CN109420525B - Metal iridium catalyst of 2, 2' -bis-benzimidazole ligand and method for synthesizing N-methylated primary amine by using metal iridium catalyst - Google Patents
Metal iridium catalyst of 2, 2' -bis-benzimidazole ligand and method for synthesizing N-methylated primary amine by using metal iridium catalyst Download PDFInfo
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Abstract
The invention discloses a metal iridium catalyst of a 2, 2' -bisbenzimidazole ligand and a method for synthesizing N-methylated primary amine by using the metal iridium complex containing the bisimidazole ligand as a catalyst activation source, wherein the methylation reaction is carried out on methanol with wide source and low toxicity and aromatic primary amine. Compared with the prior art, only weak base needs to be added in the reaction process, the reaction temperature is 120 ℃, nitrogen protection is not needed, and harsh conditions such as high temperature, high pressure, long-time reaction and the like are needed; meanwhile, the byproduct is only generated by water, and the environment pollution is avoided, so the method has wide development prospect.
Description
Technical Field
The invention belongs to the technical field of metal organic chemistry and organic synthetic chemistry, and particularly relates to a metal iridium catalyst and a synthetic method of N-methylated primary amine thereof.
Background
N-methylated primary amine reaction is an important organic synthesis reaction and is widely applied to synthesis of natural products, fine chemicals, pharmaceuticals and key intermediates. (a) Carey, f.a.; sundberg, r.j.advanced Organic Chemistry,4th ed.; kluwer Academic: New York, 2001; part B, Chapter 3.2.5.B) Aurelio, l.; brownlee, r.t.c.; hughes, A.B.chem.Rev.2004,104, 5823-5846.). For example, paliperidone hydrochloride has a remarkable inhibitory effect on platelet-derived growth factor receptors and vascular endothelial growth factor receptors, and has an inhibitory effect on multiple tumors such as non-small cell lung cancer, renal cell carcinoma, sarcoma and the like.
The main synthesis method of N-methylated primary amine is that the conventional method is that halogenated methane or dimethyl sulfate is used as a methylating agent to perform nucleophilic substitution reaction with amine. The method uses highly toxic raw materials, a large amount of alkali, generates halogen acid salt as a byproduct to pollute the environment, generates disubstituted methylation products at the same time, has low selectivity, and also causes low atomic efficiency of the reaction (a) F.A.Carey, R.J.Sundberg, Advanced Organic Chemistry,4th ed.; kluwer Academic: New York, 2001; part B, Chapter 3.2.5; b) R.N.Salvator, C.H.Yoon, K.W.Jung, Tetrahedron 2001,57, 7785-.
In recent years, the activation of methanol as a methylating agent by using a metal catalyst of ruthenium, iridium, manganese or the like has attracted much attention. (a) T.t.dang, b.ramalingam, m.a.seayad, ACS catal.2015,5,4082-4088.b) f.li, j.j.xie, h.shan, c.sun, l.chen, RSC adv.2012,2, 8645-; b) s.michlik, t.hill, r.kempe, adv.synth.catal.2012,354, 847-862; c) j.campos, l.s.sharninghausen, g.m.manas, r.h.crabtree, inorg.chem.2015,54,5079-5084.d) s.elangovan, j.neumann, j.b.sortais, k.junge, c.darcel, m.beller, nat.commu.2016, 7, 12641-: firstly, dehydrogenating methanol under the action of a transition metal catalyst to generate aldehyde and a transition metal hydrogen complex; then, formaldehyde and nucleophilic reagent amine compound are subjected to condensation reaction to generate condensation product and water; finally, the condensation product is subjected to reductive hydrogenation to generate an N-methylation product, and simultaneously, the transition metal hydrogen complex is dehydrogenated to complete the catalyst circulation. The methanol with wide sources and low toxicity is used as a methylating agent, only water is generated as a byproduct in the reaction, the method is environment-friendly, and the reaction atom economy is high. However, the catalytic synthesis needs high temperature (150 ℃), long reaction time (48h), a large amount of strong base, nitrogen protection and other harsh conditions. From the aspects of synthesis and environment, the development of a novel metal catalyst is urgently needed to realize that the reaction condition of N-methylated primary amine is milder and the environment is more friendly.
