CN102126994B - Benzophenone hydrazone derivative and preparation method and application thereof - Google Patents

Benzophenone hydrazone derivative and preparation method and application thereof Download PDF

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CN102126994B
CN102126994B CN201010040040.0A CN201010040040A CN102126994B CN 102126994 B CN102126994 B CN 102126994B CN 201010040040 A CN201010040040 A CN 201010040040A CN 102126994 B CN102126994 B CN 102126994B
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benzophenone
directly key
hydrazone derivatives
benzophenone hydrazone
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CN102126994A (en
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彭伟立
陈杰
郁林军
许勇华
夏旭建
刑家华
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Corp
Sinochem Lantian Co Ltd
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Sinochem Lantian Co Ltd
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Abstract

The invention provides a benzophenone hydrazone derivative shown as a structural formula [F], wherein R1 is halogen, alkyl with 1-4 carbon atoms, alkoxyl with 1-4 carbon atoms, halogenated alkyl with 1-4 carbon atoms or halogenated alkoxyl with 1-4 carbon atoms; R2 is hydrogen, alkyl with 1-4 carbon atoms or cyclopropyl; R3 is alkyl with 1-4 carbon atoms or halogenated alkyl with 1-4 carbon atoms; R4, R5 and R6 are independently selected from hydrogen, halogen, nitryl, nitrile group, hydroxyl, alkyl with 1-4 carbon atoms, halogenated alkyl with 1-4 carbon atoms, alkoxyl with 1-4 carbon atoms, (substituted) phenoxyl, halogenated alkoxyl with 1-4 carbon atoms, formic acid and alkali metal salts thereof, formic acid ester group with 1-6 carbon atoms, formamide or N-C1-4 alkyl or phenyl substituted formamide; X is amido or hydrogen; and Y is methylene or a direct bond. The invention also provides a preparation method of the benzophenone hydrazone derivative shown as the structural formula [F] and application of the derivative as an agricultural chemical insecticide.

Description

A kind of benzophenone hydrazone derivatives, Preparation Method And The Use
Invention field
The present invention relates to a kind of benzophenone hydrazone compounds, Preparation Method And The Use.
Background technology
The research of benzophenone hydrazone compounds is started to the eighties in last century, but high-activity compound patent report concentrates on nearly ten years, even had in recent years super-active compound (10ppm is following) to be found.These compounds all have following general structural formula:
According to substituent R 1, R 2, R 3, R 4with the difference of substituting group number m, n and form different compounds, U.S. Pat 5340837 (formula II), US6077866 (formula II I) and Japanese Patent JP8041013A (structural formula IV), JP10182625A (structural formula V), JP10109971A (structural formula VI) etc. all have report.These different compounds are to the good insecticidal activity of the equal tool of nematode, acarid and mythimna separata, particularly generally effective to lepidoptera pest, and other organic-biological body and people and animals are shown as to middle low toxicity mostly.
Calendar year 2001, Zhejiang Chemical Industry Science and Technology Group Co.,Ltd (national southern agricultural chemicals initiative base, Zhejiang, center) has found the phenyl methanesulfonamide acid esters compound that a class is new, the patent No.: ZL 01119493.6, denomination of invention: sterilant benzophenone hydrazone derivative.Think that through research in a few years and evaluation this is that a class has good insecticidal, low toxicity Environmental compatibility is good, synthesis technique is simple, DEVELOPMENT PROSPECT is good phenyl methanesulfonamide esters of gallic acid sterilant.Representation compound chemical structural formula is as follows:
Report to this compounds has: the commercial MEtaflumiZon (US5543573) in 2007 of BASF AG, Novartis Co.,Ltd's compound (EP662472) in 1993, SUMITOMO CHEMICAL company compound (JP7149708) in 1994, Beyer Co., Ltd of Japan compound (JP10182625) in 1996, the patent (US 5358965) of Japan's agricultural chemicals application, the patent (WO0023422) that Otsuka company of Japan applies in 2000 in patent (JP10109971) and the Agro-KanBsho company of application in 1998, similar patent also has EP462456, US6306798, JP07053501, WO2001001781, WO9206076 and WO2002032226 etc.
Summary of the invention
The object of the present invention is to provide one to possess bioactive benzophenone hydrazone derivatives, Preparation Method And The Use.
For achieving the above object, the invention provides following technical scheme:
A kind of benzophenone hydrazone derivatives, has structural formula shown in formula [F]:
Wherein:
R1 is halogen, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4haloalkyl or C 1-C 4halogenated alkoxy;
R2 is hydrogen, C 1-C 4alkyl or cyclopropyl;
R3 is C 1-C 4alkyl or C 1-C 4haloalkyl;
R4, R5, R6 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group, (replacement) phenoxy group, C 1-C 4halogenated alkoxy, formic acid and an alkali metal salt thereof, formic acid C 1～6ester group, methane amide or N-C 1-4alkyl or phenyl substituted formamides;
X is amido or oxygen;
Y is methylene radical or direct key.
Above-mentioned R1 can be positioned at arbitrary unsubstituted position on phenyl ring, is preferably placed at 3 or 4 of phenyl ring; R1 is preferably chlorine, fluorine or trifluoromethyl.
Above-mentioned R2 is preferably methyl.
Above-mentioned R3 is preferably methyl or trifluoromethyl.
Above-mentioned X is preferably amido.
Above-mentioned Y is preferably direct key.
Above-mentioned R4, R5, R6 can be positioned at arbitrary unsubstituted position on phenyl ring; R4, R5, R6 are preferably hydrogen, halogen, nitro, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or manthanoate independently.
Benzophenone hydrazone derivatives of the present invention, comprises that N-X is cis-isomeride and/or trans-isomer(ide), and two kinds of isomer can mix with any ratio.
Benzophenone hydrazone derivatives of the present invention can be synthetic by following reactions steps:
The synthetic of intermediate A can be taked following methods:
(1) benzene that R1 replaces, paranitrobenzoyl chloride adds aluminum chloride in chlorinated paraffin solvent in batches, reacts to obtain intermediate A;
(2) bromobenzene that R1 replaces obtains Grignard reagent with reactive magnesium in ether solvent, then reacts to obtain intermediate A with paranitrobenzoyl chloride.
Intermediate A tin protochloride, sodium polysulphide or palladium carbon-hydrogen reducing nitro obtain intermediate B.
Intermediate B and R3 replace SULPHURYL CHLORIDE or sulphonic acid anhydride reaction under acid binding agent exists obtains intermediate C, and acid binding agent can be selected triethylamine or salt of wormwood.
The reaction under acid binding agent exists of intermediate C and haloalkane or sulfuric acid diformazan (second) ester obtains intermediate D, and haloalkane can be selected methyl iodide, and acid binding agent can be selected triethylamine or salt of wormwood.
Can have two synthesis routes by the synthetic target product F of intermediate D, one is:
4 (or 3 or 2)-R1-4 '-R3SO 2hydrazine hydrate or the oxammonium hydrochloride of N (R2) Y-benzophenone (being intermediate D) and 1-10 equivalent, in alcoholic solvent, at 0 ℃, at solvent refluxing temperature, reaction obtains 4 (or 3 or 2)-R1-4 '-R3SO 2the hydrazine hydrate dehydration condensation intermediate (being intermediate E) of N (R2) Y-benzophenone;
In the time using oxammonium hydrochloride, need to add acid binding agent;
4 (or 3 or 2)-R1-4 '-R3SO 2the phenyl isocyanate that the represented R4R5R6 of the hydrazine hydrate dehydration condensation intermediate (being intermediate E) of N (R2) Y-benzophenone and structural formula [I] replaces is in ether solvent, at 0 ℃, at solvent refluxing temperature, reaction obtains the described benzophenone hydrazone derivatives of structural formula [F].
In above-mentioned synthesis route, R1, R2, R3, R4, R5, R6, X and Y group are corresponding with the group on benzophenone hydrazone derivatives target product structural formula [F] Suo Shu, wherein:
R1 is halogen, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4haloalkyl or C 1-C 4halogenated alkoxy;
R2 is hydrogen, C 1-C 4alkyl or cyclopropyl;
R3 is C 1-C 4alkyl or C 1-C 4haloalkyl;
R4, R5, R6 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group, (replacement) phenoxy group, C 1-C 4halogenated alkoxy, formic acid and an alkali metal salt thereof, formic acid C 1～6ester group, methane amide or N-C 1-4alkyl or phenyl substituted formamides;
X is amido or oxygen;
Y is methylene radical or direct key.
Above-mentioned R1 can be positioned at arbitrary unsubstituted position on phenyl ring, is preferably placed at 3 or 4 of phenyl ring; R1 is preferably chlorine, fluorine or trifluoromethyl.
Above-mentioned R2 is preferably methyl.
Above-mentioned R3 is preferably methyl or trifluoromethyl.
Above-mentioned X is preferably amido.
Above-mentioned Y is preferably direct key.
