CN106146350A - A kind of new method of synthesizing amino methylcarbamoyl oximino ester derivant - Google Patents
A kind of new method of synthesizing amino methylcarbamoyl oximino ester derivant Download PDFInfo
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- CN106146350A CN106146350A CN201610579619.1A CN201610579619A CN106146350A CN 106146350 A CN106146350 A CN 106146350A CN 201610579619 A CN201610579619 A CN 201610579619A CN 106146350 A CN106146350 A CN 106146350A
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- isonitrile
- oxime
- methylcarbamoyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
Abstract
The invention belongs to pesticide chemical synthesis technical field, disclose a kind of by aryl ketoxime, isonitrile with the new method of water synthesizing amino methylcarbamoyl oximino ester derivant.The method specifically includes following steps: in reaction bulb, adding aryl ketoxime, isonitrile and water is raw material, it is reacting by heating under conditions of catalyst, alkali are solvent as additive, organic solvent in palladium salt, gained reactant liquor is cooled to room temperature then purification after terminating by reaction, obtains oxime carbamate derivant.The method that the process employs the organic synthesis of palladium chtalyst, activates the oxygen hydrogen bond of oxime under the effect of palladium catalyst, is inserted into isonitrile, obtains carbamic acid oxime fat under conditions of water is as nucleopilic reagent, and isonitrile can be as the source of amide group.The reaction raw materials of the method is simple and easy to get, and operation is safe and simple, course of reaction environmental friendliness, and substrate applicability is wide, and functional group compatibility is strong, has potential practical value.The method has extensive use in pesticide, medical synthesis.
Description
Technical field
The invention belongs to pesticide chemical synthesis technical field, particularly to one by aryl ketoxime, isonitrile, water synthesizing amino
The new method of methylcarbamoyl oximino ester derivant.
Background technology
The compound of oxime carbamate class has quite varied biological pesticide activity, be a lot of bioactive molecule and
The important feature unit of pesticide molecule.To this end, researcher has carried out substantial amounts of research to this compounds, find amino first
Acid oxime ester compound has a suppression antibacterial, parasite killing and the important function such as inhibitor as enzyme.Although this compounds has
There is the most important application, but regrettably the synthetic method of oxime carbamate compounds is the most few.
Build prior synthesizing method oxime to be used and the isocyanates of oxime carbamate analog derivative
(S.Y.Sita,C.M.Conway,K.Xie,R.Bertekap,C.Bourin,K.D.Burris,
Bioorg.Med.Chem.Lett.20(2010)1272–1277.V.S.Georgiev,G.A.Bennett,L.A.Radov,
D.K.Kamp,Arch.Pharm.(Weinheim)320.465-470(1987).C.Saturninoa,S.Petrosino,
A.Ligresti,C.Palladino,G.D.Martino,T Bisogno,V.D.Marzo,and L.A.Trusso,
Bioorganic&Medicinal Chemistry Letters 20(2010)1210–1213).The problem that this type of method is maximum
It is that the isocyanates using more difficult synthesis is reaction raw materials, the economical difference of step；In addition, compatible for some functional groups
Property difference is also an in esse difficult problem.Therefore, the synthesis building multiple oxime carbamate analog derivative that development environment is friendly
Method is constantly subjected to the extensive concern of scientific circles and industrial quarters.
In Synthetic Organic Chemistry, isonitrile is a kind of organic synthesis building block having very much Research Significance, practical value.In recent years
Come, based on isonitrile participate in organic reaction receive significant attention (T.Hirai, L.-B.Han, J.Am.Chem.Soc.2006,
128,7422；H.Jiang,B.Liu,Y.Li,A.Wang,H.Huang,Org.Lett.2011,13,1028-1031；F.Zhou,
K.Ding,Q.Cai,Chem.Eur.J.2011,17,12268；H.Jiang,B.Liu,Y.Li,A.Wang,H.Huang,
Org.Lett.2011,13,1028；T.Nanjo,C.Tsukano,Y.Takemoto,Org.Lett.2012,14,4270；
T.Vlaar,R.C.Cioc,P.Mampuys,B.U.W.Maes,R.V.A.Orru,E.Ruijter,Angew.Chem.2012,
124,13235；Angew.Chem.Int.Ed.2012,51,13058；L.D.Miranda,E.H.-Va′zquez′
J.Org.Chem.2015,80,10611-10623；J.Liu,Z.Liu,P.Liao,L.Zhang,T.Tu,and X.Bi,
Angew.Chem.Int.Ed.2015,54,1–6).But there is presently no and utilize isonitrile to be directly synthesized carbamic acid oxime for raw material
The report of esters derivative.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of synthesizing amino
The new method of methylcarbamoyl oximino ester derivant.The method, with aryl ketoxime, isonitrile and water as raw material, under the catalysis of palladium salt, is gone here and there
Connection reaction, one-step synthesis oxime carbamate derivant.The reaction raw materials of the method is simple and easy to get, and operation is safe and simple,
Course of reaction environmental friendliness, substrate applicability is wide, and functional group compatibility is strong, has potential practical value.
