y＝6.1727+1.9192x 0.926
4-10 72h y＝6.2322+2.0331x 0.9459
4-17 72h y＝6.6478+2.2114x 0.9871
KC1 72h y＝6.7477+1.1711x 0.9118
As can be seen from the above table: in a virulence regression formula y ═ a + bx, b values of virulence curves of the four compounds 2-2, 4-3, 4-10 and 4-17 to plutella xylostella in the listed examples of the invention are much larger than that of a known compound KC1, which indicates that the concentration of the compound in the invention is sensitive to the virulence of the plutella xylostella, and the insecticidal activity of the compound to the plutella xylostella is also obviously increased along with the increase of the concentration of the compound; namely, the larger the x value of the medicine amount is, the higher the y value of the finally obtained medicine effect is, the better the medicine effect is; in combination with the drug cost of the field, under the condition of obtaining the same drug effect, the compound of the invention only needs less dosage to obtain the same drug effect as the KC1 compound, so that the drug dosage of the compound of the invention is gradually reduced, and the application cost is greatly reduced.
Test example 3: field pesticide effect test on the control effect of diamondback moth;
in view of the toxicity baseline data analysis, the four compounds 2-2, 4-3, 4-10 and 4-17 in the patent of the invention and the known compound KC1 are subjected to a field efficacy test on the plutella xylostella. The test crop is broccoli, and the variety is green ridge No. 8. The original test medicine is dissolved into 3400-6700 mg/L solution by using mixed solution of acetone and N' -dimethylformamide in equal ratio, and then diluted into 5mg/L and 50mg/L solution by using 1% Tween-20 aqueous solution. Spraying with hand-held sprayer at 675L/hm2The amount of the liquid medicine is sprayed, the whole plant is uniformly sprayed, and the plants are repeatedly arranged for 3 times and randomly arranged in blocks. 1 day before the test is sprayed with the pesticide, the diamondback moth larvae raised on indoor rape seedlings are inoculated to the broccoli leaves, 5 points are taken in each cell by adopting a diagonal method before the pesticide is sprayed on the next day, 2 broccoli are fixed in each point, and the quantity of the diamondback moth larvae on 10 plants in total is investigated in each cell. Investigating population base of diamondback moth in each plot before application, 1 day, 7 days after application,The number of remaining diamondback moths was investigated on 14 days.
And (3) calculating the drug effect: the control effect was calculated from the number of insects on 2 broccoli plants in the test area.
Control effect (%) } × 100 (1- [ (insect quantity before drug application in control area × insect quantity after drug application in treatment area)/(insect quantity after drug application in control area × insect quantity before drug application in treatment area) ])
Table 1: control effect of 5 compounds on diamondback moth (2016, Jiangsu sentence capacity)
Figure GDA0001201969040000201
As can be seen from the above table, the KC1 composition in the prior art has faster drug effect, reaches the maximum drug effect about 7 days after drug application, and has a certain reduction in control effect after the drug application time is gradually prolonged, which is caused by the timeliness of the compound and the comprehensive environment in the field,
test example 4: in view of the toxicity baseline data analysis, referring to the technical scheme in experimental example 3, the field efficacy test of the plutella xylostella is carried out on four compounds 2-4, 3-5, 4-26 and 4-37 in the patent of the invention and known compounds KC1 and KC2 (compound 1.3 in CN 2014106804482).
The structural formula of KC2 is as follows:
Figure GDA0001201969040000211
Figure GDA0001201969040000212
the above table shows that the compound of the present invention has superior time efficiency and better stability compared with the compounds in the prior art, and has long-term efficacy in the field production process, particularly, the efficacy of the traditional compound is obviously reduced within 14 to 21 days after the application, but the technical scheme of the present invention has stable efficacy, does not reduce, even increases to a certain extent, and is more suitable for the field production.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and any combination or equivalent changes made on the basis of the above-mentioned embodiments are also within the scope of the present invention.

