CN107915718A - N acyl benzoyl ammoniac compounds and its application with insecticidal activity - Google Patents

N acyl benzoyl ammoniac compounds and its application with insecticidal activity Download PDF

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CN107915718A
CN107915718A CN201610880141.6A CN201610880141A CN107915718A CN 107915718 A CN107915718 A CN 107915718A CN 201610880141 A CN201610880141 A CN 201610880141A CN 107915718 A CN107915718 A CN 107915718A
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alkyl
group
acyl
contain
benzoyl
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CN107915718B (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 Zhongqi Polytron Technologies Inc
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Jiangsu Zhongqi Polytron Technologies Inc
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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
    • C07D401/04—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
    • 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
    • A01N43/56—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
    • 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
    • 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
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • 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
    • 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
    • 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
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • 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
    • C07D401/14—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

Abstract

The invention discloses a kind of N acyl benzoyl ammoniac compounds with insecticidal activity and its application; a kind of derivative of the N acyl benzoyl ammoniac compounds of general formula I; the present invention is for deficiency of the N acyls benzoyl ammoniac compounds in actual application in the prior art; certain improvement is made to its derivative; a kind of duration of efficacy length is obtained; synergy is good; the stability of compound is good; suitable for large batch of agricultural production, the derivative of the low N acyl benzoyl ammoniac compounds of the cost applied in batches.

Description

N- acyl benzoyl ammoniac compounds and its application with insecticidal activity
Technical field
The present invention relates to agricultural insecticide field, more particularly to a kind of N- acyl benzene carbon amides with insecticidal activity Class compound and its application.
Background technology
The problem of disease, worm, resistance weed problem are always puzzled plant protection service person, will solve the problems, such as that this is needed Constantly to seek the chemical pesticide of mechanism of action uniqueness.The N- acyl benzoyl Ammonia compounds researched and developed by E.I.Du Pont Company Compound is exactly a kind of new compound using ryanodine receptor as action target, representation compound chlorantraniliprole （Chlorantraniliprole, RynaxypyrTM）Show comprehensive excellent insecticidal activity and field efficacy, to lactation The evaluation results such as animal toxicity is low and Environmental compatibility is good.
Pass through the summary to largely having reported N- acyl benzoyl Ammonia compounds structures, the general formula of such material It can represent as follows：（Formula 1-1）I.e.（A）Abutment part,（B）Amide moieties and（C）Amide moieties.It is wherein right（C）Amide moieties are repaiied The work of decorations is more.
The general structure of formula 1-1 N- acyl benzoyl Ammonia compounds compounds
Patent ZL201410680448.2 discloses the general formula of a kind of pyrazol acid amide compounds and its application, wherein compound For：
In the compound, when substituent Q isWhen, such compound has one to pests such as diamondback moths Fixed insecticidal activity；But from patent it was found from, have when which is applied to diamondback moth indoors, under low concentration preferable Insecticidal effect；But in actual mechanical process, such compound formulation is put into field and is applied, insecticidal effect can substantially become Difference, this is because caused by many factors such as the temperature in field, illumination, air-flow synthesis, although disclosing related compounds in patent Analogy of the thing in field is tested, and certain insecticidal effect is obtained, however, it will be apparent that it can be seen that such compound insecticidal activity Timeliness it is shorter, it generally reached maximum efficiency at 3-7 days, after 7 days, under the insecticidal effect of compound can occur Drop.
It is moreover, dense with compound for the different types of composition with insecticidal effect, itself insecticidal effect The change of degree and change, in contrast, the insecticidal effect of the composition in the patents can be with the increasing of compound concentration Add and increase, but its synergy unobvious, when products application is in high-volume agricultural production deinsectization, it is necessary to expend substantial amounts of production Product, use cost will greatly improve.
The content of the invention
For above-mentioned problem, present invention aims at a kind of duration of efficacy length is provided, Environmental compatibility is good, Suitable for the derivative of the N- acyl benzoyl ammoniac compounds of field high-volume desinsection.
In order to achieve the above object, the technical solution adopted by the present invention is as follows：A kind of N- acyl benzoyls of general formula I The derivative of ammoniac compounds：
Wherein, R1For halogen or CN；R2For C1-C8Alkyl or halogen；
R3For H or C1-C8Alkyl；R4For H or C1-C8Alkyl；
R5Selected from following each group：OH、、、, R5In substitution Base includes R6, R7, X, R8And R9；
Substituent R6Selected from following each group：H, HHCl, or can substituted following radicals C1-C8Alkyl, C3-C6Alkane alkene Base, C3-C6Alkynyl, contain C1-C8The acyl group of alkyl, contain C1-C8The acyl group of alkoxy, contain C1-C8Acyl group, the acyl of alkylamino radical Amido, morpholine acyl group, contain C1-C8The sulfonyl of alkyl；
Substituent R7Selected from following each group：NH2, NH2HCl, or can substituted following radicals：C1-C8Alkyl, C3-C6 Alkane alkenyl, C3-C6Alkynyl, contain C1-C8The amide groups of alkyl, contain C1-C8The amide groups of alkoxy, contain C1-C8Alkylamino radical Amide groups, contain C1-C8The acyl alkyl of alkylamino radical, contain C1-C8Sulfoamido, urea groups, the morpholino amide base of alkyl.