Above-mentioned R4, R5, R6 can be positioned at arbitrary unsubstituted position on phenyl ring; R4, R5, R6 are preferably hydrogen, halogen, nitro, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or manthanoate independently.
Above-mentioned acid binding agent is preferably sodium-acetate, triethylamine or salt of wormwood.
Above-mentioned ethers is preferably ether, tetrahydrofuran (THF) or dioxane.
Another synthesis route is:
4 (or 3 or 2)-R1-4 '-R3SO 2the carbazic acid methyl esters of N (R2) Y-benzophenone (being intermediate D) and 1-5 equivalent, in benzene (benzene,toluene,xylene, ethylbenzene) class or alcoholic solvent, at 0 ℃, at solvent refluxing temperature, reaction obtains 4 (or 3 or 2)-R1-4 '-R3SO 2the carbazic acid methyl esters dehydration condensation intermediate (being intermediate G) of N (R2) Y-benzophenone;
4 (or 3 or 2)-R1-4 '-R3SO 2the aniline that the carbazic acid methyl esters dehydration condensation intermediate (being intermediate G) of N (R2) Y-benzophenone and R4R5R6 replace is in benzene class or ether solvent, at 0 ℃, at solvent refluxing temperature, reaction obtains the described benzophenone hydrazone derivatives of structural formula [F].
In above-mentioned synthesis route, R1, R2, R3, R4, R5, R6, X and Y group are corresponding with the group on benzophenone hydrazone derivatives target product structural formula [F] Suo Shu, wherein:
R1 is halogen, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4haloalkyl or C 1-C 4halogenated alkoxy;
R2 is hydrogen, C 1-C 4alkyl or cyclopropyl;
R3 is C 1-C 4alkyl or C 1-C 4haloalkyl;
R4, R5, R6 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group, (replacement) phenoxy group, C 1-C 4halogenated alkoxy, formic acid and an alkali metal salt thereof, formic acid C 1～6ester group, methane amide or N-C 1-4alkyl or phenyl substituted formamides;
X is amido or oxygen;
Y is methylene radical or direct key.
Above-mentioned R1 can be positioned at arbitrary unsubstituted position on phenyl ring, is preferably placed at 3 or 4 of phenyl ring; R1 is preferably chlorine, fluorine or trifluoromethyl.
Above-mentioned R2 is preferably methyl.
Above-mentioned R3 is preferably methyl or trifluoromethyl.
Above-mentioned X is preferably amido.
Above-mentioned Y is preferably direct key.
Above-mentioned R4, R5, R6 can be positioned at arbitrary unsubstituted position on phenyl ring; R4, R5, R6 are preferably hydrogen, halogen, nitro, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or manthanoate independently.
Above-mentioned benzene class is preferably benzene,toluene,xylene or ethylbenzene.
Above-mentioned ethers is preferably ether, tetrahydrofuran (THF) or dioxane.
The related typical compound of structural formula (I) is listed in table 1 by the present invention, and AB represents respectively the wherein one in cis-trans-isomer.
Table 1: the related typical compound of structural formula (I)
Numbering R1 R2 R3 X Y R4R5R6-Ph H1NMR (nucleus magnetic hydrogen spectrum)
F1 4-Cl CH3 CH3 NH Directly key Aniline (B)2.96(s，3H)，3.43(s，3H)，7.23-9.12 (m，15H).
F2 4-Cl CH3 CH3 NH Directly key 3,4-DCA (B)2.97(s，3H)，3.43(s，3H)， 7.25-9.38(m，13H).
F3 4-Cl CH3 CH3 NH Directly key 2,4-xylidine (A)2.31(s，3H)，2.36(s，3H)，2.86(s，3H )，3.35(s，3H)，7.05-8.14(m，13H). (B)2.31(s，3H)，2.35(s，3H)，2.97(s，3H )，3.43(s，3H)，7.05-8.14(m，13H). A∶B＝1∶1
F4 4-Cl CH3 CH3 NH Directly key 2-methyl-3-chloroaniline (A)2.45(s，3H)，2.87(s，3H)，3.35(s，3H )，7.16-8.31(m，13H). (B)2.45(s，3H)，2.97(s，3H)，3.43(s，3H )，7.15-8.30(m，13H). A∶B＝1∶1
F5 4-Cl CH3 CH3 NH Directly key 2-anisidine (A)2.87(s，3H)，3.36(s，3H)，3.99(s，3H )，6.93-9.02(m，14H) (B)2.97(s，3H)，3.43(s，3H)，3.98(s，3H )，6.93-9.04(m，14H) A∶B＝1∶1
F6 4-Cl CH3 CH3 NH Directly key 4-trifluoro-methoxyaniline (A)2.87(s，3H)，3.36(s，3H)，7.168.29 (m，14H) (B)2.97(s，3H)，3.43(s，3H)，7.20-8.28 (m，14H) A∶B＝1∶1
F7 4-Cl CH3 CH3 NH Directly key 2,4 difluorobenzene amine (B)2.95(s，3H)，3.43(s，3H)，7.03-9.41 (m，13H).
F8 4-Cl CH3 CH3 NH Directly key 3,5-xylidine (B)2.23(s，6H)，2.95(s，3H)，3.42(s，3H )，7.16-9.00(m，13H).
F9 4-Cl CH3 CH3 NH Directly key 2-trifluoro-methoxyaniline (B)2.96(s，3H)，3.43(s，3H)，7.33-9.72 (m，14H)
F10 4-Cl CH3 CH3 NH Directly key 3-trifluoro-methoxyaniline (A)2.88(s，3H)，3.36(s，3H)，6.93-8.34 (m，14H) (B)2.97(s，3H)，3.43(s，3H)，6.96-8.32 (m，14H) A∶B＝1∶1
F11 4-Cl CH3 CH3 NH Directly key 4-difluoro-methoxy-aniline (B)2.97(s，3H)，3.43(s，3H)，6.36-9.18 (m，15H)
F12 4-Cl CH3 CH3 NH Directly key 3,4-difluoroaniline
F13 4-Cl CH3 CH3 NH Directly key 3-trifluoromethyl-4-chloroaniline (B)2.96(s，3H)，3.43(s，3H)，7.36-9.46 (m，13H)
F14 4-Cl CH3 CH3 NH Directly key 3-difluoro-methoxy-aniline (A)2.89(s，3H)，3.36(s，3H)，6.30-8.33 (m，15H)
(B)2.97(s，3H)，3.43(s，3H)，6.37-8.30 (m，15H) A∶B＝1∶1
F15 4-Cl CH3 CH3 NH Directly key 3-5-trifluoromethylaniline (A)2.87(s，3H)，3.36(s，3H)，7.24-8.38 (m，14H) (B)2.98(s，3H)，3.44(s，3H)，7.32-8.37 (m，14H) A∶B＝1∶1
F16 4-Cl CH3 CH3 NH Directly key 3-monomethylaniline (B)2.28(s，3H)，2.96(s，3H)，3.43(s，3H )，7.34-9.02(m，14H).
F17 4-Cl CH3 CH3 NH Directly key 2-aminotoluene (B)2.27(s，3H)，2.96(s，3H)，3.43(s，3H )，7.34-9.08(m，14H).
F18 4-Cl CH3 CH3 NH Directly key 2,5-xylidine (A)2.35(s，3H)，2.36(s，3H)，2.87(s，3H )，3.35(s，3H)，6.87-8.23(m，13H).
F19 4-Cl CH3 CH3 NH Directly key 2,5-xylidine (B)2.20(s，3H)，2.35(s，3H)，2.98(s，3H )，3.44(s，3H)，6.88-8.23(m，13H).
F20 4-Cl CH3 CH3 NH Directly key 4-sevoflurane isopropyl amine (A)2.88(s，3H)，3.36(s，3H)，7.42-8.41 (m，14H).
F21 4-Cl CH3 CH3 NH Directly key 4-sevoflurane isopropyl amine (B)2.98(s，3H)，3.44(s，3H)，7.32-8.41 (m，14H).
F22 4-Cl CH3 CH3 NH Directly key 3,4-xylidine (A)2.25(s，3H)，2.29(s，3H)，2.87(s，3H )，3.36(s，3H)，7.12-8.14(m，13H).
F23 4-Cl CH3 CH3 NH Directly key 3,4-xylidine (B)2.25(s，3H)，2.29(s，3H)，2.97(s，3H )，3.43(s，3H)，7.11-8.14(m，13H).
F24 4-Cl CH3 CH3 NH Directly key 4-phenoxybenzamine (A)2.87(s，3H)，3.36(s，3H)，7.00-8.22 (m，19H).
F25 4-Cl CH3 CH3 NH Directly key 4-phenoxybenzamine (A)2.87(s，3H)，3.36(s，3H)，7.00-8.22 (m，19H). (B)2.98(s，3H)，3.44(s，3H)，7.02-8.22 (m，19H). A∶B＝3∶5
F26 4-Cl CH3 CH3 NH Directly key 3-chloroaniline (A)2.87(s，3H)，3.36(s，3H)，7.09-8.28 (m，14H).
