CN102432411A - Nitrogen-heterocyclic-cabbeen-palladium-iminazole complex for catalyzing application of aryl chloride in amination reaction - Google Patents
Nitrogen-heterocyclic-cabbeen-palladium-iminazole complex for catalyzing application of aryl chloride in amination reaction Download PDFInfo
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- CN102432411A CN102432411A CN201110283142XA CN201110283142A CN102432411A CN 102432411 A CN102432411 A CN 102432411A CN 201110283142X A CN201110283142X A CN 201110283142XA CN 201110283142 A CN201110283142 A CN 201110283142A CN 102432411 A CN102432411 A CN 102432411A
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N Clc1ccccc1 Chemical compound Clc1ccccc1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- TXTHKGMZDDTZFD-UHFFFAOYSA-N C(CC1)CCC1Nc1ccccc1 Chemical compound C(CC1)CCC1Nc1ccccc1 TXTHKGMZDDTZFD-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N C1NCCOC1 Chemical compound C1NCCOC1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- IDPURXSQCKYKIJ-UHFFFAOYSA-N COc1ccc(CN)cc1 Chemical compound COc1ccc(CN)cc1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 1
- WRDZMZGYHVUYRU-UHFFFAOYSA-N COc1ccc(CNc2ccccc2)cc1 Chemical compound COc1ccc(CNc2ccccc2)cc1 WRDZMZGYHVUYRU-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N Cc(cc1)ccc1Cl Chemical compound Cc(cc1)ccc1Cl NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- OLAFVASCPJETBP-UHFFFAOYSA-N Cc(cc1)ccc1N1CCOCC1 Chemical compound Cc(cc1)ccc1N1CCOCC1 OLAFVASCPJETBP-UHFFFAOYSA-N 0.000 description 1
- IAEOMPIICMWSKU-UHFFFAOYSA-N Cc(cc1)ccc1NC1C=CC=CC1 Chemical compound Cc(cc1)ccc1NC1C=CC=CC1 IAEOMPIICMWSKU-UHFFFAOYSA-N 0.000 description 1
- FQKQCCVYAJVHAF-UHFFFAOYSA-N Cc(cccc1C)c1Nc1c(C)cccc1C Chemical compound Cc(cccc1C)c1Nc1c(C)cccc1C FQKQCCVYAJVHAF-UHFFFAOYSA-N 0.000 description 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N Cc1cccc(C)c1C Chemical compound Cc1cccc(C)c1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N Cc1cccc(C)c1N Chemical compound Cc1cccc(C)c1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a method which uses the easily obtained nitrogen-heterocyclic-metals-iminazole complex as a catalyst to achieve coupling reaction between a primary amine or a secondary amine and a chloride so as to further achieve the research purpose on the formation of the carbon and nitrogen bonds. It is especially needed to point out that the catalytic system developed by the invention has a very excellent catalyzing effect on an amination between a big steric hindrance amine and steric hindrance chloride, and reactions relating to fats, and corresponding nitrogen-included compounds can be produced with a good to excellent yield. The catalytic system is cheap and easy to obtain. The reaction conditions are moderate. The catalytic system has a good industrial application prospect.
Description
Technical field
The present invention relates to N-heterocyclic carbine-palladium-imidazol complex is catalyzer, carries out the amination reaction research between primary amine or secondary amine and the aryl muriate.Can realize that through this method aryl muriate cheap and easy to get under the mild conditions is the amination reaction of substrate.Special needs to be pointed out is that this catalystsystem has very excellent catalytic effect to amination reaction between big bulky amine and the big steric hindrance muriate and the reaction that relates to aliphatic amide, well to generate corresponding nitrogenous compound to excellent yields.
Background technology
Contain in the compound that nitrogen molecule is present in biologically active, pharmaceutical activity or material property widely [a) A.Belfield, G.R.Brown, A.J.Foubister, Tetrahedron 1999,55, and 11399; B) D.O ' Hagan, Nat.Prod.Rep.2000,17,435; C) P.N.Craig, In Comprehensive Medicinal Chemistry; Ed.:C.J.Drayton; Pergamon Press:New York, 1991, Vol.8; D) N.D.McClenaghan, R.Passalacqua, F.Loiseau, S.Campagna, B.Verheyde, A.Hameurlaine, W.Dehaen, J.Am.Chem.Soc.2003,125,5356-5365; E) H.-H.Jian, J.M.Tour, J.Org.Chem.2003,68,5091; F) J.Louie, J.F.Hartwig, J.Am.Chem.Soc.1997,119,11695; G) R.A.Singer, J.P.Sadighi, S.L.Buchwald, J.Am.Chem.Soc.1998,120,213].[a) M.Kosugi, M.Kameyama, T.Migita, Chem.Lett.1983,927 since amination reaction is reported; B) A.S.Guram, R.A.Rennels, S.L.Buchwald, Angew.Chem.Int.Ed.Engl.1995,34,1348; C) J.Louie, J.F.Hartwig, Tetrahedron Lett.1995; 36,3609], the catalytic C-N linked reaction of palladium has become a kind of general and effective method [For some reviews that synthesize nitrogenous compound; Please see:a) J.F.Hartwig; Angew.Chem.Int.Ed.1998,37,2046; B) J.F.Hartwig, Acc.Chem.Res.1998,31,852; C) J.P.Wolfe, S.Wagaw, J.-F.Marcoux, S.L.Buchwald, Acc.Chem.Res.1998,31,805; D) B.H.Yang, S.L.Buchwald, J.Organomet.Chem.1999,576,125; E) J.F.Hartwig, in Modern Amination Methods; Ed.:A.Ricci; Wiley-VCH:Weinheim, 2000, pp 195-262; F) I.P.Beletskaya, A.D.Averin, Pure Appl.Chem.2004,76,1605; G) J.F.Hartwig, in Modern Arene Chemistry; Ed.:D.Astruc; Wiley-VCH:Weinheim, 2002, pp107; H) J.F.Hartwig, Acc.Chem.Res.2008,41,1534; I) S.L.Buchwald, C.Mauger, G.Mignani, U.Scholz, Adv.Synth.Catal.2006,348,23; J) D.S.Surry, S.L.Buchwald, Angew.Chem.Int.Ed.2008,47,6338].In all electrophilic reagents of linked reaction; The aryl muriate is because cheap and extensively be easy to get and become the most noticeable electrophilic reagent [a) V.V.Grushin; H.Alper, in Activation of Unreactive Bonds and Organic Synthesis; Ed.:S.Murai; Springer:Berlin, 1999; Pp 193; B) V.V.Grushin, H.Alper, Chem.Rev.1994,94,1047; C) J.-P.Corbet, G.Mignani, Chem.Rev.2006,106,2651].Have benefited from the development of some big steric hindrances, electron rich phosphine part, the aryl muriate has become electrophilic reagent [a) J.P.Wolfe, H.Tomori commonly used in the carbon nitrogen coupling reaction; J.P.Sadighi, J.