CN101012170B - N-arylation method in water solution - Google Patents
N-arylation method in water solution Download PDFInfo
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- CN101012170B CN101012170B CN2007100268602A CN200710026860A CN101012170B CN 101012170 B CN101012170 B CN 101012170B CN 2007100268602 A CN2007100268602 A CN 2007100268602A CN 200710026860 A CN200710026860 A CN 200710026860A CN 101012170 B CN101012170 B CN 101012170B
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Abstract
The invention discloses an N-arylating method in the solution, which is characterized by the following: adopting aryl halogenated and amine or nitrogenous heterocyclic aromatic compound as raw material; using water as solvent; heating under indoor temperature or traditional heating or auxiliary microwave heating; making alkaline metal or carbonate of alkaline metal, fluoride, phosphate or hydroxide as alkaline; adding surface activator; forming ternary catalytic system (copper catalyst, oxalyl hydrazine and ketone) to catalyze C-N coupling reaction.
Description
Technical field
The present invention relates to technical field of chemistry, relate in particular to a kind of N-arylation method.
Technical background
Arylamines is the important compound of a class, extensively is present in to have in the natural of physiologically active and the non-natural product, and the C-N key is formed the extensive attention that the research of reacting is subjected to people always.
The Ullmann reaction of carbon-nitrogen cross-coupling was from existing so far history (Ley, the S.V. for a long time of reported first in 1903; Thomas, A. W. Angew. Chem. Int. Ed. 2003,42,5400 and relevant quoted passage).Because this reaction is normally in high boiling polar solvent, carry out under at the copper powder of high temperature, catalytic amount or equivalent as the condition of catalyzer, thereby there is long reaction time, the subsequent disposal difficulty of reaction, the not high drawback of reaction product complexity and reaction yield.Nineteen eighty-three, people such as Migita have found that the earliest the catalytic C-N key of Pd forms reaction (Kosugi, M.; Kameyama, M.; Migita, T.Chem.Lett.1983,927), 1994, Buchwald and Hartwig developed the catalytic C-N key of Pd simultaneously independently and have formed reaction ((a) Guram, A.S.; Buchwald, S.L.J.Am.Chem.Soc.1994,116,7901; (b) Paul, F.; Patt, J.; Hartwig, J.F.J.Am.Chem.Soc.1994,116,5969).Adopt the catalytic C-N key of Pd to form the more traditional Ul lmann reaction of reaction and have condition gentleness relatively, reacting phase is to advantage such as simple, need to use high boiling organic solvent but also exist, toxicity is bigger, the price height, and to the shortcomings such as dependency of unstable and hypertoxic organophosphorus ligand, therefore, in recent years, the catalytic Ullmann of Cu reacts the very big development of having got back.People's such as Buckwald patent PCT/US02/12785 (WO 02/085838) and Ley, S.V. and; Thomas, the summary of A.W. (Ley, S.V.; Thomas, A.W.Angew.Chem.Int.Ed.2003,42,5400) in introduced the formation method of the C-N key under the copper katalysis.By adding suitable part, use the mantoquita of catalytic amount, the Ullmann reaction can be carried out under comparatively gentle condition.Yet, no matter adopt which kind of metal catalyst, the N-arylation reaction of being reported in these documents is normally carried out in organic solvent.And all price is higher for the part majority that is adopted, and is difficult to obtain.Therefore, inventing a kind of economy, environmental friendliness and the wide reaction process of suitable substrates scope is the objective requirement of current such reaction, and good application prospects will be arranged.
