CN107652200B - A method of N- aryl Zhong Fang amide is synthesized using aryl hydrazine - Google Patents
A method of N- aryl Zhong Fang amide is synthesized using aryl hydrazine Download PDFInfo
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Abstract
The invention discloses a kind of methods using aryl hydrazine synthesis N- aryl Zhong Fang amide, aryl boric acid and aryl hydrazine are added into solvent, and major catalyst and co-catalyst, then separating-purifying obtains the N- aryl Zhong Fang amide as shown in formula III after carrying out heating reflux reaction, and being passed through CO in reaction process into reaction system makes 0.1~5MPa of pressure of reaction system.Synthetic method of the invention is succinctly efficient, and using substituted phenylhydrazines, stable in the air and the organic boronic and CO that are easy to get as reaction raw materials, Metal Palladium, as co-catalyst, efficiently synthesizes Zhong Fang amide as major catalyst, copper or iron under more mild reaction condition.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of side using aryl hydrazine synthesis N- aryl Zhong Fang amide
Method.
Background technique
Amido bond is one of chemical bond mostly important in organic chemistry, constitutes the peptide in the matter protein of life
Key just belongs to amido bond.Nowadays there is 16% to be directed to amido bond in all reactions in synthetic drug molecule according to statistics
Composition, depositing for amido bond also can be largely found in many natural products, pesticide, dyestuff, functional polymer material
?.The constructive method of traditional amido bond all uses carboxylic acid and its derivative (carboxylic acid, acyl chlorides, ester, acid anhydrides) and aminated compounds
By sloughing small molecule condensation into [(a) Luo, Q.-L.；Lv,L.；Li,Y.；Tan,J.-P.；Nan,W.；Hui,
Q.Eur.J.Org.Chem.2011,2011,6916；(b)Duangkamol,C.；Jaita,S.；Wangngae,S.；
Phakhodee,W.；Pattarawarapan,M.RSC Adv.2015,5,52624；(c)Bao,Y.S.；Zhaorigetu,B.；
Agula,B.；Baiyin,M.；Jia,M.J.Org.Chem.2014,79,803；(d)Li,Y.；Zhu,F.；Wang,Z.；
Rabeah,J.；Brückner,A.；Wu, X.-F.Chem Cat Chem.2017,9,915.], but such methods generally require
Harsh reaction condition such as needs to react under acid condition, high temperature, and also there are many researchs to have invented using novel in recent years
Substrate and amine come synthesizing amide, such as primary alconol, aldehyde, N- chloromethane amide [(a) Wang, Y.；Zhu,D.；Tang,L.；Wang,S.；
Wang,Z.Angew.Chem.Int.Ed.2011,50,8917；(b)Liu,Z.；Zhang,J.；Chen,S.；Shi,E.；Xu,
Y.；Wan,X.Angew.Chem.Int.Ed.2012,51,3231；(c)Xu,W.T.；Huang,B.；Dai,J.J.；Xu,J.；
Xu,H.J.Org.Lett.2016,18,3114.(d)Krishnamoorthy,R.；Lam,S.Q.；Manley,C.M.；Herr,
R.J.J.Org.Chem.2010,75,1251.], these reactions are novel enough, but atom utilization is lower, reaction process with
And post-processing is complicated.Therefore, it invents and a kind of efficiently synthesizes amide under mild conditions and the higher method of atom utilization is aobvious
It obtains particularly important.
Summary of the invention
It is above-mentioned to overcome the purpose of the present invention is to provide a kind of method using aryl hydrazine synthesis N- aryl Zhong Fang amide
Defect of the existing technology, synthetic method of the invention is succinctly efficient, and with substituted phenylhydrazines, stable in the air and what is be easy to get has
Machine boric acid and CO are reaction raw materials, Metal Palladium as major catalyst, copper or iron as co-catalyst, in more mild reaction item
Zhong Fang amide is efficiently synthesized under part.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A method of N- aryl Zhong Fang amide is synthesized using aryl hydrazine, the aryl boron as shown in formula I is added into solvent
Acid and the aryl hydrazine as shown in formula II and major catalyst and co-catalyst, then carry out separating-purifying after heating stirring reaction
The N- aryl Zhong Fang amide as shown in formula III is obtained, CO is passed through into reaction system in reaction process makes the pressure of reaction system
For 0.1~5MPa；
Wherein, R1And R2Selected from hydrogen, methyl, ethyl, fluorine, chlorine or bromine.
Further, the molar ratio of the aryl boric acid and aryl hydrazine is (10~1): 1.