F27 4-Cl CH3 CH3 NH Directly key 3-chloroaniline (B)2.97(s，3H)，3.43(s，3H)，7.10-8.28 (m，14H).
F28 4-Cl CH3 CH3 NH Directly key 23 dimethyl aniline (A)2.30(s，3H)，2.35(s，3H)，2.87(s，3H )，3.35(s，3H)，7.02-8.21(m，13H).
F29 4-Cl CH3 CH3 NH Directly key 23 dimethyl aniline (B)2.30(s，3H)，2.35(s，3H)，2.98(s，3H )，3.44(s，3H)，7.03-8.21(m，13H).
F30 4-Cl CH3 CH3 NH Directly key 2,3-dichlorphenamide bulk powder (A)2.88(s，3H)，3.36(s，3H)，7.21-9.23 (m，13H). (B)2.91(s，3H)，3.40(s，3H)，7.21-9.23 (m，13H). A∶B＝1∶1.3
F31 4-Cl CH3 CH3 NH Directly key 2-chloroaniline (A)2.87(s，3H)，3.36(s，3H)，7.01-9.12 (m，14H).
F32 4-Cl CH3 CH3 NH Directly key 2-chloroaniline (B)2.98(s，3H)，3.44(s，3H)，7.01-9.12 (m，14H).
F33 4-Cl CH3 CH3 NH Directly key 3.5-dichlorphenamide bulk powder (A)2.88(s，3H)，3.36(s，3H)，7.09-8.31 (m，13H).
F34 4-Cl CH3 CH3 NH Directly key 3.5-dichlorphenamide bulk powder (B)2.97(s，3H)，3.43(s，3H)，7.06-8.30 (m，13H).
F35 4-Cl CH3 CH3 NH Directly key 2,6-xylidine (A)2.27(s，6H)，2.86(s，3H)，3.34(s，3H )，7.09-8.45(m，13H).
F36 4-Cl CH3 CH3 NH Directly key 2,6-xylidine (B)2.34(s，6H)，2.96(s，3H)，3.42(s，3H )，7.13-7.81(m，12H).
F37 4-Cl CH3 CH3 NH Directly key 4-phenetidine (A)1.40-1.43(t，3H)，2.87(s，3H)， 3.35(s，3H)，4.0-4.05(q，2H)，6.88-8.0 9(m，14H)
F38 4-Cl CH3 CH3 NH Directly key 4-phenetidine (B)1.40-1.44(t，3H)，2.97(s，3H)， 3.43(s，3H)，4.0-4.06(q，2H)，6.89-8.0 9(m，14H)
F39 4-Cl CH3 CH3 NH Directly key 2,4-xylidine (A)2.31(s，3H)，2.36(s，3H)，2.86(s，3H )，3.35(s，3H)，7.05-8.14(m，13H).
F40 4-Cl CH3 CH3 NH Directly key 2,4-xylidine (B)2.31(s，3H)，2.35(s，3H)，2.97(s，3H )，3.43(s，3H)，7.05-8.14(m，13H).
F41 4-Cl CH3 CH3 NH Directly key 2-methyl-3-chloroaniline (A)2.45(s，3H)，2.87(s，3H)，3.35(s，3H )，7.16-8.31(m，13H).
F42 4-Cl CH3 CH3 NH Directly key 2-methyl-3-chloroaniline (B)2.45(s，3H)，2.97(s，3H)，3.43(s，3H )，7.15-8.30(m，13H).
F43 4-Cl CH3 CH3 NH Directly key 3-trifluoro-methoxyaniline (A)2.88(s，3H)，3.36(s，3H)，6.93-8.34 (m，14H)
F44 4-Cl CH3 CH3 NH Directly key 3-trifluoro-methoxyaniline (B)2.97(s，3H)，3.43(s，3H)，6.96-8.32 (m，14H)
F45 4-Cl CH3 CH3 NH Directly key 4 trifluoro-methoxyanilines (A)2.87(s，3H)，3.36(s，3H)，7.16-8.29 (m，14H)
F46 4-Cl CH3 CH3 NH Directly key 4-trifluoro-methoxyaniline (B)2.97(s，3H)，3.43(s，3H)，7.20-8.28 (m，14H)
F47 4-Cl CH3 CH3 NH Directly key 3-difluoro-methoxy-aniline (A)2.89(s，3H)，3.36(s，3H)，6.30-8.33 (m，15H)
F48 4-Cl CH3 CH3 NH Directly key Factory's difluoro-methoxy-aniline (B)2.97(s，3H)，3.43(s，3H)，6.378.30 (m，15H)
F49 4-Cl CH3 CH3 NH Directly key 3-5-trifluoromethylaniline (A)2.87(s，3H)，3.36(s，3H)，7.24-8.38 (m，14H)
F50 4-Cl CH3 CH3 NH Directly key 3-5-trifluoromethylaniline (B)2.98(s，3H)，3.44(s，3H)，7.32-8.37 (m，14H)
F51 4-Cl CH3 CH3 NH Directly key 4-5-trifluoromethylaniline (A)2.88(s，3H)，3.36(s，3H)，7.39-8.43 (m，14H)
F52 4-Cl CH3 CH3 NH Directly key 4 5-trifluoromethylanilines (B)2.97(s，3H)，3.44(s，3H)，7.32-8.42 (m，14H)
F53 4-Cl CH3 CH3 NH Directly key 2-anisidine (A)2.87(s，3H)，3.36(s，3H)， 3.99(s，3H)，6.93-9.02(m，14H)
F54 4-Cl CH3 CH3 NH Directly key 2-anisidine (B)2.97(s，3H)，3.43(s，3H)，3.98(s，3H )，6.93-9.04(m，14H)
F55 4-Cl CH3 CH3 NH Directly key 2-fluoroaniline (A)2.87(s，3H)，3.36(s，3H)，7.00-8.62 (m，14H)
F56 4-Cl CH3 CH3 NH Directly key 2-fluoroaniline (B)2.97(s，3H)，3.43(s，3H)，7.04-8.62 (m，14H)
F57 4-Cl CH3 CH3 NH Directly key 2,5-dichlorphenamide bulk powder (B)2.98(s，3H)，3.44(s，3H)，7.33-9.15 (m，13H)
F58 4-Cl CH3 CH3 NH Directly key 4-N-methyl-p-nitroaniline (A)2.88(s，3H)，3.36(s，3H)，7.32-8.62 (m，14H)
F59 4-Cl CH3 CH3 NH Directly key 4-N-methyl-p-nitroaniline (B)2.98(s，3H)，3.44(s，3H)，7.32-8.62 (m，14H)
F60 4-Cl CH3 CH3 NH Directly key 3-N-methyl-p-nitroaniline (A)2.88(s，3H)，3.37(s，3H)，7.41-8.50 (m，14H)
F61 4-Cl CH3 CH3 NH Directly key 3-N-methyl-p-nitroaniline (B)2.98(s，3H)，3.44(s，3H)，7.32-8.38 (m，14H)
F62 4-Cl CH3 CH3 NH Directly key 2-methyl-4-nitrophenylamine (A)2.51(s，3H)，2.88(s，3H)，3.36(s，3H )，7.33-8.73(m，13H)
F63 4-Cl CH3 CH3 NH Directly key 2-methyl-4-nitrophenylamine (B)2.51(s，3H)，2.99(s，3H)，3.44(s，3H )，7.35-8.74(m，13H)
F64 4-Cl CH3 CH3 NH Directly key 4-chloroaniline (A)2.87(s，3H)，3.36(s，3H)，7.31-8.25 (m，14H)
F65 4-Cl CH3 CH3 NH Directly key 4-chloroaniline (B)2.98(s，3H)，3.43(s，3H)，7.31-8.25 (m，14H)
F66 4-Cl CH3 CH3 NH Directly key 4-tertiary butyl aniline (A)1.32(s，9H)，2.86(s，3H)，3.35(s，3H )，7.31-8.17(m，14H)
F67 4-Cl CH3 CH3 NH Directly key The tertiary factory of 4-base base aniline (B)1.32(s，9H)，2.96(s，3H)，3.42(s，3H )，7.31-8.16(m，14H)
F68 4-Cl CH3 CH3 NH Directly key 3-fluoroaniline (A)2.87(s，3H)，3.35(s，3H)，6.78-8.31 (m，14H)
F69 4-Cl CH3 CH3 NH Directly key 3-fluoroaniline (B)2.97(s，3H)，3.43(s，3H)，6.80-8.30 (m，14H)
F70 4-Cl CH3 CH3 0 Directly key 2-aminotoluene (A)2.35(s，3H)，2.89(s，3H)，3.38(s，3H )，7.09-8.37(m，13H). (B)2.35(s，3H)，2.94(s，3H)，3.41(s，3H )，7.09-8.37(m，13H). A∶B＝1∶1
F71 4-Cl CH3 CH3 O Directly key 4-tertiary butyl aniline (A)1.32(s，9H)，2.89(s，3H)， 3.37(s，3H)，7.35-8.11(m，13H). (B)1.32(s，9H)，2.94(s，3H)，3.40(s，3H )，7.35-8.11(m，13H). A∶B＝1∶1
F72 4-Cl CH3 CH3 O Directly key 2,6-Diethyl Aniline (A)1.23-1.27(t，3H)，2.67-2.73(q，2H) ，2.94(s，3H)，3.40(s，3H)， 7.167.85(m，12H).