People such as Pell ó n have reported the catalytic C-N linked reaction of copper in the aqueous solution ((a) Pell ó n, R.F.; Carrasco, R.; Rod é s, L.Synth.Comm.1993,23 (10), 1447; (b) Pel l6n, R.F.; Est é vez-Braun, A.; Docampo, M.L.; Mart í n, A.; Ravelo, A.G.Synlett2005, (10), 1606), have the aryl halides of carboxyl and the reaction of amine but only be confined to the ortho position.People such as Twieg reported cuprous iodide catalytic be synthetic method (Lu, the Z. of arylamines in the aqueous solution of part with the 2-dimethylaminoethanol; Twieg, R.J.TetrahedronLett.2005,46,2997), but only be confined to aromatic halogenate and amino acid or with certain water miscible short-chain fat amine is arranged and has the reaction of the aliphatic amide of hydroxyl.Reported the linked reaction of aromatic halogenate and ammoniacal liquor or short-chain alkyl amine in the catalytic aqueous solution of copper sulfate in the European patent EP 0549263.But above-mentioned reaction all can only be carried out at specific compound, thereby can not promote the use of.And (Huang, X. are reacted in the formation of C-N key in the catalytic aqueous solution of Pd of people such as Buchwald report; Anderson, K.W.; Zim, D.; Jiang, L.; Klapars, A.; Buchwald, S.L.J.Am.Chem.Soc.2003,125,6653) then the cost because of catalyst system have defective.It is part with the acylhydrazone that the applicant once proposed patent application (CN 1803760A), overcome the shortcoming that exists in the conventional art C-N linked reaction method to a certain extent, provide a kind of easy, quick, reaction conditions is gentle, the N-arylation method of environmental friendliness and process economy, but the reaction effect for some specific substrate is good not enough, and there is restriction in the scope of application.
The present invention is under Guangdong Province's natural science fund assistance, the research of carrying out for the N-arylation method that a kind of economy, gentleness, environmental friendliness, wide application range of substrates are provided.
Summary of the invention
The object of the present invention is to provide a kind of easy, reaction conditions is gentle, the N-arylation method of wide application range of substrates, environmental friendliness, process economy, overcomes the shortcoming that exists in the C-N linked reaction method in the prior art.
The present invention is the formation method of C-N key in a kind of aqueous solution, with aryl halides and amine or nitrogen heterocyclic ring aromatic compound is raw material, with water as solvent, reaction or employing traditional heating or microwave-assisted heating under room temperature, carbonate, fluorochemical, phosphoric acid salt and oxyhydroxide with basic metal or alkaline-earth metal are alkali, by adding tensio-active agent, it is characterized in that the three-element catalytic system catalysis C-N linked reaction that constitutes with various copper catalysts, oxalyl hydrazine and ketone.
Involved reaction can adopt following reaction formula to represent among the present invention:
Wherein X-is selected from bromine or iodine.
R is selected from the substituting group of 2-on the aromatic ring or 3-or 4-position, or two on the aromatic ring replaces or multi-substituent; Can be H ,-NO2 ,-CN ,-COOH, ethanoyl, alkyl, alkoxyl group, aryl, halogen, trifluoromethyl etc. but not only be confined to these substituting groups.
R
1R
2NH is selected from primary amine or secondary amine, can be aromatic amine, aliphatic amide or nitrogen-containing heterocycle compound; Specifically comprise and contain the straight or branched alkyl, the cycloalkyl of C5-C7, benzyl, (substituting group is an alkyl to substituted benzyl, alkoxyl group etc.) etc. Armeen, secondary amine, or five to the heptatomic cyclic secondary amine, or contains the primary amine of aromatic substituent (aromatic substituent is benzene or has alkyl, substituent benzene such as alkoxyl group).
R
1R
2NH also can be selected from and contain NH intra-annular heterocyclic aromatic compound (can have one or more substituting groups on the heterocycle, substituting group can be an alkyl, aryl etc.), as imidazoles, pyrroles, pyrazoles, glyoxal ethyline, benzoglyoxaline, benzo nitrogen triazole etc.
It is characterized in that: described catalyzer is a copper catalyst, and described part is two parts of oxalyl hydrazine and ketone.
Concrete reaction process of the present invention is: copper catalyst, oxalyl hydrazine, ketone, aryl halides, amine, alkali, tensio-active agent and water are added in microwave reaction pipe or the round-bottomed flask successively, adopt the mode stirring reaction of microwave-assisted heating or common heating bath heating or direct room temperature reaction; After reaction finished, separating reaction mixed solution and purifying obtained N-arylation product.