-J.Yin, S.L.Buchwald; J.Org.Chem.2000,65,1158; B) N.Kataoka, Q.Shelby, J.P.Stambuli, J.F.Hartwig, J.Org.Chem.2002,67,5553; C) F.Rataboul, A.Zapf, R.Jackstell, S.Harkal, T.Riermeier, A.Monsees, U.Dingerdissen, M.Beller, Chem.Eur.J.2004,10,2983; D) S.Urgaonkar, J.-H.Xu, J.G.Verkade, J.Org.Chem.2003,68,8416; E) D.Liu, W.-Z.Gao, Q.Dai, X.-M.Zhang, Org.Lett.2005,7,4907; F) R.A.Singer, S.Caron, R.E.McDermott, P.Arpin, N.M.Do, Synthesis 2003,1727; G) G.Y.Li, Angew.Chem.Int.Ed.2001,40,1513; H) G.-S.Chen, W.H.Lam, W.S.Fok, H.W.Lee, F.Y.Kwong, Chem.Asian J.2007,2,306; I) L.Ackermann, J.H.Spatz, C.J.Gschrei, R.Born, A.Althammer, Angew.Chem.Int.Ed.2006,45,7627; J) S.Rodriguez, B.Qu, N.Haddad, D.C.Reeves, W.-J.Tang, H.Lee, D.Krishnamurthy, C.H.Senanayake, Adv.Synth.Catal.2011,353,533; K) R.J.Lundgren, A.Sappong-Kumankumah, M.Stradiotto, Chem.Eur.J.2010,16,1983].Usually, the phosphine part of high catalytic activity often costs an arm and a leg, to air-sensitive and poisonous, therefore, big limitations its widespread use in industry.Also just owing to this reason, develop cheap and to the part of air-stable and be applied to just seem day by day in the catalytic carbon nitrogen coupling reaction of transition metal palladium necessary.In this regard, and N-heterocyclic carbine [For some selected reviews on NHCs, please see:a) W.A.Herrmann, Angew.Chem.Int.Ed.2002,41,1290; B) N.Marion, S.P.Nolan, Acc.Chem.Res.2008,41,1440; C) E.Peris, R.H.Crabtree, Coord.Chem.Rev.2004,248,2239; D) W.A.Herrmann; K.
D.v.Preysing; K.S.Schneider; J.Organomet.Chem.2003,687,229; E) F.E.Hahn, M.C.Jahnke, Angew.Chem.Int.Ed.2008,47,3122; F) F.Glorius, N-Heterocyclic Carbenes in Transition Metal Catalysis; Springer-Verlag:Berlin, Germany, 2007; G) S.P.Nolan, N-Heterocyclic Carbenes in Synthesis; Wiley-VCH:Weinheim, Germany, 2006; H) S.D í ez-Gonz á lez, S.P.Nolan, Coord.Chem.Rev.2007,251,874; I) E.A.B.Kantchev, C.J.O ' Brien, M.G.Organ, Angew.Chem.Int.Ed.2007; 46,2768], has higher stability than phosphine part usually, as the strong rival of phosphine part to air and heat; In the muriatic amination reaction of the catalytic aryl of transition metal palladium, important effect [a) J.-Y.Li, M.-J.Cui, A.-J.Yu, Y.-J.Wu have been played; J.Organomet.Chem.2007,692,3732; B) L.J.Goo β en, J.Paetzold, O.Briel, A.Rivas-Nass, R.Karch, B.Kayser, Synlett 2005,275; C) M.S.Viciu, R.M.Kissling, E.D.Stevens, S.P.Nolan, Org.Lett.2002,4,2229; D) M.S.Viciu, R.A.Kelly, III, E.D.Stevens, F.Naud, M.Studer, S.P.Nolan, Org.Lett.2003,5,1479; E) Z.Jin, S.-X.Guo, X.-P.Gu, L.-L.Qiu, H.-B.Song, J.-X.Fang, Adv.Synth.Catal.2009,351,1575; F) M.G.Organ, M.Abdel-Hadi, S.Avola, I.Dubovyk, N.Hadei, E.A.B.Kantchev, C.J.O ' Brien, M.Sayah, C.Valente, Chem.Eur.J.2008,14,2443; G) M.S.Viciu, O.Navarro, R.F.Germaneau, R.A.Kelly, III, W.Sommer, N.Marion, E.D.Stevens, L.Cavallo, S.P.Nolan, Organometallics 2004,23, and 1629; H) Z.Jin, L.-L.Qiu, Y.-Q.Li, H.-B.Song, J.-X.Fang, Organometallics 2010,29, and 6578; I) J.Broggi, H.Clavier, S.P.Nolan, Organometallics 2008,27, and 5525; J) N.Marion, O.Navarro, J.-G.Mei, E.D.Stevens, N.M.Scott, S.P.Nolan, J.Am.Chem.Soc.2006,128,4101].Although these considerable progress have been arranged, from document, can find the example of the linked reaction between big sterically hindered amine and the big sterically hindered muriate lacking very; Only have only several ortho position four substituted diaryl amine synthetic example [a) C.V.Reddy that successfully are applied to; V.Jesudoss, J.G.Verkade, J.Org.Chem.2008; 73,3047; B) S.Rodriguez, B.Qu, N.Haddad, D.C.Reeves, W.-J.Tang, H.Lee, D.Krishnamurthy, C.H.Senanayake, Adv.Synth.Catal.2011,353,533; C) L.J.Goo β en, J.Paetzold, O.Briel, A.Rivas-Nass, R.Karch, B.Kayser, Synlett 2005,275; D) N.Marion, O.Navarro, J.-G.Mei, E.D.Stevens, N.M.Scott; S.P.Nolan, J.Am.Chem.Soc.2006,128,4101.e) A.Ehrentraut, A.Zapf; M.Beller, J.Mol.Catal.A:Chem.2005,182-183,515].In addition, alkylamine is eliminated reaction because β-hydrogen takes place easily in catalytic chain, also be challenging substrate in the amination reaction.Therefore; Development be simple and easy to complex compound, and realize with the aryl muriate be substrate at amination reaction, the application of particularly big sterically hindered substrate in amination reaction; And with the alkylamine is that substrate is realized their application in carbonnitrogen bond forms, and remains a very challenging problem.
Summary of the invention
The problem that the present invention will solve is to provide a kind of method: be simple and easy to N-heterocyclic carbine-palladium metal-imidazol complex be catalyzer, realize the linked reaction between aryl muriate and aryl or the alkylamine, reach the purpose of carbon-nitrogen bond formation.
Reaction related among the present invention can be represented with following general formula:
Wherein X can be iodine, bromine or chlorine, further is recommended as chlorine.
R wherein
1Represent 2-, 3-, the substituting group on the 4-position, or represent two replacement or multi-substituents on the aromatic ring.R
1Can be H, C
1-C
6Alkoxyl group, NO
2, CN, COR
3(R
3Be H, C
1-C
6Alkyl, aryl etc.), COOR
4(R
4Can be H or C
1-C
6Alkyl), C
1-C
6Alkyl, aryl, NR
4R
5(R
4, R
5Be H, C
1-C
6Alkyl, benzyl or aryl etc.).R
1Also represent the aromatic ring of benzo, like naphthalene nucleus.Described aryl is recommended as phenyl, and (substituting group is C to substituted-phenyl
1-C
6Alkyl, C
1-C
6Alkoxyl group), naphthyl, five arrive seven-membered ring heteroaryl for example pyridine, pyrroles, imidazoles, furans, thiophene etc.
