CN109879834A - A kind of 3- amino -2- cyanoacrylate compound and its application - Google Patents

A kind of 3- amino -2- cyanoacrylate compound and its application Download PDF

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Publication number
CN109879834A
CN109879834A CN201910198401.5A CN201910198401A CN109879834A CN 109879834 A CN109879834 A CN 109879834A CN 201910198401 A CN201910198401 A CN 201910198401A CN 109879834 A CN109879834 A CN 109879834A
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unsubstituted
substituent group
group
alkyl
amino
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Inventor
谭波
王洪雷
曹杨
马海军
刁亚梅
蔡义强
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JIANGSU PESTICIDE RESEARCH INSTITUTE Co Ltd
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JIANGSU PESTICIDE RESEARCH INSTITUTE Co Ltd
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Abstract

The invention discloses a kind of 3- amino -2- cyanoacrylate compound and its application, compound has general formula shown in formula (I), and the present invention prepares a kind of cyanoacrylate Mannic base type fungicide.The fungicide has excellent control efficiency to sickle-like bacteria, and because of the alkalinity of its Mannich base, allows it and common inorganic acid and organic acid to generate salt, is soluble in water.

Description

A kind of 3- amino -2- cyanoacrylate compound and its application
Technical field
And its, in particular to 3- amino -2- cyanoacrylate compound and its answer the invention belongs to disinfectant use in agriculture With.
Background technique
Compound with enamine ester structure has special bioactivity, and it is anti-usually to may be used as medicine, veterinary drug, pesticide Microbial inoculum.Cyanoacrylate compound specially kills sickle-like bacteria activity, the unique mechanism of action, Yi Jike since it has The characteristics of to reduce fusarium toxin,
2-cyano-3-amino-3-phenylancryic acetate, -3 ethyl phenylacrylate (pesticide name 2-cyano-3-amino-3-phenylancryic acetate) of -3 amino of (Z) 2- cyano is Jiangsu Province's agriculture The cyanoacrylate fungicide that limited liability company, medicine research institute independently formulates, was applied for a patent in 2001 (CN1317483A).The compound is efficient, micro- poison, wide spectrum, low-residual, environmentally friendly, to the phytopathy as caused by sickle-like bacteria Evil has protection and therapeutic effect, can be applied to wheat scab, cotton wilt, banana Panama caused by prevention and treatment sickle-like bacteria Disease, bakanae disease of rice, watermelon blight etc..It is one of the pesticide species of domestic only a few initiative invention, but 2-cyano-3-amino-3-phenylancryic acetate As other -2 amino-acrylonitrile acid esters of 3- amino, there is it to be difficult to overcome the problems, such as, that is, very for general solubility It is small, it limits its scope of application.
Summary of the invention
Goal of the invention: the present invention utilizes the characteristic of Mannich base in the ammonia of 3- amino -2- cyanoacrylate compound Aminomethyl is introduced on base, is prepared one kind 3- amino -2- cyanoacrylate Mannic base type compound, is passed through aminomethyl Introduce the physicochemical properties for improving original structure, at the same using Mannich base unstable and retain former compound sterilization it is living Property.
Technical solution: the 3- amino -2- cyanoacrylate chemical combination of the present invention indicated by following general formula (I) Object:
Wherein: wherein: R H, unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6Alkyl, nothing Substitution or the C with substituent group2-C6Alkenyl, unsubstituted or with substituent group C2-C6It is alkynyl, unsubstituted or with substituent group C3-C6Naphthenic base, halogen, CN, NO2, hydroxyl, unsubstituted or with substituent group C1-C6Alkoxy, it is unsubstituted or have substituent group C1-C6Epoxy alkyl, unsubstituted or with substituent group C1-C4Alkyl groups in the halogenalkoxy, unsubstituted or with substituent group C1-C6Alkane sulphur Base, unsubstituted or with substituent group C1-C4Alkyl sulfino, unsubstituted or with substituent group C1-C4Alkyl sulphonyl, nothing Substitution or the C with substituent group2-C4Alkoxy carbonyl, unsubstituted or with substituent group C2-C6Acyl group, it is unsubstituted or have take The C of Dai Ji3-C6Trialkylsilkl, unsubstituted or with substituent group C2-C8Dialkyl amido, it is unsubstituted or have replace The C of base3-C6Naphthene amino, unsubstituted or phenyl with substituent group, unsubstituted or phenoxy group with substituent group, it is unsubstituted or Benzyl with substituent group, unsubstituted or 6 yuan of hetero-aromatic rings with substituent group or unsubstituted or 5 yuan of heteroaryls with substituent group Ring；
R1For unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6Alkyl, it is unsubstituted or have take The C of Dai Ji2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C2-C6Naphthenic base, Halogen, CN, NO2, hydroxyl, unsubstituted or with substituent group C1-C6Alkoxy, unsubstituted or with substituent group C1-C4Alkane sulphur Base, unsubstituted or with substituent group C1-C4Alkyl sulfino, unsubstituted or with substituent group C1-C4Alkyl sulphonyl, nothing Substitution or the C with substituent group2-C6Alkoxy carbonyl, unsubstituted or with substituent group C1-C6It is alkoxy carbonyloxy group, unsubstituted Or the C with substituent group1-C6Acyl amino, unsubstituted or with substituent group C2-C4Alkyl amino, it is unsubstituted or have replace The C of base2-C8Dialkyl amido, unsubstituted or with substituent group C3-C6Naphthene amino, unsubstituted or with substituent group C2-C6 Acyl group, unsubstituted or with substituent group C1-C6Alkoxy amino, unsubstituted or with substituent group C3-C6Alkyl amino-carbonyl, C unsubstituted or with substituent group1-C6Alkoxycarbonyl amino, unsubstituted or with substituent group C2-C8Dialkylaminocarbonyl, C unsubstituted or with substituent group3-C6It is trialkylsilkl, unsubstituted or phenyl with substituent group, unsubstituted or have The phenoxy group of substituent group, unsubstituted or benzyl with substituent group, it is unsubstituted or have 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, nothing Replace or have 5 circle heterocyclic ring of substituent group or hetero-aromatic ring；
R2For H, unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6It is alkyl, unsubstituted or have The C of substituent group2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C2-C6Cycloalkanes Base, halogen, CN, NO2, hydroxyl, unsubstituted or with substituent group C1-C4Alkoxy, unsubstituted or with substituent group C1-C4Halogen Alkoxy, unsubstituted or with substituent group C1-C4Alkylthio group, unsubstituted or with substituent group C1-C4Alkyl sulfino, nothing Substitution or the C with substituent group1-C4Alkyl sulphonyl, unsubstituted or with substituent group C3-C6Alkyl amino-carbonyl, it is unsubstituted or C with substituent group1-C6Alkoxy amino, unsubstituted or with substituent group C2-C4Alkoxy carbonyl, it is unsubstituted or have take The C of Dai Ji1-C6Alkoxycarbonyl amino, unsubstituted or with substituent group C2-C4Acyl group, C unsubstituted or with substituent group3- C6Trialkylsilkl, C unsubstituted or with substituent group2-C8Dialkyl amido, unsubstituted or with substituent group C3-C6 Naphthene amino, unsubstituted or phenyl with substituent group, unsubstituted or phenoxy group with substituent group, it is unsubstituted or have replace It is the benzyl of base, unsubstituted or with 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, unsubstituted or there is 5 circle heterocyclic ring of substituent group or hetero-aromatic ring；
Or the R1With R2Coupled nitrogen forms the ring K containing 2-6 carbon atom；The ring K may also include optionally Another nitrogen, sulphur or oxygen atom, or C (=O), SO or S (O) are selected from including 1 or 22Ring members, the ring K can be chosen From C1-C2Alkyl, halogen, CN, NO2, hydroxyl, C1-C2Hydroxyalkyl and C1-C21-4 group of alkoxy arbitrarily replaces；
R3For H, unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6It is alkyl, unsubstituted or have The C of substituent group2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C2-C6Cycloalkanes Base, halogen, CN, NO2, hydroxyl, unsubstituted or with substituent group C1-C4Alkoxy, unsubstituted or with substituent group C1-C4Halogen Alkoxy, unsubstituted or with substituent group C1-C4Alkylthio group, unsubstituted or with substituent group C1-C4Alkyl sulfino, nothing Substitution or the C with substituent group1-C4Alkyl sulphonyl, unsubstituted or with substituent group C2-C4Alkoxy carbonyl, it is unsubstituted or C with substituent group2-C4Acyl group, unsubstituted or with substituent group C3-C6Trialkylsilkl, it is unsubstituted or have replace The C of base2-C8Dialkyl amido, unsubstituted or with substituent group C3-C6Naphthene amino, unsubstituted or with substituent group benzene It is base, unsubstituted or phenoxy group with substituent group, unsubstituted or there is 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, unsubstituted or have 5 circle heterocyclic ring of substituent group or hetero-aromatic ring；
R4For H, unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6It is alkyl, unsubstituted or have The C of substituent group2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C2-C6Cycloalkanes Base or C unsubstituted or with substituent group2-C6Epoxy alkyl, halogen, CN, NO2, it is hydroxyl, unsubstituted or with substituent group C1-C4Alkoxy, unsubstituted or with substituent group C1-C4Alkyl groups in the halogenalkoxy, unsubstituted or with substituent group C1-C4Alkylthio group, C unsubstituted or with substituent group1-C4Alkyl sulfino, unsubstituted or with substituent group C1-C4It is alkyl sulphonyl, unsubstituted Or the C with substituent group2-C4Alkoxy carbonyl, unsubstituted or with substituent group C2-C4Acyl group, it is unsubstituted or have substituent group C3-C6Trialkylsilkl, unsubstituted or with substituent group C2-C8Dialkyl amido, C3-C6It is naphthene amino, unsubstituted Or it is the phenyl with substituent group, unsubstituted or phenoxy group with substituent group, unsubstituted or benzyl with substituent group, unsubstituted Or with 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, unsubstituted or there is 5 circle heterocyclic ring of substituent group or hetero-aromatic ring；
The G is 5 or 6 yuan of non-aromatic carbocycles or heterocycle, it includes optional 1 or 2 selected from C (=O), SO or S (O)2 Ring members, and available be selected from C1-C2Alkyl, halogen, CN, NO2And C1-C2Any selection of 1-4 of alkoxy replaces；
Described R, R1、R2、R3And R4It can each be replaced by following one or more groups: C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C3-C6Naphthenic base, C1-C6Alkylhalide group, C2-C4Haloalkenyl, C2-C4Alkynyl halide, C3-C6Halogen naphthenic base, halogen, CN, NO2, hydroxyl, isocyanide oxygroup, cyanato-, amino, thiocyanogen, imino group, C1-C4Alkoxy, C1-C4Alkyl groups in the halogenalkoxy, C1-C4Alkane sulphur Base, C2-C6Acyl group, C2-C6Acyloxy, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyloxysulfonyl, C1- C4Alkyl amino, C2-C6Alkoxy carbonyl, C1-C6Alkoxy carbonyloxy group, C1-C6Alkoxycarbonyl amino, (C1-C6Alkoxy) sulphur For carbonyl, (C1-C6Alkylthio group) thiocarbonyl, C1-C6Acyl amino, C1-C6Alkoxy amino, C1-C6Alkyl amino carbonyl oxy, C3-C6Trialkylsilkl, C2-C8Dialkyl amido, C3-C6Cycloalkyl amino, C3-C6(alkyl) cycloalkyl amino, C2-C6 Alkyl amino-carbonyl, C3-C8Dialkyl amino carbonyl, phenyl, benzyl, phenoxy group, anilino-, 5 yuan of hetero-aromatic rings and 6 yuan of hetero-aromatic rings.