Substituent X is CH or N；
Substituent R8Selected from following each group：H, or can substituted following radicals C1-C8Alkyl, C3-C8Cycloalkyl or C3-C6 Heterocyclylalkyl；
Substituent R9Selected from following each group：H, or can substituted following radicals C1-C8Alkyl, C3-C8Cycloalkyl or C3-C6 Heterocyclylalkyl；
Substituent R8And R9Further include both and R5The C that middle N is formed together2-C6Heterocycloalkane.
Substituent R of the present invention6Or R7In substituted group be selected from halogen, C1-C4Alkyl, C1-C4Alkoxy Or nitro.
R of the present invention1Preferably Cl or CN.
R of the present invention2Preferably CH3Or Cl.
R of the present invention3Preferably H or CH3, R4Preferably H or CH3。
R of the present invention6Preferably HHCl can substituted following radicals：Contain C1-C4The acyl group of alkyl, contain There is C1-C4The acyl group of alkoxy, contain C1-C4The acyl group of alkylamino radical, morpholine acyl group, contain C1-C4The sulfonyl of alkyl；It substitutes Base is selected from halogen, C1-C4Alkyl or C1-C4Alkoxy
R of the present invention6Preferably contain C1-C4The acyl group of alkoxy, contain C1-C4The acyl group of alkylamino radical；Its substituent selects From halogen, C1-C4Alkyl or C1-C4Alkoxy.
R of the present invention6Preferably H ,-HHCl, tertiary fourth oxygen acyl group, mesyl, morpholine acyl group, N- methyl amine acyls Base, N, N- dimethyl amines acyl group, acetyl group or methoxy acyl group.
The R of the present invention7Preferably NH2、NH2HCl can substituted following radicals：Contain C1-C4Alkyl Amide groups, contain C1-C4The amide groups of alkoxy, contain C1-C8The amide groups of alkylamino radical, contain C1-C8The acyl group of alkylamino radical is sub- Methyl, urea groups, contain C1-C8Sulfoamido, the morpholino amide base of alkyl；Its substituent is selected from halogen, C1-C4Alkyl or C1-C4 Alkoxy
R of the present invention7Preferably NH2、NH2HCl, 3- methyl urea groups, acetamido, 3,3- dimethyl urea groups, methylsulfonyl Amido, methoxy amide groups, N- ethylamines sulfonylethene, tert-butoxycarbonylamino.
Table 1 lists the structure and its physical property of the compound of partial Formula I.
The structure and physical property of 2 partial Formula of table, I compound
The structure and physical property of 3 partial Formula of table, I compound
The structure and physical property of 4 partial Formula of table, I compound
The part of compounds of formula of I of the present invention1HNMR（DMSO-d6, 300 MHz）Data are as follows：
Compound 2-1 1.20 (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)。
Compound 2-2 1.28 (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)。
Compound 2-3 1.52 (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)。
Compound 2-4 1.42 (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)。
Compound 2-5 1.42 (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)。
Compound 2-6 1.50 (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)。
Compound 2-7 1.28 (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)。
Compound 2-8 1.29 (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)。
Compound 2-10 1.16 (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)。
Compound 2-11 1.39 (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)。
Compound 2-13 1.23 (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)。
Compound 2-14 1.28 (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)。
Compound 2-15 1.26 (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)。
Compound 3-2 0.83 (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)。
Compound 3-3 1.32 (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)。
Compound 3-5 1.30 (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)。
Compound 3-7 1.06 (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)。
Compound 3-8 1.20 (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)。
Compound 3-9 1.37 (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)。
Compound 3-11 1.17 (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)。
Compound 3-12 1.27 (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)。
Compound 3-13 1.29 (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)。
Compound 3-14 1.25 (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)。
Compound 3-16 1.22 (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)。
Compound 4-1 1.49 (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)。
Compound 4-2 2.16 (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)。
Compound 4-3 1.52 (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)。
Compound 4-4 2.16 (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)。
Compound 4-18 1.46 (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)。
Compound 4-19 1.28 (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)。
Compound 4-20 1.71 (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)。
Compound 4-21 1.29 (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)。
Compound 4-22 1.5 (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)。
Compound 4-23 0.48 (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)。
Compound 4-24 0.38 (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)。
Compound 4-25 1.40 (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)。
Compound 4-27 1.53 (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)。
Compound 4-28 1.74-1.89 (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)。
Compound 4-29 1.50 (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)。