Further, the molar ratio of the aryl boric acid, major catalyst and co-catalyst is (100~1): 1:1.
Further, the heating stirring reaction temperature is 20~150 DEG C, and the time is for 24 hours.
Further, the major catalyst is palladium acetate, palladium chloride, bi triphenyl phosphorus palladium chloride, 1,2- diphenyl
Any one in phosphorus ferrocene palladium chloride, four triphenyl phosphorus palladiums.
Further, the co-catalyst is copper powder, stannous chloride, copper chloride, cuprous iodide, copper oxide, nano oxygen
Change copper, iron chloride, frerrous chloride, any one in nano ferriferrous oxide.
Further, the solvent is methylene chloride, acetonitrile, DMF, DMSO, dioxane, n-hexane, hexamethylene, second
Nitrile, methyl phenyl ethers anisole, any one in toluene.
Further, the aryl boric acid as shown in formula I and the aryl hydrazine as shown in formula II and main reminder are added into solvent
After agent and co-catalyst, the concentration of aryl boric acid in a solvent is 0.05~2 mol/L.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention uses aryl boric acid, and aryl hydrazine, tri- component of gas CO directly synthesize N- aryl Zhong Fang amide, and use is organic
Aryl boric acid and aryl hydrazine do not need to react under severe conditions by insertion CO to constitute amido bond, and product is easy to point
From yield is higher.
Detailed description of the invention
Fig. 1 is product prepared by embodiment 11H NMR spectra；
Fig. 2 is product prepared by embodiment 113C NMR spectra；
Fig. 3 is product prepared by embodiment 21H NMR spectra；
Fig. 4 is product prepared by embodiment 213C NMR spectra；
Fig. 5 is product prepared by embodiment 31H NMR spectra；
Fig. 6 is product prepared by embodiment 313C NMR spectra；
Fig. 7 is product prepared by embodiment 41H NMR spectra；
Fig. 8 is product prepared by embodiment 413C NMR spectra；
Fig. 9 is product prepared by embodiment 51H NMR spectra；
Figure 10 is product prepared by embodiment 513C NMR spectra；
Figure 11 is product prepared by embodiment 61H NMR spectra；
Figure 12 is product prepared by embodiment 613C NMR spectra；
Figure 13 is product prepared by embodiment 71H NMR spectra；
Figure 14 is product prepared by embodiment 713C NMR spectra；
Figure 15 is product prepared by embodiment 81H NMR spectra；
Figure 16 is product prepared by embodiment 813C NMR spectra；
Figure 17 is product prepared by embodiment 91H NMR spectra；
Figure 18 is product prepared by embodiment 913C NMR spectra；
Figure 19 is product prepared by embodiment 101H NMR spectra；
Figure 20 is product prepared by embodiment 1013C NMR spectra；
Figure 21 is product prepared by embodiment 111H NMR spectra；
Figure 22 is product prepared by embodiment 1113C NMR spectra；
Figure 23 is product prepared by embodiment 121H NMR spectra；
Figure 24 is product prepared by embodiment 1213C NMR spectra；
Figure 25 is product prepared by embodiment 131H NMR spectra；
Figure 26 is product prepared by embodiment 1313C NMR spectra.
Specific embodiment
Embodiments of the present invention are described in further detail below:
A method of N- aryl Zhong Fang amide is synthesized using aryl hydrazine, the aryl boron as shown in formula I is added into solvent
Acid and the aryl hydrazine as shown in formula II and major catalyst and co-catalyst, wherein the molar ratio of aryl boric acid and aryl hydrazine is
The molar ratio of 10:1~1:1, aryl boric acid, major catalyst and co-catalyst are 100:1:1~1:1:1, and aryl boric acid is in solvent
In concentration be 0.05~2 mol/L, CO is passed through into reaction system makes 0.1~5MPa of pressure of reaction system, then exists
Separating-purifying obtains the N- aryl Zhong Fang amide as shown in formula III after carrying out heating stirring reaction for 24 hours at a temperature of 20~150 DEG C；
Wherein, R1And R2Selected from hydrogen, methyl, ethyl, fluorine, chlorine, bromine；Major catalyst is palladium acetate, palladium chloride, bi triphenyl
Phosphorus palladium chloride, 1,2- diphenylphosphine ferrocene palladium chloride (Pd (dppf) Cl2), any one in four triphenyl phosphorus palladiums；
Co-catalyst is copper powder, stannous chloride, copper chloride, cuprous iodide, copper oxide, nano cupric oxide, iron chloride, frerrous chloride, receives
Rice ferroso-ferric oxide in any one；Solvent be methylene chloride, acetonitrile, DMF, DMSO, dioxane, n-hexane, hexamethylene,
Acetonitrile, methyl phenyl ethers anisole, any one in toluene.