Preferably, the R is selected from: C unsubstituted or with substituent group1-C6Alkyl, unsubstituted or with substituent group C2- C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C3-C6Naphthenic base, unsubstituted or tool It is the phenyl of substituted base, unsubstituted or benzyl with substituent group, unsubstituted or 5 yuan of heteroaromatics with substituent group, unsubstituted Or 6 yuan of heteroaromatics with substituent group.
Preferably, the R1It is selected from: unsubstituted or G, unsubstituted or with substituent group C with substituent group1-C6Alkyl, C unsubstituted or with substituent group2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, it is unsubstituted or have substituent group C3-C6Naphthenic base, unsubstituted or phenyl with substituent group, unsubstituted or benzyl with substituent group, it is unsubstituted or have take For 6 circle heterocyclic ring of base or hetero-aromatic ring, unsubstituted or there is 5 circle heterocyclic ring of substituent group or hetero-aromatic ring；
The R2It is selected from: H, unsubstituted or with substituent group C1-C6Alkyl, unsubstituted or the phenyl with substituent group, nothing Replace or the benzyl with substituent group, unsubstituted or there is 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, unsubstituted or with substituent group 5 Circle heterocyclic ring or hetero-aromatic ring；
Or the R1With R2Coupled nitrogen forms ring K, the ring K containing 2-6 carbon atom and may also include optionally another One nitrogen, sulphur or oxygen atom；The ring K can be selected from C1-C2Alkyl, halogen, CN, NO2, hydroxyl, C1-C2Hydroxyalkyl and C1- C21-4 group of alkoxy arbitrarily replaces；
The R1And R2It can each be replaced by following one or more groups: hydroxyl, CN, thiocyanogen, NO2、C1-C4Alcoxyl Base, C1-C4Alkyl groups in the halogenalkoxy, C1-C6Alkylhalide group, C2-C4Haloalkenyl, C2-C4Alkynyl halide, C1-C4Alkylthio group, C1-C6Alkyl, C2-C4Alkene Base, C2-C4Alkynyl, C1-C6Alkoxy carbonyloxy group, C1-C6Alkoxycarbonyl amino, C1-C6Acyl amino, C1-C4Acyloxy, C1- C6Alkyl amino carbonyl oxy, imino group, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyloxysulfonyl, (C1- C6Alkoxy) thiocarbonyl, (C1-C6Alkylthio group) thiocarbonyl, C3-C6Naphthenic base, C3-C6Halogen naphthenic base, halogen, isocyanide oxygen Base, cyanato-, amino, C2-C6Acyl group, C3-C8Dialkyl amino carbonyl, C1-C4Alkyl amino, C1-C6Alkoxy amino, C2-C6 Alkoxy carbonyl, C3-C6Trialkylsilkl, C2-C8Dialkyl amido, C3-C6Cycloalkyl amino, C3-C6(alkyl) naphthenic base Amino, C2-C6Alkyl amino-carbonyl, phenyl, benzyl, phenoxy group, anilino-, 5 yuan of hetero-aromatic rings and 6 yuan of hetero-aromatic rings.
Preferably, the R3It is selected from: H, unsubstituted or with substituent group C1-C6It is alkyl, unsubstituted or with substituent group C2-C6Alkenyl, unsubstituted or with substituent group C2-C6It is alkynyl, unsubstituted or phenyl with substituent group, unsubstituted or have The phenoxy group of substituent group, it is unsubstituted or with 6 yuan of hetero-aromatic rings of substituent group, it is unsubstituted or have 5 yuan of hetero-aromatic rings of substituent group.
Preferably, the R4It is selected from: C unsubstituted or with substituent group1-C6It is alkyl, unsubstituted or with substituent group C2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, it is unsubstituted or have 5 circle heterocyclic ring of substituent group.
Preferably, the R is selected from: C unsubstituted or with substituent group1-C6Alkyl, unsubstituted or with substituent group benzene Base, five yuan of heteroaromatics or unsubstituted or hexa-atomic heteroaromatic with substituent group unsubstituted or with substituent group, five yuan of virtues Heterocycle is thiazole, thiophene or furans, and the hexa-atomic heteroaromatic is pyridine.
Preferably, the R3It is selected from: H, phenyl, chlorphenyl, 6 yuan of hetero-aromatic rings or 5 yuan of hetero-aromatic rings.
Preferably, the R1For C1-C6Alkyl, C2-C6Alkenyl, CH2CH3OH、CH2CH3OCH3、CF2CH2OCH3、 CH2CH2OCF2CF2H、CH2CN、CF3、CH2CH2SCN、CH2CHCH2、CH2CCH、CH2CH2Cl、CH2COOC2H5、CH2CH2SCH3、 CH2CH2OCH2CH2Cl、CH2CH2NO2、CH2CH2Si(C2H5)3、CH2CH2Si(CH3)3、CH2CH2OC2H5、CH2CH2OCOOC2H5、 CH2CH2NHCOOC2H5、CH2CH2NHCOCH3、CH2CH3OCOCH3、CH2CH2OCONHC2H5、CH2CH(OCH3)2、CH2COCH3、 CH2CH=NCH3、CH2CH=N-OCH3、CH2CNHOCH3、CH2CNHN(CH3)2、CH2CH2N(CH3)2、CH2CHO、 CH2CH2OHCH2OH、CH2CHCH2CH2、CH2SOCH3、CH2SO2CH3、CH2SO3CH3、CH2SO2、CH2CH2N(CH3)2、 CH2CH2NCH3COCH3、CH2CH2ONCOCH3、CH2CH2OSO2CH3、CH2(C=S) OC2H5、CH2CH2OCONHC2H5、CH2CSN (CH3)2, phenyl, benzyl, hydroxy phenyl, chlorphenyl, acetylphenyl, cyclopenta, cyclohexyl, butyrolactone base, lactim Base, cyclopentanone base, 1,3- dioxolane base；
The R2For C1-C6Alkyl, CH2CH3OH、CH2COOC2H5；
Or the R1With R2The ring K that coupled nitrogen is formed is selected from K1-K14Any one of:
Preferably, the R is C1-C6Alkyl, phenyl, thiazolyl, thienyl, furyl or pyridyl group；The R3For H, furan It mutters base, pyridyl group, phenyl or chlorphenyl；The R4For C1-C6Alkyl, tetrahydrofuran base.
In statement above, " alkyl " word both can be used alone, and can also use in portmanteau word, such as " alkylthio group " or It is used in " alkylhalide group ", C1-C6It includes linear or branched alkyl group to alkyl, such as methyl, ethyl, n-propyl, isopropyl, or different Butyl include normal-butyl, sec-butyl, isobutyl group, tert-butyl, amyl or hexyl and its isomers." 1-2 alkyl " word refers to Being 1 or 2 can be used alkyl-substituted position.
“C2-C6Alkenyl " refers to linear chain or branched chain alkenyl, and such as 1- acrylic, 2- acrylic and different butylene include 1- Cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, amylene includes, 1- pentenyl, 2- pentenyl, 3- pentenyl, 4- pentenyl, 1- methyl- 2- cyclobutenyl, 2- methyl-2-butene base and hexene isomers include 1- hexenyl, 2- hexenyl, 3- hexenyl, 4- hexenyl, The C2-6 alkenyl such as 5- hexenyl；" alkenyl " also includes polyenoid, such as 1,2- allene base and 2,4- hexadienyl；In addition, of the invention Described in alkenyl further include cycloalkenyl.
“C2-C6Alkynyl " includes straight chain and branch alkynyl, such as 1- propinyl, 2-propynyl and different butynyls, and pentynyl And hexynyl isomers；" alkynyl " also includes the group containing multiple three keys, such as 2,5- adipic alkynyl.
“C3-C6Naphthenic base " includes cyclopropyl, cyclobutyl cyclopenta, cyclohexyl etc..
" halogen " word, it can be individually or in portmanteau word such as " alkylhalide group ", including fluorine, chlorine, bromine or iodine, and And in portmanteau word such as in " alkylhalide group " in use, described alkyl can partially or even wholly be replaced with halogen atom, halogen atom It can be same or different.The example of alkylhalide group includes ClCHCH3、F3C, ClCH2, CF3CH2And CF3CCl2, remaining can be arranged That lifts has 1,2- dichloro n-propyl, 1- fluorine normal-butyl, perfluor n-pentyl etc.." haloalkenyl ", " alkynyl halide " and " alkyl groups in the halogenalkoxy " etc. It defines similar with " alkylhalide group ".The example of haloalkenyl includes (Cl2) C=CHCH2And CF3CH2CH=CHCH2.The reality of " alkynyl halide " Example includes HC ≡ CCHCl, CF3C ≡ C, CCl3C ≡ and FCH2C≡CCH2.The example of " alkyl groups in the halogenalkoxy " includes CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O。
“C1-C6Alkoxy " includes, such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy and different butoxy, and penta Oxygroup and hexyloxy isomers." alkoxyalkyl " refers to thering is alkoxy substitution, the reality of " alkoxyalkyl " on alkyl Example includes CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2And CH3CH2OCH2CH2。
“C1-C6Alkylthio group " includes branch or straight-chain alkylthio, such as methyl mercapto, ethylmercapto group and different rosickyite bases, fourth sulphur Base, penta sulfenyl and own sulfenyl isomers.
“C1-C4Alkyl sulfino " includes methylsulfinyl, ethylsulfinyl, terf-butylsulfinyl etc..
“C1-C4Alkyl sulphonyl " includes methyl sulphonyl, ethylsulfonyl, tert. butylsulfonyl etc..
“C1-C4Alkyloxysulfonyl " includes methoxysulfonyl, ethoxysulfonyl etc..
“C2-C4Alkoxy carbonyl " include methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, N-butoxycarbonyl, tert-butoxycarbonyl etc..
“C2-C6Acyl group " includes methyl carbonyl, ethylcarbonyl group, n-propyl carbonyl, Isopropylcarbonyl, n-butylcarbonyl, tertiary fourth Base carbonyl etc..
“C3-C6Trialkylsilkl " includes；Trimethyl silyl, triethylsilyl, tertbutyldimethylsilyl chloride The trialkyls such as silylation replace silicyl etc..
“C2-C8Dialkyl amido " includes dimethylamino, diethylamino etc..
“C3-C6Naphthene amino " cyclopropylamino, Cyclobutylamino, clopentylamino, Cyclohexylamino etc..
“C2-C6Alkoxy carbonyl " include methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, N-butoxycarbonyl, tert-butoxycarbonyl etc..
“C3-C6Alkyl amino-carbonyl " includes amino carbonyl, Dimethylaminocarbonyl.
“C1-C6Alkoxycarbonyl amino " includes methyloxycarbonylamino, ethoxycarbonylamino group, positive propoxy carbonyl ammonia Base, isopropoxycarbonylamino etc..
“C2-C8Dialkylaminocarbonyl " includes Dimethylaminocarbonyl, diethylaminocarbonyl etc..
“C1-C6Acyl amino " includes Formylamino, acetyl-amino, propanoylamino, bytyry amino, isopropyl Carbonylamino etc..
“C1-C4Acyl group " includes formoxyl, acetyl group, propiono etc..
“C1-C4Acyloxy " includes formyloxy, acetoxyl group, propionyloxy etc..
“(C1-C6Alkoxy) thiocarbonyl " it include methoxyl group (thiocarbonyl) base, ethyoxyl (thiocarbonyl) base, positive third Oxygroup (thiocarbonyl) base, isopropoxy (thiocarbonyl) base, n-butoxy (thiocarbonyl) base, isobutoxy (thiocarbonyl) Base, sec-butoxy (thiocarbonyl) base, tert-butoxy (thiocarbonyl) base etc..