R
2Represent the 2-on the aromatic amine, 3-, one of 4-position replaces, two replacement or multi-substituents.R
2Can be C
1-C
6The straight or branched alkyl, C
1-C
6Alkoxyl group.Described aryl is recommended as phenyl, and (substituting group is C to substituted-phenyl
1-C
6Alkyl, C
1-C
6Alkoxyl group), naphthyl, five arrive seven-membered ring heteroaryl for example pyridine, pyrroles, imidazoles, furans, thiophene etc.
R
3Can be H, C
1-C
6Alkyl.
In the reaction of the present invention, used N-heterocyclic carbine-metal-imidazol complex consumption is recommended as 0.001-10mol% (with respect to aryl halide), and the mol ratio between employed amine and the halogenide is recommended as 1: 1 to 5: 1.
The reaction temperature of carrying out is recommended as-10-150 ℃, especially be recommended as 60-120 ℃.Reaction times is recommended as 2-24 hour.
In the reaction of the present invention, employed alkali can be KHCO
3, K
2CO
3, Na
2CO
3, Cs
2CO
3, NaHCO
3, CH
3COOK, CH
3ONa, CsF, K
3PO
43H
2O, NaOH, KOH, KO
tBu, NaO
tBu or the like.
In the reaction of the present invention, employed solvent can be the mixed solvent of water, THF, benzene, toluene, dioxane or organic solvent and water.
In the N-heterocyclic carbine-metal that relates among the present invention-imidazol complex:
R wherein
4And R
5Group can be H, C
1-C
6Alkoxyl group, C
1-C
6Alkyl.
Wherein Y can I
-, Br
-, Cl
-, CH
3COO
-, CF
3COO
-, OSO
2CF
3Or the like.
R wherein
6Can be C
1-C
6Alkyl, aryl is also represented the aromatic ring of benzo, like naphthalene nucleus.
Metal center M can be iron, copper, silver, nickel, palladium, cobalt, rhodium, ruthenium or the like, further is recommended as palladium metal.
Employed catalyzer is easy to preparation among the present invention, and can synthesize in a large number, to air and steam quite stable.And, use this catalyzer, can realize that the aryl muriate is the application of substrate in carbon-nitrogen coupling.Other system of reporting in this catalystsystem and the document is compared low price.And from imidazole salts, through one the step can synthesize corresponding N-heterocyclic carbine-metal-imidazol complex, be highly susceptible to synthesizing.The reaction easy handling that this catalystsystem developed, very low to the requirement of reaction conditions, particularly can realize the linked reaction of big steric hindrance substrate having favorable industrial application prospect.
Embodiment
To help to understand the present invention through following embodiment, but be not restricted to content of the present invention.
Instance 1
The reaction of chlorinated benzene and morphine beautiful jade
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (4.6mg 1.0mol%), heavily steams 1,4-dioxane (1.0mL), the morphine beautiful jade (70 μ L, 0.8mmol), chlorinated benzene (74 μ L, 0.7mmol).This reaction mixture was stirred 3 hours down at 70 ℃.Rotary Evaporators solvent evaporated, rapid column chromatography obtain n-phenylmorpholine coffee beautiful jade, yield 96%.
1H?NMR(500MHz，CDCl
3，TMS)δ3.17(t，J＝5.0Hz，4H)，3.87(t，J＝5.0Hz，4H)，6.88-6.94(m，3H，Ar)，7.26-7.31(m，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ49.4，66.9，115.7，120.0，129.2，151.3.
Instance 2
The reaction of chlorinated benzene and piperidines
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (4.6mg 1.0mol%), heavily steams 1,4-dioxane (1.0mL), piperidines (79 μ L, 0.8mmol), chlorinated benzene (74 μ L, 0.7mmol).This reaction mixture was stirred 3 hours down at 90 ℃.Rotary Evaporators solvent evaporated, rapid column chromatography obtain the N-Phenylpiperidine, yield 82%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.48-1.52(m，2H)，1.61-1.66(m，4H)，3.08(t，J＝5.5Hz，4H)，6.75(t，J＝7.5Hz，1H，Ar)，6.87(d，J＝8.5Hz，2H，Ar)，7.16-7.19(m，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ24.3，25.9，50.7，116.5，119.2，129.0，152.3.
Embodiment 3
The reaction of chlorinated benzene and Pyrrolidine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (4.6mg 1.0mol%), heavily steams 1,4-dioxane (1.0mL), Pyrrolidine (66 μ L, 0.8mmol), chlorinated benzene (74 μ L, 0.7mmol).This reaction mixture was stirred 3 hours down at 90 ℃.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-phenyl Pyrrolidine, yield 65%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.99-2.02(m，4H)，3.29(t，J＝6.5Hz，4H)，6.58(d，J＝7.5Hz，2H，Ar)，6.66(t，J＝7.5Hz，1H，Ar)，7.23(dd，J＝8.5，7.5Hz，2H，Ar).
13CNMR(125MHz，CDCl
3)δ25.4，47.6，111.7，115.4，129.1，148.0.
Embodiment 4
The reaction of chlorinated benzene and N-methylbenzylamine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (4.6mg 1.0mol%), heavily steams 1,4-dioxane (1.0mL), the N-methylbenzylamine (103 μ L, 0.8mmol), chlorinated benzene (74 μ L, 0.7mmol).This reaction mixture was stirred 3 hours down at 70 ℃.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-phenyl-N-methylbenzylamine, yield 88%.
1H?NMR(500MHz，CDCl
3，TMS)δ3.02(s，3H，Me)，4.53(s，2H)，6.71(t，J＝7.5Hz，1H，Ar)，6.75(d，J＝8.0Hz，2H，Ar)，7.20-7.25(m，5H，Ar)，7.31(t，J＝7.0Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ38.5，56.6，112.3，116.5，126.7，126.8，128.5，129.2，139.0，149.7.
Embodiment 5
The reaction of chlorinated benzene and methylphenylamine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (4.6mg 1.0mol%), heavily steams 1,4-dioxane (1.0mL), methylphenylamine (88 μ L, 0.8mmol), chlorinated benzene (74 μ L, 0.7mmol).This reaction mixture was stirred 3 hours down at 80 ℃.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N, N-phenylbenzene-methylamine, yield 86%.
1H?NMR(500MHz，CDCl
3，TMS)δ3.33(s，3H，Me)，6.95-6.99(m，2H，Ar)，7.03-7.05(m，4H，Ar)，7.27-7.30(m，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ40.2，120.4，121.2，129.2，149.0.
Instance 6
The reaction of chlorinated benzene and aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), aniline (88 μ L, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains pentanoic, yield 95%.