Below with reference to embodiment, the invention will be described in further detail:
Embodiment 1
The preparation of N- phenylbenzamaide:
The phenyl boric acid of 1.5mmol is dissolved in the reactor for filling 5mL methyl phenyl ethers anisole, 1mmol phenylhydrazine is added under stiring, with
0.05mmol palladium acetate is major catalyst, and 0.05mmol Cu is co-catalyst, and CO gas is passed through into reaction system to be made in system
Pressure reaches 2MPa, heating stirring 24 hours at 100 DEG C, with carrying out for TLC monitoring reaction, is concentrated after fully reacting, through column
Chromatography, obtains 99mg white solid, yield 50%, and structure of title compound formula is as follows:
As depicted in figs. 1 and 2, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.27(s,1H),8.00–
7.91 (m, 3H), 7.78 (d, J=7.6Hz, 2H), 7.65-7.49 (m, 3H), 7.36 (t, J=7.9Hz, 2H), 7.11 (t, J=
7.4Hz,1H).13C-NMR(101MHz,DMSO-d6)δ165.50,139.12,134.94,131.51,128.56,128.34,
127.60,123.61,120.30.
Embodiment 2
The preparation of N- (4- aminomethyl phenyl) benzamide:
The phenyl boric acid of 1mmol is dissolved in the reactor for filling 5mL methylene chloride, 1mmol is added under stiring to methyl
Phenylhydrazine, using 0.1mmol palladium chloride as major catalyst, 0.1mmol stannous chloride is co-catalyst, and CO gas is passed through into reaction system
Body makes pressure in system reach 1MPa, heating stirring 24 hours at 20 DEG C, is carried out with what TLC monitoring was reacted, after fully reacting
Concentration obtains 116mg white solid through column chromatography for separation, yield 55%, and structure of title compound formula is as follows:
As shown in Figure 3 and Figure 4, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ
10.17(s,1H),7.99–7.91(m,2H),7.70–7.62(m,2H),7.64–7.54(m,1H),7.53(dd,J
=8.2,6.5Hz, 2H), 7.16 (d, J=8.3Hz, 2H), 2.29 (s, 3H)13C-NMR(101MHz,DMSO-d6)δ165.28,
136.60,135.01,132.54,131.39,128.94,128.31,127.54,120.34,20.46.
Embodiment 3
The preparation of N- (4- chlorphenyl) benzamide:
The phenyl boric acid of 5mmol is dissolved in the reactor for filling 5mL acetonitrile, 1mmol is added under stiring to chlorophenyl hydrazine, with
0.1mmol bi triphenyl phosphorus palladium chloride is major catalyst, and 0.1mmol cuprous iodide is co-catalyst, is led into reaction system
Entering CO gas makes pressure in system reach 5MPa, heating stirring 24 hours at 80 DEG C, with carrying out for TLC monitoring reaction, reacts
Concentration after completely obtains 111mg white solid through column chromatography for separation, yield 48%, and structure of title compound formula is as follows:
As shown in Figure 5 and Figure 6, product nuclear-magnetism characterizes:1H-NMR(400MHz,Chloroform-d)δ7.91–7.86(m,
2H), 7.67-7.56 (m, 3H), 7.52 (dd, J=8.2,6.6Hz, 2H), 7.39-7.33 (m, 2H)13C-NMR(101MHz,
Chloroform-d)δ165.16,135.98,134.13,131.59,129.06,128.64,128.40,126.50,120.88
Embodiment 4
The preparation of 4- Methyl-N-phenyl benzamide:
The 4- methylphenylboronic acid of 10mmol is dissolved in the reactor for filling 5mLDMF, 1mmol phenylhydrazine is added under stiring,
With 0.1mmol Pd (dppf) Cl2For catalyst, 0.1mmol copper chloride is co-catalyst, and CO gas is passed through into reaction system
Reach pressure in system 0.1MPa (in balloon, normal pressure), heating stirring 24 hours at 150 DEG C, with TLC monitoring reaction into
Row, is concentrated after fully reacting, through column chromatography for separation, obtains 129mg white solid, yield 61%, structure of title compound formula is such as
Under:
As shown in Figure 7 and Figure 8, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.14(s,1H),7.87(d,
J=8.2Hz, 2H), 7.77 (d, J=9.5Hz, 2H), 7.34 (t, J=7.1Hz, 4H), 7.09 (t, J=7.4Hz, 1H), 2.39
(s,3H).13C-NMR(101MHz,DMSO-d6)δ165.29,141.49,139.20,132.05,128.85,128.52,
127.63,123.48,120.31,20.97.