The purpose of the present invention is realized by following proposal:
The new method of a kind of synthesizing amino methylcarbamoyl oximino ester derivant, specifically includes following steps:
In reaction bulb, add aryl ketoxime, isonitrile and water are raw material, palladium salt be catalyst, alkali as additive, have
Machine solvent is reacting by heating under conditions of solvent, and gained reactant liquor is cooled to room temperature then purification after terminating by reaction, obtains institute
The oxime carbamate derivant stated.
Its reaction is shown below:
Described reacting by heating refers to stirring reaction 3～12h at 80～100 DEG C.
Described aryl ketoxime can be acetophenone oxime, 4-fluorophenethyl ketoxime, 4-chloro-acetophenone oxime, 4-itrile group acetophenone oxime,
3-chloro-acetophenone oxime, 2-chloro-acetophenone oxime, 2-acetonaphthone oxime, 3,4-dimethoxy-acetophenone oxime, phenylpropyl alcohol ketoxime, benzo ring hexanone
At least one in oxime, 6-methoxyl group benzo cyclohexanone-oxime, benzocyclohepta ketoxime.
Described isocyanide can be that tert-butyl isonitrile, normal-butyl isonitrile, 1,1,3,3-tetramethyl butyl isonitrile, cyclopenta are different
At least one in nitrile, cyclohexyl isonitrile, 1-isonitrile base diamantane (obsolete), p-methoxyphenyl isonitrile.
The mol ratio of aryl ketoxime, isonitrile and water used is 1:1:(5～10).
Preferably, the mol ratio of aryl ketoxime, isonitrile and water used is 1:1:5.
Described palladium salt can be tetra-triphenylphosphine palladium, in three (dibenzalacetone) two palladium, bi triphenyl phosphorus palladium chloride
At least one.
Palladium salt used is (0.01-0.05) with the mol ratio of aryl ketoxime: 1.
Preferably, palladium salt used is 0.03:1 with the mol ratio of aryl ketoxime.
Described additive is sodium acetate or cesium carbonate.
Described organic solvent can be at least in toluene, N,N-dimethylformamide, acetonitrile and 1,2-dichloroethanes
Kind.
Described purification refers to reacting liquid filtering, and then decompression is distilled off solvent to obtain crude product, then will slightly produce
Thing is through column chromatographic isolation and purification.
In described column chromatography, eluent used is the mixed solvent of petroleum ether and ethyl acetate；Petroleum ether and acetic acid
Proportion value between ethyl ester is (10～200): 1.
The oxime carbamate derivant of gained is cis-configuration (Z).
The mechanism of the present invention is: with aryl oxime, isonitrile, water as reaction raw materials, using palladium salt as catalyst, using alkali as adding
Add next step substituted oxime carbamate of synthesis of effect of agent.Existing be directly synthesized carbamic acid oxime fat mainly use oxime and
The coupling reaction of isocyanates realizes without metal when, and other kinds of synthetic method is the most common.And utilize isonitrile
It is the method that raw material is directly synthesized that carbamic acid oxime lipid derivant is the organic synthesis that have employed palladium chtalyst with oxime, at palladium chtalyst
The lower oxygen hydrogen bond activating oxime of the effect of agent, is inserted into isonitrile, obtains carbamic acid oxime under conditions of water is as nucleopilic reagent
Fat, isonitrile can be as the source of amide group.Such method have benefited from transition metal-catalyzed organic synthesis field send out
Exhibition, makes us can therefrom draw the synthetic method that new thought development is new.
The present invention, relative to prior art, has such advantages as and beneficial effect:
The new method of the synthesizing amino methylcarbamoyl oximino ester of the present invention.Reaction raw materials is simple and easy to get, and operation is safe and simple, instead
Answering process environment friendly, substrate applicability is wide, and functional group compatibility is strong, and Atom economy is good.The method has in pesticide, medicine
There is extensive use.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 1-9 products therefrom.
Fig. 2 is the carbon-13 nmr spectra figure of embodiment 1-9 products therefrom.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 10 products therefrom.
Fig. 4 is the carbon-13 nmr spectra figure of embodiment 10 products therefrom.
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 11 products therefrom.
Fig. 6 is the carbon-13 nmr spectra figure of embodiment 11 products therefrom.
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 12 products therefrom.
Fig. 8 is the carbon-13 nmr spectra figure of embodiment 12 products therefrom.
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 13 products therefrom.
Figure 10 is the carbon-13 nmr spectra figure of embodiment 13 products therefrom.