F73 4-Cl CH3 CH3 O Directly key 2,6-Diethyl Aniline (B)1.23-1.27(t，3H)，2.67-2.72(q，2H) ， 2.88(s，3H)，3.36(s，3H)，7.15-7.76(m， 12H).
F74 4-Cl CH3 CH3 O Directly key 3-5-trifluoromethylaniline 2.95(s，3H)，3.41(s，3H)，7.38-8.32(m， 13H)
F75 4Cl CH3 CH3 O Directly key 3-trifluoromethyl-4-chloroaniline (A)2.89(s，3H)，3.38(s，3H)，7.26-8.30 (m，12H). (B)2.95(s，3H)，3.40(s，3H)，7.26-8.30 (m，12H). A∶B＝1∶1
F76 4-Cl CH3 CH3 O Directly key 2-fluoroaniline (A)2.89(s，3H)，3.38(s，3H)，7.06-8.57 (m，13H). (B)2.95(s，3H)，3.41(s，3H)，7.06-8.57 (m，12H). A∶B＝4∶1
F77 4-Cl CH3 CH3 O Directly key 3-monomethylaniline (B)2.37(s，3H)，2.95(s，3H)，3.41(s，3H )，6.96-8.13(m，13H).
F78 4-Cl Bt CH3 NH Directly key 2-aminotoluene (A)1.13-1.17(t，3H)，2.25(s，3H)，2.89
(s，3H)，3.72-3.78(q，2H)，7.02-8.28(m ，13H). (B)1.18-1.22(t，3H)，2.40(s，3H)，2.99 (s，3H)，3.78-3.83(q，2H)，7.02-8.28(m ，13H). A∶B＝3∶1
F79 4-Cl Bt CH3 NH Directly key 4-tertiary butyl aniline (B)1.25-1.28(t，3H)，1.30(s，9H)，， 2.99(s，3H)3.81-3.86(q，2H)， 7.25-8.12(m，13H).
F80 4-Cl Bt CH3 NH Directly key 2,6-Diethyl Aniline (A)1.20-1.23(t，6H)，1.23-1.27(t，3H) ，2.94(s，3H)，2.60-2.64(q，4H)，3.82-3 .86(q，2H)，7，11-8.43(m，14H).
F81 4-Cl Bt CH3 NH Directly key 3-5-trifluoromethylaniline (A)1.16-1.19(t，3H)，2.91(s，3H)， 3.75-3.81(q，2H)，7.25-8.38(m，14H). (B)1.25-1.29(t，3H)，3.00(s，3H)， 3.81-3.86(q，2H)，7.25-8.38(m，14H). A∶B＝2∶1
F82 4-Cl Bt CH3 NH Directly key 3-monomethylaniline (A)1.15-1.19(t，3H)，2.34(s，3H)，2.90 (s，3H)，3.75-3.80(q，2H)，6.94-8.21(m ，14H). (B)1.18-1.22(t，3H)，2.37(s，3H)，2.94 (s，3H)，3.80-3.85(q，2H)，6.94-8.21(m ，14H). A∶B＝4∶1
F83 4-Cl H CH3 NH Directly key 2-aminotoluene (A)2.40(s，3H)，3.16(s，3H)，6.94-8.27 (m，14H).
F84 4Cl H CH3 NH Directly key 2,6-Diethyl Aniline (A)1.231.27(t，3H)，3.04(s，3H)，2.68 -2.74(q，2H)，7.14-7.93(m，14H). (B)1.24-1.27(t，3H)，3.14(s，3H)， 2.69-2.74(q，2H)，7.14-7.93(m，14H). A∶B＝1∶1
F85 4-Cl H CH3 NH Directly key 3-5-trifluoromethylaniline (A)3.18(s，3H)，6.79-8.38(m，15H).
F86 4-Cl H CH3 NH Directly key 3-trifluoromethyl-4-chloroaniline (A)3.17(s，3H)，7.15-8.39(m，14H).
F87 4-Cl H CH3 NH Directly key 2-fluoroaniline (A)3.18(s，3H)，7.01-8.63(m，15H).
F88 4-Cl H CH3 NH Directly key 2-aminotoluene (A)2.38(s，3H)，3.18(s，3H)，6.95-8.22 (m，14H).
F89 4-Cl CH3 CH3 O Directly key 2.4-difluoroaniline (A)2.89(s，3H)，3.38(s，3H)，6.89-8.46 (m，12H). (B)2.94(s，3H)，3.41(s，3H)，6.89-8.46 (m，12H). A∶B＝1∶2
F90 4-Cl CH3 CH3 O Directly key 3.4-dichlorphenamide bulk powder (A)2.89(s，3H)，3.37(s，3H)，7.26-8.25 (m，12H). (B)2.94(s，3H)，3.40(s，3H)，7.26-8.25 (m，12H). A∶B＝1∶1
F91 4-Cl CH3 CH3 O Directly key 2.3-dichlorphenamide bulk powder (A)2.90(s，3H)，3.38(s，3H)，7.24-9.28 (m，12H). (B)2.95(s，3H)，3.41(s，3H)，7.24-9.28 (m，12H). A∶B＝1∶2
F92 4-Cl CH3 CH3 O Directly key 2-anisidine (A)2.89(s，3H)，3.38(s，3H)，3.93(s，3H )，6.91-8.95(m，13H). (B)2.94(s，3H)，3.41(s，3H)，6.91-8.95 (m，13H). A∶B＝1∶1
F93 4-Cl CH3 CH3 O Directly key 2,5-xylidine (B)2.29(s，3H)，2.35(s，3H)，2.94(s，3H )，3.41(s，3H)，6.91-8.32(m，12H).
F94 4-Cl CH3 CH3 O Directly key 2-trifluoro-methoxyaniline (A)2.89(s，3H)，3.38(s，3H)，7.12-9.10 (m，13H).
F95 4-Cl CH3 CH3 O Directly key 2,3,4-trifluoromethyl aniline (A)2.90(s，3H)，3.38(s，3H)，6.97-8.40 (m，11H).
F96 4-Cl CH3 CH3 O Directly key 4-5-trifluoromethylaniline (A)2.89(s，3H)，3.38(s，3H)，7.27-8.20 (m，13H).
F97 4-Cl CH3 CH3 O Directly key 3-5-trifluoromethylaniline (B)2.95(s，3H)，3.41(s，3H)，7.27-8.31 (m，13H).
F98 4-Cl CH3 CH3 O Directly key 3,5-difluoroaniline (B)2.95(s，3H)，3.41(s，3H)，6.57-8.26 (m，12H).
F99 4-Cl CH3 CH3 O Directly key 3,5-xylidine (B)2.32(s，6H)，2.94(s，3H)，3.41(s，3H )，6.79-8.10(m，12H).
F100 4-Cl CH3 CH3 O Directly key 3,4-difluoroaniline (A)2.89(s，3H)，3.38(s，3H)，7.12-8.20 (m，12H). (B)2.95(s，3H)，3.41(s，3H)，7.12-8.20 (m，12H). A∶B＝1∶1
F101 4-Cl CH3 CH3 O Directly key 3-anisidine (A)2.90(s，3H)，3.38(s，3H)，3.83(s，3H )，6.698.13(m，13H). (B)2.95(s，3H)，3.41(s，3H)， 3.83(s，3H)，6.69-8.13(m，13H). A∶B＝1∶1
F102 4-Cl CH3 CH3 O Directly key Aniline (A)2.89(s，3H)，3.38(s，3H)，7.13-8.17 (m，14H). (B)2.94(s，3H)，3.41(s，3H)，7.13-8.17 (m，14H). A∶B＝1∶1
F103 4-Cl CH3 CH3 O Directly key 4-monomethylaniline (A)2.89(s，3H)，3.37(s，3H)，2.34(s，3H )，7.15-8.13(m，13H). (B)2.94(s，3H)，3.40(s，3H)，2.34(s，3H )，7.15-8.13(m，13H). A∶B＝1∶1
F104 4-Cl CH3 CH3 O Directly key 4-trifluoro-methoxyaniline (B)2.95(s，3H)，3.41(s，3H)，7.22-8.22 (m，13H).
F105 4-Cl CH3 CH3 O Directly key 3-trifluoro-methoxyaniline (B)2.95(s，3H)，3.41(s，3H)，7.00-8.23 (m，13H).