Embodiment 5
The preparation of the bromo- N- phenylbenzamaide of 4-:
By being dissolved in the reactor for filling 5mLDMSO to bromobenzeneboronic acid for 2mmol, 1mmol phenylhydrazine is added under stiring, with
0.02mmol tetra-triphenylphosphine palladium is catalyst, and 0.02mmol copper powder is co-catalyst, and CO gas is passed through into reaction system to be made
Pressure is 0.1MPa (in balloon, normal pressure) in system, and heating stirring 24 hours at 150 DEG C are carried out with what TLC monitoring was reacted,
It is concentrated after fully reacting, through column chromatography for separation, obtains 132mg white solid, yield 48%, structure of title compound formula is as follows:
As shown in Figure 9 and Figure 10, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.31(s,1H),7.95–
7.88 (m, 2H), 7.81-7.70 (m, 4H), 7.40-7.32 (m, 2H), 7.12 (t, J=7.4Hz, 1H)13C-NMR(101MHz,
DMSO-d6)δ164.49,138.91,133.97,131.36,129.76,128.59,125.27,123.79,120.37.
Embodiment 6
The preparation of 3- methyl-N- (2- aminomethyl phenyl) benzamide:
Methylphenylboronic acid between 2mmol is dissolved in the reactor for filling 5mL dioxane, 1mmol is added under stiring
O-methyl-benzene hydrazine, with 0.5mmol Pd (dppf) Cl2For catalyst, 0.5mmol nano cupric oxide is co-catalyst, to reactant
CO gas is passed through in system makes pressure in system reach 3MPa, heating stirring 24 hours at 100 DEG C, with TLC monitoring reaction into
Row, is concentrated after fully reacting, through column chromatography for separation, obtains 117mg white solid, yield 52%, structure of title compound formula is such as
Under:
As is illustrated by figs. 11 and 12, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ9.86(s,1H),7.83–
7.74(m,2H),7.46–7.37(m,2H),7.36–7.13(m,4H),2.40(s,3H),2.23(s,3H).13C-NMR
(101MHz,DMSO-d6)δ165.32,137.67,136.41,134.47,133.69,132.04,130.25,128.26,
128.14,126.57,125.95,125.91,124.70,20.95,17.90.
Embodiment 7
The preparation of 3- methyl-N- (4- aminomethyl phenyl) benzamide:
Methylphenylboronic acid between 2mmol is dissolved in the reactor for filling 6mL n-hexane, 1mmol pairs is added under stiring
Procarbazine, using 0.05mmol palladium chloride as catalyst, 0.05mmol iron chloride is co-catalyst, and CO is passed through into reaction system
Gas makes pressure in system reach 2MPa, heating stirring 24 hours at 90 DEG C, with carrying out for TLC monitoring reaction, fully reacting
After be concentrated, through column chromatography for separation, obtain 128mg white solid, yield 57%, structure of title compound formula is as follows:
As shown in Figure 13 and Figure 14, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.12(s,1H),7.83–
7.71 (m, 2H), 7.72-7.57 (m, 2H), 7.50-7.33 (m, 2H), 7.15 (d, J=8.2Hz, 2H), 2.40 (s, 3H),
2.28(s,3H).13C-NMR(101MHz,DMSO-d6)δ165.39,137.59,136.66,135.03,132.47,131.94,
128.92,128.19,128.04,124.71,120.31,20.92,20.45.
Embodiment 8
The preparation of 3- methyl-N- (4- chlorphenyl) benzamide:
Methylphenylboronic acid between 1mmol is dissolved in the reactor for filling 5mL hexamethylene, 1mmol pairs is added under stiring
Chlorophenyl hydrazine, using 1mmol bi triphenyl phosphorus palladium chloride as catalyst, 1mmol frerrous chloride is co-catalyst, into reaction system
Being passed through CO gas makes pressure in system reach 5MPa, heating stirring 24 hours at 80 DEG C, is carried out with what TLC monitoring was reacted, instead
It should be concentrated afterwards completely, through column chromatography for separation, obtain 135mg white solid, yield 55%, structure of title compound formula is as follows:
As shown in Figure 15 and Figure 16, product nuclear-magnetism characterizes:1H-NMR(400MHz,Chloroform-d)δ7.73–7.58
(m,4H),7.45–7.32(m,4H),2.46(s,3H).13C-NMR(101MHz,Chloroform-d)δ165.83,138.83,
136.54,134.63,132.80,129.48,129.11,128.73,127.74,123.92,121.35,21.40.