Figure 11 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 14 products therefrom.
Figure 12 is the carbon-13 nmr spectra figure of embodiment 14 products therefrom.
Figure 13 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 15 products therefrom.
Figure 14 is the carbon-13 nmr spectra figure of embodiment 15 products therefrom.
Figure 15 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 16 products therefrom.
Figure 16 is the carbon-13 nmr spectra figure of embodiment 16 products therefrom.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
In embodiment, agents useful for same all can be buied from market routine.
Embodiment 1
25 milliliters of test tubes add 0.2 mM of acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, three (dibenzalacetone) two palladium and sodium acetate of 0.4 mM of 0.006 mM, add 2 milliliters of toluene as molten
Agent, after stirring is reacted 12 hours under the conditions of 80 DEG C, stops heating and stirring, is cooled to room temperature, add ethyl acetate after filtration
Extracting three times, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, used
Column chromatography eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 21%.The nuclear-magnetism of products therefrom
Resonance hydrogen spectrogram is as it is shown in figure 1, carbon-13 nmr spectra figure is as in figure 2 it is shown, explanation successfully synthesizes product.
Embodiment 2
25 milliliters of test tubes add 0.2 mM of l acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the bi triphenyl phosphorus palladium chloride of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent,
After stirring is reacted 12 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and extract
Three times, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, post layer used
Analysis eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 33%.The nuclear magnetic resonance, NMR of products therefrom
Hydrogen spectrogram is as it is shown in figure 1, carbon-13 nmr spectra figure is as in figure 2 it is shown, explanation successfully synthesizes product.
Embodiment 3
25 milliliters of test tubes add 0.2 mM of acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, addition 2mL toluene is as solvent, at 80 DEG C of bars
After stirring is reacted 12 hours under part, stop heating and stirring, be cooled to room temperature, after filtration, add ethyl acetate extraction three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 68%.The hydrogen nuclear magnetic resonance spectrogram of products therefrom
As it is shown in figure 1, carbon-13 nmr spectra figure is as in figure 2 it is shown, explanation successfully synthesizes product.
Embodiment 4
25 milliliters of test tubes add 0.2 mM of acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, at 90 DEG C
Under the conditions of stirring reaction 12 hours after, stop heating and stirring, be cooled to room temperature, after filtration add ethyl acetate extract three times,
Magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography used is washed
De-liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 54%.The proton nmr spectra of products therefrom
Figure is as it is shown in figure 1, carbon-13 nmr spectra figure is as in figure 2 it is shown, explanation successfully synthesizes product.
Embodiment 5
25 milliliters of test tubes add 0.2 mM of acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, at 100 DEG C
Under the conditions of stirring reaction 12 hours after, stop heating and stirring, be cooled to room temperature, after filtration add ethyl acetate extract three times,
Magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography used is washed
De-liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 40%.The proton nmr spectra of products therefrom
Figure is as it is shown in figure 1, carbon-13 nmr spectra figure is as in figure 2 it is shown, explanation successfully synthesizes product.
Embodiment 6
25 milliliters of test tubes add 0.2 mM of acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, at 80 DEG C
Under the conditions of stirring reaction 6 hours after, stop heating and stirring, be cooled to room temperature, after filtration add ethyl acetate extract three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 67%.The hydrogen nuclear magnetic resonance spectrogram of products therefrom
As it is shown in figure 1, carbon-13 nmr spectra figure is as in figure 2 it is shown, explanation successfully synthesizes product.
Embodiment 7
25 milliliters of test tubes add 0.2 mM of acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the cesium carbonate of 0.4 mM, add 2 milliliters of toluene as solvent, at 80 DEG C
Under the conditions of stirring reaction 3 hours after, stop heating and stirring, be cooled to room temperature, after filtration add ethyl acetate extract three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 18%.The hydrogen nuclear magnetic resonance spectrogram of products therefrom
As it is shown in figure 1, carbon-13 nmr spectra figure is as in figure 2 it is shown, explanation successfully synthesizes product.
Embodiment 8
25 milliliters of test tubes add 0.2 mM of acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of DMFs
(DMF), as solvent, after stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add after filtration
Entering ethyl acetate to extract three times, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target
Product, column chromatography eluent used be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 20%.Institute
Obtain the hydrogen nuclear magnetic resonance spectrogram of product as it is shown in figure 1, carbon-13 nmr spectra figure is as in figure 2 it is shown, explanation successfully synthesizes product.
Embodiment 9
25 milliliters of test tubes add 0.2 mM of acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, at 80 DEG C
Under the conditions of stirring reaction 3 hours after, stop heating and stirring, be cooled to room temperature, filter, be subsequently adding ethyl acetate extraction three
Time, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and productivity is 66%.
Column chromatography eluent wherein used be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent.