“(C1-C6Alkylthio group) thiocarbonyl " (methyl mercapto) thiocarbonyl, (ethylmercapto group) thiocarbonyl, (positive rosickyite base) sulphur For carbonyl, (isopropyisulfanyl) thiocarbonyl, (positive butylthio) thiocarbonyl, (isobutylthio) thiocarbonyl, (secondary butylthio) sulphur For carbonyl, (tertiary butylthio) thiocarbonyl etc..
" hydroxy phenyl " includes 2- hydroxy phenyl, 3- hydroxy phenyl, 4- hydroxy phenyl etc.；" chlorphenyl " 2- chlorphenyl, 3- Chlorphenyl, 4- chlorphenyl；" acetylphenyl " includes 2- acetylphenyl, 3- acetylphenyl, 4- acetylphenyl etc..
" heterocycle " or " heterocycle system " refers to that wherein at least one annular atom is not carbon, and is respectively selected from containing 1~4 The heteroatomic ring or ring system of nitrogen, oxygen and sulphur, condition are that each heterocycle contains not more than 4 nitrogen, not more than 2 oxygen and not more than 2 sulphur atoms, heterocycle can be connected by replacing the hydrogen on described carbon or nitrogen-atoms with any one available carbon or nitrogen." virtue It is ring " word means complete unsaturated carbocyclic ring or heterocycle, wherein polycyclic system is that (aromatics herein is referred to ring system aromatics Meet H ü ckel rule)." hetero-aromatic ring " word refers to complete aromatic ring, and wherein at least one annular atom is not carbon, and is contained There are the 1-4 hetero atoms for being respectively selected from nitrogen, oxygen and sulphur, condition is that each heterocycle contains not more than 4 nitrogen, not more than 2 oxygen, no More than two sulphur (aromatics refers to meeting H ü ckel rule herein).Heterocycle can be by replacing the hydrogen on described carbon or nitrogen And it is connected with any one available carbon or nitrogen." aromatic heterocycle system " word includes complete aromatic heterocycle and miscellaneous bicyclic, wherein extremely The ring of a few polycyclic system is aromatics (aromatics herein refers to meeting H ü ckel rule)." thick miscellaneous bicyclic ring system " word contains The ring system being made of by one 2 condensed rings, wherein at least one annular atom are not carbon, as defined above, be can be It is aromatics or non-aromatic.
" 6 yuan of hetero-aromatic rings " includes pyridyl group, pyrimidine radicals, pyrazinyl, pyridazinyl, triazine radical；Pyridyl group includes pyridine -2- Base, pyridin-3-yl, pyridin-4-yl etc.；Pyrimidine radicals includes pyrimidine -2-base, pyrimidine-4-yl, pyrimidine -5- base etc.；Pyrazinyl includes Pyrazine -2- base, pyrazine -3- base；Pyridazinyl includes pyridazine -3- base, pyridazine -4- base etc..
" 5 yuan of hetero-aromatic rings " includes pyrrole radicals, imidazole radicals, pyrazolyl, triazolyl, tetrazole radical, furyl, thienyl, oxazole Base, thiazolyl, oxadiazoles base, thiadiazolyl group etc.；Pyrrole radicals includes pyrroles -1- base, pyrroles -2- base, pyrroles's -3- base etc.；Imidazoles Base includes imidazoles -1- base, imidazoles -2- base, imidazol-4 yl, imidazoles -5- base etc.；Pyrazolyl includes pyrazol-1-yl, pyrazoles -3- Base, pyrazoles -4- base, pyrazoles -5- base etc.；Triazolyl includes 1,2,3- triazol-1-yl, 1,2,3- triazole-4-yl, 1,2,3- tri- Azoles -5- base, 1,2,4- triazol-1-yl, 1,2,4- triazole -3- base, 1,2,4- triazole -5- base etc.；Tetrazole radical includes tetrazolium -1- Base, tetrazolium -2- base etc.；Furyl includes furans -2- base, furans -3- base；Thienyl includes thiophene -2- base, thiene-3-yl etc.； Oxazolyl includes oxazole -2- base, oxazole -4- base, oxazole -5- base etc.；Isoxazole -3- base, isoxazole 4- base, isoxazole -5- base Deng；Thiazolyl includes thiazol-2-yl, thiazole-4-yl, thiazole -5- base etc.；Isothiazole -3- base, isothiazole -4- base, isothiazole - 5- base etc.；Oxadiazoles base includes 1,2,4- oxadiazoles -3- base, 1,2,4- oxadiazoles -5- base, 1,3,4- oxadiazoles -2- base etc.；Thiophene Di azoly includes 1,2,4- thiadiazoles -3- base, 1,2,4- thiadiazoles -5- base, 1,3,4- thiadiazoles -2- base etc..
In the present invention, 5 or 6 yuan of non-aromatic carbocycles or heterocycle include cyclohexyl, cyclopenta, tetrahydrofuran base, oxinane Base, nafoxidine, piperidyl, hexahydropyrimidine base, piperazinyl, tetrahydro-thienyl, dithianyl, dioxanes base, tetrahydro thiapyran base Deng.
In the present invention, " unsubstituted " refers to parent nucleus group, unless otherwise specified, does not have the record of " substituted base " and only uses It is then " unsubstituted " when the radical name of parent nucleus is recorded.
In the present invention, " substituted base " refers to that any hydrogen atom in the group of parent nucleus is same or different with parent nucleus by structure Group replaces, and substituent group can be one or more, and when the substituent group with 2 or more, substituent group can be identical or different.
“C1-C6" indicate to be the carbon atom number of parent nucleus group to be 1-6, the carbon atom number do not include in substituent group carbon it is former The number of son.
" substituent group " is just not particularly limited as long as chemically allowing, having the effect of of the invention.
The total number of carbon atoms in substituent group passes through " Ci-Cj" indicate, wherein i and j is 1~6 number, for example, C1- C3Alkyl sulfonyl basis representation mesyl is to the third sulfonyl；C2Alkoxyalkyl indicates CH3OCH2；C3Alkoxyalkyl expression, such as CH3CH(OCH3), CH3OCH2CH2Or CH3CH2OCH2；And C4Alkoxyalkyl indicates that the alkoxy in total containing 4 carbon atoms replaces Alkyl different isomer, example has CH3CH2CH2OCH2And CH3CH2OCH2CH2.In the above description, when the chemical combination of formula (I) When object contains a heterocycle, all substituent groups all pass through the hydrogen replaced on described carbon or nitrogen, pass through available carbon or nitrogen It is connected on this ring.When a group contains the substituent group that can be hydrogen, such as R3, then when this substituent group is hydrogen When, it is believed that described group is unsubstituted.
The salt agriculturally used, is not particularly limited, for example, the inorganic acid salts such as hydrochloric acid, sulfuric acid, acetic acid, lactic acid etc. are organic The salt of acid；Alkali metal, alkaline-earth metal, transition metal salt；The salt etc. of the organic bases such as ammonia, triethylamine, tri-n-butylamine, pyridine, hydrazine.
There may be one or more stereoisomers for the compound of the present invention.Various stereoisomers include enantiomer, Diastereoisomer, atropisomers and geometric isomer.Those skilled in the art understands, when a kind of stereoisomer phase For other content of isomer more or when coming out from other isomer separations, this stereoisomer can be shown more The beneficial effect of high activity and/or presentation.In addition, why those skilled in the art are it is also known that go separation, enrichment, and/or choosing Prepare to selecting property described stereoisomer.Therefore, the compound of the present invention can be single three-dimensional with the mixture of stereoisomer Isomers, or with a kind of presence of optical active forms.The present invention includes the compound selected from formula (I), N- oxide and its agriculture The salt being applicable in industry, those skilled in the art understand that not all nitrogen-containing heterocycle can form N- oxide, because in order to It is oxidized to oxide, nitrogen needs a pair of of lone pair electrons；Those skilled in the art is also, it is understood which nitrogen-containing heterocycle can be formed N- oxide.Those skilled in the art is also, it is understood that tertiary amine can form N- oxide.Prepare the N- oxide of heterocycle and tertiary amine Synthetic method is well known to those skilled in the art, including with peroxy acid such as Peracetic acid and metachloroperbenzoic acid (MCPBA) Hydrogen peroxide, alkyl hydroperoxide such as tert-butyl hydroperoxide, sodium perborate and dioxiranes such as dimethyl Dioxirane, these methods for preparing N- oxide have been introduced extensively in the literature or summary, are exemplified below referring to document: T.L.Gilchrist in Comprehensive Organic Synthesis, vol.7, pp748-750, S.V.Ley, Ed., Pergamon Press；M.Tisler and B.Stanovnik in Comprehensive Heterocyclic Chemistry, vol.3, pp18-19, A.J.Boulton and A.McKillop, Eds., Pergamon Press； M.R.Grimmett and B.R.T.Keene in Advances in Heterocyclic Chemistry, vol.43, Pp139-151, A.R.Katritzky, Ed., Academic Press；M.Tisler and B.Stanovnik in Advances in Heterocyclic Chemistry, vol.9, pp285-291, A.R.Katritzky and A.J.Boulton, Eds., Academic Press；and G.W.H.Cheeseman and E.S.G.Werstiuk in Advances in Heterocyclic Chemistry, vol.22, pp390-392, A.R.Katritzky and A.J.Boultou, Eds., Academic Press.
The reaction route of above-mentioned 3- amino -2- cyanoacrylate compound are as follows:
Reaction will be heated, formula (I) chemical combination is obtained in organic solvent containing raw material (a), with raw material (b) and raw material (c) Object；
Compound and formaldehyde (or other aldehyde) and aminated compounds it can be seen from above reaction equation containing active hydrogen The compound with structure (I) is obtained by condensation reaction, those skilled in the art different with (c) structure according to raw material (a), (b) Member can choose the condition of reaction generation: such as temperature, pressure, reaction time.
Further, the substituent group on raw material (c) is in addition to substituent group described above, R1 and R2 N atom connected to it It is formed containing 2-6 carbon atom and another optional nitrogen, the ring of sulphur or oxygen atom, being formed by ring can further be substituted.
Substituent group in reaction equation defines same as above.
Preferably, the organic solvent is one of toluene, six alkane of dioxy and dichloroethanes or a variety of.
Preferably, the heating temperature is 70-110 DEG C.
The present invention also provides application of the above-mentioned 3- amino -2- cyanoacrylate compound on prevention and treatment sickle-like bacteria.
Sickle-like bacteria includes Fusarinm solani, fusarium moniliforme, wheel branch sickle-like bacteria, Fusarium oxysporum, the raw sickle-like bacteria of layer, semi-nudity Sickle-like bacteria, glue fusarium oxysporum, Fusarium graminearum, pear fusarium oxysporum, single lattice sickle-like bacteria, quasi- branch sickle-like bacteria, Fusarium nivale, sheet Color sickle-like bacteria, fusarium avenaceum, Fusarium equiseti, gibberella saubinetii etc..
The utility model has the advantages that the present invention prepares the disinfectant use in agriculture of one kind 3- amino -2- cyanoacrylate compound.This is killed Microbial inoculum has an excellent control efficiency to sickle-like bacteria, and because its Mannich base alkalinity, allow it and common nothing Machine acid and organic acid generate salt, are soluble in water.
Specific embodiment
One, prepared by compound
Embodiment 1:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 21.2g (0.1mol) 2-cyano-3-amino-3-phenylancryic acetate (- 3 ethyl phenylacrylate of 2- cyano -3- amino) is suspended in 600g dichloroethane solution, 17.4g (0.2mol) Morpholine is added in the solution, and system is warming up to 70 DEG C, at such a temperature, the formaldehyde of 17.5g35% in 30 minutes (0.2mol) aqueous solution is added drop-wise in reaction solution, and after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, cools to 0 degree, Unreacted reactant, split-phase are filtered out, dichloroethanes is mutually concentrated to get the Mannich base of 2-cyano-3-amino-3-phenylancryic acetate, is recrystallized to give 10g cyanogen alkene bacterium The morpholine Mannich base of ester, i.e. compound N are O.1.