Below the inventive method is further described:
(1) with water be reaction solvent, inexpensive, environmental friendliness;
(2) reaction can at room temperature be carried out, and the reaction times is 24-120h, is preferably 48-96h; The reaction heating can be adopted the mode of microwave-assisted heating or common heating bath heating.During the microwave-assisted heating, temperature of reaction is 60-180 ℃, is preferably 80-140 ℃, and the reaction times is 1-30min, is preferably 2-10min; When common heating bath was heated, temperature of reaction was 50-100 ℃, is preferably 80-100 ℃, and the reaction times is 2-24h, is preferably 4-12h;
(3) reactant aryl halides can be that replace or non-replacement, and the mol ratio of aryl halides and amine is preferably 1: 1 to 1: 4;
(4) employed copper catalyst can be the oxide compound of metallic copper, copper and various monovalence or cupric salt such as cupric oxide, Red copper oxide, copper sulfate, cupric nitrate, cupric chloride, cuprous chloride, cuprous iodide, neutralized verdigris etc. but be not limited only to that these are several, and the mol ratio of catalyzer and substrate aryl halides is preferably 1: 40 to 1: 2;
(5) employed part is two parts of oxalyl hydrazine and ketone, ketone can be chain ketone or cyclic ketones, can be single ketones or diketone, as acetone, butanone, 2,5 own-diketone, 2,3 fourths-diketone, cyclopentanone, pimelinketone etc. but be not limited only to that these are several, the mole of used part oxalyl hydrazine and ketone are preferably than being 1: 1 to 1: 6; The mole of hydrazides and catalyzer is preferably than being 2: 1 to 20: 1;
(6) used alkali can be carbonate, phosphoric acid salt, fluorochemical, borate and the oxyhydroxide etc. of basic metal or alkaline-earth metal but be not limited only to that these are several; The mol ratio of alkali and substrate aryl halides is preferably 1: 1 to 3: 1;
(7) employed tensio-active agent can be quaternary ammonium salts, season phosphonium salt class, dodecane sulfonate class, PEG class but but be not limited only to that these are several; The mol ratio of tensio-active agent and substrate aryl halides is preferably 1: 20 to 1: 1.
That the inventive method has is simple to operate, wide application range of substrates, product simply are easy to characteristics such as separation, productive rate height, process economy and environmental friendliness.And because the handiness of reaction conditions, can be according to actual needs, the mode (reaction times is short) of selecting room temperature reaction (energy-conservation, as be adapted to heat-labile substrate, but the reaction times to be longer relatively) accordingly or adopting microwave-assisted to heat.In addition, with water as reaction solvent, with the reacting phase ratio of reporting in the document of the same type, effectively improved the environment friendly of reaction, conform to the requirement of Green Chemistry development more, especially wide application range of substrates is having broad application prospects aspect the preparation of natural product, medicine and agricultural chemicals.
Embodiment
Below in conjunction with embodiment content of the present invention is described further.
Synthesizing of embodiment 1:N-p-methoxyphenyl aniline
With 2mg (0.025 mmol) CuO, 24mg (0.2mmol) oxalyl hydrazine, 114mg (1.0mmol) 2,5-hexanedione, 187mg (1.0mmol) be to the methoxyl group bromobenzene, 279mg (3.0mmol) aniline, 112mg (2.0mmol) KOH, 32mg (0.1mmol) TBAB, 5.0ml H
2O adds in the 50ml round-bottomed flask, stirring reaction 72h under the room temperature condition.After reaction stops, use ethyl acetate extraction, washing, the saturated common salt washing behind the anhydrous magnesium sulfate drying, is filtered, underpressure distillation is desolvated, the reaction mixture that obtains is purified by [eluent: petrol ether/ethyl acetate (30: 1)] through the silicagel column column chromatography for separation, gets N-p-methoxyphenyl aniline 165mg, yield 83%.
ESI-MS：m/z＝200[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝7.15-7.09(m，2H)，6.98(d，J＝8.7Hz，2H)，6.83-6.74(m，5H)，5.45(brs，1H)，3.71(s，3H)。
Synthesizing of embodiment 2:N-phenylbenzylamine
With 5mg (0.025mmol) CuI, 59mg (0.5mmol) oxalyl hydrazine, 294mg (3.0mmol) pimelinketone, 102mg (0.5mmol) iodobenzene, 214mg (2.0mmol) benzylamine, 84mg (1.5mmol) KOH, 80mg (0.25mmol) TBAB, 1.5ml H
2O adds in the 8ml microwave reaction pipe, and 80W reacts 2min under 130 ℃ of conditions.After reaction stops, use ethyl acetate extraction, washing, the saturated common salt washing behind the anhydrous magnesium sulfate drying, is filtered, underpressure distillation is desolvated, the reaction mixture that obtains is purified by [eluent: petrol ether/ethyl acetate (30: 1)] through the silicagel column column chromatography for separation, gets N-phenylbenzylamine 87mg, yield 95%.