Disclosure of Invention
The invention aims to provide a metallic iridium catalyst and a synthetic method of N-methylated primary amine thereof.
The invention is realized by the following technical scheme:
the metallic iridium catalyst (formula I) of the 2, 2' -bis-benzimidazole ligand has the following structure:
a method for synthesizing the above catalyst, which comprises reacting dichloro (pentamethylcyclopentadienyl) iridium dimer (formula II)
[Cp*IrCl2]2
II
Is subjected to metal complex reaction with benzo-bisimidazole (formula III)
The reaction formula is
The specific synthesis steps are as follows: adding dichloro (pentamethylcyclopentadienyl) iridium dimer II, bis-benzimidazole III and solvent N, N-dimethylformamide into a reaction vessel, heating for several hours under the protection of nitrogen, cooling to room temperature, and filtering to obtain the target product.
Wherein, the dosage of the bisbenzimidazole is 2.2 equivalents of dichloro (pentamethylcyclopentadienyl) iridium dimer; the reaction temperature is 60 +/-10 ℃; the reaction time is not less than 12 hours.
Method for the synthesis of N-methylated primary amines (formula IV):
which comprises reacting an amine (formula V)
Methylation reaction with methanol (formula VI)
MeOH
VI
The reaction is carried out in the presence of a metal iridium catalyst of a 2, 2' -bis-benzimidazole ligand and a base, and the general formula of the reaction is
Wherein R is1Selected from the group consisting of methylphenyl, methoxyphenyl, trifluoromethylphenyl, halophenyl, pyridyl, pyrazinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, methylphenylsulfonyl, methoxyphenylsulfonyl, trifluoromethylphenylsulfonyl, halophenylsulfonyl.
The specific synthesis steps are as follows: adding amine, methanol, a metal iridium catalyst of a 2, 2' -bisbenzimidazole ligand and alkali into a reaction vessel, reacting the reaction mixture in an oil bath for several hours, cooling to room temperature, removing the solvent by rotary evaporation, and separating by a column to obtain the target compound.
Further, the base is selected from cesium carbonate; the molar ratio of the catalyst to the amine was 1.0 mol%; the molar ratio of base to amine is 0.3-0.5 equivalents; the reaction is carried out at 120 plus or minus 10 ℃; the reaction time is more than 12 hours.
Compared with the prior art, the iridium complex catalyst with the bisimidazole ligand is used for activating the methylation reaction of methanol with wide sources and low toxicity and amine, only 0.3-0.5 equivalent of weak base needs to be added in the reaction process, the reaction temperature is 120 +/-10 ℃, the reaction time is only over 12 hours, the reaction condition is milder, only water is generated as a byproduct, no environmental hazard is caused, and the reaction atom economy is high. Therefore, the reaction meets the requirement of green chemistry and has wide development prospect.
Detailed Description
The following examples are shown to illustrate certain embodiments of the present invention and should not be construed as limiting the scope of the invention. Many modifications, variations and changes in materials, methods and reaction conditions may be made simultaneously with respect to the disclosure herein. All such modifications, variations and changes are intended to fall within the spirit and scope of the present invention.
Example 1:
[Cp*Ir(BiBzImH2)Cl][Cl]
dichloro (pentamethylcyclopentadienyl) iridium dimer (100mg,0.126mmol), bisbenzimidazole (65mg,0.277mmol,2.2equiv), and N, N-dimethylformamide (3mL) were added in that order to a 25mL k tube. Reacting at 60 ℃ for 12 hours under the protection of nitrogen, and cooling to room temperature. Filtration and washing with petroleum ether gave the desired product as a yellow solid. Yield: 65 percent of
1H NMR(500MHz,CDCl3)δ14.9(br s,2H),7.78(d,J＝8.4Hz,2H),7.70(d,J＝8.4Hz,2H),7.50(t,J＝7.2Hz,2H),7.45(t,J＝7.2Hz,2H),1.84(s,15H)；13C NMR(125MHz,CDCl3)δ144.1,138.9,134.2,126.2,125.1,116.5,115.0,87.6,10.2.HRMS-EI(70eV)m/z calcd for C24H25ClIrN4[M+H]+597.1392,found 597.1397.。
The single crystal structure is as follows:
single crystal structure: bond length (10)-10m), bond angle (degrees): Ir-N1,2.145 (11); Ir-N3,2.117 (13); Ir-C5 (Cp), 2.159 (16); Ir-Cl,2.400 (5); N1-Ir-N3,75.9 (5); N1-Ir-Cl1,86.5 (3); N3-Ir-Cl1,89.0(4).