1H?NMR(500MHz，CDCl
3，TMS)δ5.69(s，1H)，6.92(t，J＝7.5Hz，2H，Ar)，7.07(d，J＝7.5Hz，4H，Ar)，7.26(t，J＝7.5Hz，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ117.8，121.0，129.3，143.1.
Instance 7
The reaction of 4-methyl chlorobenzene and aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), aniline (88 μ L, 0.96mmol), 4-methyl chlorinated benzene (95 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-4-tolyl aniline, yield 89%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.30(s，3H，Me)，5.59(s，1H)，6.87(t，J＝7.5Hz，1H，Ar)，6.99-7.01(m，4H，Ar)，7.08(d，J＝8.0Hz，2H，Ar)，7.21-7.25(m，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ20.7，116.8，118.8，120.2，129.3，129.8，130.9，140.2，143.8.
Instance 8
The reaction of 3-methyl chlorobenzene and aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), aniline (88 μ L, 0.96mmol), 3-methyl chlorinated benzene (94 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain 3-methyl-N-phenylaniline, yield 94%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.30(s，3H，Me)，5.64(s，1H)，6.75(d，J＝7.5Hz，1H，Ar)，6.87-6.93(m，3H，Ar)，7.06(d，J＝7.5Hz，2H，Ar)，7.15(t，J＝7.5Hz，1H，Ar)，7.24-7.27(m，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ21.5，114.9，117.8，118.5，120.9，121.9，129.1，129.3，139.2，143.1，143.2.
Instance 9
The reaction of 2-methyl chlorobenzene and aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), aniline (88 μ L, 0.96mmol), 2-methyl chlorinated benzene (94 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-2-tolyl aniline, yield 92%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.24(s，3H，Me)，5.36(s，1H)，6.87-6.96(m，4H，Ar)，7.11-7.25(m，5H，Ar).
13C?NMR(125MHz，CDCl
3)δ17.9，117.4，118.8，120.4，122.0，126.7，128.3，129.3，130.9，141.2，144.0.
Instance 10
The reaction of 4-methoxyl group chlorobenzene and aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), aniline (88 μ L, 0.96mmol), 4-methoxyl group chlorinated benzene (98 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-4-p-methoxy-phenyl aniline, yield 82%.
1H?NMR(500MHz，DMSO)δ3.71(s，3H，OMe)，6.70(t，J＝7.5Hz，1H，Ar)，6.84-6.88(m，2H，Ar)，6.91(d，J＝7.5Hz，2H，Ar)，7.04(d，J＝8.5Hz，2H，Ar)，7.15(dd，J＝8.5，7.5Hz，2H，Ar).
13C?NMR(125MHz，DMSO)δ55.2，114.5，114.8，118.3，120.3，129.1，136.1，145.1，153.8.
Instance 11
The reaction of 3-methoxyl group chlorobenzene and aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), aniline (88 μ L, 0.96mmol), 3-methyl chlorinated benzene (98 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-3-p-methoxy-phenyl aniline, yield 97%.
1H?NMR(500MHz，CDCl
3，TMS)δ3.76(s，3H，OMe)，6.49-6.51(m，1H，Ar)，6.67(d，J＝7.5Hz，2H，Ar)，6.95(t，J＝7.5Hz，1H，Ar)，7.11(d，J＝7.5Hz，2H，Ar)，7.16(t，J＝8.0Hz，1H，Ar)，7.23-7.28(m，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ55.2，103.6，106.6，110.5，118.6，121.6，129.3，130.1，142.5，144.2，160.7.
Instance 12
The reaction of 4-chloro-acetophenone and aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), aniline (88 μ L, 0.96mmol), the 4-chloro-acetophenone (104 μ L, 0.8mmol).This reaction mixture refluxed was stirred 8 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-4-acetylphenyl aniline, yield 77%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.53(s，3H，Me)，7.00(d，J＝9.0Hz，2H，Ar)，7.08(t，J＝7.5Hz，1H，Ar)，7.19(d，J＝7.5Hz，2H，Ar)，7.35(t，J＝7.5Hz，2H，Ar)，7.87(d，J＝9.0Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ26.1，114.4，120.7，123.3，129.0，129.5，130.6，140.6，148.4，196.4.
Instance 13
The reaction of 3-chloropyridine and aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), aniline (88 μ L, 0.96mmol), the 3-chloropyridine (76 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-3-pyridyl aniline, yield 85%.
1H?NMR(500MHz，CDCl
3，TMS)δ5.79(s，1H)，7.00(t，J＝7.5Hz，1H，Ar)，7.08(d，J＝7.5Hz，2H，Ar)，7.17(dd，J＝8.5，4.5Hz，1H，Ar)，7.30(dd，J＝8.5，7.5Hz，2H，Ar)，7.40-7.42(m，1H，Ar)，8.16(dd，J＝4.5，1.0Hz，1H，Ar)，8.38(d，J＝2.5Hz，1H，Ar).
13C?NMR(125MHz，CDCl
3)δ118.3，122.0，123.4，123.7，129.5，139.8，140.1，141.8，141.9.
Instance 14
The reaction of chlorinated benzene and 4-methoxybenzylamine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (198.0mg, 1.7mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), the 4-methoxybenzylamine (210 μ L, 1.6mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-4-methoxy-benzyl aniline, yield 80%.
1H?NMR(500MHz，CDCl
3，TMS)δ3.81(s，3H，OMe)，4.26(s，2H)，6.65(d，J＝7.5Hz，2H，Ar)，6.72(t，J＝7.5Hz，1H，Ar)，6.89(d，J＝9.0Hz，2H，Ar)，7.19(dd，J＝8.5，7.5Hz，2H，Ar)，7.30(d，J＝9.0Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ47.8，55.3，112.8，114.0，117.5，128.8，129.2，131.4，148.2，158.9.
Instance 15
The reaction of chlorinated benzene and benzylamine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (198.0mg, 1.7mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), benzylamine (176 μ L, 1.6mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains Phenhenzamine, yield 80%.
1H?NMR(500MHz，CDCl
3，TMS)δ4.04(s，1H)，4.35(s，2H)，6.66(d，J＝8.0Hz，2H，Ar)，6.74(t，J＝7.5Hz，1H，Ar)，7.20(dd，J＝8.0，7.5Hz，2H，Ar)，7.26-7.40(m，5H，Ar).
13C?NMR(125MHz，CDCl
3)δ48.3，112.8，117.6，127.2，127.5，128.6，129.2，139.4，148.1.
Instance 16
The reaction of chlorinated benzene and hexahydroaniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), hexahydroaniline (111 μ L, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-benzyl ring hexylamine, yield 91%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.14-1.26(m，3H)，1.33-1.42(m，2H)，1.64-1.67(m，1H)，1.74-1.78(m，2H)，2.05-2.07(m，2H)，3.23-3.28(m，1H)，3.51(br，1H)，6.59(d，J＝7.5Hz，2H，Ar)，6.66(t，J＝7.5Hz，1H，Ar)，7.15(t，J＝7.5Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ25.0，25.9，33.5，51.7，113.1，116.8，129.2，147.4.