Claims (10)

1. A derivative of an N-acylalkylbenzoyl amide compound of the general formula I:
Figure DEST_PATH_IMAGE001
wherein R is1Is halogen or CN; r2Is C1-C8Alkyl or halogen;
R3is H or C1-C8An alkyl group; r4Is H or C1-C8An alkyl group;
R5selected from the following groups:
Figure DEST_PATH_IMAGE002
、
Figure DEST_PATH_IMAGE003
、
Figure DEST_PATH_IMAGE004
；R5wherein the substituent comprises R6，R7，X，R8And R9；
Substituent R6Selected from the following groups: h, H & HCl, or C1-C8Alkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl radical, containing C1-C8Acyl of alkyl, containing C1-C8Acyl of alkoxy, containing C1-C8Acyl, acylamino, morpholinoyl of alkylamino, containing C1-C8A sulfonyl group of an alkyl group;
substituent R7Selected from the following groups: NH (NH)2，NH2HCl, or C1-C8Alkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl radical, containing C1-C8Amide group of alkyl group, containing C1-C8Amide group of alkoxy group, containing C1-C8Amide group of alkylamino group, containing C1-C8Acyl methyl group of alkylamino radical, containing C1-C8Alkyl sulfonamide, ureido, morpholinamide;
the substituent X is CH or N;
substituent R8Selected from the following groups: h, or C1-C8Alkyl radical, C3-C8Cycloalkyl radical, C3-C6A heterocycloalkyl group;
substituent R9Selected from the following groups: h, or C1-C8Alkyl radical, C3-C8Cycloalkyl radical, C3-C6A heterocycloalkyl group;
substituent R8And R9Also includes both and R5C formed by N together2-C6The heterocyclic alkane of (1).
2. The derivative of an N-acylalkylbenzoyl amide compound according to claim 1, characterized in that the substituent R6Or R7The following groups in (1): c1-C8Alkyl radical, C3-C6Alkenyl radical, C3-C6Alkynyl radical, containing C1-C8Acyl of alkyl, containing C1-C8Acyl of alkoxy, containing C1-C8Acyl, acylamino, morpholinoyl of alkylamino, containing C1-C8Sulfonyl of alkyl radicals, containing C1-C8Amide group of alkyl group, containing C1-C8Amide group of alkoxy group, containing C1-C8Amide group of alkylamino group, containing C1-C8Acylalkyl group of alkylamino group, containing C1-C8Alkyl sulfonamide and ureido, wherein the substituents in the above groups may be substituted by: halogen, C1-C4Alkyl radical, C1-C4Alkoxy or nitro.
3. The derivative of an N-acyl alkyl benzoyl amide compound of claim 1, wherein R is1Is Cl or CN.
4. The derivative of an N-acyl alkyl benzoyl amide compound of claim 1, wherein R is2Is CH3Or Cl.
5. The derivative of an N-acyl alkyl benzoyl amide compound of claim 1, wherein R is3Is H or CH3， R4Is H or CH3。
6. The derivative of an N-acyl alkyl benzoyl amide compound of claim 1, wherein R is6To contain C1-C4Acyl of alkoxy, containing C1-C4Acyl of alkylamino; the substituent is selected from halogen and C1-C4Alkyl or C1-C4An alkoxy group.
7. The derivative of an N-acyl alkyl benzoyl amide compound of claim 1, wherein R is6Is H, -H.HCl, tert-butoxyacyl, methylsulfonyl, morpholinoyl, N-methylaminoacyl, N-dimethylaminoyl, acetyl or methoxyacyl.
8. The derivative of an N-acyl alkyl benzoyl amide compound of claim 1, wherein R is7Is NH2、NH2HCl, 3-methylureido, acetamido, 3-dimethylureido, methanesulfonamido, methoxyamido, N-ethylaminoacylethylene,Tert-butoxy amide group.
9. Use of derivatives of N-acylalkylbenzoyl amides of general formula I according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 for the preparation of pesticides in the agricultural field.
10. An insecticidal composition comprising the derivative of the N-acyl alkyl benzoyl amide compound with the general formula I in claim 1 and an agriculturally acceptable carrier, wherein the weight percentage of the active components in the composition is 0.1-99.5%.
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