Embodiment 2:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.01mol) 2-cyano-3-amino-3-phenylancryic acetate (2- cyano -3- amino -3- ethyl phenylacrylate) is suspended in 60g toluene solution, 1.42g (0.02mol) four Hydrogen pyrroles is added in the solution, and system is warming up to 110 DEG C, at such a temperature, furfural (0.2mol) drop of 1.92g in 30 minutes It is added in the reaction solution, after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, and 0 degree is cooled to, unreacted reactant is filtered out, Split-phase, after toluene is mutually concentrated O.8 column chromatography for separation obtains 0.5g compound N.
Embodiment 3:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.01mol) 2-cyano-3-amino-3-phenylancryic acetate (- 3 ethyl phenylacrylate of 2- cyano -3- amino) is suspended in 60g toluene solution, 1.74g (0.02mol) morphine Quinoline is added in the solution, and system is warming up to 110 DEG C, at such a temperature, -4 formaldehyde of pyridine of 2.14g (0.2mol) in 30 minutes It is added drop-wise in the reaction solution, after completion of dropwise addition, the reaction was continued at such a temperature 4 hours, cools to 0 DEG C, filters out unreacted Object, split-phase, column chromatography for separation obtains the Mannich base of 0.6g 2-cyano-3-amino-3-phenylancryic acetate after toluene is mutually concentrated, and compound N is O.15.
Embodiment 4:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.01mol) 2-cyano-3-amino-3-phenylancryic acetate (- 3 ethyl phenylacrylate of 2- cyano -3- amino) is suspended in 60g toluene solution, 17.6g (0.02mol) tetrahydro Pyrroles is added in the solution, and system is warming up to 110 DEG C, at such a temperature, the benzaldehyde drop of 2.12g (0.2mol) in 30 minutes It is added in the reaction solution, after completion of dropwise addition, the reaction was continued at such a temperature 4 hours, and 0 DEG C is cooled to, unreacted reactant is filtered out, Split-phase, after toluene is mutually concentrated O.22 column chromatography for separation obtains 0.85g compound N.
Embodiment 5:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.01mol) 2-cyano-3-amino-3-phenylancryic acetate (- 3 ethyl phenylacrylate of 2- cyano -3- amino) is suspended in 60g dichloroethane solution, 2.58g (0.02mol) Di-n-butylamine is added in the solution, and system is warming up to 70 DEG C, at such a temperature, the formaldehyde of 1.75g35% in 30 minutes (0.02mol) aqueous solution is added drop-wise in reaction solution, and after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, cools to 0 degree, Unreacted reactant, split-phase are filtered out, after dichloroethanes is mutually concentrated O.44 column chromatography for separation obtains 0.3g compound N.
Embodiment 6:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.01mol) 2-cyano-3-amino-3-phenylancryic acetate (- 3 ethyl phenylacrylate of 2- cyano -3- amino) is suspended in 60g dioxane solution, 2.66g (0.02mol) Diethanol amine is added in the solution, and system is warming up to 110 DEG C, at such a temperature, the formaldehyde of 17.5g35% in 30 minutes (0.2mol) aqueous solution is added drop-wise in reaction solution, and after completion of dropwise addition, the reaction was continued at such a temperature 16 hours, cools to 0 DEG C, Unreacted reactant is filtered out, extracts 3 extractions with ethyl acetate 50ml, column chromatography for separation obtains 0.56g after ethyl acetate layer is concentrated Cyanoacrylate compound, i.e. compound N are O.45.
Embodiment 7:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.1mol) 2-cyano-3-amino-3-phenylancryic acetate (- 3 ethyl phenylacrylate of 2- cyano -3- amino) is suspended in 60g toluene solution, 3.88g (0.2mol) dibenzyl Amine is dissolved in 30g toluene solution and is added in the solution, and system is warming up to 70 DEG C, at such a temperature, 1.75g35% in 30 minutes Formaldehyde (0.2mol) aqueous solution is added drop-wise in reaction solution, and after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, cools to 0 DEG C, unreacted reactant, split-phase are filtered out, column chromatography for separation obtains 1.0g cyanoacrylate compound after toluene is mutually concentrated NO.88。
Embodiment 8:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.01mol) 2-cyano-3-amino-3-phenylancryic acetate (- 3 ethyl phenylacrylate of 2- cyano -3- amino) is suspended in 60g dichloroethane solution, 2.26g (0.2mol) Methyl-cyclohexyl base amine is added in the solution, and system is warming up to 70 DEG C, at such a temperature, the formaldehyde of 1.75g35% in 30 minutes (0.02mol) aqueous solution is added drop-wise in reaction solution, and after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, cools to 0 DEG C, Unreacted reactant, split-phase are filtered out, after dichloroethanes is mutually concentrated O.94 column chromatography for separation obtains 1.0g compound N.
Embodiment 9:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.01mol) 2-cyano-3-amino-3-phenylancryic acetate (- 3 ethyl phenylacrylate of 2- cyano -3- amino) is suspended in 60g dichloroethane solution, 2.58g (0.02mol) Diethylamine is added in the solution, and system is warming up to 70 DEG C, at such a temperature, the formaldehyde of 1.75g35% in 30 minutes (0.2mol) aqueous solution is added drop-wise in reaction solution, and after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, cools to 0 DEG C, Unreacted reactant, split-phase are filtered out, after dichloroethanes is mutually concentrated O.101 column chromatography for separation obtains the compound N of 0.3g.
Embodiment 10:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.52g (0.01mol) - 3 phenylacrylic acid N-butyl of 2- cyano -3- amino is dissolved in 60g dichloroethane solution, and 1.74g (0.02mol) morpholine adds Entering into the solution, system is warming up to 70 DEG C, at such a temperature, formaldehyde (0.02mol) aqueous solution of 1.75g35% in 30 minutes It is added drop-wise in reaction solution, after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, and 0 DEG C is cooled to, unreacted reactant is filtered out, Split-phase, after dichloroethanes is mutually concentrated O.118 column chromatography for separation obtains 1.0g compound N.
Embodiment 11:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.1mol) - 3 (pyridin-3-yl)-ethyl acrylate of 2- cyano -3- amino is dissolved in 60g dichloroethane solution, 1.74g (0.2mol) Coffee quinoline is added in the solution, and system is warming up to 70 DEG C, at such a temperature, the formaldehyde (0.2mol) of 1.75g35% in 30 minutes Aqueous solution is added drop-wise in reaction solution, and after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, is cooled to 0 degree, is filtered out not Reactant, split-phase, column chromatography for separation obtains 0.5g cyanoacrylate compound NO.125 after dichloroethanes is mutually concentrated.
Embodiment 12:
In the four-hole bottle equipped with thermometer, mechanical stirring, reflux condenser and dropping funel, by 2.12g (0.01mol) - 3 (pyridin-3-yl)-ethyl acrylate of 2- cyano -3- amino is dissolved in 60g dichloroethane solution, 1.7g (0.2mol) hexahydro Pyridine is added in the solution, and system is warming up to 70 DEG C, at such a temperature, the formaldehyde (0.2mol) of 1.75g35% in 30 minutes Aqueous solution is added drop-wise in reaction solution, and after completion of dropwise addition, the reaction was continued at such a temperature 1 hour, is cooled to 0 degree, is filtered out not Reactant, split-phase, column chromatography for separation obtains 0.8g Mannich base NO.132 after dichloroethanes is mutually concentrated.
Two, property measures
In the compound of the present invention shown in table 1-12 that method identical with above-mentioned manufacturing method will be used to obtain, The wherein specific synthesis condition of compound listed in table and parameter are as follows:
O.1-7 synthetic method is the method provided in embodiment 1 to compound N；O.8-14 synthetic method is to implement to compound N The method provided in example 2；The compound N method that O.15-21 synthetic method provides for embodiment 3；O.22-28, compound N closes It is the method that embodiment 4 provides at method；The compound N method that O.29-44 synthetic method provides for embodiment 5；Compound NO.45-87 synthetic method is the method that embodiment 6 provides；Compound 88-93 synthetic method is the side that embodiment 7 provides Method；The compound N method that O.94-99 synthetic method provides for embodiment 8；O.100-117 synthetic method is real to compound N The method that the offer of example 9 is provided；The compound N method that O.118-124 synthetic method provides for embodiment 10；Compound N is O.125- 131 synthetic methods are the method that embodiment 11 provides；O.132-138 synthetic method is what embodiment 12 provided to compound N Method.