Example 2:
n-methylaniline
N-methylbenzenamine
Aniline (46mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 92 percent of
1HNMR(500MHz,CDCl3)δ7.19(t,J＝7.7Hz,2H,ArH)),6.7(t,J＝7.4Hz,1H,ArH),6.6(d,J＝8.1Hz,2H,ArH),2.8(s,2H,CH3)；13C NMR(125MHz,CDCl3)δ149.2,129.1,117.1,112.3,30.6.。
Example 3:
4-chloro-N-methylaniline
4-chloro-N-methylbenzenamine
P-chloroaniline (71mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 90 percent of
1HNMR(500MHz,CDCl3)δ7.11(d,J＝8.8Hz,2H,ArH),6.51(d,J＝8.8Hz,2H,ArH),3.69(br s,1H,NH),2.79(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ147.8,128.8,121.5,113.5,30.6.。
Example 4:
3-chloro-N-methylaniline
3-chloro-N-methylbenzenamine
3-chloroaniline (71mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL Km tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 89 percent
1H NMR(500MHz,CDCl3)δ7.06(t,J＝8.1Hz,1H,ArH),6.64(d,J＝2.1Hz,1H,ArH),6.54(t,J＝8.1Hz,1H,ArH),6.43(dd,J＝8.4Hz and 2.2Hz,1H,ArH),2.78(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ150.4,134.9,130.0,116.9,111.8,110.7,30.4.。
Example 5:
4-fluoro-N-methylaniline
4-fluoro-N-methylbenzenamine
Para-fluoroaniline (54mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL k-tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 93 percent
1HNMR(500MHz,CDCl3)δ6.89(t,J＝9.1Hz,2H,ArH),6.51(m,2H,ArH),2.8(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ156.6,154.8,148.6,115.6,130.0,31.2.。
Example 6:
2-fluoro-N-methylaniline
2-fluoro-N-methylbenzenamine
2-fluoroaniline (54mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL Kjeldahl tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 87 percent of
1H NMR(500MHz,CDCl3)δ7.01(t,J＝8.0Hz,1H,ArH),6.95(dd,J＝3.9Hz and 8.0Hz,1H,ArH),6.68(t,J＝8.0Hz,1H,ArH),6.59-6.63(m,1H,ArH),3.93(br s,1H,NH),2.87(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ152.4,150.6,145.7(d,JC-F＝11.9Hz),124.5(d,JC-F＝3.9Hz),116.2(d,JC-F＝6.6Hz),114.0(d,JC-F＝18.3Hz),113.4(d,JC-F＝2.8Hz),31.3.。
Example 7:
3, 5-difluoro-N-methylaniline
3,5-difluoro-N-methylbenzenamine
3, 5-difluoroaniline (64mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusel tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 94 percent of
1HNMR(500MHz,CDCl3)δ6.13-6.09(m,1H,ArH),6.07-6.05(m,2H,ArH),3.92(br s,1H,NH),2.79(d,J＝5.2Hz,3H,CH3)；13C NMR(125MHz,CDCl3)δ164.2,151.5,90.0-94.8,92.0,30.4。
Example 8:
4-bromo-N-methylaniline
4-bromo-N-methylbenzenamine
Para-bromoaniline (97mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 83 percent
1HNMR(500MHz,CDCl3)δ7.15(d,J＝8.9Hz,2H,ArH),6.34(d,J＝8.8Hz,2H,ArH),2.67(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ148.1,131.7,113.8,108.6,30.5.。
Example 9:
4-trifluoromethoxy-N-methylaniline
N-methyl-4-(trifluoromethoxy)benzenamine
P-trifluoromethoxyaniline (95mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusel tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 92 percent of
1H NMR(500MHz,CDCl3)δ7.03(d,J＝8.7Hz,2H,ArH),6.51(d,J＝8.8Hz,2H,ArH),2.82(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ148.1,140.3,122.3,119.7(q,JC-F＝255.6Hz),112.5,30.8.。