ESI-MS：m/z＝184[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝7.27-7.16(m，5H)，7.09-7.04(m，2H)，6.61(t，J＝7.5Hz,2H)，6.52(d，J＝7.5Hz，1H)，4.21(s，2H)，3.90(brs，1H)。
Synthesizing of embodiment 3:N-p-nitrophenyl aniline
With 19mg (0.1mmol) CuI, 59mg (0.5mmol) oxalyl hydrazine, 57mg (0.5mmol) 2,5-hexanedione, 202mg (1.0mmol) be to the nitro bromobenzene, 372mg (4.0mmol) aniline, 424mg (2.0mmol) K
3PO
4, 80mg (0.25mmol) TBAB, 5.0ml H
2O adds in the 50ml round-bottomed flask, stirring reaction 48h under the room temperature condition.After reaction stops, use ethyl acetate extraction, washing, the saturated common salt washing behind the anhydrous magnesium sulfate drying, is filtered, underpressure distillation is desolvated, the reaction mixture that obtains is purified by [eluent: petrol ether/ethyl acetate (10: 1)] through the silicagel column column chromatography for separation, gets N-p-nitrophenyl aniline 160mg, yield 75%.
ESI-MS：m/z＝215[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝8.02(d，J＝9.?0Hz，2H)，7.30(m，2H)，7.17-7.05(m，3H)，6.86(d，J＝9.0Hz，2H)，6.29(s，1H)。
Synthesizing of embodiment 4:N-o-methyl-phenyl-benzylamine
With 63mg (0.25mmol) CuSO
45H
2O, 59mg (0.5mmol) oxalyl hydrazine, 216mg (3.0mmol) butanone, the adjacent methyl bromobenzene of 171mg (1.0mmol), 321mg (3.0mmol) benzylamine, 168mg (3.0mmol) KOH, 322mg (1.0mmol) TBAB, 10ml H
2O adds in the 50ml round-bottomed flask, reflux 12h.After reaction stops, use ethyl acetate extraction, washing, the saturated common salt washing behind the anhydrous magnesium sulfate drying, is filtered, underpressure distillation is desolvated, the reaction mixture that obtains is purified by [eluent: petrol ether/ethyl acetate (30: 1)] through the silicagel column column chromatography for separation, gets N-o-methyl-phenyl-benzylamine 138mg, yield 70%.
ESI-MS：m/z＝198[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝7.31-7.16(m，5H)，7.03-6.97(m，2H)，6.61-6.51(m，2H)，4.29(s，2H)，3.78(brs，1H)，2.09(s，3H)。
Embodiment 5:N-is synthetic to the acetylphenyl benzylamine
With 14mg (0.1mmol) Cu
2O, 30mg (0.2 mmol) oxalyl hydrazine, 126mg (1.5mmol) cyclopentanone, 100mg (0.5mmol) be to the ethanoyl bromobenzene, 214mg (2.0mmol) benzylamine, 325mg (1.0mmol) Cs
2CO
3, 136mg (0.5mmol) SDS-Na, 1.5ml H
2O adds in the 8ml microwave reaction pipe, and 80W reacts 10min under 80 ℃ of conditions.After reaction stops; use ethyl acetate extraction; washing; the saturated common salt washing behind the anhydrous magnesium sulfate drying, is filtered; underpressure distillation is desolvated; the reaction mixture that obtains is purified by [eluent: petrol ether/ethyl acetate (5: 1)] through the silicagel column column chromatography for separation, gets N-to acetylphenyl benzylamine 96mg, yield 85%.