Compound 4-30 2.16 (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)。
Compound 4-31 1.53 (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)。
Compound 4-32 2.16 (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)。
Compound 4-37 1.29 (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- acyls benzoyl Ammonia compound derivatives represented containing the present invention by general formula I or its can pharmaceutically connect The salt received can prepare insecticide, be used to control various harmful insects especially as the agrohorticultural insecticide of active ingredient, such as Agronomy harmful insect, storage of granular materials harmful insect, hygienic harmful insect, nematode etc., these are to paddy, fruit tree, vegetables, other works Thing, flowers and ornamental plant etc. are harmful, they have significant insecticidal effect, such as to lepidoptera pest, including cotton boll Worm, beet armyworm, diamondback moth, cabbage caterpillar, rice leaf roller and striped rice borer etc., homoptera pest such as leafhopper, plant hopper, aphid, powder Lice etc., Diptera pest such as housefly, Liriomyza, mosquito class etc., the pest such as Orthoptera and coleoptera etc..The thus compound of the present invention It can be used as protecting the insecticide of the plants such as agricultural, gardening.Certainly, the harmful organism that compound of the invention can prevent is not limited to State the scope of citing.Adjacent the methylamino heterocyclic carbamate derivatives or its pharmaceutically acceptable salt of the present invention are active component, with And agriculturally acceptable carrier can be made into Pesticidal combination, the weight percentage of active component is 0.1- in composition 99.5%。
The agronomy of the present invention is killed into agent generally according to common agricultural chemicals preparation method common formulation is made.
That is, N- acyls benzoyl Ammonia compound derivatives or its salt and optional auxiliary agent that I is represented Blended by proper proportion and suitable inert carrier, by dissolving, disperseing, suspending, mixing, impregnating, adsorbing or adhewsive action, system Into suitable formulation, such as suspension, missible oil, solubility concentrate, wettable powder, granule, pulvis, tablet, pack etc..
Inert carrier for use in the present invention is either solid can also be liquid.As the original that can be used as solid carrier Material, for illustration be soy meal, grain dust, wood powder, bark powder, sawdust, tobacco stem powder, walnut parting, chaff, cellulose powder, Vegetables extraction residue, synthetic polymer or resin-oatmeal, clay (such as kaolin, bentonite and acid clay), talcum (such as Talcum and pyrophyllite), silicon dioxide powder or thin slice (such as diatomite, silicon are husky, mica and hard charcoal (the polymolecularity silicic acid of synthesis, Also referred to as finely pulverized hydrated SiO 2 or silicate hydrate, some commercially available products contain calcium silicates as main Component), activated carbon, Cosan, float stone, calcined diatomite, the brick ground, flying dust, sand, calcium carbonate, calcium phosphate and other nothings Machine or mineral dust, plastic carrier (such as polyethylene, polypropylene and Vingon), chemical fertilizer (such as ammonium sulfate, phosphoric acid Ammonium, ammonium nitrate, urea, ammonium chloride) and compost.These carriers can be used alone, or be used as mixture.
The material that can be used as liquid-carrier is selected from such material, themselves has dissolubility, although or not molten Solution property still can be by auxiliary agent dispersion of active ingredients compound.Common liquid-carrier, such as water；Organic solvent such as toluene, two Toluene, hexamethylene, methanol, butanol, ethylene glycol, acetone, dimethylformamide, ether, dimethyl sulfoxide, animal and plant oil and fat Fat acid；Common surfactant such as emulsifying agent and dispersant, including anion surfactant, cationic surfactant, Nonionic surfactant and amphoteric surfactant；Other auxiliary agents, such as wetting agent, thickener.
When the compound or its salt of the invention represented by general formula I is used as the active ingredient in insecticide, in the desinsection Content in agent can make choice in the range of 0 .1% to 99.5%, and can be determined suitably according to dosage form and application process Active component content.In general, contain 5% to 50% in aqueous emulsion（Percentage by weight, similarly hereinafter）The active ingredient, it is excellent It is 10% to 40% to select its content；Containing 5% to 50% active ingredient in microemulsion, preferred content is 10% to 30%；In missible oil In containing 1% to 90% active ingredient, preferably its content is 10% to 80%.
For example, for the aqueous emulsion, microemulsion, can be by the compounds of this invention as active component and solvent and surface The auxiliary agents such as activating agent are uniformly mixed and are made, and dilutable water is to prescribed concentration during use.For the wettable powder, The compounds of this invention as active component, solid carrier and surfactant etc. can be mixed and be crushed and be made, made Used time is diluted with water.Certainly, the processing method of preparation is not limited to the above.Those skilled in the art can be according to institute Active ingredient and application target etc. are stated, selects suitable method.