The structural characterization data of products therefrom are as follows:
IR(KBr):2969,2364,1750,1652,1457,1317,1257,1051,938cm-1
1H NMR(400MHz,CDCl3) δ 7.65 (dd, J=7.8,1.5Hz, 2H), 7.43 (t, J=7.3Hz, 3H), 6.35
(s, 1H), 2.40 (s, 3H), 1.41 (s, 9H), as shown in Figure 1.
13C NMR(100MHz,CDCl3)δ159.3,153.4,135.0,130.4,128.6,126.6,50.8,28.7,
14.3ppm, as shown in Figure 2.
ESI-HRMS:C13H18N2NaO2[M+Na]+Value of calculation: 257.1260, experiment value: 257.1262.
Infer that products therefrom obtains structure according to data above as follows:Illustrate successfully to close
Become target product.
Embodiment 10
In 25 milliliters of test tubes add 0.2 mM of 4-fluorophenethyl ketoxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, 80
After stirring is reacted 3 hours under the conditions of DEG C, stop heating and stirring, be cooled to room temperature, after filtration, add ethyl acetate extraction three times,
Magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography used is washed
De-liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 54%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2970,1749,1676,1457,1318,1262,1051,940cm-1
1H NMR(400MHz,CDCl3) δ 7.66 (dd, J=7.8,5.6Hz, 2H), 7.10 (t, J=8.3Hz, 2H), 6.25
(s, 1H), 2.39 (s, 3H), 1.41 (s, 9H), as shown in Figure 3.
13C NMR(100MHz,CDCl3)δ165.3,162.8,158.3,153.2,131.1,128.7,128.6,115.8,
115.6,50.9,28.7,14.4ppm, as shown in Figure 4.
ESI-HRMS:C13H17FN2NaO2[M+Na]+Value of calculation: 275.1166, experiment value: 275.1169.
Infer that products therefrom obtains structure according to data above as follows:Illustrate successfully
Synthesize target product.
Embodiment 11
In 25 milliliters of test tubes add 0.2 mM of 4-chloro-acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, 80
After stirring is reacted 3 hours under the conditions of DEG C, stop heating and stirring, be cooled to room temperature, after filtration, add ethyl acetate extraction three times,
Magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography used is washed
De-liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 52%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2981,1748,1642,1452,1370,1183,1048,937cm-1
1H NMR(400MHz,CDCl3) δ 7.68 (d, J=8.2Hz, 2H), 7.26 (d, J=8.3Hz, 2H), 5.20 (s,
1H), 2.26 (s, 3H), 1.33 (s, 9H), as shown in Figure 5.
13C NMR(100MHz,CDCl3)δ167.1,163.0,137.4,136.1,128.6,128.4,51.0,28.8,
18.0ppm, as shown in Figure 6.
ESI-HRMS:C13H17ClN2NaO2[M+Na]+Value of calculation: 291.0871, experiment value: 291.0869.
Infer that products therefrom obtains structure according to data above as follows:It is illustrated as
Merit has synthesized target product.
Embodiment 12
0.2 mM of 4-itrile group acetophenone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mmoles is added in 25 milliliters of test tubes
Your water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent,
After stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and extract three
Time, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography used
Eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 63%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2971,1742,1499,1368,1261,1050,940cm-1
1H NMR(400MHz,CDCl3) δ 7.78 (d, J=8.3Hz, 2H), 7.71 (d, J=8.4Hz, 2H), 6.11 (s,
1H), 2.41 (s, 3H), 1.41 (s, 9H), as shown in Figure 7.
13C NMR(100MHz,CDCl3)δ157.8,152.7,139.3,132.4,127.3,118.1,113.9,51.1,
28.7,14.2ppm, as shown in Figure 8.
ESI-HRMS:C14H17N3NaO2[M+Na]+Value of calculation: 282.1213, experiment value: 282.1211.
Infer that products therefrom obtains structure according to data above as follows:It is illustrated as
Merit has synthesized target product.
Embodiment 13
The 3-chloro-acetophenone oxime of 0.2 mM, the tertiary butane isonitrile of 0.2 mM, 1 mmoles is added in 25 milliliters of test tubes
Your water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent,
After stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and extract three
Time, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography used
Eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 65%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2970,1749,1620,1457,1367,1261,1051,943cm-1
1H NMR(400MHz,CDCl3) δ 7.64 (s, 1H), 7.54 (d, J=7.7Hz, 1H), 7.43 (d, J=8.1Hz,
1H), 7.36 (t, J=7.8Hz, 1H), 6.22 (s, 1H), 2.39 (s, 3H), 1.42 (s, 9H), as shown in Figure 9.