It should give explanation, in table, Me indicates that methyl, Et indicate that ethyl, Pr indicate that propyl, iPr indicate isopropyl, n-Bu Indicate that normal-butyl, iBu indicate that isobutyl group, t-Bu indicate that tert-butyl, s-Bu are sec-butyl, Ph expression phenyl.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
Table 10
Table 11
Table 12
Compound N is O.1:HNMR (400MH, DMSO) δ (7.71 (d, 2H)；7.40(m,2H)；7.33(dd,1H)；6.50 (s, 1H), 4.20 (q, 2H)；3.80 (t, 4H)；3.75 (s, 2H) 7；2.50 (t, 4H)；1.35(t,3H))
Compound N is O.2:HNMR (400MH, DMSO) δ (7.71 (d, 2H)；7.40(m,2H)；7.33(dd,1H)；6.50 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H)；2.35 (s, 8H)；2.26 (s, 3H) 1.30 (t, 3H))
Compound N is O.3:HNMR (400MH, DMSO) δ 400MH, DMSO) δ (7.71 (d, 2H)；7.40(m,2H)；7.33 (dd,1H)；6.50 (s, 1H), 4.20 (q, 2H) 3.72 (s, 2H)；3.45 (t, 2H)；2.53 (t, 2H), 2.35 (dd, 8h) 1.30 (t,3H))
Compound N is O.4:HNMR (400MH, DMSO) δ 400MH, DMSO) δ (7.71 (d, 2H)；7.40(m,2H)；7.33 (dd,1H)；6.50 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H)；2.80 (t, 4H)；2.50 (t, 4H)；1.25(t,3H))
Compound N is O.5:HNMR (400MH, DMSO) δ 400MH, DMSO) δ (7.71 (d, 2H)；7.40(m,2H)；7.33 (dd,1H)；6.50 (s, 1H), 4.20 (q, 2H)；3.70 (s, 2H)；2.80 (t, 4H)；2.60 (t, 4H)；1.35(t,3H)
Compound N is O.6:HNMR (400MH, DMSO) δ 400MH, DMSO) and δ (7.71, (d, 2H)；7.40(m,2H)；7.33 (dd,1H)；6.50 (s, 1H), 4.20 (q, 2H)；3.70 (s, 2H)；3.60 (t, 4H)；2.38 (t, 4H)；1.45(t,3H))
Compound N is O.7:HNMR (400MH, DMSO) δ 400MH, DMSO) δ (7.71 (d, 2H)；7.40(m,2H)；7.33 (dd,1H)；6.50 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H)；2.80 (q, 4H)；2.50 (q, 4H)；1.35(t,3H)
Compound N is O.8:HNMR (400MH, DMSO) δ 7.71 (dd, 2H)；7.50(dd,1H)；7.40(,m,2H,)；7.33 (t, 1H), 6.62 (dd, 1H)；6.42(dd,1H)；6.5 (s, 1H), 5.27 (s, 1H) 4.20 (q, 2H)；2.25 (t, 4H)； 1.59 (t, 4H)；1.35(t,3H)
Compound N is O.9:HNMR (400MH, DMSO) δ 7.71 (d, 2H)；7.50(dd,1H)；7.40(m,2H,)；7.33 (t, 1H), 6.62 (dd, 1H)；6.42(dd,1H)；6.5 (s, 1H), 5.27 (s, 1H) 4.20 (q, 2H)；3.51 (s, 2H)； 2.73 (t, 2H)；2.54 (t, 2H) 1.35 (t, 3H))
Compound N is O.10:HNMR (400MH, DMSO) δ 7.71, dd, 2H)；7.50(dd,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.62 (dd, 1H)；6.42(dd,1H)；6.5 (s, 1H), 5.27 (s, 1H) 4.44 (s, 2H) 4.20 (q, 2H)； 3.57 (t, 2H)；2.54 (t, 2H) 1.35 (t, 3H)
Compound N is O.11:HNMR (400MH, DMSO) δ 7.71 (d, 2H)；7.50(dd,1H)；7.40(,m,2H,)；7.33 (t, 1H), 6.62 (dd, 1H)；6.42(dd,1H)；6.5 (s, 1H), 5.27 (s, 1H) 4.20 (q, 2H)；3.62(s,2H)2.65 (t, 2H)；2.60 (t, 2H) 1.35 (t, 3H)
Compound N is O.12:HNMR (400MH, DMSO) δ 7.71 (d, 2H)；7.50(dd,1H)；7.40(,m,2H,)；7.33 (t, 1H), 6.62 (dd, 1H)；6.42(dd,1H)；6.5 (s, 1H), 5.27 (s, 1H) 4.20 (q, 2H)；3.64(s,2H)2.65 (t, 2H)；2.60 (t, 2H) 1.29 (t, 3H)
Compound N is O.13:HNMR (400MH, DMSO) δ 7.71 (d, 2H)；7.50(dd,1H)；7.40(,m,2H,)；7.33 (t, 1H), 6.62 (dd, 1H)；6.42(dd,1H)；6.5 (s, 1H), 5.27 (s, 1H) 4.48 (s, 2H)；4.20(q,2H)； 3.58 (t, 2H)；2.85 (t, 2H) 1.29 (t, 3H)
Compound N is O.14:HNMR (400MH, DMSO) δ 7.71 (d, 2H)；7.50(dd,1H)；7.40(,m,2H,)；7.33 (t, 1H), 6.62 (dd, 1H)；6.42(dd,1H)；6.5 (s, 1H), 5.27 (s, 1H) 4.20 (q, 2H)；3.43(s,2H)3.50 (s, 2H)；2.68 (t, 2H) 2.46 (t, 2H) 2.40 (t, 2H) 1.35 (t, 3H)
Compound N is O.15:HNMR (400MH, DMSO) δ (8.55 (dd, 2H) 7.71, dd, 2H)；7.55(dd,2H)；7.40 (,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.04 (s, 1H) 4.20 (dd, 2H)；3.80 (dd, 4H)；37；2.50 (dd, 4H)；1.35(t,3H)；
Compound N is O.16:HNMR (400MH, DMSO) δ (8.55 (dd, 2H) 7.71 (dd, 2H)；7.55(dd,2H)；7.40 (,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.04 (s, 1H)；4.20(dd,2H)；3.80 (dd, 4H)；；2.50 (dd, 4H), 2.35 (dd, 4H)；2.26 (s, 3H) 1.30 (t, 3H)
Compound N is O.17:HNMR (400MH, DMSO) δ (8.55 (dd, 2H) 7.71 (dd, 2H)；7.55(dd,2H)；7.40 (,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.04 (s, 1H)；4.20(dd,2H)；3.45(dd,2H)；2.76 (dd, 4h)；2.60(dd,4H)；1.35 (t, 3H)
Compound N is O.18:HNMR (400MH, DMSO) δ (8.55 (dd, 2H) 7.71 (dd, 2H)；7.55(dd,2H)；7.40 (,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.04 (s, 1H)；4.20(dd,2H)；2.73 (dd, 4H)；2.40(dd, 4H)；1.29(t,3H)
Compound N is O.19:HNMR (400MH, DMSO) δ (8.55 (dd, 2H) 7.71 (dd, 2H)；7.55(dd,2H)；7.40 (,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.04 (s, 1H)；4.20(dd,2H)；2.78(dd,4H)；2.50 (dd, 4H)；1.29 (t, 3H)
Compound N is O.20:HNMR (400MH, DMSO) δ (8.55 (dd, 2H) 7.71 (dd, 2H)；7.55(dd,2H)；7.40 (,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.04 (s, 1H)；4.20(dd,2H)；3.51 (dd, 4H) 2.85 (dd, 4H)； 1.35 (t, 4h)
Compound N is O.21:HNMR (400MH, DMSO) δ (8.55 (dd, 2H) 7.71 (d, 2H)；7.55(dd,2H)；7.40 (,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.04 (s, 1H)；4.20(q,2H)；2.86(dd,4H)；2.62(t,4h) 1.32(t,3H))
Compound N is O.22:HNMR (400MH, DMSO) δ (7.71 (d, 2H)；7.40 (m, 2H)；7.43(dd,2H)；7.33 (m,2H)；7.30(dd,1H)；7.26 (dd, 1H)；6.50 (s, 1H)；5.24(s,1H)；4.20(q,2H)；2.25(m,4H)； 1.66(t,4H)；1.25(t,3H))
Compound N is O.23:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.40 (m, 2H)；7.43(dd,2H)；7.33 (m,2H)；7.30(dd,1H)；7.26 (dd, 1H)；6.50 (s, 1H)；5.24(s,1H)；4.20(q,2H)；3.51(s,2H)； 2.60(t,2H)；2.54(t,2H)；1.35(t,3H)
Compound N is O.24:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.40 (m, 2H)；7.43(dd,2H)；7.33 (m,2H)；7.30(dd,1H)；7.26 (dd, 1H)；6.50 (s, 1H)；5.24(s,1H)；4.44(s,1H)；4.20(q,2H)； 3.57(t,2H)；2.43(t,2H)；1.29 (t, 3H)
Compound N is O.25:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.40 (m, 2H)；7.43(dd,2H)；7.33 (m,2H)；7.30(dd,1H)；7.26 (dd, 1H)；6.50 (s, 1H)；5.24(s,1H)；4.20(q,2H)；3.62(s,2H)； 2.72(t,2H)；2.60(t,2H)；1.25(t,3H)
Compound N is O.26:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.40 (m, 2H)；7.43(dd,2H)；7.33 (m,2H)；7.30(dd,1H)；7.26 (dd, 1H)；6.50 (s, 1H)；5.24(s,1H)；4.20(q,2H)；3.64(s,2H)； 2.70-2.30(m,4H)；1.29(t,3H)
Compound N is O.27:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.40 (m, 2H)；7.43(dd,2H)；7.33 (m,2H)；7.30(dd,1H)；7.26 (dd, 1H)；6.50 (s, 1H)；5.24(s,1H)；4.62(s,2H)；4.20(q,2H)； 3.62(t,2H)；1.29(t,3H)
Compound N is O.28:HNMR (400MH, DMSO) δ (7.71 (d, 2H)；7.40 (m, 2H)；7.43(dd,2H)；7.33 (m,2H)；7.30(dd,1H)；7.26 (dd, 1H)；6.50 (s, 1H)；5.24(s,1H)；4.20 (q, 2H)；3.53(s,2H)； 3.43(t,2H)；2.4-2.6(m,6H)；1.29(t,3H)
Compound N is O.29:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H)；2.26 (s, 6H)；1.35(t,3H)；
Compound N is O.30:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.75 (s, 2H) 7；2.75 (q, 4H)；1.35(t,3H)；1.02 (t, 3H)
Compound N is O.31:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.75 (s, 2H) 7；2.75 (q, 2H)；2.26 (s, 3H)；1.35(t,3H)；
Compound N is O.32:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.75 (s, 2H) 7；2.75 (q, 2H)；2.26 (s, 3H)；1.35(t,3H)
Compound N is O.33:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.72 (s, 2H)；2.46(t,2H)；2.26(s,3H)；1.44(m,2H)；1.29(t,3H)； 1.0(t,3H)
Compound N is O.34:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.72(s,2H)；2.69(m,1H)；1.35(t,3H)；1.05(d,6H)
Compound N is O.35:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.75(s,2H)；2.46(t,2H),1.30-1.409(m,7H)；0.9(t,3H)
Compound N is O.36:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.72(s,2H)；2.26(s,3H)；1.27-1.30(s,12H)
Compound N is O.37:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.72(s,2H)；2.79(m,1H)；2.46(s,3H)；1.46(q,-2H)；1.29(t, 3H)；1.12(d,3H)；0.9(t,3H)
Compound N is O.38:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.75(s,2H)；2.64(q,2H)；2.46(t,2H)；1.46(m,2H)；1.29(t,3H)； 1.03(t,3H)；0.9(t,3H)
Compound N is O.39:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.72(s,1H)；2.69(q,2H)；2.64(m,1H)；1.29(t,3H)；1.07(d,6H)； 1.02(t,3H)
Compound N is O.40:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.76(s,2H)；2.64 (q, 2H)；2.46 (t, 2H)；1.29-1.36(m,7H)；1.02 (t, 3H)；0.9 (t, 3H)
Compound N is O.41:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.78 (s, 1H)；2.64 (t, 3H)；2.03 (d, 2H)；1.67 (m, 1H)；1.29 (t, 3H)； 0.88 (d, 6H)
Compound N is O.42:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.72 (s, 2H)；2.64 (q, 2H) 2.09 (d, 2H)；1.67 (m, 1H)；1.29 (t, 3H)； 1.02 (t, 3H)；0.9 (d, 6H)
Compound N is O.43:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.72 (s, 2H)；2.46 (t, 4H)；1.29 (t, 3H)；0.92 (t, 6H)
Compound N is O.44:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (dd, 2H)；3.72 (s, 2H)；2.46 (t, 4H)；1.29-1.35 (m, 11H)；0.9 (t, 6H)
Compound N is O.45:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)；3.45(t,4H)；2.53(t,4H)；1.29(t,3H)
Compound N is O.46:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H)；3.45(t,2H)；2.53(t,2H)；2.26(s,3H)；1.29(t,3H)
Compound N is O.47:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H) 3.72 (s, 2H)；3.60 (s, 2H)；3.30(s,3H)；2.64(t,2H)；2.51(t,2H)； 1.29(t,3H)；1.02(t,3H)
Compound N is O.48:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.79 (t, 2H) 3.72 (s, 2H) 3.30 (s, 3H)；2.35(s,3H)；1.29 (t, 3H) chemical combination Object 49:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (being 2H)；3.60 (t, 2H)；2.51 (t, 2H)；2.35 (s, 3H) 1.29 (t, 3H)
Compound N is O.50:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)；3.48(s,2H)；2.26(s,3H)；1.29(t,3H)
Compound N is O.51:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)2.26(s,3H)；1.29(t,3H)
Compound N is O.52:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H)；3.08 (t, 2H) 2.55 (t, 2H)；2.26 (s, 3H)；1.29 (t, 3H)
Compound N is O.53:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.87 (dd, 1H)；5.19-5.25 (m, 2H)；4.20(q,2H)；3.72 (s, 2H)；3.02 (d, 2H)；2.64 (q, 2H)；1.29(t,3H)；1.05(t,3H)
Compound N is O.54:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.87 (s, 2H)；3.72 (s, 2H)；2.65 (s, 1H)；1.29(t,3H)；1.05(t,3H)
Compound N is O.55:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H)；3.48 (t, 2H) 2.64 (m, 4H)；1.29(t,3H)；1.05(t,3H)
Compound N is O.56:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20-4.4 (m, 6H)；3.72 (s, 2H) 3.28 (s, 4H) 1.29 (t, 9H)
Compound N is O.57:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H) 2.5-2.65 (m, 6H) 2.05 (s, 3H) 1.29 (t, 3H)；1.05(t,3H)
Compound N is O.58:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.95 (t, 2H) 3.72 (s, 2H) 3.6-2.7 (m, 4H) 2.64 (q, 2H) 2.51 (t, 2H)； 1.29(t,3H)；1.05(t,3H)
Compound N is O.59:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 5.48 (s, 2H)；4.20(q,2H)；3.80 (s, 2H)；2.64 (q, 2H)；1.29(t,3H)；1.05(t,3H)
Compound N is O.60:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)；2.42(t,2H)；2.26(s,3H)；1.29(t,3H)；0.9 (tri, 9H) 0.66 (q, 6H)
Compound N is O.61:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)；2.42(t,2H)；2.26(s,3H)；1.29(t,3H)；0.09 (s, 9H)
Compound N is O.62:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)；3.60 (t, 2H)；3.50 (t, 2H)；2.51 (t, 2H)；2.26(s,3H)； 1.29 (t, 3H)；1.29(t,3H)；1.10 (t, 3H)