Example 10:
n, 4-methanesulfonyl aniline
N-methyl-4-(methylsulfonyl)benzenamine
4-Methanesulfonylaniline (86mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL Kjeldahl tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 95 percent
1HNMR(500MHz,CDCl3)δ7.69(d,J＝8.8Hz,2H,ArH),6.6(d,J＝9Hz,2H,ArH),4.39(br s,1H,NH),3.00(s,3H,CH3),2.89(d,J＝5.2Hz,3H,CH3)；13C NMR(125MHz,CDCl3)δ153.1,129.2,126.9,111.3,45.0,30.0.。
Example 11:
n-methyl-4-cyanoaniline
4-(methylamino)benzonitrile
4-cyanoaniline (59mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (82mg,0.25mmol,0.5equiv.), and methanol (1mL) were added sequentially to a 25mL Kjeldahl tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 82 percent of
1H NMR(500MHz,CDCl3)δ7.41(d,J＝8.7Hz,2H,ArH),6.54(d,J＝8.7Hz,2H,ArH),4.42(br s,1H,NH),2.86(d,J＝4.9Hz,3H,CH3)；13C NMR(125MHz,CDCl3)δ152.2,133.5,120.6,117.7,98.0,29.8.。
Example 12:
4-acetyl-N-methylaniline
1-(4-(methylamino)phenyl)ethanone
4-Aminoacetophenone (68mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL Kjeldahl tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 92 percent of
1H NMR(500MHz,CDCl3)δ7.83(d,J＝8.8Hz,2H,ArH),6.55(d,J＝8.8Hz,2H,ArH),4.31(br s,1H,NH),2.89(d,J＝5.3Hz,3H,CH3),2.50(s,3H)；13C NMR(125MHz,CDCl3)δ196.4,153.1,130.7,126.5,110.9,30.1,26.0.。
Example 13:
4-methylaminobenzoic acid methyl ester
methyl 4-(methylamino)benzoate
Methyl p-aminobenzoate (76mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL Kjeldahl tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 78 percent of
1H NMR(500MHz,CDCl3)δ7.86(d,J＝8.8Hz,2H,ArH),6.53(d,J＝8.8Hz,2H,ArH),4.27(br s,1H,NH),3.84(s,3H,3H),2.86(s,3H)；13C NMR(125MHz,CDCl3)δ167.4,152.9,131.4,118.0,111.0,51.4,30.0.。
Example 14:
n, 4-dimethylaniline
N,4-dimethylbenzenamine
P-methylaniline (61mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (82mg,0.25mmol,0.5equiv.), and methanol (1mL) were added to a 25mL Kjeldahl tube in that order. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 85 percent of
1HNMR(500MHz,CDCl3)δ6.99(d,J＝8.2Hz,2H,ArH),6.54(d,J＝8.3Hz,2H,ArH),2.80(s,3H,CH3),2.23(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ147.1,129.6,126.4,31.0,20.3.。
Example 15:
3-methoxy-N-methylaniline
3-methoxy-N-methylbenzenamine
M-methoxyaniline (69mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (82mg,0.25mmol,0.5equiv.), and methanol (1mL) were added sequentially to a 25mL krusel tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 91 percent
1HNMR(500MHz,CDCl3)δ7.08(t,J＝8.1Hz,1H,ArH),6.27(dd,J＝8.8Hz and 2.2Hz,1H,ArH),6.26(dd,J＝8.3Hz and 1.9Hz,1H,ArH),3.77(s,3H,CH3),2.8(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ160.8,150.7,129.8,105.6,102.3,98.3,55.0,30.6.。
Example 16:
3-chloro-N, 4-dimethylaniline
3-chloro-N,4-dimethylbenzenamine
3-chloro-p-toluidine (70.8mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 94 percent of