Instance 17
The reaction of 3-methoxyl group chlorinated benzene and hexahydroaniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), hexahydroaniline (111 μ L, 0.96mmol), 3-methoxyl group chlorinated benzene (98 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-3-p-methoxy-phenyl hexahydroaniline, yield 93%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.10-1.27(m，3H)，1.32-1.40(m，2H)，1.62-1.66(m，1H)，1.73-1.77(m，2H)，2.04-2.07(m，2H)，3.20-3.26(m，1H)，3.76(s，3H，OMe)，6.14(t，J＝2.5Hz，1H，Ar)，6.19-6.24(m，2H，Ar)，7.05(t，J＝8.0Hz，1H，Ar).
13C?NMR(125MHz，CDCl
3)δ25.0，25.9，33.5，51.7，55.1，99.1，101.8，106.4，129.9，148.8，160.9.
Instance 18
The reaction of chlorinated benzene and 3-monomethylaniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), the 3-monomethylaniline (105 μ L, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-3-aminomethyl phenyl aniline, yield 93%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.30(s，3H，Me)，5.64(s，1H)，6.75(d，J＝7.5Hz，1H，Ar)，6.87-6.93(m，3H，Ar)，7.06(d，J＝7.5Hz，2H，Ar)，7.15(t，J＝7.5Hz，1H，Ar)，7.24-7.27(m，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ21.5，114.9，117.8，118.5，120.9，121.9，129.1，129.3，139.2，143.1，143.2.
Instance 19
The reaction of chlorinated benzene and 2-aminotoluene
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2-aminotoluene (103 μ L, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-2-aminomethyl phenyl aniline, yield 92%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.24(s，3H，Me)，5.36(s，1H)，6.87-6.96(m，4H，Ar)，7.11-7.25(m，5H，Ar).
13C?NMR(125MHz，CDCl
3)δ17.9，117.4，118.8，120.4，122.0，126.7，128.3，129.3，130.9，141.2，144.0.
Instance 20
The reaction of chlorinated benzene and 4-anisidine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), the 4-anisidine (119mg, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-4-p-methoxy-phenyl aniline, yield 94%.
1H?NMR(500MHz，DMSO)δ3.71(s，3H，OMe)，6.70(t，J＝7.5Hz，1H，Ar)，6.84-6.88(m，2H，Ar)，6.91(d，J＝7.5Hz，2H，Ar)，7.04(d，J＝8.5Hz，2H，Ar)，7.15(dd，J＝8.5，7.5Hz，2H，Ar).
13C?NMR(125MHz，DMSO)δ55.2，114.5，114.8，118.3，120.3，129.1，136.1，145.1，153.8.
Instance 21
Chlorinated benzene and 2, the reaction of 6-xylidine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2, the 6-xylidine (120 μ L, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2,6-3,5-dimethylphenyl aniline, yield 86%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.24(s，6H，2Me)，5.21(br，1H)，6.52-6.54(m，2H，Ar)，6.77(t，J＝7.0Hz，1H，Ar)，7.09-7.19(m，5H，Ar).
13C?NMR(125MHz，CDCl
3)δ18.3，113.5，118.2，125.7，128.5，129.2，135.9，138.2，146.2.
Instance 22
The reaction of chlorinated benzene and 2
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2 (136 μ L, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2, and 4,6-trimethylphenyl aniline, yield 97%.
1H?NMR(500MHz，DMSO)δ2.07(s，6H，2Me)，2.23(s，3H，Me)，6.36(d，J＝7.5Hz，2H，Ar)，6.55(t，J＝7.5Hz，1H，Ar)，6.91(s，2H，Ar)，7.04(t，J＝7.5Hz，2H，Ar).
13CNMR(125MHz，DMSO)δ18.0，20.5，112.2，116.3，128.9，129.0，134.3，135.6，135.8，147.2.
Instance 23
Chlorinated benzene and 2, the reaction of 6-diisopropyl aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2, the 6-diisopropyl aniline (182 μ L, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2,6-diisopropyl phenyl aniline, yield 92%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.14(d，J＝7.0Hz，12H，4Me)，3.20(hep，J＝7.0Hz，2H)，6.48(d，J＝7.5Hz，2H，Ar)，6.71(t，J＝7.5Hz，1H，Ar)，7.14(dd，J＝8.5，7.5Hz，2H，Ar)，7.22(d，J＝7.5Hz，2H，Ar)，7.30(dd，J＝8.5，7.0Hz，1H，Ar).
13C?NMR(125MHz，CDCl
3)δ23.8，28.2，112.9，117.6，123.8，127.2，129.2，135.1，147.6，148.1.
Instance 24
2, the reaction of 6-dimethylated chlorobenzene and 2-aminotoluene
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2-aminotoluene (104 μ L, 0.96mmol), 2, the 6-dimethylated chlorobenzene (106 μ L, 0.8mmol).This reaction mixture was stirred 4 hours 115 ℃ of refluxed.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2,6-3,5-dimethylphenyl o-toluidine, yield 99%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.19(s，6H，2Me)，2.34(s，3H，Me)，4.94(s，1H)，6.15(d，J＝8.0Hz，1H，Ar)，6.71(t，J＝7.5Hz，1H，Ar)，6.97(t，J＝7.5Hz，1H，Ar)，7.07-7.14(m，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ17.6，18.2，111.8，118.1，122.5，125.5，126.9，128.5，130.2，135.5，138.7，144.1.
Instance 25
2,6-dimethylated chlorobenzene and 2, the reaction of 6-xylidine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2, the 6-xylidine (118 μ L, 0.96mmol), 2, the 6-dimethylated chlorobenzene (106 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N, N-two (2, the 6-dimethyl benzene) amine, yield 99%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.01(s，12H，4Me)，4.79(s，1H)，6.84(t，J＝7.5Hz，2H，Ar)，6.97(d，J＝7.5Hz，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ19.1，121.7，128.7，129.6，141.8.
Instance 26
2, the reaction of 6-dimethylated chlorobenzene and 2
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg, 1.0mol%); Heavily steam toluene (1.0mL), 2 (134 μ L; 0.96mmol), 2, and the 6-dimethylated chlorobenzene (106 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2,6-3,5-dimethylphenyl-2, yield 99%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.99(s，6H，2Me)，2.00(s，6H，2Me)，2.26(s，3H，Me)，4.71(s，1H)，6.78-6.81(m，3H，Ar)，6.96(d，J＝7.5Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ19.0，19.1，20.6，120.9，128.5，128.8，129.2，130.5，131.5，139.0，142.2.
Instance 27
2,6-dimethylated chlorobenzene and 2, the reaction of 6-diisopropyl aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg; 1.0mol%), heavily steam toluene (1.0mL), 2,6-diisopropyl aniline (181 μ L; 0.96mmol), 2, and the 6-dimethylated chlorobenzene (106 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2,6-3,5-dimethylphenyl-2,6-diisopropyl aniline, yield 99%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.12(d，J＝7.0Hz，12H，4Me)，1.98(s，6H，2Me)，3.15(hep，J＝7.0Hz，2H)，4.79(s，1H)，6.72(t，J＝7.5Hz，1H，Ar)，6.94(d，J＝7.5Hz，2H，Ar)，7.11-7.16(m，3H，Ar).