In addition to the compound as active component represented by general formula I, insecticide of the invention can include it Its insecticide, acaricide, fungicide, insect growth regulator, IGR, plant growth regulator and soil conditioner etc. are any applicable Active ingredient.
For the present invention insecticide use, may be selected common application method, as cauline leaf spraying, it is used for ponds, native Earth processing and seed treatment etc..For example, when using cauline leaf spraying, the compound as active component represented by general formula I Aqueous emulsion, microemulsion or the missible oil that concentration range is 1 to 1000ppm can be used, preferred concentration is 1 to 500ppm.
The advantage of the invention is that：The derivative of N- acyls benzoyl ammoniac compounds in the prior art of the invention Structure on adjust, for such compound shortcoming present in application in the prior art, find a kind of medicine Duration length is imitated, synergy is good, and the stability of compound is good, and suitable for large batch of agricultural production, the cost applied in batches is low N- acyl benzoyl ammoniac compounds derivative.
Embodiment
With reference to embodiment, the present invention is described in further detail.
Unless otherwise stated, the following term used in the specification and in the claims has implication discussed below：
" alkyl " represents the aliphatic group of the saturation of 1-20 carbon atom, including straight chain and branched group（Number mentioned in the present invention Word scope, such as " 1-20 ", refer to the group, are at this time alkyl, can contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms Deng until including 20 carbon atoms）.Alkyl containing 1-4 carbon atom is known as low alkyl group.When low alkyl group does not have substituent When, it is called unsubstituted low alkyl group.It is further preferred that alkyl is the medium sized alkyl for having 1-8 carbon atom, such as Methyl, ethyl, propyl group, 2- propyl group, normal-butyl, isobutyl group, the tert-butyl group, amyl group etc..Preferably, alkyl is to have 1-4 carbon atom Low alkyl group, such as methyl, ethyl, propyl group, 2- propyl group, normal-butyl, isobutyl group or tert-butyl group etc..
" alkane alkenyl " represents the undersaturated aliphatic group containing at least one carbon-carbon double bond C=C of 2-20 carbon atom, bag Include straight chain and branched group（The digital scope mentioned in this specification, such as " 2-20 ", refer to the group, can contain 2 at this time Carbon atom, 3 carbon atoms etc., until including 20 carbon atoms）.Alkane alkenyl containing 2-6 carbon atom is known as lower alkenyl. When lower alkenyl does not have substituent, unsubstituted lower alkenyl is called.It is further preferred that alkane alkenyl is that have 3-6 The medium sized alkyl of carbon atom.
" alkynyl " represents the undersaturated aliphatic group containing at least one carbon carbon C ≡ C of 2-20 carbon atom, including straight chain And branched group（The digital scope mentioned in this specification, such as " 1-20 ", refer to the group, can contain 2 carbon originals at this time Son, 3 carbon atoms etc., until including 20 carbon atoms）.Alkynyl containing 2-6 carbon atom is known as low-grade alkynyl.When rudimentary alkynes When base does not have substituent, unsubstituted low-grade alkynyl is called.It is further preferred that alkynyl is have 3-6 carbon atom medium big Small alkynyl.
" acyl group " expression-(C=O)-group or-(C=O) H groups.
“（C1-C8 alkyl）Acyl group " represents the acyl group with substituent C1-C8 alkyl, wherein " C1-C8 " represents that alkyl takes The carbon number of Dai Jizhong is 1 to 8, such as acetyl group, positive propiono, iso-propionyl, positive bytyry etc..
“（C1-C8 alkoxyl）Acyl group " represents the acyl group with substituent C1-C8 alkoxyl, such as methoxyl group acyl group, second Epoxide acyl group, positive propoxy acyl group, isopropoxy acyl group, n-butoxy acyl group, tert-butoxy acyl group etc..
" alkoxy " expression " alkyl-O- " group, wherein alkyl are as defined above.
" alkylamino radical " represent with one or two alkyl substituent amine groups, such as " alkyl-NH- " or "（Alkyl） 2N- " groups, wherein alkyl are as defined above.
“（C1-C8 alkylamino radicals）Acyl group, " represent the acyl group with C1-C8 alkylamino radical substituents.
" amide groups " expression " H (C=O)-NH- " group.
" morpholine acyl group " representsGroup." sulfonyl " expression "-S (=O) 2- " groups.
“（C1-C8 alkyl）Sulfonyl " represents " sulfonyl with C1-C8 alkyl substituents " group.
" acyl alkyl " expression "-(C=O)-alkyl-" or " H (C=O)-alkyl-" group.Wherein alkyl is as defined above institute State, the preferred low alkyl group of the alkyl in the group, particularly methylene or ethylidene.