13C NMR(100MHz,CDCl3)δ158.2,153.0,136.9,134.7,130.4,129.9,126.8,124.8,
51.0,28.7,14.4ppm, as shown in Figure 10.
ESI-HRMS:C13H17ClN2NaO2[M+Na]+Value of calculation: 291.0871, experiment value: 291.0868.
Infer that products therefrom obtains structure according to data above as follows:It is illustrated as
Merit has synthesized target product.
Embodiment 14
The 2-chloro-acetophenone oxime of 0.2 mM, the tertiary butane isonitrile of 0.2 mM, 1 mmoles is added in 25 milliliters of test tubes
Your water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent,
After stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and extract three
Time, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography used
Eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 69%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2969,1751,1627,1457,1366,1261,1049,936cm-1
1H NMR(400MHz,CDCl3) δ 7.44 (d, J=7.6Hz, 1H), 7.35 (dt, J=14.0,6.8Hz, 3H),
6.23 (s, 1H), 2.38 (s, 3H), 1.38 (s, 9H), as shown in figure 11.
13C NMR(100MHz,CDCl3)δ160.3,153.1,135.4,132.5,130.6,130.2,130.0,126.9,
50.9,28.7,17.7ppm, as shown in figure 12.
ESI-HRMS:C13H17ClN2NaO2[M+Na]+Value of calculation: 291.0871, experiment value: 291.0868.
Infer that products therefrom obtains structure according to data above as follows:Illustrate successfully to close
Become target product.
Embodiment 15
In 25 milliliters of test tubes add 0.2 mM β-acetonaphthone oxime, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, 80
After stirring is reacted 3 hours under the conditions of DEG C, stop heating and stirring, be cooled to room temperature, after filtration, add ethyl acetate extraction three times,
Magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, and column chromatography used is washed
De-liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 57%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2959,2360,2338,1740,1646,1469,1364,1260,1052,954cm-1
1H NMR(400MHz,CDCl3)δ8.09(s,1H),7.86(s,4H),7.57–7.52(m,2H),6.38(s,1H),
2.53 (s, 3H), 1.44 (s, 9H), as shown in figure 13.
13C NMR(100MHz,CDCl3)δ159.2,153.4,134.2,132.9,132.3,128.6,128.4,127.7,
127.3,127.3,126.7,123.2,50.9,28.8,14.2ppm, as shown in figure 14.
ESI-HRMS:C17H21N2O2[M+H]+Value of calculation: 285.1598, experiment value: 285.1598.
Infer that products therefrom obtains structure according to data above as follows:It is illustrated as
Merit has synthesized target product.
Embodiment 16
Adding the 3 of 0.2 mM in 25 milliliters of test tubes, 4-dimethoxy-acetophenone oxime, the tertiary butane of 0.2 mM are different
Nitrile, the water of 1 mM, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene conducts
Solvent, after stirring is reacted 3 hours under the conditions of 80 DEG C, stops heating and stirring, is cooled to room temperature, add ethyl acetate after filtration
Extracting three times, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, used
Column chromatography eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 60%.
The structural characterization data of products therefrom are as follows:
IR (KBr): 2968,1745,1498,1457,1368,1148,943cm-1
1H NMR(400MHz,CDCl3) δ 7.16 (d, J=8.8Hz, 2H), 6.82 (d, J=8.2Hz, 1H), 6.23 (s,
1H), 3.85 (s, 6H), 2.31 (s, 3H), 1.34 (s, 9H), as shown in figure 15.
13C NMR(100MHz,CDCl3) δ 158.9,153.5,151.1,148.9,127.5,120.2,110.7,109.1,
55.9,55.9,50.7,28.7,14.1, as shown in figure 16.
ESI-HRMS:C15H22N2O4[M+Na]+Value of calculation: 317.1472, experiment value: 317.1474.
Infer that products therefrom obtains structure according to data above as follows:It is illustrated as
Merit has synthesized target product.
Embodiment 17
25 milliliters of test tubes add the phenylpropyl alcohol ketoxime of 0.2 mM, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4mmol, add 2 milliliters of toluene as solvent, at 80 DEG C of bars
After stirring is reacted 3 hours under part, stop heating and stirring, be cooled to room temperature, after filtration, add ethyl acetate extraction three times, sulphuric acid
Magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluent used
Being the petroleum ether of 20:1 for volume ratio: ethyl acetate mixed solvent, productivity is 75%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2972,1748,1638,1458,1366,1261,1053,947cm-1
1H NMR(400MHz,CDCl3) δ 7.64 (dd, J=7.8,1.7Hz, 2H), 7.44 (ddd, J=7.7,5.4,
2.2Hz, 3H), 6.37 (s, 1H), 2.90 (q, J=7.6Hz, 2H), 1.41 (s, 9H), 1.18 (t, J=7.6Hz, 3H).