13C?NMR(125MHz，CDCl
3)δ19.3，23.4，28.0，119.6，123.2，124.8，125.7，129.5，138.8，143.1，144.1.
Instance 28
2,4, the reaction of 6-trimethylammonium chlorobenzene and 2-aminotoluene
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2-aminotoluene (106 μ L, 0.96mmol), 2,4,6-trimethylammonium chlorobenzene (122mg, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2, and 4,6-trimethylphenyl o-toluidine, yield 95%.
1H?NMR(500MHz，CDCl
3，TMS)δ2.14(s，6H，2Me)，2.30(s，3H，Me)，2.31(s，3H，Me)，4.85(s，1H)，6.13(d，J＝8.0Hz，1H，Ar)，6.67(t，J＝7.5Hz，1H，Ar)，6.94-7.10(m，3H，Ar)，7.11(d，J＝7.5Hz，1H，Ar).
13C?NMR(125MHz，CDCl
3)δ17.6，18.1，20.9，111.5，117.8，122.1，126.9，129.2，130.2，135.1，135.6，136.0，144.5.
Instance 29
2,4,6-trimethylammonium chlorobenzene and 2, the reaction of 6-xylidine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2, the 6-xylidine (120 μ L, 0.96mmol), 2,4,6-trimethylammonium chlorobenzene (128mg, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2,6-3,5-dimethylphenyl-2, yield 98%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.99(s，6H，2Me)，2.00(s，6H，2Me)，2.26(s，3H，Me)，4.71(s，1H)，6.78-6.81(m，3H，Ar)，6.96(d，J＝7.5Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ19.0，19.1，20.6，120.9，128.5，128.8，129.2，130.5，131.5，139.0，142.2.
Instance 30
2,4, the reaction of 6-trimethylammonium chlorobenzene and 2
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg, 1.0mol%); Heavily steam toluene (1.0mL), and 2 (136 μ L, 0.96mmol); 2,4, and 6-trimethylammonium chlorobenzene (129mg, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N, N-two (2,4, the 6-trimethylphenyl) amine, yield 92%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.97(s，12H，4Me)，2.24(s，6H，2Me)，4.60(s，1H)，6.78(s，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ19.0，20.5，129.3，129.4，130.7，139.5.
Instance 31
2,4,6-trimethylammonium chlorobenzene and 2, the reaction of 6-diisopropyl aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg, 1.0mol%); Heavily steam toluene (1.0mL), 2, the 6-diisopropyl aniline (182 μ L, 0.96mmol); 2,4, and 6-trimethylammonium chlorobenzene (127mg, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2, and 4,6-trimethylphenyl-2,6-diisopropyl aniline, yield 86%.
1H?NMR(300MHz，CDCl
3，TMS)δ1.11(d，J＝6.9Hz，12H，4Me)，1.95(s，6H，2Me)，2.22(s，3H，Me)，3.12(hep，J＝6.9Hz，2H)，4.69(s，1H)，6.75(s，2H，Ar)，7.09(s，3H，Ar).
13C?NMR(125MHz，CDCl
3)δ19.2，20.4，23.4，28.0，123.2，124.2，126.4，129.1，130.0，139.2，140.5，143.4.
Instance 32
2, the reaction of 6-di-isopropyl chlorobenzene and 2-aminotoluene
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2-aminotoluene (106 μ L, 0.96mmol), 2,6-di-isopropyl chlorobenzene (157mg, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-2-aminomethyl phenyl-2,6-diisopropyl aniline, yield 92%.
1H?NMR(300MHz，CDCl
3，TMS)δ1.11(d，J＝6.6Hz，6H，2Me)，1.16(d，J＝6.6Hz，6H，2Me)，2.34(s，3H，Me)，3.10(hep，J＝6.6Hz，2H)，4.89(s，1H)，6.11(d，J＝8.0Hz，1H，Ar)，6.66(t，J＝7.5Hz，1H，Ar)，6.94(t，J＝8.0Hz，1H，Ar)，7.12(d，J＝7.5Hz，1H，Ar)，7.21-7.30(m，3H，Ar).
13C?NMR(125MHz，CDCl
3)δ17.6，23.0，24.7，28.2，111.4，117.5，121.3，123.8，126.95，127.03，130.1，135.7，146.0，147.3.
Instance 33
2,6-di-isopropyl chlorobenzene and 2, the reaction of 6-xylidine
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), 2, the 6-xylidine (120 μ L, 0.96mmol), 2,6-di-isopropyl chlorobenzene (159mg, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2,6-3,5-dimethylphenyl-2,6-diisopropyl aniline, yield 93%.
1H?NMR(500MHz，CDCl
3，TMS)δ1.12(d，J＝7.0Hz，12H，4Me)，1.98(s，6H，2Me)，3.15(hep，J＝7.0Hz，2H)，4.79(s，1H)，6.72(t，J＝7.5Hz，1H，Ar)，6.94(d，J＝7.5Hz，2H，Ar)，7.11-7.16(m，3H，Ar).
13C?NMR(125MHz，CDCl
3)δ19.3，23.4，28.0，119.6，123.2，124.8，125.7，129.5，138.8，143.1，144.1.
Instance 34
2, the reaction of 6-di-isopropyl chlorobenzene and 2
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg, 1.0mol%); Heavily steam toluene (1.0mL), 2 (136 μ L; 0.96mmol), 2, and 6-di-isopropyl chlorobenzene (154mg, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2, and 4,6-trimethylphenyl-2,6-diisopropyl aniline, yield 91%.
1H?NMR(300MHz，CDCl
3，TMS)δ1.11(d，J＝6.9Hz，12H，4Me)，1.95(s，6H，2Me)，2.22(s，3H，Me)，3.12(hep，J＝6.9Hz，2H)，4.69(s，1H)，6.75(s，2H，Ar)，7.09(s，3H，Ar).
13C?NMR(125MHz，CDCl
3)δ19.2，20.4，23.4，28.0，123.2，124.2，126.4，129.1，130.0，139.2，140.5，143.4.
Instance 35
2,6-di-isopropyl chlorobenzene and 2, the reaction of 6-diisopropyl aniline
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg; 1.0mol%), heavily steam toluene (1.0mL), 2,6-diisopropyl aniline (182 μ L; 0.96mmol), 2, and 6-di-isopropyl chlorobenzene (163mg, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N, N-two (2, the 6-diisopropyl phenyl) amine, yield 86%.
1H?NMR(300MHz，CDCl
3，TMS)δ1.09(d，J＝6.6Hz，24H，8Me)，3.08(hep，J＝6.6Hz，4H)，4.87(br，1H)，6.98-7.10(m，6H，Ar).