F106 4-Cl CH3 CH3 O Directly key 2,4-xylidine (A)2.89(s，3H)，3.37(s，3H)，2.30(s，3H )，2.31(s，3H)，7.00-8.12(m，12H).
F107 4-Cl CH3 CH3 O Directly key 2-methyl-3-chloroaniline (A)2.88(s，3H)，3.36(s，3H)，2.42(s，3H )，7.20-8.40(m，12H).
F108 4-Cl CH3 CH3 O Directly key 3-difluoro-methoxy-aniline (B)2.95(s，3H)，3.41(s，3H)，6.36-8.21 (m，14H).
F109 4-Cl CH3 CH3 NH Directly key 4-monomethylaniline (A)2.34(s，3H)，2.87(s，3H)，3.34(s，3H )，7.16-8.17(m，14H).
F110 4-Cl CH3 CH3 NH Directly key 3,5-difluorobenzene (A)2.87(s，3H)，3.34(s，3H)，7.01-8.35
Amine (m，13H).
F111 4-Cl CH3 CH3 NH Directly key 2,3,4-trifluoromethyl aniline (A)2.88(s，3H)，3.36(s，3H)，6.95-8.51 (m，12H).
F112 4-Cl CH3 CH3 NH Directly key 3-anisidine (A)2.84(s，3H)，3.36(s，3H)，3.84(s，3H )，6.66-8.25(m，13H). (B)2.98(s，3H)，3.44(s，3H)，3.84(s，3H )，6.66-8.25(m，13H). A∶B＝1∶1
F113 4-Cl Bt CH3 NH Directly key 3-trifluoromethyl-4-chloroaniline (A)1.18-1.22(t，3H)，3.77-3.82(q，2H) ，2.91(s，3H)，7.27-8.37(m，14H). (B)1.26-1.30(t，3H)，3.81-3.86(q，2H) ，3.00(s，3H)，7.27-8.37(m，14H). A∶B＝2∶1
F114 4-Cl Bt CH3 NH Directly key 2-fluoroaniline (A)1.14-1.18(t，3H)，3.73-3.78(q，2H) ，2.90(s，3H)，7.06-8.63(m，14H). (B)1.26-1.30(t，3H)，3.83-3.86(q，2H) ，3.00(s，3H)，7.06-8.63(m，14H). A∶B＝4∶1
F115 4-Cl Bt CH3 NH Directly key 2,4 difluorobenzene amine (A)1.15-1.19(t，3H)，3.75-3.80(q，2H) ，2.90(s，3H)，6.88-8.48(m，13H). (B)1.26-1.30(t，3H)，3.82-3.88(q，2H) ，3.00(s，3H)，7.06-8.63(m，13H). A∶B＝1∶2
F116 4Cl Bt CH3 NH Directly key 4-chloroaniline (A)1.16-1.20(t，3H)，3.76-3.81(q，2H) ，2.92(s，3H)，7.25-8.28(m，14H). (B)1.26-1.30(t，3H)，3.81-3.86(q，2H) ，3.00(s，3H)，7.25-8.28(m，14H). A∶B＝2∶1
F117 4Cl Bt CH3 NH Directly key 2,3-dichlorphenamide bulk powder (A)1.15-1.18(t，3H)，3.75-3.81(q，2H) ，2.90(s，3H)，7.16-8.11(m，13H). (B)1.22-1.28(t，3H)，3.773.85(q，2H) ，3.00(s，3H)，7.16-8.11(m，13H). A∶B＝2∶1
F118 4-Cl Bt CH3 NH Directly key 2-anisidine (A)1.17-1.20(t，3H)，3.77-3.82 (q，2H)，2.91(s，3H)， 6.94-9.06(m，14H). (B)1.26-1.30(t，3H)，3.82-3.87(q，2H) ，3.00(s，3H)，6.94-9.06(m，14H). A∶B＝1∶2
F119 4-Cl Bt CH3 NH Directly key 2,5-xylidine (A)1.16-1.19(t，3H)，3.75-3.80 (q，2H)，2.33(s，6H)，2.91(s，3H)， 6.88-8.23(m，13H). (B)1.27-1.30(t，3H)，3.82-3.87(q，2H) ，3.00(s，3H)，2.36(s，3H)，6.88-8.23 (m，13H). A∶B＝2∶1
F120 4-Cl Bt CH3 NH Directly key 2-trifluoro-methoxyaniline (A)1.14-1.18(t，3H)，3.74-3.78 (q，2H)，2.90(s，3H)， 7.07-8.95(m，14H). (B)1.22-1.27(t，3H)，3.82-3.86(q，2H) ，3.00(s，3H)，7.07-8.95(m，14H). A∶B＝2∶1
F121 4-Cl Bt CH3 NH Directly key 2,3,4-trifluoro (A)1.14-1.18(t，3H)，3.76-3.80
Aniline (q，2H)，2.90(s，3H)， 6.93-8.51(m，12H). (B)1.24-1.29(t，3H)，3.82-3.86(q，2H) ，3.00(s，3H)，7.07-8.95(m，12H). A∶B＝1∶1
F122 4-Cl Bt CH3 NH Directly key 4-5-trifluoromethylaniline (A)1.16-1.20(t，3H)，3.76-3.80 (q，2H)，2.91(s，3H)， 7.25-8.43(m，14H). (B)1.26-1.30(t，3H)，3.81-3.86(q，2H) ，3.00(s，3H)，7.25-8.43(m，14H). A∶B＝3∶1
F123 4-Cl Bt CH3 NH Directly key 3-5-trifluoromethylaniline (A)1.17-1.20(t，3H)，3.76-3.81 (q，2H)，2.92(s，3H)， 7.26-8.39(m，14H). (B)1.26-1.30(t，3H)，3.84-3.87(q，2H) ，3.01(s，3H)，7.26-8.39(m，14H). A∶B＝3∶1
F124 4-Cl CH3 CF3 NH Directly key 3-trifluoro-methoxyaniline (A)3.51(s，3H)，6.98-8.33(m，14H). (B)3.59(s，3H)，6.98-8.33(m，14H). A∶B＝1∶1
F125 4-Cl CH3 CF3 NH Directly key 2-methyl-3-chloroaniline (A)2.47(s，3H)，3.50(s，3H)，7.16-8.30 (m，13H). (B)2.47(s，3H)，3.59(s，3H)，7.16-8.30 (m，13H). A∶B＝1∶1
F126 4Cl CH3 CF3 NH Directly key 2,3-dichlorphenamide bulk powder (B)3.59(s，3H)，7.219.23(m，13H).
F127 4-Cl CH3 CF3 NH Directly key 3-difluoro-methoxy-aniline (A)3.51(s，3H)，6.38-8.31(m，15H). (B)3.59(s，3H)，6.38-8.31(m，15H). A∶B＝1∶1
F128 4F CH3 CH3 NH Directly key Aniline (A)2.88(s，3H)，3.36(s，3H)，7.128.27 (m，15H).
F129 4-F CH3 CH3 NH Directly key Aniline (B)2.98(s，3H)，3.44(s，3H)，7.07-8.27 (m，15H).
F130 4-F CH3 CH3 NH Directly key 2-methyl-3-chloroaniline (A)2.47(s，3H)，2.88(s，3H)，3.36(s，3H )，7.18-8.33(m，13H).
F131 4-F CH3 CH3 NH Directly key 2-methyl-3-chloroaniline (B)2.47(s，3H)，2.98(s，3H)，3.44(s，3H )，7.06-8.33(m，13H).
F132 4-F CH3 CH3 NH Directly key 2,5-xylidine (A)2.35(s，3H)，2.36(s，3H)，2.86(s，3H )，3.35(s，3H)，6.87-8.24(m，13H).
F133 4-F CH3 CH3 NH Directly key 2,5-xylidine (B)2.33(s，3H)，3.35(s，3H)，2.97(s，3H )，3.43(s，3H)，6.87-8.23(m，13H).
F134 4-F CH3 CH3 NH Directly key 2,3-dichlorphenamide bulk powder (B)3.44(s，3H)，2.98(s，3H)，7.07-8.32 (m，13H).
F135 4-F CH3 CH3 NH Directly key 2,6-Diethyl Aniline (A)1.24-1.28(t，3H)，2.69-2.75(q，2H) ，2.86(s，3H)，3.35(s，3H)，7.17-7.92 (m，13H).
F136 4-F CH3 CH3 NH Directly key 2,6-Diethyl Aniline (B)1.24-1.28(t，3H)，2.69-2.75(q，2H) ，2.96(s，3H)，3.43(s，3H)，7.04-7.88 (m，13H).
F137 4-F CH3 CH3 NH Directly key 2,4-xylidine (A)2.31(s，3H)，2.36(s，3H)，2.86(s，3H )，3.35(s，3H)，7.05-8.15(m，13H).
F138 4-F CH3 CH3 NH Directly key 2,4-xylidine (B)2.31(s，3H)，2.36(s，3H)，2.97(s，3H )，3.43(s，3H)，7.05-8.15(m，13H).