ESI-MS：m/z＝226[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝7.82(d，J=8.7Hz，2H)，7.34-7.30(m，5H)，6.60(d，J=8.7Hz，2H)，4.62(brs，1H)，4.41(d，J=4.8Hz，2H)，2.50(s，3H)。
Synthesizing of embodiment 6:N-p-methoxyphenyl morphine quinoline
With 7mg (0.1mmol) Cu, 59mg (0.5mmol) oxalyl hydrazine, 228mg (2.0mml) 2,5-hexanedione, 187mg (1.0mmol) be to the methoxyl group bromobenzene, 174mg (2.0mmol) morphine quinoline, 112mg (2.0mmol) KOH, 161mg (0.5mmol) TBAB, 10ml H
2O adds in the 50ml round-bottomed flask, reflux 6h.After reaction stops, use ethyl acetate extraction, washing, the saturated common salt washing behind the anhydrous magnesium sulfate drying, is filtered, underpressure distillation is desolvated, the reaction mixture that obtains is purified by [eluent: petrol ether/ethyl acetate (20: 1)] through the silicagel column column chromatography for separation, gets N-p-methoxyphenyl morphine quinoline 129mg, yield 67%.
ESI-MS：m/z＝194[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝6.92-6.84(m，4H)，3.88(t，J＝4.7Hz，4H)，3.48(s，3H)，3.07(t，J＝4.7Hz，4H)。
Synthesizing of embodiment 7:N-p-methoxyphenyl-N-n-propyl amine
With 2mg (0.025mmol) CuO, 30mg (0.25mmol) oxalyl hydrazine, 87mg (1.5mmol) acetone, 117mg (0.5mmol) be to the methoxyl group iodobenzene, 118mg (2.0mmol) Tri N-Propyl Amine, 56mg (1.0mmol) KOH, PEG400 (0.2mL), 1.5ml H
2O adds in the 8ml microwave reaction pipe, and 80W reacts 5min under 120 ℃ of conditions.After reaction stops, use ethyl acetate extraction, washing, the saturated common salt washing behind the anhydrous magnesium sulfate drying, is filtered, underpressure distillation is desolvated, the reaction mixture that obtains is purified by [eluent: petrol ether/ethyl acetate (30: 1)] through the silicagel column column chromatography for separation, gets N-p-methoxyphenyl-N-n-propyl amine 55mg, yield 67%.
ESI-MS：m/z＝166[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝6.79(d，J＝9.0，2H)，6.59(d，J＝8.7，2H)，3.76(s，3H)，3.09(t，J＝7.2Hz，2H)，2.88(brs，1H)，1.67-1.56(m，2H)，1.49-1.41(m，2H)，0.98(t，J＝7.2Hz，3H)。
Synthesizing of embodiment 8:N-p-methoxyphenyl imidazoles
With 4mg (0.05mmol) CuO, 30mg (0.25mmol) oxalyl hydrazine, 57mg (0.5mml) 2,5-hexanedione, 94mg (0.5mmol) be to the methoxyl group bromobenzene, 136mg (2.0mmol) imidazoles, 138mg (1.0mmol) K
2CO
3, 80mg (0.25mmol) TBAB, 1.5ml H
2O adds in the 8ml microwave reaction pipe, and 80W reacts 5min under 140 ℃ of conditions.After reaction stops, using ethyl acetate extraction, washing, saturated common salt washing, behind the anhydrous magnesium sulfate drying, filter, underpressure distillation is desolvated, the reaction mixture that obtains is purified by [eluent: pure ethyl acetate] through the silicagel column column chromatography for separation, gets N-p-methoxyphenyl imidazoles 77mg, yield 89%.
ESI-MS：m/z＝175[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝7.75(s，1H)，7.29(d，J＝8.7Hz，2H)，7.18(d，J＝7.2Hz，2H)，6.97(d，J＝8.7Hz，2H)，3.85(s，3H)。
Synthesizing of embodiment 9:N-p-methoxyphenyl benzoglyoxaline
With 8mg (0.1mmol) CuO, 59mg (0.5mmol) oxalyl hydrazine, 294mg (3.0mml) pimelinketone, 94mg (0.5mmol) is to the methoxyl group bromobenzene, 177mg (1.5mmol) benzoglyoxaline, 28mg (0.5mmol) KOH, 255mg (0.5mmol) n-hexadecyl three normal-butyl bromination phosphines, 1.5ml H
2O adds in the 8ml microwave reaction pipe, and 80W reacts 10min under 140 ℃ of conditions.After reaction stops, use ethyl acetate extraction, washing, the saturated common salt washing behind the anhydrous magnesium sulfate drying, is filtered, underpressure distillation is desolvated, the reaction mixture that obtains is purified by [eluent: petrol ether/ethyl acetate (1: 3)] through the silicagel column column chromatography for separation, gets N-p-methoxyphenyl benzoglyoxaline 73mg, yield 65%.