13C?NMR(125MHz，CDCl
3)δ23.5，27.8，122.7，123.8，140.4，140.9.IR(neat)ν3724，3629，3600，2948，2864，2357，2335，1748，1731，1537，1455，1441，1332，1270，1250，1104，1045，931，888，864，786，741，668cm
-1.MS(ESI，m/z)：338[M+1]
+；HRMS(EI)：Calcd.for?C
24H
36N[M]
+：338.2847；Found：338.2842.
Instance 36
The reaction of chlorinated benzene and NSC 9824
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), NSC 9824 (88 μ L, 0.96mmol), chlorinated benzene (82 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-phenyl NSC 9824, yield 74%.
1HNMR(500MHz，CDCl
3，TMS)δ0.89(t，J＝6.5Hz，3H)，1.26-1.41(m，10H)，1.56-1.63(m，2H)，3.10(t，J＝7.0Hz，2H)，3.59(s，1H)，6.60(d，J＝7.5Hz，2H，Ar)，6.68(t，J＝7.5Hz，1H，Ar)，7.17(t，J＝7.5Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，22.6，27.2，29.3，29.4，29.5，31.8，44.2，112.9，117.3，129.2，148.4.
Obtain N, N-phenylbenzene NSC 9824, yield 23%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.87(t，J＝7.0Hz，3H)，1.26-1.30(m，10H)，1.62-1.68(m，2H)，3.67(t，J＝7.5Hz，2H)，6.93(t，J＝7.5Hz，2H，Ar)，6.98(d，J＝7.5Hz，4H，Ar)，7.24-7.27(m，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，22.6，27.1，27.5，29.3，29.4，31.8，52.4，120.9，121.0，129.2，148.1.
Instance 37
The reaction of 4-methyl chlorinated benzene and NSC 9824
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), NSC 9824 (88 μ L, 0.96mmol), 4-methyl chlorinated benzene (96 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-4-aminomethyl phenyl NSC 9824, yield 75%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.89(t，J＝7.0Hz，3H)，1.23-1.42(m，10H)，1.58-1.63(m，2H)，2.24(s，3H，Me)，3.08(t，J＝7.0Hz，2H)，6.54(d，J＝8.0Hz，2H，Ar)，6.99(d，J＝8.0Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，20.3，22.6，27.2，29.3，29.4，29.6，31.8，44.4，112.9，126.3，129.7，146.3.
Obtain N, N-two (4-aminomethyl phenyl) NSC 9824, yield 23%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.87(t，J＝7.0Hz，3H)，1.26-1.29(m，10H)，1.61-1.64(m，2H)，2.29(s，6H，2Me)，3.61(t，J＝7.5Hz，2H)，6.86(d，J＝8.0Hz，4H，Ar)，7.05(d，J＝8.0Hz，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，20.6，22.6，27.1，27.4，29.3，29.4，31.8，52.5，120.8，129.7，130.2，146.0.IR(neat)ν3021，2954，2917，2850，1605，1565，1504，1464，1356，1228，1175，1124，1070，1013，801，721cm
-1.MS(EI，m/z)(％)：309(22，M
+)，210(100)；HRMS(EI)：Calcd.for?C
22H
31N[M]
+：309.2457；Found：309.2459.
Instance 38
The reaction of 3-methyl chlorinated benzene and NSC 9824
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), NSC 9824 (88 μ L, 0.96mmol), 3-methyl chlorinated benzene (96 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-3-aminomethyl phenyl NSC 9824, yield 68%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.89(t，J＝6.5Hz，3H)，1.26-1.31(m，10H)，1.58-1.64(m，2H)，2.28(s，3H，Me)，3.09(t，J＝7.0Hz，2H)，6.44(d，J＝7.5Hz，2H，Ar)，6.52(d，J＝7.5Hz，1H，Ar)，7.06(t，J＝7.5Hz，1H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，21.6，22.6，27.2，29.3，29.4，29.6，31.8，44.1，109.9，113.5，118.0，129.1，139.0，148.6.IR(neat)ν3418，3389，3046，2952，2919，2851，1727，1600，1586，1484，1325，1300，1260，1177，1163，1094，989，837，761，686cm
-1.MS(EI，m/z)(％)：219(M
+，16)，120(100)；HRMS(EI)：Calcd.for?C
15H
25N[M]
+：219.1987；Found：219.1989.
Obtain N, N-two (3-aminomethyl phenyl) NSC 9824, yield 26%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.88(t，J＝7.0Hz，3H)，1.26-1.29(m，10H)，1.62-1.66(m，2H)，2.29(s，6H，2Me)，3.64(t，J＝7.5Hz，2H)，6.75-6.79(m，6H，Ar)，7.14(t，J＝7.5Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，21.6，22.6，27.1，27.5，29.3，29.4，31.8，52.4，118.0，121.6，121.8，129.0，138.9，148.2.IR(neat)ν3035，2952，2919，2847，1727，1596，1575，1484，1452，1358，1264，1166，1134，1094，989，855，761，711，686cm
-1.MS(EI，m/z)(％)：309(20，M
+)，210(100)；HRMS(EI)：Calcd.for?C
22H
31N[M]
+：309.2457；Found：309.2460.
Instance 39
The reaction of 2-methyl chlorinated benzene and NSC 9824
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), NSC 9824 (88 μ L, 0.96mmol), 2-methyl chlorinated benzene (96 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-2-aminomethyl phenyl NSC 9824, yield 16%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.90(t，J＝7.0Hz，3H)，1.25-1.45(m，10H)，1.64-1.70(m，2H)，2.13(s，3H，Me)，3.15(t，J＝7.0Hz，2H)，3.44(br，1H)，6.61-6.66(m，2H，Ar)，7.05(d，J＝7.5Hz，1H，Ar)，7.13(t，J＝7.5Hz，1H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，17.4，22.6，27.2，29.3，29.4，29.6，31.8，44.0，109.6，116.6，121.7，127.1，130.0，146.4.
Obtain N, N-two (2-aminomethyl phenyl) NSC 9824, yield 60%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.87(t，J＝7.0Hz，3H)，1.25-1.32(m，10H)，1.58-1.64(m，2H)，2.05(s，6H，2Me)，3.39(t，J＝8.0Hz，2H)，6.90-6.96(m，4H，Ar)，7.09-7.14(m，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，18.7，22.6，27.2，28.1，29.3，29.4，31.8，53.2，122.7，122.8，126.2，131.4，133.2，148.8.IR(neat)ν3017，2948，2919，2851，1593，1575，1484，1455，1372，1260，1217，1123，1108，1033，982，747，714cm
-1.MS(EI，m/z)(％)：309(21，M
+)，210(100)，94(18)；HRMS(EI)：Calcd.for?C
22H
31N[M]
+：309.2457；Found：309.2456.
Instance 40
The reaction of 4-methoxyl group chlorinated benzene and NSC 9824
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), NSC 9824 (88 μ L, 0.96mmol), 4-methoxyl group chlorinated benzene (98 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.Rotary Evaporators solvent evaporated, rapid column chromatography obtain N-4-p-methoxy-phenyl NSC 9824, yield 85%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.88(t，J＝7.0Hz，3H)，1.28-1.39(m，10H)，1.57-1.63(m，2H)，3.06(t，J＝7.0Hz，2H)，3.75(s，3H，OMe)，6.59(d，J＝8.5Hz，2H，Ar)，6.78(d，J＝8.5Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，22.6，27.2，29.3，29.4，29.7，31.8，45.2，55.9，114.2，115.0，142.8，152.1.