Compound N is O.63:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.50 (t, 2H) 4.20 (t, 4H)；3.72(s,2H)；2.62 (t, 2H) 2.26 (s, 3H)；1.29 (t, 6H)
Compound N is O.64:HNMR (400MH, DMSO) δ (8.03 (s, 1H) 7.71 (dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.10-4.20 (m, 4H)；3.75 (s, 2H)；3.26 (t, 2H)；2.53 (t, 2H)；2.30 (s, 3H) 1.29 (t, 6H)
Compound N is O.65:HNMR (400MH, DMSO) δ (8.03 (s, 1H) 7.71 (dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (t, 2H) 3.75 (s, 2H)；3.14 (t, 2H)；(2.53 t, 2H)；2.30 (s, 3H)；1.84 (s, 3H)；1.29 (t, 3H)
Compound N is O.66:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.35 (t, 2H)；4.20 (q, 2H) 3.75 (s, 2H)；2.52 (t, 2H) 2.26 (s, 3H)；2.15 (s, 3H) 1.20 (t, 3H))
Compound N is O.67:HNMR (400MH, DMSO) δ (8.03 (s, 1H) 7.71 (dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.40 (t, 2H)；4.40 (q, 2H)；3.72 (s, 2H)；3.04 (q, 2H)；2.62 (t, 2H)；2.26 (s, 3H)；1.29 (t, 3H)；1.05 (t, 3H)
Compound N is O.68:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.33 (t, 1H)；4.20 (q, 2H)；3.72 (s, 2H)；3.50 (s, 6H)；2.66 (d, 2H)；2.26 (s, 3H)； 1.28 (t, 3H)
Compound N is O.69:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.33 (t, 1H)；4.20 (q, 2H)；3.72 (s, 2H)；3.52 (s, 2H)；2.26 (s, 3H)；2.13 (s, 3H) 1.29 (t, 3H)
Compound N is O.70:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.33 (t, 1H)；4.20 (q, 2H)；3.72 (s, 2H)；2.68 (d, 2H)；2.26(s., 1H)；1.29(t,3H)；0.82(s,3H)
Compound N is O.71:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.33 (t, 1H)；4.20 (q, 2H)；3.90(s,3H)；3.72 (s, 2H)；2.68 (d, 2H)； 2.26(s.,1H)；1.29(t,3H)；
Compound N is O.72:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.33 (t, 1H)；4.20 (q, 2H)；3.72 (s, 2H)；3.40(s,3H)；2.68(s,2H) 2.26(s.,1H)；1.29(t,3H)；
Compound N is O.73:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.33 (t, 1H)；4.20 (q, 2H)；3.72 (s, 2H)；3.02(s,6H)；2.68(s,2H)； 2.26(s.,1H)；1.29(t,3H)；
Compound N is O.74:HNMR (400MH, DMSO) δ (9.72 (s, 1H)；7.71 (dd, 2H)；7.50(s,1H)；7.40 (,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H)；3.47 (d, 2H)；2.26(s.,1H)； 1.29(t,3H)；
Compound N is O.75:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H)；3.5-3.8(m,6H)；(2.38-2.66 dd, 2H) 2.26(s.,1H)；1.29(t,3H)；
Compound N is O.76:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H)；2.26(s.,1H)；2.09(d,2H)1.29(t,3H)； 0.35-0.45(m,5H)
Compound N is O.77:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72 (s, 2H)；3.64 (s, 2H)；2.50 (s, 3H)；2.26 (s, 3H), 1.29 (t, 3H)
Compound N is O.78:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.48 (s, 2H) 4.20 (q, 2H)；3.72 (s, 2H)；2.86 (s, 2H)；2.26 (s, 3H), 1.29 (t, 3H)
Compound N is O.79:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.48 (s, 2H) 4.20 (q, 2H)；3.90 (s, 3H)；3.72 (s, 2H)；2.26 (s, 3H), 1.29 (t, 3H)
Compound N is O.80:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H), 4.48 (s, 2H) 4.20 (q, 2H)；3.72 (s, 2H)；2.87 (s, 6H)；2.26 (s, 3H), 1.29 (t, 3H)
Compound N is O.81:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H)；4.20 (q, 2H)；3.72 (s, 2H) 2.37 (s, 4H) 2.26 (2,9H) 1.29 (t, 3H)
Compound N is O.82:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H)；4.20 (q, 2H)；3.72(s,2H)；3.47(s,3H)；3.30(t,2H)；2.53(t,2H)； 2.40(s,3H)；2.26(s,3H)；1.29(t,3H)；
Compound N is O.83:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H)；4.20 (q, 2H)；3.72(s,2H)；3.63(t,2H)；2.53(t,3H)；2.26(s,3H)； 2.04(s,3H)；1.29(t,3H)；
Compound N is O.84:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H)；4.20 (q, 2H)；3.72(s,2H)；3.63(t,2H)；3.18(s,3H)；2.26(s,3H)； 1.29(t,3H)；
Compound N is O.85:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H)；4.20 (q, 2H)；3.72(s,2H)；3.58(q,2H)；2.68(s,2H)；2.26(s,3H)； 1.29(t,3H)；1.10(t,3H)；
Compound N is O.86:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H)；4.20 (q, 2H)；3.72(s,2H)；3.15(q,2H)；2.68(s,2H)；2.26(s,3H)； 1.29-1.40(m,6H)；
Compound N is O.87:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.50(s,1H)；7.40(,m,2H,)； 7.33 (t, 1H), 6.5 (s, 1H)；4.20 (q, 2H)；3.72(s,2H)；3.06(s,6H)；2.68(s,2H)；2.26(s,3H)； 1.29(t,3H)
Compound N is O.88:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.2-7.4 (m, 13H), 6.5 (s, 1H)； 4.20 (q, 2H)；3.72(s,2H)；3.62(s,4H)；1.29(t,3H)
Compound N is O.89:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.2-7.4 (m, 5H), 6.98 (d, 2H)； 6.75(dd,1H)；(6.5 s, 1H)；4.71(s,2H)；4.20 (q, 2H)；3.06(s,3H)；1.29(t,3H)
Compound N is O.90:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.2-7.4 (m, 3H), 6.98 (d, 2H)； 6.75(d,2H)；6.5 (s, 1H)；4.71(s,2H)；4.20 (q, 2H)；3.06(s,3H)；1.29(t,3H)
Compound N is O.91:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.2-7.4 (m, 7H), 6.5 (s, 1H)； 4.20 (q, 2H)；3.72(s,2H)；3.6(s,2H)；2.26(s,3H)；1.29(t,3H)
Compound N is O.92:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.2-7.4 (m, 5H), 7.10 (s+d), 2H) 6.5 (s, 1H)；4.71(s,2H)；4.20 (q, 2H)；3.06(s,3H)；2.50(s,3H)；1.29(t,3H)；
Compound N is O.93:HNMR (400MH, DMSO) δ (7.71 (dd, 2H)；7.2-7.4 (m, 5H), 6.90 (d, 2H)； 6.5 (s, 1H)；4.20 (q, 2H)；3.72(s,2H)；3.6(s,2H)；2.80(s,3H)；2.26(s,3H)；1.29(t,3H)
Compound N is O.94:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)；2.57(dd,1H)；2.26(s,3H)；1.1-1.5(m,8H)；
Compound N is O.95:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)；2.57(dd,1H)；2.26(s,3H)；1.55-1.7(m,4H)；1.49(t,3H)
Compound N is O.96:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.35 (t, 2H)；4.20(q,2H)；3.72(s,2H)；3.43(t,1H)；2.55(m,2H)；2.26(s,3H)；1.49 (t,3H)；
Compound N is O.97:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.72(s,2H)；2.73(dd,2H)；2..29(m,1H)；2.26(s,3H)；1.9-2.15(m, 3H)；1.29(t,3H)；
Compound N is O.98:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (q, 2H)；3.76(s,3H)；3.72(s,3H)；3.56(t,1H)；2.00-2.25(m,2H)；2.26(s, 3H)；1.29(t,3H)；
Compound N is O.99:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.95 (dd, 2H)；4.10-4.20(m,3H)；3.70-4.00(dd,2H)；3.72(s,3H)；3.56(t,1H)； 2.00-2.40(m,2H)；2.26(s,3H)；1.29(t,3H)；
Compound N is O.100:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.26(s,6H)；1.29(t,3H)；
Compound N is O.101:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.40(q,4H)；1.29(t,3H)；1.20(t,6H)
Compound N is O.102:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.40(q,2H)；2.26(s,3H)；1.29(t,3H)；1.20(t,3H)；
Compound N is O.103:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.40(t,2H)；2.26(s,3H)；1.43(m,2H)；1.29(t,3H)；1.20(t,3H)；
Compound N is O.104:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.69(m 1H)；2.26(s,3H)；1.29(t,3H)；1.07(d,6H)；
Compound N is O.105:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.40(t,2H)；2.26(s,3H)；1.65(m,2H)；1.43(m,2H)；1.29(t,3H)； 1.20(t,3H)；
Compound N is O.106:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.26(s,3H)；1.29(t,3H)；1.20(s,9H)；
Compound N is O.107:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.19,2.44(dd,2H)；2.26(s,3H)；1.67(m,1H)；.1.29(t,3H)；0.9 (t,6H)；
Compound N is O.108:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 8H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.79(m,1H)；2.26(s,3H)；1.46(m,2H)；1.29(t,3H)；1.15 (t, 3H)； 0.9(t,3H)；
Compound N is O.109:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.26(s,6H)；1.29(t,3H)；
Compound N is O.110:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.40(q,4H)；1.29(t,3H)；1.20(t,6H)
Compound N is O.111:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.40(q,2H)；2.26(s,3H)；1.29(t,3H)；1.20(t,3H)；
Compound N is O.112:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.40(t,2H)；2.26(s,3H)；1.43(m,2H)；1.29(t,3H)；1.20(t,3H)；
Compound N is O.113:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.69(m 1H)；2.26(s,3H)；1.29(t,3H)；1.07(d,6H)；
Compound N is O.114:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.40(t,2H)；2.26(s,3H)；1.65(m,2H)；1.43(m,2H)；1.29(t,3H)； 1.20(t,3H)；
Compound N is O.115:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.26(s,3H)；1.29(t,3H)；1.20(s,9H)；
Compound N is O.116:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.19,2.44(dd,2H)；2.26(s,3H)；1.67(m,1H)；.1.29(t,3H)；0.9 (t,6H)；
Compound N is O.117:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.3-75 (m, 7H)), 6.5 (s, 1H), 5.15(s,1H))4.20(q,2H)；2.79(m,1H)；2.26(s,3H)；1.46(m,2H)；1.29(t,3H)；1.15 (t, 3H)； 0.9(t,3H)；
Compound N is O.118:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 3.97 (t, 2H)；3.75 (s, 2H)；3.65 (t, 4H))；2.50 (t, 4H)；1.62(m,2H)；1.45 (m, 2H)； 0.95(t,3H)；
Compound N is O.119:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 3.75 (s, 2H)；3.55(t,4H)；2.50(t,4H)；1.40(s,9H)
Compound N is O.120:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 3.6-3.79 (m, 8H)；2.50(t,4H)；1.97(m,1H)；0.90 (d, 6H)
Compound N is O.121:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.20 (t, 2H)；3.72 (s 2H), 3.65 (t, 4H)；2.50(t,4H),1.73(m,2H)；0.90(t,3H)
Compound N is O.122:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.87 (m, 1H)；3.72(s,3H)；3.65(t,4H)；2.50(t,4H)；1.32(d,6H))
Compound N is O.123:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.89 (s, 2H)；3.72(s,3H)；3.65(t,4H)；3.32(s,1H)2.50(t,4H))
Compound N is O.124:HNMR (400MH, DMSO) δ (7.71, dd, 2H)；7.40(,m,2H,)；7.33 (t, 1H), 6.5 (s, 1H), 4.41 (t, 2H)；4.16(dd,2H)；3.72(s,2H)；3.65(t,4H)3.80(m,2H)；2.50(t,4H)； 1.80-1.90(m,4H)
Compound N is O.125:HNMR (400MH, DMSO) δ (8.88, (d, 1H)；8,62(dd,1H)；8.18(m,1H)； 7.68(dd,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.80 (t, 4H)；3.75 (s, 2H) 7；2.50 (t, 4H)；1.35(t, 3H)；
Compound N is O.126:HNMR (400MH, DMSO) δ (8.45, (d, 1H)；7.2-7.68(m,3H)；6.5 (s, 1H), 4.20(q,2H)；3.80 (t, 4H)；3.75 (s, 2H) 7；2.50 (t, 4H)；1.35(t,3H)；)
Compound N is O.127:HNMR (400MH, DMSO) δ (8.54, (d, 2H)；7.68(d,2H)；6.5 (s, 1H), 4.20 (q,2H)；3.80 (t, 4H)；3.75 (s, 2H) 7；2.50 (t, 4H)；1.35(t,3H)；)
Compound 128:HNMR (400MH, DMSO) δ (8.54, (m, 2H)；7.68(d,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.80 (t, 4H)；3.75 (s, 2H) 7；2.50 (t, 4H)；1.35(t,3H)；)
Compound N O.129:NMR (400MH, DMSO) δ (8.05, (m, 2H)；7.48(d,1H)；6.5 (s, 1H), 4.20 (q,2H)；3.80 (t, 4H)；3.75 (s, 2H) 7；2.50 (t, 4H)；1.35(t,3H)；)
Compound N O.130:NMR (400MH, DMSO) δ (9.53, (s, 1H)；8.60(s,1H)；6.5 (s, 1H), 4.20 (q,2H)；3.80 (t, 4H)；3.75 (s, 2H) 7；2.50 (t, 4H)；1.35(t,3H)；)
Compound N O.131:NMR (400MH, DMSO) δ (6.5 (s, 1H), 4.20 (q, 2H)；3.80 (t, 4H)；3.75 (s, 2H)7；2.50 (t, 4H)；2.20(t,2H)；1.30(m,7H)；)0.90(m,3H)
Compound N is O.132:HNMR (400MH, DMSO) δ (8.88, (d, 1H)；8,62(dd,1H)；8.18(m,1H)； 7.68(dd,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H) 2.45 (t, 4H)；1.53(m,5H)；1.29(t,3H)；)
Compound N is O.133:HNMR (400MH, DMSO) δ (8.88, (d, 1H)；8,62(dd,1H)；8.18(m,1H)； 7.68(dd,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H) 2.35 (s, 8H)；1.29(t,3H)；)