" sulfoamido " represents the amine groups with one or two sulfonyl substituent, such as.
" halogen " represents fluorine, chlorine, bromine or iodine group.
The exemplary manufacturing process of the present invention is as follows, but it lies in less than and limits the scope of the invention in any way；It is logical Formula chemical compounds I can be prepared by reaction equation 1-6, and wherein substituent is outer unless specified otherwise limits as before.
1）Work as R5During representative-OH, general formula compound I can be prepared by reaction equation 1：
Reaction equation 1：
In alkaline conditions, III and II in suitable solvent, temperature obtain target for reaction 0.5-48 h under -20 DEG C to boiling point Compound（Ⅰ-1）.
As available for the alkali in the reaction, organic base can be enumerated, as pyridine, triethylamine, 4-dimethylaminopyridine or N-methylmorpholine etc., and inorganic base, such as potassium carbonate, sodium hydroxide.To every general Formula compound III or general formula compound II, the dosage of alkali can suitably select within the scope of 1 mol to molar excess number.
Suitable solvent is selected from halogenated alkane, acetone, benzene, toluene, ethyl acetate, acetonitrile, propionitrile, tetrahydrofuran, dioxy Six rings, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide etc..The synthesis of raw material III uses known method, Such as the method described in CN1541063A.
After the reaction was complete, the reaction mixture containing expected product is subjected to separating treatment according to commonsense method, if necessary Purified by recrystallization, column chromatography etc., it is hereby achieved that expected product.
2）Work as R5RepresentWhen, general formula compound I can pass through reaction equation 2-1 or reaction equation 2-2 systems It is standby：
Reaction equation 2-1：
Wherein, R6Representative can substituted C1-C3Alkyl, can substituted C3-C6Alkane alkenyl, can substituted C3-C6Alkynyl, can Substituted alkoxy acyl；
In the presence of atent solvent and condensing agent, general formula compound I -1 is condensed to yield the derivative of general formula I -2 with general formula compound IV Thing.
The atent solvent used in the reaction can be any solvent, as long as it is carried out without prejudice to reaction.Such as Tetrahydrofuran, ether, dioxanes, chloroform, dichloromethane and dichloroethanes etc..
As the condensing agent used in the reaction, any condensing agent can be used, as long as it is synthesized in general acid amides Middle use.Condensing agent, which can be selected from, includes Mukaiyama reagents（Such as 2- chloro-n-methyl pyridine  iodide）, 1,3- dicyclohexyl Carbodiimide（DCC）, carbonyl dimidazoles（CDI）With phosphorus cyanic acid diethylester（Diethyl phosphorocyanidate, DEPC）, 2- (7- azos benzotriazole)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid esters（HATU）.The condensation dosage used can be 1 Mol is to suitably selecting within the scope of molar excess number.
As available for the alkali in the reaction, organic base can be enumerated, as pyridine, triethylamine, 4-dimethylaminopyridine or N-methylmorpholine etc., and inorganic base, such as potassium carbonate, sodium hydroxide.To every general Formula compound VI or general formula compound I -1, the dosage of alkali can suitably select within the scope of 1 mol to molar excess number.
For reaction temperature, which can be in -10 DEG C of reflux temperatures to suitable solvent used.Reaction time is because of reaction Scale or temperature and it is different, generally when some minutes are small to 48 in the range of suitably determined.
After the reaction was complete, the reaction mixture containing expected product is subjected to separating treatment according to commonsense method, if necessary Purified by recrystallization, column chromatography etc., it is hereby achieved that expected product.
Reaction equation 2-2：
I -1 with halogenating agent in solvent-free or suitable solvent, temperature obtain target for -20 DEG C to reaction 0.5-24 h under boiling point Chemical compounds I -1 '.Halogenating agent is selected from thionyl chloride, oxalic acid, solid light, double light, phosgene, phosphorus trichloride or phosphorus oxychloride etc..Suitably Solvent is selected from halogenated alkane, acetone, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane etc..
In alkaline conditions, in polarity or apolar aprotic solvent, at moderate temperatures, chemical compounds I -1 ' and compound （Ⅳ）Reaction obtains general formula compound（Ⅰ-2）.Wherein：The alkali is alkali metal hydroxide, alkali carbonate, alkali metal Bicarbonate or organic base；The polarity or apolar aprotic solvent are halogenated alkane, benzene, toluene, amide-type, nitrile are molten Agent.The alkali metal hydroxide is sodium hydroxide or potassium hydroxide, and the alkali carbonate is sodium carbonate or carbonic acid Potassium, the alkali metal hydrogencarbonate are sodium acid carbonate or saleratus, and the organic base is pyridine, triethylamine, 4- diformazans Aminopyridine or N-methylmorpholine；The amide solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, diformazan Sulfoxide or 1-methyl-2-pyrrolidinone；The nitrile solvents are acetonitrile or propionitrile.Above-mentioned suitable temperature is-10-30 DEG C, excellent Elect-5-0 DEG C as.