Obtain N, N-two (4-aminomethyl phenyl) NSC 9824, yield 10%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.87(t，J＝7.0Hz，3H)，1.26-1.29(m，10H)，1.59-1.63(m，2H)，3.55(t，J＝7.5Hz，2H)，3.78(s，6H，2MeO)，6.81(d，J＝8.5Hz，4H，Ar)，6.88(d，J＝8.5Hz，4H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，22.6，27.1，27.5，29.3，29.4，31.8，53.0，56.5，114.6，122.1，142.5，154.2.IR(neat)ν2927，2847，1737，1571，1502，1459，1437，1365，1235，1173，1036，816cm
-1.MS(EI，m/z)(％)：341(M
+，36)，242(100)，210(47)，91(47)；HRMS(EI)：Calcd.for?C
22H
31NO
2[M]
+：341.2355；Found：341.2353.
Instance 41
2, the reaction of 6-dimethylated chlorobenzene and NSC 9824
Under the nitrogen protection, in reaction tubes, add successively potassium tert.-butoxide (114.0mg, 1.0mmol), catalyzer (5.2mg 1.0mol%), heavily steams toluene (1.0mL), NSC 9824 (88 μ L, 0.96mmol), 2, the 6-dimethylated chlorobenzene (106 μ L, 0.8mmol).This reaction mixture refluxed was stirred 4 hours.The Rotary Evaporators solvent evaporated, rapid column chromatography obtains N-2,6-3,5-dimethylphenyl NSC 9824, yield 62%.
1H?NMR(500MHz，CDCl
3，TMS)δ0.89(t，J＝7.0Hz，3H)，1.28-1.38(m，10H)，1.55-1.61(m，2H)，2.29(s，6H，2Me)，2.97(t，J＝7.5Hz，2H)，6.81(t，J＝7.5Hz，1H，Ar)，6.99(d，J＝7.5Hz，2H，Ar).
13C?NMR(125MHz，CDCl
3)δ14.1，18.5，22.6，27.2，29.3，29.5，31.2，31.8，48.7，121.5，128.9，129.1，146.5.
Claims (5)
1. the present invention relates to a kind of is catalyzer with N-heterocyclic carbine-metal-imidazol complex, realizes the linked reaction between aryl muriate and aryl or the alkylamine, reaches the purpose that carbon-nitrogen bond forms.Can represent with following general formula:
Wherein X can be iodine, bromine or chlorine, further is recommended as chlorine.
R wherein
1Represent 2-, 3-, the substituting group on the 4-position, or represent two replacement or multi-substituents on the aromatic ring.R
1Can be H, C
1-C
6Alkoxyl group, NO
2, CN, COR
3(R
3Be H, C
1-C
6Alkyl, aryl etc.), COOR
4(R
4Can be H or C
1-C
6Alkyl), C
1-C
6Alkyl, aryl, NR
7R
8(R
7, R
8Be H, C
1-C
6Alkyl, benzyl or aryl etc.).R
1Also represent the aromatic ring of benzo, like naphthalene nucleus.Described aryl is recommended as phenyl, and (substituting group is C to substituted-phenyl
1-C
6Alkyl, C
1-C
6Alkoxyl group), naphthyl, five arrive seven-membered ring heteroaryl for example pyridine, pyrroles, imidazoles, furans, thiophene etc.
R
2Represent the 2-on the aromatic amine, 3-, one of 4-position replaces, two replacement or multi-substituents.R
2Can be C
1-C
6The straight or branched alkyl, C
1-C
6Alkoxyl group.Described aryl is recommended as phenyl, and (substituting group is C to substituted-phenyl
1-C
6Alkyl, C
1-C
6Alkoxyl group), naphthyl, five arrive seven-membered ring heteroaryl for example pyridine, pyrroles, imidazoles, furans, thiophene etc.
R
3Can be H, C
1-C
6Alkyl.
In the reaction of the present invention, used N-heterocyclic carbine-metal-imidazol complex consumption is recommended as 0.001-10mol% (with respect to aryl halide), and the mol ratio between employed amine and the halogenide is recommended as 1: 1 to 5: 1.
The reaction temperature of carrying out is recommended as-10-150 ℃, especially be recommended as 60-120 ℃.Reaction times is recommended as 2-24 hour.
In the reaction of the present invention, employed alkali can be KHCO
3, K
2CO
3, Na
2CO
3, Cs
2CO
3, NaHCO
3, CH
3COOK, CH
3ONa, CsF, K
3PO
43H
2O, NaOH, KOH, KO
tBu, NaO
tBu or the like.
In the reaction of the present invention, employed solvent can be the mixed solvent of water, THF, benzene, toluene, dioxane or organic solvent and water.
In the N-heterocyclic carbine-metal that relates among the present invention-imidazol complex:
R wherein
4And R
5Group can be H, C
1-C
6Alkoxyl group, C
1-C
6Alkyl.
Wherein X can I
-, Br
-, Cl
-, CH
3COO
-, CF
3COO
-, OSO
2CF
3Or the like.
R wherein
6Can be C
1-C
6Alkyl, aryl is also represented the aromatic ring of benzo, like naphthalene nucleus.
Metal center M can be iron, copper, silver, nickel, palladium, cobalt, rhodium, ruthenium or the like, further is recommended as palladium metal.
2. the linked reaction between a kind of aryl muriate as claimed in claim 1 and primary amine or the secondary amine is characterized in that catalyzer is N-heterocyclic carbine-metal-imidazol complex.
3. in the metal catalyst as claimed in claim 1, metal center M can iron, copper, silver, nickel, palladium, cobalt, rhodium, ruthenium or the like.
4. the linked reaction between a kind of aryl muriate as claimed in claim 1 and primary amine or the secondary amine is characterized in that described alkali can be KHCO
3, K
2CO
3, Na
2CO
3, Cs
2CO
3, NaHCO
3, CH
3COOK, CH
3ONa, CsF, K
3PO
43H
2O, NaOH, KOH, KO
tBu, NaO
tBu or the like.
5. the linked reaction between a kind of aryl muriate as claimed in claim 1 and primary amine or the secondary amine is characterized in that described solvent can be the mixed solvent of water, THF, benzene, toluene, dioxane or organic solvent and water.
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| CN104549504A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | NHC-metal-imidazole structured catalyst and preparation method thereof |
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| CN103691485A (en) * | 2013-12-19 | 2014-04-02 | 天津大学 | Method for preparing hydroquinone by catalytic hydrogenation, catalyst used by method and preparation method of catalyst |
| CN103691485B (en) * | 2013-12-19 | 2015-11-18 | 天津大学 | The method of hydroquinones and the catalyst of use thereof and preparation method is prepared for catalytic hydrogenation |
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