Compound N is O.134:HNMR (400MH, DMSO) δ (8.88, (d, 1H)；8,62(dd,1H)；8.18(m,1H)； 7.68(dd,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H)；3.45(t,2H)；2.53(t,2H)；2.35(s,8H) 1.29(t,3H)；)
Compound N is O.135:HNMR (400MH, DMSO) δ (8.88, (d, 1H)；8,62(dd,1H)；8.18(m,1H)； 7.68(dd,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H) 2.73 (t, 4H)；2.50(t,4H)；1.29(t,3H)；)
Compound N is O.136:HNMR (400MH, DMSO) δ (8.88, (d, 1H)；8,62(dd,1H)；8.18(m,1H)； 7.68(dd,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H)；2.70(m,8H)；1.29(t,3H))
Compound N is O.137:HNMR (400MH, DMSO) δ (8.88, (d, 1H)；8,62(dd,1H)；8.18(m,1H)； 7.68(dd,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H)；3.51 (t, 4H) 2.91 (t, 4H)；1.29 (t, 3H))
Compound N is O.138:HNMR (400MH, DMSO) δ (8.88, (d, 1H)；8,62(dd,1H)；8.18(m,1H)； 7.68(dd,1H)；6.5 (s, 1H), 4.20 (q, 2H)；3.75 (s, 2H)；2.66 (t, 4H)；2.50 (t, 4H)；1.29 (t, 3H).
Mannich base fungicide of the present invention is not only used in common preparation such as aqueous emulsion, suspending agent and water dispersant, More due to the alkalinity of its Mannich base, it is allowed to generate salt, the compound of preparation with common inorganic acid and organic acid NO.1-138 is soluble in water, and if compound N is O.55 in 5% hydrochloric acid of salt, the solubility of sulfuric acid, acetic acid, polyacrylic acid is shown in Table 13.
13 compound N of the table O.55 solubility in acid solution
Three, Application Example
The measurement of 3.1 toxicities
3.1.1 test method
Here is that a compounds of this invention is main pathogenic bacteria --- sickle-like bacteria of the active component for wheat scab Killing effect；
Test method: mycelial growth rate method；
Evaluation method: the bioactivity of compound is evaluated with Toxicity baseline and EC50, EC90.
3.1.2 test result
Test result of 14 the compounds of this invention of table to wheat scab
It can be seen that the physicochemical properties that introduce improvement original structure of the present invention by aminomethyl from the result of table 14, The unstable of Mannich base is utilized simultaneously and retains the bactericidal activity of former compound.

Claims (10)

1. a kind of 3- amino -2- cyanoacrylate compound indicated by following general formula (I):
Wherein: R H, unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6It is alkyl, unsubstituted or have The C of substituent group2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C3-C6Cycloalkanes Base, halogen, CN, NO2, hydroxyl, unsubstituted or with substituent group C1-C6Alkoxy, unsubstituted or with substituent group C1-C6Ring Oxyalkyl, unsubstituted or with substituent group C1-C4Alkyl groups in the halogenalkoxy, unsubstituted or with substituent group C1-C6Alkylthio group, nothing take Generation or the C with substituent group1-C4Alkyl sulfino, unsubstituted or with substituent group C1-C4Alkyl sulphonyl, unsubstituted or tool The C of substituted base2-C4Alkoxy carbonyl, unsubstituted or with substituent group C2-C6Acyl group, unsubstituted or with substituent group C3- C6Trialkylsilkl, unsubstituted or with substituent group C2-C8Dialkyl amido, unsubstituted or with substituent group C3-C6 Naphthene amino, unsubstituted or phenyl with substituent group, unsubstituted or phenoxy group with substituent group, it is unsubstituted or have replace The benzyl of base, unsubstituted or 6 yuan of hetero-aromatic rings with substituent group or unsubstituted or 5 yuan of hetero-aromatic rings with substituent group；
R1For unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6Alkyl, it is unsubstituted or have substituent group C2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C2-C6Naphthenic base, halogen, CN、NO2, hydroxyl, unsubstituted or with substituent group C1-C6Alkoxy, unsubstituted or with substituent group C1-C4Alkylthio group, nothing Substitution or the C with substituent group1-C4Alkyl sulfino, unsubstituted or with substituent group C1-C4Alkyl sulphonyl, it is unsubstituted or C with substituent group2-C6Alkoxy carbonyl, unsubstituted or with substituent group C1-C6It is alkoxy carbonyloxy group, unsubstituted or have The C of substituent group1-C6Acyl amino, unsubstituted or with substituent group C2-C4Alkyl amino, unsubstituted or with substituent group C2- C8Dialkyl amido, unsubstituted or with substituent group C3-C6Naphthene amino, unsubstituted or with substituent group C2-C6Acyl group, nothing Substitution or the C with substituent group1-C6Alkoxy amino, unsubstituted or with substituent group C3-C6Alkyl amino-carbonyl, it is unsubstituted or C with substituent group1-C6Alkoxycarbonyl amino, unsubstituted or with substituent group C2-C8Dialkylaminocarbonyl, it is unsubstituted or C with substituent group3-C6It is trialkylsilkl, unsubstituted or phenyl with substituent group, unsubstituted or with substituent group It is phenoxy group, unsubstituted or benzyl with substituent group, unsubstituted or there is 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, unsubstituted or tool Substituted 5 circle heterocyclic ring of base or hetero-aromatic ring；
R2For H, unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6Alkyl, it is unsubstituted or have replace The C of base2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C2-C6Naphthenic base, halogen Element, CN, NO2, hydroxyl, unsubstituted or with substituent group C1-C4Alkoxy, unsubstituted or with substituent group C1-C4Alkyl halide oxygen Base, unsubstituted or with substituent group C1-C4Alkylthio group, unsubstituted or with substituent group C1-C4It is alkyl sulfino, unsubstituted Or the C with substituent group1-C4Alkyl sulphonyl, unsubstituted or with substituent group C3-C6It is alkyl amino-carbonyl, unsubstituted or have The C of substituent group1-C6Alkoxy amino, unsubstituted or with substituent group C2-C4Alkoxy carbonyl, it is unsubstituted or have substituent group C1-C6Alkoxycarbonyl amino, unsubstituted or with substituent group C2-C4Acyl group, C unsubstituted or with substituent group3-C6Three AIkylsilyl groups, C unsubstituted or with substituent group2-C8Dialkyl amido, unsubstituted or with substituent group C3-C6Cycloalkanes It is amino, unsubstituted or phenyl with substituent group, unsubstituted or phenoxy group with substituent group, unsubstituted or with substituent group It is benzyl, unsubstituted or with 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, unsubstituted or there is 5 circle heterocyclic ring of substituent group or hetero-aromatic ring；
Or the R1With R2Coupled nitrogen forms the ring K containing 2-6 carbon atom；The ring K may also include optionally another A nitrogen, sulphur or oxygen atom, or C (=O), SO or S (O) are selected from including 1 or 22Ring members, the ring K can by be selected from C1- C2Alkyl, halogen, CN, NO2, hydroxyl, C1-C2Hydroxyalkyl and C1-C21-4 group of alkoxy arbitrarily replaces；
R3For H, unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6Alkyl, it is unsubstituted or have replace The C of base2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C2-C6Naphthenic base, halogen Element, CN, NO2, hydroxyl, unsubstituted or with substituent group C1-C4Alkoxy, unsubstituted or with substituent group C1-C4Alkyl halide oxygen Base, unsubstituted or with substituent group C1-C4Alkylthio group, unsubstituted or with substituent group C1-C4It is alkyl sulfino, unsubstituted Or the C with substituent group1-C4Alkyl sulphonyl, unsubstituted or with substituent group C2-C4It is alkoxy carbonyl, unsubstituted or have The C of substituent group2-C4Acyl group, unsubstituted or with substituent group C3-C6It is trialkylsilkl, unsubstituted or with substituent group C2-C8Dialkyl amido, unsubstituted or with substituent group C3-C6Naphthene amino, unsubstituted or the phenyl with substituent group, nothing Replace or the phenoxy group with substituent group, unsubstituted or there is 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, unsubstituted or with substituent group 5 circle heterocyclic rings or hetero-aromatic ring；
R4For H, unsubstituted or G with substituent group, unsubstituted or with substituent group C1-C6Alkyl, it is unsubstituted or have replace The C of base2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C2-C6Naphthenic base or C unsubstituted or with substituent group2-C6Epoxy alkyl, halogen, CN, NO2, hydroxyl, unsubstituted or with substituent group C1-C4Alkane Oxygroup, unsubstituted or with substituent group C1-C4Alkyl groups in the halogenalkoxy, unsubstituted or with substituent group C1-C4It is alkylthio group, unsubstituted Or the C with substituent group1-C4Alkyl sulfino, unsubstituted or with substituent group C1-C4It is alkyl sulphonyl, unsubstituted or have The C of substituent group2-C4Alkoxy carbonyl, unsubstituted or with substituent group C2-C4Acyl group, unsubstituted or with substituent group C3-C6 Trialkylsilkl, unsubstituted or with substituent group C2-C8Dialkyl amido, C3-C6It is naphthene amino, unsubstituted or have It is the phenyl of substituent group, unsubstituted or phenoxy group with substituent group, unsubstituted or benzyl with substituent group, unsubstituted or have It is 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, unsubstituted or there is 5 circle heterocyclic ring of substituent group or hetero-aromatic ring；
The G is 5 or 6 yuan of non-aromatic carbocycles or heterocycle, it includes optional 1 or 2 selected from C (=O), SO or S (O)2Ring at Member, and it is available selected from C1-C2Alkyl, halogen, CN, NO2And C1-C2Any selection of 1-4 of alkoxy replaces；
Described R, R1、R2、R3And R4It can each be replaced by following one or more groups: C1-C6Alkyl, C2-C4Alkenyl, C2-C4 Alkynyl, C3-C6Naphthenic base, C1-C6Alkylhalide group, C2-C4Haloalkenyl, C2-C4Alkynyl halide, C3-C6Halogen naphthenic base, halogen, CN, NO2, hydroxyl Base, isocyanide oxygroup, cyanato-, amino, thiocyanogen, imino group, C1-C4Alkoxy, C1-C4Alkyl groups in the halogenalkoxy, C1-C4Alkylthio group, C2- C6Acyl group, C2-C6Acyloxy, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyloxysulfonyl, C1-C4Alkyl Amino, C2-C6Alkoxy carbonyl, C1-C6Alkoxy carbonyloxy group, C1-C6Alkoxycarbonyl amino, (C1-C6Alkoxy) thio carbonyl Base, (C1-C6Alkylthio group) thiocarbonyl, C1-C6Acyl amino, C1-C6Alkoxy amino, C1-C6Alkyl amino carbonyl oxy, C3-C6 Trialkylsilkl, C2-C8Dialkyl amido, C3-C6Cycloalkyl amino, C3-C6(alkyl) cycloalkyl amino, C2-C6Alkylamino Carbonyl, C3-C8Dialkyl amino carbonyl, phenyl, benzyl, phenoxy group, anilino-, 5 yuan of hetero-aromatic rings and 6 yuan of hetero-aromatic rings.