3）Work as R6Represent HHCl or can be substituted（C1-C8）Alkanoyl, can substituted aminoacyl, can be substituted Morpholine acyl group,（C1-C8）During alkyl sulphonyl, prepared using reaction equation 3：
Reaction equation 3：
I -2 with acid in solvent-free or suitable solvent, temperature obtain target chemical combination for -20 DEG C to reaction 0.5-48 h under boiling point Thing I -3.Acid is selected from inorganic acid such as hydrochloric acid, the concentrated sulfuric acid etc.；Organic acid such as trifluoroacetic acid, p-methyl benzenesulfonic acid etc..Suitable solvent Selected from halogenated alkane, acetone, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane etc..Raw material（Ⅰ-2）Synthetic route is shown in reaction equation 2-1 or reaction equation 2-2.
In alkaline conditions, in polarity or apolar aprotic solvent, at moderate temperatures, compound（Ⅰ-3）With acylation Agent（Ⅴ）Reaction obtains general formula compound（Ⅰ-4）.Wherein：The alkali is alkali metal hydroxide, alkali carbonate, alkali gold Belong to bicarbonate or organic base；The polarity or apolar aprotic solvent are halogenated alkane, benzene, toluene, amide-type, nitrile Solvent.The alkali metal hydroxide is sodium hydroxide or potassium hydroxide, and the alkali carbonate is sodium carbonate or carbon Sour potassium, the alkali metal hydrogencarbonate are sodium acid carbonate or saleratus, and the organic base is pyridine, triethylamine, 4- bis- Methylamino pyridine or N-methylmorpholine；The amide solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, two First sulfoxide or 1-methyl-2-pyrrolidinone；The nitrile solvents are acetonitrile or propionitrile.Wherein acylating agent（Ⅴ）For R6-O-、R6-Cl Or R6-Br.Above-mentioned suitable temperature is-10-30 DEG C, is preferably-5-0 DEG C.
4）Work as R5RepresentWhen, general formula compound I can be prepared by reaction equation 4-1 or reaction equation 4-2：
Reaction equation 4-1：
Reaction equation 4-2：
R7Representative can substituted C1-C3Alkyl, can substituted C3-C6Alkane alkenyl, can substituted C3-C6Alkynyl, can be taken Generation（C1-C8）Alkyl, can substituted alcoxyl amide groups；X represents C-H or N.
Reaction condition of the reaction condition of reaction equation 4-1 with reference to reaction equation 2-1.
Reaction condition of the reaction condition of reaction equation 4-2 with reference to reaction equation 2-2.
5）Work as R7Represent HHCl or can substituted alkylamidoalkyl,（C1-C8）Alkyl sulphonyl amide groups, can be taken The aminoacyl amido in generation, can substituted morpholine acyl group；When X represents N, prepared using reaction equation 5：
Reaction equation 5：
（Ⅰ-7）Synthesis condition with reference to reaction equation 3 reaction condition.I -5 synthetic route of raw material is shown in reaction equation 2-1 or reaction equation 2- 2。
6）Work as R5RepresentWhen, general formula compound I can be prepared by reaction equation 6-1 or reaction equation 6-2：
Reaction equation 6-1：
Reaction equation 6-2：
R8Or R9Represent H, substitution C1-C8Alkyl, C3-C8Cycloalkyl or C3-C6Heterocyclylalkyl, R8And R9Can be identical, also can be different； Or R8And R9C is formed together with the nitrogen connected2-C6Heterocycloalkane.
Reaction condition of the reaction condition of reaction equation 6-1 with reference to reaction equation 2-1.
Reaction condition of the reaction condition of reaction equation 6-2 with reference to reaction equation 2-2.
The test example using the compounds of this invention as the insecticide of active ingredient will be described below.But implementation of the invention Mode is not limited to herein below.
Test example 1：To the insecticidal effect of diamondback moth；
3 instar larvaes are selected, insecticidal effect test is carried out using leaching leaf feeding method.According to the building form of example of formulations 3, it incite somebody to action this Insecticide is respectively prepared in the compound of inventive embodiments.Obtained insecticide emulsifiable concentrate is diluted with pure water, it is uniformly mixed Close the liquid of concentration needed for obtaining.Luxuriant dish is chosen, cleans and dries, leaf dish is made with card punch, soak 10 seconds and take in liquid Go out, load after naturally dry in culture dish.Per ware, 3 instar larvae of access diamondback moth 10, is repeated 3 times, and investigates 1d, 2d and 3d Dead borer population, count the death rate, evaluate its insecticidal effect.