F139 4-F CH3 CH3 NH Directly key 3-trifluoro-methoxyaniline (A)2.87(s，3H)， 3.36(s，3H)，6.96-8.34(m，14H).
F140 4-F CH3 CH3 NH Directly key 3-trifluoro-methoxyaniline (B)2.97(s，3H)，3.43(s，3H)，6.96-8.34 (m，14H).
F141 4-F CH3 CH3 NH Directly key 3-difluoro-methoxy-aniline (A)2.87(s，3H)，3.36(s，3H)，6.37-8.32 (m，15H). (B)2.97(s，3H)，3.43(s，3H)，6.37-8.32 (m，15H) A∶B＝1∶1
F142 4-F CH3 CH3 NH Directly key 3,5-difluoroaniline (A)2.88(s，3H)，3.36(s，3H)，7.16-8.36 (m，13H). (B)2.98(s，3H)，3.44(s，3H)，7.16-8.36 (m，13H) A∶B＝2∶1
F143 4-F CH3 CH3 NH Directly key 3-anisidine (A)2.87(s，3H)，3.36(s，3H)，3.84(s，3H )，6.66-8.26(m，14H). (B)2.97(s，3H)，3.43(s，3H)，3.84(s，3H )，6.66-8.26(m，14H) A∶B＝1∶1
F144 4-F CH3 CH3 NH Directly key 4 monomethylanilines (A)2.34(s，3H)，2.88(s，3H)，3.36(s，3H )，7.16-8.20(m，14H).
F145 4-F CH3 CH3 NH Directly key 4-monomethylaniline (B)2.34(s，3H)，2.97(s，3H)，3.43(s，3H )，7.09-8.17(m，14H).
F146 4F CH3 CH3 NH Directly key 3,5-xylidine (A)2.33(s，6H)，2.87(s，3H)，3.36(s，3H )，6.76-8.17(m，13H).
F147 4F CH3 CH3 NH Directly key 3,5-xylidine (B)2.34(s，3H)，2.97(s，3H)，3.43(s，3H )，6.76-8.17(m，13H).
F148 4-F CH3 CH3 NH Directly key 3,4 difluoroanilines (A)2.87(s，3H)，3.36(s，3H)，7.11-8.24 (m，13H).
F149 4F CH3 CH3 NH Directly key 3,4-difluoroaniline (B)2.97(s，3H)，3.43(s，3H)，7.10-8.24 (m，13H).
F150 4-Cl CH3 CF3 NH Directly key 3,5-difluoroaniline (A)3.50(s，3H)，6.56-8.32(m，13H).
F151 4-Cl CH3 CF3 NH Directly key 3-anisidine (A)3.50(s，3H)，3.84(s，3H)，6.67-8.22 (m，14H).
F152 4-Cl CH3 CF3 NH Directly key 3,5-xylidine (A)3.50(s，3H)，2.34(s，6H)，6.77-8.14 (m，13H).
F153 4-Cl CH3 CF3 NH Directly key 3,4-difluoroaniline (A)3.50(s，3H)，7.14-8.22(m，13H). (B)3.58(s，3H)，7.14-8.22(m，13H). A∶B＝1∶3
F154 4F CH3 CH3 NH Directly key 3-5-trifluoromethylaniline (A)2.88(s，3H)，3.36(s，3H)，7.26-8.39 (m，14H).
F155 4-F CH3 CH3 NH Directly key 3-5-trifluoromethylaniline (B)2.98(s，3H)，3.43(s，3H)，6.98-8.39 (m，14H).
F156 4-F CH3 CH3 NH Directly key 3-fluoroaniline (A)2.87(s，3H)，3.35(s，3H)，6.78-8.32 (m，14H).
F157 4-F CH3 CH3 NH Directly key 3 fluoroanilines (B)2.97(s，3H)，3.43(s，3H)，6.78-8.32 (m，14H).
F158 4-F CH3 CH3 NH Directly key 2,4 difluorobenzene amine (B)2.96(s，3H)，3.42(s，3H)，6.86-8.82 (m，13H).
F159 4-F CH3 CH3 NH Directly key 2,3,4-trifluoromethyl aniline (B)2.96(s，3H)，3.42(s，3H)，6.93-8.50 (m，12H).
F160 4-F CH3 CH3 NH CH2 4-5-trifluoromethylaniline
F161 4-Cl CH3 CH3 NH CH2 4-trifluoro-methoxyaniline
F162 4-Cl CH3 CH3 NH Directly key 4-hydroxyanilines
F163 4-Cl CH3 CH3 NH Directly key 4-cyano-aniline
F164 4-Cl CH3 CH3 NH Directly key 4-bromaniline
F165 4-Cl CH3 CH3 NH Directly key 4-Iodoaniline
F166 4-Cl CH3 CH3 NH Directly key 4-formyloxy aniline
F167 4Cl CH3 CH3 NH Directly key 4-methyl-formiate base aniline
F168 4-Cl CH3 CH3 NH Directly key 4-formamido-aniline
F169 4-Cl CH3 CH3 NH Directly key 4-(N, N-dimethyl) formamido-aniline
F170 4-Cl CH3 CH3 NH Directly key 4-(N-phenyl) formamido-aniline
F171 4-Cl CH3 CH3 NH Directly key 4-5-trifluoromethylaniline (A)2.89(s，3H)，3.36(s，3H)，7.22-8.44 (m，14H).
F172 4-Cl CH3 CH3 NH Directly key 4-5-trifluoromethylaniline (B)2.98(s，3H)，3.44(s，3H)，7.26-8.43 (m，14H).
F173 4-Cl Cyclopropyl CH3 NH Directly key 4-5-trifluoromethylaniline
Benzophenone hydrazone derivatives of the present invention, can be for agricultural chemical insecticide.
Benzophenone hydrazone derivatives of the present invention can be used as the active constituent of chemistry of pesticide sterilant, be mixed with various liquors, missible oil, suspension agent, aqueous suspension, microemulsion, (water) emulsion, pulvis, wettable powder, soluble powder, (water dispersible) granule or capsule etc., for the pest control of the farm crop such as paddy rice, soybean, wheat, cotton, corn, vegetables and rape.
In the time being configured to chemistry of pesticide sterilant, the weight percentage of active ingredient is that the weight percentage of benzophenone hydrazone derivatives of the present invention is preferably 5～90%, all the other are acceptable carrier, and carrier at least comprises two kinds, wherein at least-and kind be tensio-active agent.
Carrier can be solid or liquid.Suitable solid carrier comprises natural or synthetic clay and silicate, for example natural silica and diatomite; Magnesium Silicate q-agent is talcum such as; Magnesium aluminum silicate is kaolinite, kaolin, polynite and mica for example; White Carbon black, calcium carbonate, light calcium carbonate; Calcium sulfate; Wingdale; Sodium sulfate; Amine salt is as ammonium sulfate, hexamethylene diamine.Liquid vehicle comprises water and organic solvent, and in the time that water is cooked solvent or thinner, organic solvent also can be used as auxiliary or antifreeze additive.Suitable organic solvent comprises aromatic hydrocarbons such as benzene, dimethylbenzene, toluene etc.; Hydrochloric ether, such as chlorinated benzene, vinylchlorid, trichloromethane, methylene dichloride etc.; Aliphatic hydrocarbon, for example petroleum fractions, hexanaphthene, light mineral oil; Alcohols, such as Virahol, butanols, ethylene glycol, glycerol and hexalin etc.; And their ether and ester; Also has ketone, for example acetone, pimelinketone and dimethyl formamide and N-methyl-pyrrolidone.
Tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; Can be ionic or non-ionic type.Nonionic emulsifier is polyoxyethylene fatty acid fat, polyoxyethylene aliphatic alcohol ether, polyoxyethylene fatty amine for example, and commercially available emulsifying agent: agriculture breast 2201B, agriculture breast 0203B, agriculture breast 100 #, agriculture breast 500 #, agriculture breast 600 #, agriculture breast 600-2 #, agriculture breast 1601, agriculture breast 2201, agriculture breast NP-10, agriculture breast NP-15, agriculture breast 507 #, agriculture breast OX-635, agriculture breast OX-622, agriculture breast OX-653, agriculture breast OX-667, peaceful breast 36 #.Dispersion agent comprises sodium lignosulfonate, pulls open powder, calcium lignin sulphonate, condensation compound of methyl naphthalene sulfonic acid and formaldehyde etc.Wetting agent is: sodium laurylsulfate, Sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate etc.
Above-mentioned chemistry of pesticide sterilant can be prepared by general method.For example, active substance is mixed with liquid solvent and/or solid carrier, add tensio-active agent as emulsifying agent, dispersion agent, stablizer, wetting agent simultaneously, can also add other auxiliary agent as tackiness agent, defoamer, oxygenant etc.