13C NMR(100MHz,CDCl3)δ164.2,153.5,134.0,130.3,128.7,126.9,50.8,28.8,
21.5,11.2ppm。
ESI-HRMS:C14H20N2NaO2[M+Na]+Value of calculation: 271.1417, experiment value: 271.1422.
Infer that products therefrom obtains structure according to data above as follows:Illustrate successfully to close
Become target product.
Embodiment 18
The benzo ring hexanone oxime of 0.2 mM, the tertiary butane isonitrile of 0.2 mM, 1 mmoles is added in 25 milliliters of test tubes
Your water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent,
After stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and extract three
Time, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography used
Eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 70%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2968,1749,1620,1456,1366,1261,1053,944cm-1.
1H NMR(400MHz,CDCl3) δ 7.93 (d, J=7.8Hz, 1H), 7.34 (t, J=7.2Hz, 1H), 7.24 (t, J
=7.5Hz, 1H), 7.18 (d, J=7.6Hz, 1H), 6.41 (s, 1H), 2.91 (t, J=6.6Hz, 2H), 2.80 2.73 (m,
2H),1.91–1.83(m,2H),1.43(s,9H)。
13C NMR(100MHz,CDCl3)δ158.2,153.4,141.0,130.4,128.9,128.8,126.4,124.5,
50.7,29.4,28.7,25.4,21.1ppm。
ESI-HRMS:C15H20N2NaO2[M+Na]+Value of calculation: 283.1417, experiment value: 283.1422.
Infer that products therefrom obtains structure according to data above as follows:Illustrate to successfully synthesize mesh
Mark product.
Embodiment 19
The 6-methoxyl group benzo cyclohexanone-oxime of 0.2 mM, the tertiary butane of 0.2 mM is added different in 25 milliliters of test tubes
Nitrile, the water of 1 mM, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene conducts
Solvent, after stirring is reacted 3 hours under the conditions of 80 DEG C, stops heating and stirring, is cooled to room temperature, add ethyl acetate after filtration
Extracting three times, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, used
Column chromatography eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 73%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2966,1741,1619,1457,1355,1258,1053,946cm-1
1H NMR(400MHz,CDCl3) δ 7.87 (d, J=8.8Hz, 1H), 6.78 (d, J=8.7Hz, 1H), 6.67 (s,
1H), 6.40 (s, 1H), 3.82 (s, 3H), 2.87 (t, J=6.2Hz, 2H), 2.76 2.70 (m, 2H), 1.89 1.81 (m,
2H),1.41(s,9H)。
13C NMR(100MHz,CDCl3)δ161.3,158.0,153.7,143.0,126.3,121.6,113.3,112.9,
55.3,50.7,29.9,28.8,25.4,21.2ppm。
ESI-HRMS:C16H22N2NaO3[M+Na]+Value of calculation: 313.1523, experiment value: 313.1527.
Infer that products therefrom obtains structure according to data above as follows:Illustrate successfully to synthesize
Target product.
Embodiment 20
The benzocyclohepta ketoxime of 0.2 mM, the tertiary butane isonitrile of 0.2 mM, 1 mmoles is added in 25 milliliters of test tubes
Your water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent,
After stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and extract three
Time, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography used
Eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 73%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2966,1743,1646,1456,1365,1259,1052,937cm-1
1H NMR(400MHz,CDCl3) δ 7.38 (dd, J=20.3,7.3Hz, 2H), 7.28 (d, J=8.0Hz, 1H),
7.18 (d, J=7.1Hz, 1H), 6.39 (s, 1H), 2.88 2.80 (m, 2H), 2.77 (d, J=5.3Hz, 2H), 1.83 1.75
(m, 2H), 1.66 (d, J=4.8Hz, 2H), 1.39 (s, 9H).
13C NMR(100MHz,CDCl3)δ166.5,153.5,139.8,134.7,130.2,129.0,127.7,126.5,
50.7,31.8,28.7,27.7,25.7,21.6ppm。
ESI-HRMS:C16H22N2NaO2[M+Na]+Value of calculation: 297.1573, experiment value: 297.1571.
Infer that products therefrom obtains structure according to data above as follows:Illustrate to successfully synthesize target
Product.
Embodiment 21
25 milliliters of test tubes add the acetophenone oxime of 0.2 mM, the tertiary butane isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, at 80 DEG C
Under the conditions of stirring reaction 3 hours after, stop heating and stirring, be cooled to room temperature, after filtration add ethyl acetate extract three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 77%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2958,1741,1624,1445,1373,1239,1158,1042,991,929,852,762,
693cm-1
1H NMR(400MHz,CDCl3) δ 7.66 (dd, J=8.0,1.5Hz, 2H), 7.47 7.40 (m, 3H), 6.45 (s,
1H), 3.33 (dd, J=13.2,7.1Hz, 2H), 2.42 (s, 3H), 1.57 (dt, J=14.9,7.5Hz, 2H), 1.38 (dd, J
=15.1,7.4Hz, 2H), 0.94 (t, J=7.3Hz, 3H)
13C NMR(100MHz,CDCl3)δ159.9,155.5,134.9,130.5,128.6,126.7,40.9,31.8,
19.9,14.4,13.7ppm
ESI-HRMS:C13H18N2NaO2[M+Na]+Value of calculation: 257.1260, experiment value: 257.1264.