2. compound according to claim 1, which is characterized in that the R is selected from: C unsubstituted or with substituent group1-C6 Alkyl, unsubstituted or with substituent group C2-C6Alkenyl, unsubstituted or with substituent group C2-C6It is alkynyl, unsubstituted or have The C of substituent group3-C6Naphthenic base, unsubstituted or phenyl with substituent group, unsubstituted or benzyl with substituent group, it is unsubstituted or 5 yuan of heteroaromatics with substituent group, unsubstituted or 6 yuan of heteroaromatics with substituent group.
3. compound according to claim 1, which is characterized in that the R1It is selected from: unsubstituted or the G with substituent group, nothing Substitution or the C with substituent group1-C6Alkyl, unsubstituted or with substituent group C2-C6It is alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, unsubstituted or with substituent group C3-C6Naphthenic base, unsubstituted or phenyl with substituent group, unsubstituted or tool The benzyl of substituted base, it is unsubstituted or with 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, it is unsubstituted or have 5 circle heterocyclic ring of substituent group or Hetero-aromatic ring；
The R2It is selected from: H, unsubstituted or with substituent group C1-C6It is alkyl, unsubstituted or phenyl with substituent group, unsubstituted Or benzyl with substituent group, it is unsubstituted or with 6 circle heterocyclic ring of substituent group or hetero-aromatic ring, it is unsubstituted or have 5 yuan of substituent group it is miscellaneous Ring or hetero-aromatic ring；
Or the R1With R2Coupled nitrogen forms the ring K containing 2-6 carbon atom, the ring K may also include it is optional another Nitrogen, sulphur or oxygen atom；The ring K can be selected from C1-C2Alkyl, halogen, CN, NO2, hydroxyl, C1-C2Hydroxyalkyl and C1-C2Alkane 1-4 group of oxygroup arbitrarily replaces；
The R1And R2It can each be replaced by following one or more groups: hydroxyl, CN, thiocyanogen, NO2、C1-C4Alkoxy, C1- C4Alkyl groups in the halogenalkoxy, C1-C6Alkylhalide group, C2-C4Haloalkenyl, C2-C4Alkynyl halide, C1-C4Alkylthio group, C1-C6Alkyl, C2-C4Alkenyl, C2- C4Alkynyl, C1-C6Alkoxy carbonyloxy group, C1-C6Alkoxycarbonyl amino, C1-C6Acyl amino, C1-C4Acyloxy, C1-C6Alkyl Amino carbonyloxy group, imino group, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyloxysulfonyl, (C1-C6Alcoxyl Base) thiocarbonyl, (C1-C6Alkylthio group) thiocarbonyl, C3-C6Naphthenic base, C3-C6Halogen naphthenic base, halogen, isocyanide oxygroup, cyanogen oxygen Base, amino, C2-C6Acyl group, C3-C8Dialkyl amino carbonyl, C1-C4Alkyl amino, C1-C6Alkoxy amino, C2-C6Alkoxy Carbonyl, C3-C6Trialkylsilkl, C2-C8Dialkyl amido, C3-C6Cycloalkyl amino, C3-C6(alkyl) cycloalkyl amino, C2-C6Alkyl amino-carbonyl, phenyl, benzyl, phenoxy group, anilino-, 5 yuan of hetero-aromatic rings and 6 yuan of hetero-aromatic rings.
4. compound according to claim 1, which is characterized in that the R3It is selected from: H, unsubstituted or with substituent group C1-C6Alkyl, unsubstituted or with substituent group C2-C6Alkenyl, unsubstituted or with substituent group C2-C6Alkynyl, it is unsubstituted or It is phenyl with substituent group, unsubstituted or phenoxy group with substituent group, unsubstituted or there are 6 yuan of hetero-aromatic rings of substituent group, without taking In generation, has 5 yuan of hetero-aromatic rings of substituent group.
5. compound according to claim 1, which is characterized in that the R4It is selected from: C unsubstituted or with substituent group1- C6Alkyl, unsubstituted or with substituent group C2-C6Alkenyl, unsubstituted or with substituent group C2-C6It is alkynyl, unsubstituted or have 5 circle heterocyclic ring of substituent group.
6. compound according to claim 1, which is characterized in that the R is selected from: C unsubstituted or with substituent group1-C6 Alkyl, unsubstituted or phenyl with substituent group, unsubstituted or five yuan of heteroaromatics with substituent group or it is unsubstituted or have take The hexa-atomic heteroaromatic of Dai Ji, five yuan of heteroaromatics are thiazole, thiophene or furans, and the hexa-atomic heteroaromatic is pyridine.
7. compound according to claim 1, which is characterized in that the R3It is selected from: H, phenyl, chlorphenyl, 6 yuan of hetero-aromatic rings Or 5 yuan of hetero-aromatic rings.
8. compound according to claim 1, which is characterized in that the R1For C1-C6Alkyl, C2-C6Alkenyl, CH2CH3OH、 CH2CH3OCH3、CF2CH2OCH3、CH2CH2OCF2CF2H、CH2CN、CF3、CH2CH2SCN、CH2CHCH2、CH2CCH、CH2CH2Cl、 CH2COOC2H5、CH2CH2SCH3、CH2CH2OCH2CH2Cl、CH2CH2NO2、CH2CH2Si(C2H5)3、CH2CH2Si(CH3)3、 CH2CH2OC2H5、CH2CH2OCOOC2H5、CH2CH2NHCOOC2H5、CH2CH2NHCOCH3、CH2CH3OCOCH3、 CH2CH2OCONHC2H5、CH2CH(OCH3)2、CH2COCH3、CH2CH=NCH3、CH2CH=N-OCH3、CH2CNHOCH3、CH2CNHN (CH3)2、CH2CH2N(CH3)2、CH2CHO、CH2CH2OHCH2OH、CH2CHCH2CH2、CH2SOCH3、CH2SO2CH3、CH2SO3CH3、 CH2SO2、CH2CH2N(CH3)2、CH2CH2NCH3COCH3、CH2CH2ONCOCH3、CH2CH2OSO2CH3、CH2(C=S) OC2H5、 CH2CH2OCONHC2H5、CH2CSN(CH3)2, phenyl, benzyl, hydroxy phenyl, chlorphenyl, acetylphenyl, cyclopenta, hexamethylene Base, butyrolactone base, lactim base, cyclopentanone base, 1,3- dioxolane base；
The R2For C1-C6Alkyl, CH2CH3OH、CH2COOC2H5；
Or the R1With R2The ring K that coupled nitrogen is formed is selected from K1-K14Any one of:
9. compound according to claim 8, it is characterised in that:
The R is C1-C6Alkyl, phenyl, thiazolyl, thienyl, furyl or pyridyl group；
The R3For H, furyl, pyridyl group, phenyl or chlorphenyl；
The R4For C1-C6Alkyl, tetrahydrofuran base.
10. application of any compound described in -9 on prevention and treatment sickle-like bacteria according to claim 1.
CN201910198401.5A 2019-03-15 2019-03-15 A kind of 3- amino -2- cyanoacrylate compound and its application Pending CN109879834A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022160466A1 (en) 2021-01-26 2022-08-04 浙江大学 2-cyanoacrylate compound, preparation method therefor and use thereof
CN115039778A (en) * 2022-07-11 2022-09-13 浙江大学 Bactericide composition for preventing and treating crop diseases caused by fusarium
WO2024007376A1 (en) * 2022-07-05 2024-01-11 浙江省化工研究院有限公司 Fungicidal compositions and uses thereof in prevention and treatment of fusarium diseases of crops

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317483A (en) * 2001-05-08 2001-10-17 江苏省农药研究所 2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops
CN101381326A (en) * 2008-10-15 2009-03-11 江苏中旗化工有限公司 2-cyano-3-(substituted) amidine-3-phenyl acrylates compounds, preparation method and use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317483A (en) * 2001-05-08 2001-10-17 江苏省农药研究所 2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops
CN1160318C (en) * 2001-05-08 2004-08-04 江苏省农药研究所 2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops
CN101381326A (en) * 2008-10-15 2009-03-11 江苏中旗化工有限公司 2-cyano-3-(substituted) amidine-3-phenyl acrylates compounds, preparation method and use thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022160466A1 (en) 2021-01-26 2022-08-04 浙江大学 2-cyanoacrylate compound, preparation method therefor and use thereof
WO2024007376A1 (en) * 2022-07-05 2024-01-11 浙江省化工研究院有限公司 Fungicidal compositions and uses thereof in prevention and treatment of fusarium diseases of crops
CN115039778A (en) * 2022-07-11 2022-09-13 浙江大学 Bactericide composition for preventing and treating crop diseases caused by fusarium
CN115039778B (en) * 2022-07-11 2023-02-24 浙江大学 Bactericide composition for preventing and treating crop diseases caused by fusarium

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