Benzophenone hydrazone derivatives of the present invention can also with weedicide, sterilant, nematocides, plant-growth regulator, fertilizer, and other sterilant or other agrochemicals mixtures are used.
Benzophenone hydrazone derivatives of the present invention and by the chemistry of pesticide sterilant of its configuration, tool has the following advantages:
(1) there is the selectivity of killing preferably, as good in securities such as wheat, soybean, cotton, paddy rice to part crop;
(3) there is rational toxicity, eco-toxicity and Environmental compatibility, belong to the environmentally friendly agricultural chemicals of low toxicity.
Embodiment
Below provide the required analytical data of detailed reaction conditions, purification process, physical constant and structural confirmation with regard to part example, it is to be noted that the present invention is not merely confined in the scope of following embodiment.
Following embodiment is using compound of the present invention as active substance component, and in the embodiment of processing preparation several herbicides formulation, all " % " all refer to weight percent, and " gai/ha " all refers to every gram of actives/hectare.
Synthesizing of embodiment 1 intermediate A
Add 25 grams of chlorobenzenes, 41.2 grams of paranitrobenzoyl chlorides and 200ml ethylene dichloride at flask, mechanical stirring is warmed up to 50 degrees Celsius, adds 34 grams of aluminum trichloride (anhydrous)s in 2 hours in batches, reflux again 1 hour, after cooling, pour in frozen water layering, extraction into, water layer divides 2 extractions with 100 milliliters of ethylene dichloride, merge organic layer, 30 milliliters of saturated common salt water washings once, are filtered after dried over sodium sulfate, after decompression precipitation, methanol crystallization obtains chloro-4 ' nitro benzophenone, the productive rates 85% of intermediate 4-.
Using the same method, use different raw materials---fluorobenzene can the fluoro-4 ' nitro benzophenones of synthetic intermediate 4-.Productive rate 80%.
In flask, add 2.45 grams of magnesium powder and 100 milliliters of anhydrous diethyl ethers, splash into 22.5 grams of m-trifluoromethyl phenyl-bromides, control splashes into speed and keeps that system is micro-boils, drip off the Grignard reagent that rear backflow obtains m-trifluoromethyl phenyl-bromide for 1 hour, add 18.55 grams of paranitrobenzoyl chlorides, stir 8 hours, add 200 milliliters of 1N dilute hydrochloric acid, layering, extraction, water layer divides 2 extractions with 100 milliliters of ether, merge organic layer, 30 milliliters of saturated common salt water washings once, after dried over sodium sulfate, filter, after decompression precipitation, methanol crystallization obtains intermediate 3-trifluoromethyl-4 ' nitro benzophenone, productive rate 45%.
The preparation of embodiment 2 intermediate B
In flask, add 350 ml waters, 145 grams of Na 2s, 9H 2o, and 17.3 can sulphur powder, heated and stirred to sulphur powder dissolves to obtain Na completely 2s 2the aqueous solution is for subsequent use.
In flask, add 75 grams of chloro-4 ' nitro benzophenone and 100 milliliters of Na of intermediate 4- 2s 2the aqueous solution, is warmed up to backflow under stirring, by remaining Na 2s 2the aqueous solution splashed in 2 hours, continued to stir 3 hours, and solution colour is by red stain Huang, cooling, had a large amount of solids to occur, filtered washing, dried to obtain chloro-4 ' aminobenzophenone, the productive rates 90% of intermediate 4-.
Using the same method, use different raw materials---' ' nitro benzophenone can fluoro-4 ' aminobenzophenone and the 3-trifluoromethyl-4 ' aminobenzophenones of synthetic intermediate 4-for nitro benzophenone and 3-trifluoromethyl-4 for 4-fluoro-4.
The preparation of embodiment 3 intermediate C
In flask, add 9.7 grams of chloro-4 ' 50 milliliters of pyridines of aminobenzophenone of intermediate 4-, under ice bath, splash into 4.8 grams of methylsulfonyl chlorides, dripping off rear continuation half an hour stirs 1 hour, pour in the 2N dilute hydrochloric acid of ice, filter washing, dry to obtain chloro-4 ' methylsulfonyl amido benzophenone, the productive rates 92% of intermediate 4-.
Using the same method, use different raw materials---' ' aminobenzophenone can fluoro-4 ' methylsulfonyl amido benzophenone and 3-trifluoromethyl-4 ' the methylsulfonyl amido benzophenone of synthetic intermediate 4-for aminobenzophenone and 3-trifluoromethyl-4 for 4-fluoro-4.
In flask, add 12.65 grams of chloro-4 ' aminobenzophenone, 50 milliliters of trichloromethanes and 5.52 grams of triethylamines of intermediate 4-, under ice bath, splash into 15.41 trifluoromethanesulfanhydride anhydrides, naturally rise to room temperature, add 10% excessive aqueous sodium hydroxide solution to stir, layering extraction, buck layer separates, 20 milliliters of chloroform washings, hcl acidifying, separate out solid, filter washing, dry to obtain intermediate 3-trifluoromethyl-4 ' methylsulfonyl amido benzophenone, productive rate 50%.
The preparation of embodiment 4 intermediate D
In flask, add 10 grams of fluoro-4 ' methylsulfonyl amido benzophenone, 4.73 grams of methyl-sulfates, 11 grams of Anhydrous potassium carbonates and 100 milliliters of acetone of 4-, reflux cooling after 8 hours, filter, after precipitation, methanol crystallization obtains fluoro-4 ' (N-methyl) methylsulfonyl amido benzophenone, the productive rates 70% of intermediate 4-.
Use the same method, use different raw materials---chloro-4 ' methylsulfonyl amido benzophenone, 3-trifluoromethyl-4 ' methylsulfonyl amido benzophenone, the ethyl sulfates of 4-, can synthesize various intermediate (as shown in structural formula (D)), (other substituting group in R1, R2, R3 representative structure formula (D)).
The preparation of embodiment 5 intermediate E
In flask, add 4 grams of chloro-4 ' (N-methyl) fluoroform sulfoamido benzophenone, 6.5 gram of 85% hydrazine hydrate and 50 milliliters of ethanol of 4-, stirring at room temperature 1 hour, reflux 6 hours, cooling, freezing rear filtration, obtains intermediate E (R1=chlorine, R2=methyl, R3=trifluoromethyl, Y=NH).
In flask, add 2.39 grams of oxammonium hydrochlorides, 2.79 grams of sodium-acetates and 60 milliliters of ethanol, add 7.35 grams of chloro-4 ' (N-methyl) methylsulfonyl amido benzophenone of 4-in batches, stirring at room temperature 1 hour, reflux 4 hours, cold filtration, washes to obtain intermediate E (R1=chlorine, R2=methyl, R3=methyl, Y=0).
Use the same method, use different raw material and oxammonium hydrochloride, can synthesize various intermediate (as shown in structural formula (E)), (other substituting group in R1, R2, R3, Y representative structure formula (E)).
The preparation of embodiment 6 intermediate G
In flask, add intermediate D, equivalent carbazic acid methyl esters and etoh solvent, reflux 8 hours, cooling, the intermediate G of filtration, (other substituting group in R1, R2, R3, representative structure formula (G)).
Embodiment 7 target compound F's is synthetic
The phenyl isocyanate and the anhydrous tetrahydro furan that in flask, add the R4R5R6 of intermediate E, equivalent to replace, stirring at room temperature 12 hours, pressure reducing and steaming solvent, silica gel column chromatography or methanol crystallization obtain target compound.
The aniline and the toluene that in flask, add the R4R5R6 of intermediate G, equivalent to replace, return stirring 12 hours, pressure reducing and steaming solvent, silica gel column chromatography or methanol crystallization obtain target compound.
Following examples 8 to embodiment 10 provide using compound of the present invention as active substance component, and the concrete instance of processing preparation several herbicides formulation, it is to be noted that the present invention is not merely confined in the scope of following example.In these formula examples, all " % " all refer to weight percent, and " gai/ha " all refers to every gram of actives/hectare.
Embodiment 8 wettable powder agent prescriptions
By compound F 17-hydroxy-corticosterone described in 15% table 11,5% sulfonated lignin (M q), 1% ethoxylated dodecyl alcohol (JFC), 40% diatomite and 44% light calcium carbonate mix equably, pulverizes, and obtains wettable powder.
Embodiment 9 emulsifiable concentrate formulations
By even the dimethylbenzene heated and stirred of No. 602, compound F 17-hydroxy-corticosterone described in 10% table 11,5% agriculture breast No. 500 (calcium salts), 5% agriculture breast, 5% METHYLPYRROLIDONE and 75%, obtain missible oil.
Embodiment 10 granula formulas
Compound F 17-hydroxy-corticosterone described in 5% table 11,1% polyvinyl alcohol (PVA), 4% naphthalenesulfonic acid-formaldehyde condensate (NMO) and 90% clay are mixed equably; pulverize; then add 20 parts of water to these 100 parts of mixtures; mediate; with extruding granulator; make 14-32 object particle, dry, obtain granule.