Infer that products therefrom obtains structure according to data above as follows:It is illustrated as
Merit has synthesized target product.
Embodiment 22
In 25 milliliters of test tubes add 0.2 mM acetophenone oxime, the 1 of 0.2 mM, 1,3,3-tetramethyl butyl is different
Nitrile, the water of 1 mM, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene conducts
Solvent, after stirring is reacted 3 hours under the conditions of 80 DEG C, stops heating and stirring, is cooled to room temperature, add ethyl acetate after filtration
Extracting three times, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, used
Column chromatography eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 73%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2954,1743,1680,1573,1447,1367,1252,1157,1081,991,937,783cm-1
1H NMR(400MHz,CDCl3) δ 7.67 7.63 (m, 2H), 7.44 (t, J=7.7Hz, 3H), 6.52 (s, 1H),
2.41(s,3H),1.75(s,2H),1.47(s,6H),1.04(s,9H)
13C NMR(100MHz,CDCl3)δ159.2,153.1,135.1,130.4,128.6,126.6,54.6,52.3,
31.6,31.5,29.0,14.4ppm
ESI-HRMS:C17H26N2NaO2[M+Na]+Value of calculation: 313.1886, experiment value: 313.1893.
Infer that products therefrom obtains structure according to data above as follows:Illustrate successfully
Synthesize target product.
Embodiment 23
25 milliliters of test tubes add the acetophenone oxime of 0.2 mM, ring penta isonitrile of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, at 80 DEG C
Under the conditions of stirring reaction 3 hours after, stop heating and stirring, be cooled to room temperature, after filtration add ethyl acetate extract three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 60%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2958,1741,1621,1573,1447,1370,1229,1059,992,911,784cm-1
1H NMR(400MHz,CDCl3) δ 7.65 (dd, J=7.9,1.5Hz, 2H), 7.49 7.41 (m, 3H), 6.34 (d, J
=5.7Hz, 1H), 4.18 4.09 (m, 1H), 2.42 (s, 3H), 2.04 (td, J=11.8,6.3Hz, 2H), 1.75 1.68 (m,
2H),1.66–1.58(m,2H),1.54–1.46(m,2H)
13C NMR(100MHz,CDCl3)δ159.9,154.9,135.0,130.5,128.6,126.7,52.9,33.1,
23.5,14.5ppm
ESI-HRMS:C14H18N2NaO2[M+Na]+Value of calculation: 269.1260, experiment value: 269.1264.
Infer that products therefrom obtains structure according to data above as follows:Illustrate successfully
Synthesize target product.
Embodiment 24
25 milliliters of test tubes add the acetophenone oxime of 0.2 mM, the hexamethylene isocyanide of 0.2 mM, 1 mM
Water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent, at 80 DEG C
Under the conditions of stirring reaction 3 hours after, stop heating and stirring, be cooled to room temperature, after filtration add ethyl acetate extract three times, sulfur
Acid magnesium is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography eluting used
Liquid be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 67%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2925,2853,1755,1496,1373,1318,1055,965cm-1
1H NMR(400MHz,CDCl3) δ 7.69 7.63 (m, 2H), 7.48 7.40 (m, 3H), 6.33 (d, J=6.8Hz,
1H), 3.72 3.63 (m, 1H), 2.42 (s, 3H), 2.02 (dd, J=12.1,3.0Hz, 2H), 1.76 1.59 (m, 4H),
1.42–1.34(m,2H),1.25(s,2H)
13C NMR(100MHz,CDCl3)δ159.8,154.6,135.0,130.5,128.7,126.7,50.0,33.2,
25.5,24.8,14.5ppm
ESI-HRMS:C15H20N2NaO2[M+Na]+Value of calculation: 283.1417, experiment value: 218.1418.
Infer that products therefrom obtains structure according to data above as follows:Illustrate successfully
Synthesize target product.
Embodiment 25
The acetophenone oxime of 0.2 mM, the 1-isocyano group diamantane (obsolete) of 0.2 mM, 1 mmoles is added in 25 milliliters of test tubes
Your water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent,
After stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and extract three
Time, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, column chromatography used
Eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 75%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2909,2852,1748,1452,1365,1275,1138,1048,974,928,761cm-1.