Embodiment 9
The preparation of 4- methyl-N- (4- fluorophenyl) benzamide:
By being dissolved in the reactor for filling 10mL acetonitrile to methylphenylboronic acid for 0.5mmol, 1mmol pairs is added under stiring
Fluorine phenylhydrazine, using 0.1mmol tetra-triphenylphosphine palladium as major catalyst, 0.1mmol nano ferriferrous oxide is co-catalyst, Xiang Fanying
CO gas is passed through in system makes pressure in system reach 2MPa, heating stirring 24 hours at 80 DEG C, with TLC monitoring reaction into
Row, is concentrated after fully reacting, through column chromatography for separation, obtains 69mg white solid, yield 60%, structure of title compound formula is such as
Under:
As shown in Figure 17 and Figure 18, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.23(s,1H),7.91–
7.84 (m, 2H), 7.84-7.75 (m, 2H), 7.34 (d, J=7.9Hz, 2H), 7.24-7.15 (m, 2H), 2.39 (s, 3H)13C-
NMR(101MHz,DMSO-d6) δ 165.21,158.16 (d, J=239Hz), 141.59,135.55,131.83,128.88,
127.62,122.08 (d, J=7.9Hz), 115.11 (d, J=22.2Hz)
Embodiment 10
The preparation of 4- ethyl-N- (3- aminomethyl phenyl) benzamide:
By being dissolved in the reactor for filling 5mL toluene to ethyl phenyl boric acid for 1.5mmol, it is added between 1mmol under stiring
Procarbazine, with 0.05mmol Pd (dppf) Cl2For major catalyst, 0.05mmol cuprous iodide is co-catalyst, to reactant
CO gas is passed through in system makes pressure in system reach 3MPa, heating stirring 24 hours at 120 DEG C, with TLC monitoring reaction into
Row, is concentrated after fully reacting, through column chromatography for separation, obtains 143mg white solid, yield 60%, structure of title compound formula is such as
Under:
As illustrated in figures 19 and 20, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.10(s,1H),7.95–
7.82 (m, 2H), 7.67-7.51 (m, 2H), 7.37 (d, J=8.0Hz, 2H), 7.22 (t, J=7.8Hz, 1H), 6.92 (d, J=
7.5Hz, 1H), 2.69 (q, J=7.6Hz, 2H), 2.31 (s, 3H), 1.22 (t, J=7.6Hz, 3H)13C-NMR(101MHz,
DMSO-d6)δ165.29,147.61,139.12,137.65,133.85,132.39,128.37,127.70,124.18,
120.79,117.43,28.04,21.20,15.41.
Embodiment 11
The preparation of 4- ethyl-N- (4- chlorphenyl) benzamide:
By being dissolved in the reactor for filling 5mL methyl phenyl ethers anisole to ethyl phenyl boric acid for 1.5mmol, 1mmol is added under stiring
To chlorophenyl hydrazine, with 0.05mmol Pd (dppf) Cl2For catalyst, 0.05mmol Cu is co-catalyst, is led into reaction system
Entering CO gas makes pressure in system reach 2MPa, heating stirring 24 hours at 100 DEG C, with carrying out for TLC monitoring reaction, reacts
Concentration after completely obtains 145mg white solid through column chromatography for separation, yield 56%, and structure of title compound formula is as follows:
As shown in figure 21 and figure, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.27(s,1H),7.93–
7.73 (m, 4H), 7.48-7.27 (m, 4H), 2.69 (q, J=7.6Hz, 2H), 1.21 (t, J=7.6Hz, 3H)13C-NMR
(101MHz,DMSO-d6)δ165.47,147.85,138.21,132.10,128.44,127.75,127.73,127.08,
121.76,28.04,15.32.