ESI-MS：m/z＝225[M+H]
+；
1H?NMR(300MHz，CDCl
3)：δ＝8.06(s，1H)，7.88-7.85(m，1H)，7.47-7.31(m，5H)，7.07(d，J＝8.7Hz，2H)，3.90(s，3H)。
Claims (7)
1. the N-arylation method in the aqueous solution may further comprise the steps:
(1) catalyzer, part, aryl halides, amine, alkali, tensio-active agent and water are added in the reaction vessel successively, adopt the mode stirring reaction of microwave-assisted heating or common heating bath heating or direct room temperature reaction, reaction expression is as follows:
In the formula, X-is selected from bromine or iodine;
R is the substituting group of 2-or 3-or 4-position on the aromatic ring, or two on the aromatic ring replace or multi-substituent, is selected from one of following: H ,-NO2 ,-CN ,-COOH, ethanoyl, alkyl, alkoxyl group, aryl, halogen, trifluoromethyl;
R
1R
2NH is primary amine or secondary amine, is selected from one of following: contain the straight or branched alkyl, the cycloalkyl of C5-C7, benzyl, the Armeen of substituted benzyl, secondary amine; Or five to the heptatomic cyclic secondary amine; Or contain the primary amine of aromatic substituent; Or contain NH at intra-annular heterocyclic aromatic compound; R on the described product
1R
2The R of N-group
1, R
2With R
1R
2R among the NH
1, R
2Group is identical;
2) after reaction finished, separating reaction mixed solution and purifying obtained N-arylation product;
It is characterized in that: described catalyzer is a copper catalyst, and described part is two parts of oxalyl hydrazine and ketone.
2. the N-arylation method in the aqueous solution as claimed in claim 1, it is characterized in that described catalyzer is one of following: the oxide compound of metallic copper, copper, cupprous salt, cupric salt, the mol ratio of catalyzer and substrate aryl halides is 1: 40 to 1: 2.
3. the N-arylation method in the aqueous solution as claimed in claim 1 or 2 is characterized in that described catalyzer is one of following: cupric oxide, Red copper oxide, copper sulfate, cupric nitrate, cupric chloride, cuprous chloride, cuprous iodide, neutralized verdigris.
4. the N-arylation method in the aqueous solution as claimed in claim 1 is characterized in that described part is two parts of oxalyl hydrazine and ketone, and the mol ratio of used oxalyl hydrazine and ketone is 1: 1 to 1: 6; The mol ratio of oxalyl hydrazine and catalyzer is 2: 1 to 20: 1.
5. as the N-arylation method in the claim 1 or the 4 described aqueous solution, it is characterized in that described ketone is chain ketone or cyclic ketones.
6. as the N-arylation method in the claim 1 or the 4 described aqueous solution, it is characterized in that described ketone is single ketones or diketone.
7. as the N-arylation method in the claim 1 or the 4 described aqueous solution, it is characterized in that described ketone is one of following: acetone, butanone, 2,5-hexanedione, 2,3-dimethyl diketone, cyclopentanone, pimelinketone.
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| CN101691318B (en) * | 2009-06-29 | 2013-05-29 | 中山大学 | N-arylation method taking substituted adipic dihydrazide as ligand in aqueous phase system |
| CN101774874B (en) * | 2010-01-25 | 2013-05-29 | 中山大学 | N-arylating method using pyrrole-2-hydrazide compound as ligand in aqueous phase system |
| CN102050687B (en) * | 2010-11-30 | 2014-04-23 | 中山大学 | Method for preparing aromatic primary amine by taking ammonia water as ammonia source in water phase system |
| CN102382058A (en) * | 2011-08-26 | 2012-03-21 | 浙江工业大学 | Preparation method of N-aryl-heterocyclic nitrogen compound |
| CN104370817A (en) * | 2014-11-13 | 2015-02-25 | 中科院广州化学有限公司 | 5-aryl-5H-dibenzo[b,f] azepine-10(11H) ketone compounds and preparation method thereof |
| CN106883132B (en) * | 2017-01-18 | 2019-03-22 | 中山大学 | One kind replaces the copper that hydrazides is ligand to be catalyzed C-N coupling method with N, N- bis- |
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