1H NMR(400MHz,CDCl3) δ 7.66 (dd, J=8.0,1.6Hz, 2H), 7.46 7.39 (m, 3H), 6.29 (s,
1H), 2.41 (s, 3H), 2.11 (s, 3H), 2.04 (d, J=2.7Hz, 6H), 1.70 (s, 6H)
13C NMR(100MHz,CDCl3)δ159.1,152.9,135.1,130.4,128.6,126.6,51.2,41.6,
36.3,29.4,14.4
ESI-HRMS:C19H24N2NaO2[M+Na]+: value of calculation: 335.1730, experiment value: 335.1730.
Infer that products therefrom obtains structure according to data above as follows:It is illustrated as
Merit has synthesized target product.
Embodiment 26
The acetophenone oxime of 0.2 mM, the p-methoxyphenyl isocyanide of 0.2 mM, 1 milli is added in 25 milliliters of test tubes
Mole water, the four triphenyl phosphorus palladiums of 0.006 mM and the sodium acetate of 0.4 mM, add 2 milliliters of toluene as solvent,
After stirring is reacted 3 hours under the conditions of 80 DEG C, stop heating and stirring, be cooled to room temperature, add ethyl acetate after filtration and extract
Three times, magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, obtains target product, post layer used
Analysis eluent be volume ratio be the petroleum ether of 20:1: ethyl acetate mixed solvent, productivity is 58%.
The structural characterization data of products therefrom are as follows:
IR(KBr):2929,2836,1735,1599,1413,1372,1245,1177,1007,913cm-1
1H NMR(400MHz,CDCl3) δ 8.27 (s, 1H), 7.71 (d, J=6.6Hz, 2H), 7.51 7.40 (m, 5H),
6.89 (d, J=8.9Hz, 2H), 3.80 (s, 3H), 2.49 (s, 3H)
13C NMR(100MHz,CDCl3)δ160.6,156.6,152.7,134.7,130.7,130.0,128.7,126.8,
121.8,114.3,55.5,14.7ppm
ESI-HRMS:C16H16N2NaO3[M+Na]+Value of calculation: 307.1053, experiment value: 307.1057.
Infer that products therefrom obtains structure according to data above as follows:Explanation
Successfully synthesize target product.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the new method of a synthesizing amino methylcarbamoyl oximino ester derivant, it is characterised in that comprise the following steps:
In reaction bulb, adding aryl ketoxime, isonitrile and water is raw material, is that catalyst, alkali are as additive, You Jirong in palladium salt
Agent is reacting by heating under conditions of solvent, and gained reactant liquor is cooled to room temperature then purification after terminating by reaction, obtains described
Oxime carbamate derivant.
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 1, it is characterised in that:
Described aryl ketoxime is acetophenone oxime, 4-fluorophenethyl ketoxime, 4-chloro-acetophenone oxime, 4-itrile group acetophenone oxime, 3-chlorobenzene
Acetophenone oxime, 2-chloro-acetophenone oxime, 2-acetonaphthone oxime, 3,4-dimethoxy-acetophenone oxime, phenylpropyl alcohol ketoxime, benzo ring hexanone oxime, 6-
At least one in methoxyl group benzo cyclohexanone-oxime, benzocyclohepta ketoxime.
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 1, it is characterised in that:
Described isonitrile is tert-butyl isonitrile, normal-butyl isonitrile, 1,1,3,3-tetramethyl butyl isonitrile, cyclopenta isonitrile, hexamethylene
At least one in base isonitrile, 1-isonitrile base diamantane (obsolete), p-methoxyphenyl isonitrile.
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 1, it is characterised in that:
Described palladium salt is tetra-triphenylphosphine palladium, in three (dibenzalacetone) two palladium, bi triphenyl phosphorus palladium chloride at least
A kind of.
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 1, it is characterised in that:
The mol ratio of aryl ketoxime, isonitrile and water used is 1:1:(5～10).
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 1, it is characterised in that:
Palladium salt used is (0.01-0.05) with the mol ratio of aryl ketoxime: 1.
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 1, it is characterised in that:
Described organic solvent is toluene, toluene, DMF, acetonitrile, 1,2-dichloroethanes；Described additive
For sodium acetate or cesium carbonate.
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 1, it is characterised in that:
Described reacting by heating refers to stirring reaction 3～12h at 80～100 DEG C.
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 1, it is characterised in that:
Described purification refers to reacting liquid filtering, and then decompression is distilled off solvent to obtain crude product, then by crude product warp
Column chromatographic isolation and purification.
The new method of synthesizing amino methylcarbamoyl oximino ester derivant the most according to claim 9, it is characterised in that:
In described column chromatography, eluent used is the mixed solvent of petroleum ether and ethyl acetate；Petroleum ether and ethyl acetate
Between proportion value be (10～200): 1.
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