Embodiment 11 biological activity determinations:
Below below implementing to provide, provide and use compound of the present invention to carry out the example of biological activity determination, it is to be noted that the present invention is not merely confined in the scope of following example.
The following method of Insecticidal Activity experimental evidence is carried out:
Take the preparation of certain mass, adding distil water dilution is mixed with the liquid of measuring desired concn.Screening concentration is 500,100,20mg/L, chemicals treatment amount of liquid medicine 10mL.Test target is designated as oriental armyworm (Mythima sBparata), Nilaparvata lugen (brown planthopper) (Nilaparvata lugBns), carmine spider mite (TBtranychus cinnabarnus), aphis craccivora (Aphis mBdicagini), small cabbage moth (PlutBlla xylostBlla), prodenia litura (ProdBnia litura) etc.
(1) Brown Planthopper screening---spray method
Rice seedlings is fixed in culture dish with white quartz sand, connects and use CO 2anaesthetize 3 mid-term in age nymph, be placed under POTTBR spray tower and spray.After spraying, cover with transparent plastics cup, after mark, be put in observation ward.Check result after 72h.
(2) oriental armyworm screening---soak seedling feeding method
After leaf of Semen Maydis is fully infiltrated in liquid, naturally dries in the shade, puts into culture dish, connect 3 mid-term in age larva, add a cover mark and be placed in observation ward.Check result after 72h.
(3) small cabbage moth screening---pickling process
Wild cabbage sheet is cut, punched into disk, be then dipped in 20s in liquid, be put in Φ 9cm plastic culture dish (5/ware), connect 15/ware of small cabbage moth 2 instar larvaes, put a filter paper, add a cover.Be placed in 26 ℃ of indoor cultivation, check result after 72h.Test repeats 4 times.Touch polypide with tip tweezers, be reactionlessly considered as dead worm
(4) carmine spider mite screening---pickling process
Broad Bean Leaves is broken into leaf dish, and the back side is placed on fritter cotton upward, is placed in plastic culture dish, adds a small amount of water, connects carmine spider mite and becomes mite.After becoming mite stable on blade, blade is fully sucked to blade surface water droplet with thieving paper rapidly after infiltration 5s in liquid, be again placed on cotton, air-dry.Check result after 72h.
(5) aphis craccivora screening---pickling process
Broad Bean Leaves is cut off to two ends, and the back side is placed on fritter cotton upward, is placed in plastic culture dish, adds a small amount of water, becomes aphid to produce aphid if connect aphis craccivora.After 24h, remove into aphid, continue after cultivation 2d, blade fully to be infiltrated after 5s in liquid, be again placed on cotton natural airing.Check result after 24h.
(6) prodenia litura screening---pickling process
Wild cabbage sheet is cut, beaten and get wild cabbage roundleaf with punch tool, in liquid, soak 20s, dry.Put into the six hole plastics casings with circular hole (Φ 2cm), 3, every hole.Access 1/hole of prodenia litura larva in 3 mid-term in age, puts into observation ward.Check result after 72h.Test repeats 4 times.Touch polypide with tip tweezers, be reactionlessly considered as dead worm.
Test statistics: add up the dead borer population of each processing and the borer population of living, calculate mortality ratio.
CK contrast mortality ratio < 20%, test-results is credible, and test-results is proofreaied and correct, and when CK contrast mortality ratio < 5%, can not proofread and correct.
The raw test-results of surveying shows: the compounds of this invention has good insecticidal activity, particularly to lepidoptera pest, as oriental armyworm, small cabbage moth, prodenia litura etc. have the insecticidal activity of wide spectrum, " mg/L " all refer to every milligram of actives/liter.
Under 500mg/L concentration, F1-F30, F33, F34, F37-F88, F110, F111, F115, F116, F120, F122, F123 is greater than 80% to the mortality ratio of oriental armyworm.
Under 100mg/L concentration, F19, F171, F172, F21, F26-F30, F33, F34, F36, F38-F47, is greater than 80% to the mortality ratio of prodenia litura.
Under 100mg/L concentration, F55-F69, F74, F81, F85, F86, F88, F111, F115, F116, F122, F123 is greater than 80% to the mortality ratio of small cabbage moth.

Claims (11)

1. a benzophenone hydrazone derivatives, the structural formula shown in [F] that it is characterized in that thering is formula:
Wherein:
R1 is halogen, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4haloalkyl or C 1-C 4halogenated alkoxy;
R2 is hydrogen, C 1-C 4alkyl or cyclopropyl;
R3 is C 1-C 4alkyl or C 1-C 4haloalkyl;
R4, R5, R6 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group, C 1-C 4halogenated alkoxy, formyloxy and formyloxy an alkali metal salt, formic acid C 1～6ester group, formamido-or N-C 1-4alkyl or phenyl substituted formyl amido;
X is amido or oxygen;
Y is methylene radical or direct key.
2. according to a kind of benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that described R1 is chlorine, fluorine or trifluoromethyl, R1 is positioned at 3 or 4 of phenyl ring.
3. according to a kind of benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that described R2 is methyl, described R3 is methyl or trifluoromethyl.
4. according to a kind of benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that described X is amido, described Y is direct key.
5. according to a kind of benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that described R4, R5, R6 are independently selected from hydrogen, halogen, nitro, methyl, trifluoromethyl, methoxyl group, trifluoromethoxy or formic acid ester group.
6. according to a kind of benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that described N-X is cis-isomeride and/or trans-isomer(ide).
7. prepare the method according to benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that comprising the following steps:
4-R1-4 '-R3SO 2hydrazine hydrate or the oxammonium hydrochloride of N (R2) Y-benzophenone and 1-10 equivalent, in alcoholic solvent, at 0 ℃, at solvent refluxing temperature, reaction obtains 4-R1-4 '-R3SO 2the hydrazine hydrate dehydration condensation intermediate of N (R2) Y-benzophenone;
In the time using oxammonium hydrochloride, need to add acid binding agent;
4-R1-4 '-R3SO 2the phenyl isocyanate that the represented R4R5R6 of the hydration callosity dehydration condensation intermediate of N (R2) Y-benzophenone and structural formula [I] replaces is in ether solvent, at 0 ℃, at solvent refluxing temperature, reaction obtains according to benzophenone hydrazone derivatives claimed in claim 1;
Wherein:
R1 is halogen, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4haloalkyl or C 1-C 4halogenated alkoxy;
R2 is hydrogen, C 1-C 4alkyl or cyclopropyl;
R3 is C 1-C 4alkyl or C 1-C 4haloalkyl;
R4, R5, R6 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group, C 1-C 4halogenated alkoxy, formyloxy and formyloxy an alkali metal salt, formic acid C 1～6ester group, formamido-or N-C 1-4alkyl or phenyl substituted formyl amido;
X is amido or oxygen;
Y is methylene radical or direct key.
According to preparation claimed in claim 7 according to the method for benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that described acid binding agent is sodium-acetate, triethylamine or salt of wormwood, described ethers is ether, tetrahydrofuran (THF) or dioxane.
9. prepare the method according to benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that comprising the following steps:
4-R1-4 '-R3SO 2the carbazic acid methyl esters of N (R2) Y-benzophenone and 1-5 equivalent, in benzene class or alcoholic solvent, described benzene kind solvent is selected from benzene,toluene,xylene or ethylbenzene, and at 0 ℃, at solvent refluxing temperature, reaction obtains 4-R1-4 '-R3SO 2the carbazic acid methyl esters dehydration condensation intermediate of N (R2) Y-benzophenone;
4-R1-4 '-R3SO 2the aniline that the carbazic acid methyl esters dehydration condensation intermediate of N (R2) Y-benzophenone and R4R5R6 replace is in benzene class or ether solvent, and at 0 ℃, at solvent refluxing temperature, reaction obtains according to benzophenone hydrazone derivatives claimed in claim 1;
Wherein:
R1 is halogen, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4haloalkyl or C 1-C 4halogenated alkoxy;
R2 is hydrogen, C 1-C 4alkyl or cyclopropyl;
R3 is C 1-C 4alkyl or C 1-C 4haloalkyl;
R4, R5, R6 are independently selected from hydrogen, halogen, nitro, itrile group, hydroxyl, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group, C 1-C 4halogenated alkoxy, formyloxy and formyloxy an alkali metal salt, formic acid C 1～6ester group, formamido-or N-C 1-4alkyl or phenyl substituted formyl amido;
X is amido or oxygen;
Y is methylene radical or direct key.
According to preparation claimed in claim 9 according to the method for benzophenone hydrazone derivatives claimed in claim 1, it is characterized in that described benzene class is benzene,toluene,xylene or ethylbenzene, described ethers is ether, tetrahydrofuran (THF) or dioxane.
11. 1 kinds according to benzophenone hydrazone derivatives claimed in claim 1 purposes, it is characterized in that for agricultural chemical insecticide.
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