Embodiment 12
The preparation of the chloro- N- of 4- (3- aminomethyl phenyl) benzamide:
By being dissolved in chlorophenylboronic acid in the reactor for filling 5mL methyl phenyl ethers anisole for 1.5mmol, it is added between 1mmol under stiring
Procarbazine, with 0.05mmol Pd (dppf) Cl2For major catalyst, 0.05mmol cuprous iodide is co-catalyst, to reactant
CO gas is passed through in system makes pressure in system reach 2MPa, heating stirring 24 hours at 100 DEG C, with TLC monitoring reaction into
Row, is concentrated after fully reacting, through column chromatography for separation, obtains 147mg white solid, yield 60%, structure of title compound formula is such as
Under:
As shown in figure 23 and figure 24, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.23(s,1H),8.13–
7.81 (m, 2H), 7.70-7.46 (m, 4H), 7.24 (t, J=7.8Hz, 1H), 6.94 (d, J=7.7Hz, 1H), 2.31 (s,
3H).13C-NMR(101MHz,DMSO-d6)δ164.29,138.83,137.74,136.30,133.65,129.54,128.42,
128.40,124.48,120.93,117.58,21.17.
Embodiment 13
The preparation of the chloro- N- of 4- (4- fluorophenyl) benzamide:
By being dissolved in the reactor for filling 5mL toluene to chlorophenylboronic acid for 2mmol, 1mmol is added under stiring to fluorobenzene
Hydrazine, with 0.2mmol Pd (dppf) Cl2For catalyst, 0.2mmol stannous chloride is co-catalyst, and CO is passed through into reaction system
Gas makes pressure in system reach 3MPa, heating stirring 24 hours at 120 DEG C, with carrying out for TLC monitoring reaction, fully reacting
After be concentrated, through column chromatography for separation, obtain 137mg white solid, yield 55%, structure of title compound formula is as follows:
As illustrated in figs. 25 and 26, product nuclear-magnetism characterizes:1H-NMR(400MHz,DMSO-d6)δ10.36(s,1H),8.05–
7.91 (m, 2H), 7.87-7.74 (m, 2H), 7.62 (d, J=8.6Hz, 2H), 7.20 (t, J=8.9Hz, 2H)13C-NMR
(101MHz,DMSO-d6) δ 164.29,158.34 (d, J=240.5Hz), 136.39,135.27 (d, J=2.6Hz),
133.44,129.54,128.44,122.24 (d, J=7.9Hz), 115.17 (d, J=22.3Hz).
Claims (6)
1. a kind of method using aryl hydrazine synthesis N- aryl Zhong Fang amide, which is characterized in that be added as shown in formula I into solvent
Aryl boric acid and the aryl hydrazine as shown in formula II and major catalyst and co-catalyst, after then carrying out heating stirring reaction
Separating-purifying obtains the N- aryl Zhong Fang amide as shown in formula III, and being passed through CO into reaction system in reaction process makes reactant
The pressure of system is 0.1~5MPa；
Wherein, R1And R2Selected from hydrogen, methyl, ethyl, fluorine, chlorine or bromine；
The major catalyst is palladium acetate, palladium chloride, bi triphenyl phosphorus palladium chloride, 1,2- diphenylphosphine ferrocene dichloride
Any one in palladium, four triphenyl phosphorus palladiums；
The co-catalyst is copper powder, stannous chloride, copper chloride, cuprous iodide, copper oxide, nano cupric oxide, iron chloride, chlorine
Change ferrous, any one in nano ferriferrous oxide.
2. a kind of method using aryl hydrazine synthesis N- aryl Zhong Fang amide according to claim 1, which is characterized in that institute
The molar ratio of the aryl boric acid and aryl hydrazine stated is (10~1): 1.
3. a kind of method using aryl hydrazine synthesis N- aryl Zhong Fang amide according to claim 1, which is characterized in that institute
The molar ratio of aryl boric acid, major catalyst and the co-catalyst stated is (100~1): 1:1.
4. a kind of method using aryl hydrazine synthesis N- aryl Zhong Fang amide according to claim 1, which is characterized in that institute
The heating stirring reaction temperature stated is 20~150 DEG C, and the time is for 24 hours.
5. a kind of method using aryl hydrazine synthesis N- aryl Zhong Fang amide according to claim 1, which is characterized in that institute
The solvent stated is methylene chloride, in acetonitrile, DMF, DMSO, dioxane, n-hexane, hexamethylene, acetonitrile, methyl phenyl ethers anisole, toluene
Any one.
6. a kind of method using aryl hydrazine synthesis N- aryl Zhong Fang amide according to claim 1, which is characterized in that
After the aryl boric acid as shown in formula I and the aryl hydrazine as shown in formula II and major catalyst and co-catalyst is added in solvent, virtue
The concentration of ylboronic acid in a solvent is 0.05~2 mol/L.
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