Part is supplied in the compound of examination, and following compounds are preferable to the prevention effect of diamondback moth when concentration is 20 ppm, The death rate is more than 80%：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、4-32 ~ 4-40。
Test example 2：The Toxicity baseline of diamondback moth is measured；
By the compound in patent of the present invention and known compound KC1（Compound 1.4 in CN2014106804482）Do to small The Toxicity baseline measure of diamond-back moth；The structural formula of KC1 is as follows：
。
Select six concentration：2 ppm, 1 ppm, 0.5 ppm, 0.1 ppm, 0.05 ppm and 0.01 ppm are carried out to pickles The Toxicity baseline measure of moth, experiment process are as shown in the table with test example 1, the toxicity regression formula of part of compounds：
As can be seen from the above table：In toxicity regression formula y=a+bx, 2-2,4-3,4-10 and 4- in the embodiment that the present invention enumerates 17 this four compounds are more much larger than known compound KC1 to the b values of the virulence curve of diamondback moth, show to change in patent of the present invention The drug concentration of compound is more sensitive to diamondback moth virulence, is improved with drug concentration, insecticidal activity of the compound for diamondback moth Also dramatically increase；I.e. dosage x values are bigger, and higher in the drug effect y values finally obtained, drug effect is better；With reference to crop field medication into This, in the case where obtaining identical drug effect, compound of the invention only needs less dosage to obtain and KC1 compounds Identical drug effect, this causes the compound dosage of the present invention to gradually reduce, is greatly reduced using cost.
Test example 3：To the field control effectiveness test of diamondback moth prevention effect；
In view of Toxicity baseline data analysis, we to this four compounds of 2-2,4-3,4-10,4-17 in patent of the present invention and Known compound KC1 does the field control effectiveness test to diamondback moth.Trial crops are broccoli, and kind is green ridge 8.For trying active compound With acetone: N`N`-dimethylformamide etc. is dissolved into the solution of 3400 ~ 6700mg/L than mixed liquor, then with 1% Tween-20 water Solution is diluted to the solution of 5mg/L and 50mg/L.Sprayed with hand-held atomizer, by 675 L/hm2Liquid volume is sprayed, and plant is complete Strain even spraying, 3 repetitions, random district's groups arrangement.1 day before experiment spray, with the diamondback moth children raised on indoor Brassica Napus Seedling Worm connects worm to broccoli blade, takes at 5 points using diagonal method in every cell before dispenser in second day, every fix 2 plants it is blue and white Dish, diamondback moth worm amount on 10 plant is investigated per cell altogether.Each cell diamondback moth insect population is investigated before dispenser, 1 day after dispenser, Residual diamondback moth quantity is investigated respectively within 7 days, 14 days.
Drug effect calculates：Preventive effect is calculated with the worm amount in trial zone on 2 plants of broccolis.
Prevention effect (%)=1- [（Worm amount after worm amount × treatment region dispenser before the dispenser of check plot）/（Worm after the dispenser of check plot Worm amount before amount × treatment region dispenser）]} ×100
Table 1：Prevention effect of 5 kinds of compounds to diamondback moth（2016, Transition In Jurong, Jiangsu）
As seen from the above table, the drug effect of the compositions of KC1 in the prior art of the invention is very fast, and reaches within 7 days or so after dispenser maximum Medication effect, after administration time gradually extends, decline to a certain extent is presented in its preventive effect, this is because compound is in itself Timeliness and field integrated environment caused by,
Test example 4：In view of Toxicity baseline data analysis, the technical solution in reference experiment example 3, to the 2-4 in patent of the present invention, This four compounds of 3-5,4-26,4-37 and known compound KC1 and KC2（Compound 1.3 in CN2014106804482）Do To the field control effectiveness test of diamondback moth.
The structural formula of KC2 is as follows：
As seen from the above table, the timeliness of compound of the invention compared with the prior art in compound be it is more outstanding, stablize Property it is more preferable, during Production of Large Fields, have the long period drug effect, particularly after administration 14-21 days, traditional chemical combination Thing is within the period, and drug effect can occur significantly to decline, and technical scheme, its efficacy stability, not only will not Decline, or even there is also rising to a certain extent, be more applicable for the production in crop field.
It should be noted that above-mentioned is only presently preferred embodiments of the present invention, not it is used for limiting the protection model of the present invention Enclose, any combination or equivalents made on the basis of above-described embodiment belong to protection scope of the present invention.

Claims (10)

  1. A kind of 1. derivative of the N- acyl benzoyl ammoniac compounds of general formula I：
    Wherein, R1For halogen or CN；R2For C1-C8Alkyl or halogen；
    R3For H or C1-C8Alkyl；R4For H or C1-C8Alkyl；
    R5Selected from following each group：OH、、、, R5In substitution Base includes R6, R7, X, R8And R9；
    Substituent R6Selected from following each group：H, HHCl, or can substituted following radicals C1-C8Alkyl, C3-C6Alkane alkene Base, C3-C6Alkynyl, contain C1-C8The acyl group of alkyl, contain C1-C8The acyl group of alkoxy, contain C1-C8Acyl group, the acyl of alkylamino radical Amido, morpholine acyl group, contain C1-C8The sulfonyl of alkyl；
    Substituent R7Selected from following each group：NH2, NH2HCl, or can substituted following radicals：C1-C8Alkyl, C3-C6Alkane Alkenyl, C3-C6Alkynyl, contain C1-C8The amide groups of alkyl, contain C1-C8The amide groups of alkoxy, contain C1-C8The acyl of alkylamino radical Amido, contain C1-C8The acyl alkyl of alkylamino radical, contain C1-C8Sulfoamido, urea groups, the morpholino amide base of alkyl
    Substituent X is CH or N；
    Substituent R8Selected from following each group：H, or can substituted following radicals C1-C8Alkyl, C3-C8Cycloalkyl or C3-C6 Heterocyclylalkyl；
    Substituent R9Selected from following each group：H, or can substituted following radicals C1-C8Alkyl, C3-C8Cycloalkyl or C3-C6 Heterocyclylalkyl；
    Substituent R8And R9Further include both and R5The C that middle N is formed together2-C6Heterocycloalkane.
  2. 2. the derivative of N- acyls benzoyl ammoniac compounds as claimed in claim 1, it is characterised in that described takes For base R6Or R7In substituted group be selected from halogen, C1-C4Alkyl, C1-C4Alkoxy or nitro.
  3. 3. the derivative of N- acyls benzoyl ammoniac compounds as claimed in claim 1, it is characterised in that the R1 Preferably Cl or CN.
  4. 4. the derivative of N- acyls benzoyl ammoniac compounds as claimed in claim 1, it is characterised in that the R2 Preferably CH3Or Cl.
  5. 5. the derivative of N- acyls benzoyl ammoniac compounds as claimed in claim 1, it is characterised in that the R3 Preferably H or CH3, R4Preferably H or CH3。
  6. 6. the derivative of N- acyls benzoyl ammoniac compounds as claimed in claim 1, it is characterised in that the R6 Preferably contain C1-C4The acyl group of alkoxy, contain C1-C4The acyl group of alkylamino radical；Its substituent is selected from halogen, C1-C4Alkyl or C1-C4Alkoxy.
  7. 7. the derivative of N- acyls benzoyl ammoniac compounds as claimed in claim 1, it is characterised in that the R6 Preferably H ,-HHCl, tertiary fourth oxygen acyl group, mesyl, morpholine acyl group, N- methyl amines acyl group, N, N- dimethyl amines acyl group, second Acyl group or methoxy acyl group.
  8. 8. the derivative of N- acyls benzoyl ammoniac compounds as claimed in claim 1, it is characterised in that the R7 Preferably NH2、NH2HCl, 3- methyl urea groups, acetamido, 3,3- dimethyl urea groups, methylsulfonyl amido, methoxy amide groups, N- Ethylamine sulfonylethene, tert-butoxycarbonylamino.
  9. 9. the N- acyl benzoyl Ammonia chemical combination of the general formula I as described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 The derivative of thing prepares the application of insecticide in agriculture field.
  10. 10. a kind of Pesticidal combination, contains spreading out for the general formula IN- acyl benzoyl ammoniac compounds described in claim 1 Biological and agriculturally acceptable carrier, the weight percentage of active component is 0.1~99.5% in composition.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1541063A (en) * 2001-08-13 2004-10-27 ��Ļ���Ű˾ Method for controlling particular insects by applying anthranilamide compounds
CN104447688A (en) * 2013-11-25 2015-03-25 中国中化股份有限公司 Pyrazole amide compound and application thereof
WO2016070562A1 (en) * 2014-11-05 2016-05-12 江苏中旗作物保护股份有限公司 Anthranilic diamide compound and use thereof

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Publication number Priority date Publication date Assignee Title
TWI283164B (en) * 2001-09-21 2007-07-01 Du Pont Anthranilamide arthropodicide treatment

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1541063A (en) * 2001-08-13 2004-10-27 ��Ļ���Ű˾ Method for controlling particular insects by applying anthranilamide compounds
CN104447688A (en) * 2013-11-25 2015-03-25 中国中化股份有限公司 Pyrazole amide compound and application thereof
WO2016070562A1 (en) * 2014-11-05 2016-05-12 江苏中旗作物保护股份有限公司 Anthranilic diamide compound and use thereof

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