1HNMR(500MHz,CDCl3)δ7.41(d,J＝2.2Hz,1H,ArH),7.09(d,J＝1.9Hz,1H,ArH),5.69(br s,1H,NH),3.07(s,3H,CH3),2.51(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ148.4,134.7,123.9,112.4,111.2,30.7,18.8.。
Example 17:
n-methyl-2-naphthylamine
N-methylnaphthalen-2-amine
2-naphthylamine (72mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL Kjeldahl tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 84 percent
1HNMR(500MHz,CDCl3)δ7.78(m,2H,ArH),7.44(m,2H,ArH),7.37(t,J＝8Hz,1H,ArH),7.24(s,1H,ArH),4.43(br s,1H,NH),3.07(s,3H,CH3),3.02(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ147.0,135.3,128.8,127.6,127.5,126.3,125.9,121.9,117.9,103.7,30.6.。
Example 18:
n, 5-dimethylpyridin-2-amine
N,5-dimethylpyridin-2-amine
5-methyl-2-aminopyridine (61mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusel tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 90 percent of
1H NMR(500MHz,CDCl3)δ7.91(s,1H,ArH),7.23(m,1H,ArH),6.30(d,J＝8.4Hz,1H,ArH),4.59(br s,1H,NH),2.87(s,3H,CH3),2.16(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ157.8,147.4,138.2,121.1,105.7,29.1,17.2.。
Example 19:
n-methylpyridin-2-amine
N-methylpyridin-2-amine
2-aminopyridine (54mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (82mg,0.25mmol,0.5equiv.), and methanol (1mL) were added sequentially to a 25mL krusel tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 88 percent
1H NMR(500MHz,CDCl3)δ8.07(d,J＝5.2Hz,1H,ArH),7.40(t,J＝7.2Hz,1H,ArH),6.55(d,J＝6.1Hz,1H,ArH),6.35(dd,J＝1.1and 8.4Hz,1H,ArH),4.86(br s,1H,ArH),2.89(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ159.5,147.9,137.2,112.4,106.0,28.8。
Example 20:
n-methylpyrazin-2-amine
Pyrazin-2-ylamine
Aminopyrazine (42mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusel tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 95 percent
1HNMR(500MHz,CDCl3)δ7.99(s,1H,ArH),7.89(s,1H,ArH),7.8(d,J＝2.8Hz,1H,ArH),4.71(br s,1H,NH),2.97(d,J＝5.2Hz,3H,CH3)；13C NMR(125MHz,CDCl3)δ155.2,141.7,132.0,131.7,28.0.。
Example 21:
6-chloro-N-4-methylbenzothiazol-2-amine
6-chloro-N,4-dimethylbenzo[d]thiazol-2-amine
6-chloro-4-methylaminobenzothiazole (99mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added to a 25mL gram-vial in that order. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 92 percent of
1HNMR(500MHz,CDCl3)δ7.41(d,J＝2.1Hz,1H,ArH),7.09(s,1H,ArH),7.37(t,J＝8Hz,1H,ArH),5.69(br s,1H,NH),3.07(s,3H,CH3),2.5(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ168.1,150.2,131.0,129.5,127.0,126.0,117.9,31.9,18.2.。
Example 22:
n-methyl-1-benzylbenzothiazol-2-amines
1-benzyl-N-methyl-1H-benzo[d]imidazol-2-amine
2-amino-1-benzylbenzothiazole (112mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added to a 25mL krusel tube in that order. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 94 percent of
1HNMR(500MHz,CDCl3)δ7.53(d,J＝7.8Hz,1H,ArH),7.35-7.28(m,3H,ArH),7.15-7.13(m,3H,ArH),7.07-7.03(m,2H,ArH),5.08(s,2H,CH2),4.01(br s,1H,NH),3.07(d,J＝5.13Hz,3H,CH3)；13C NMR(125MHz,CDCl3)δ155.1,142.2,135.4,134.9,129.1,128.0,126.3,121.4,119.7,107.3,45.5,30.0.。
Example 23:
n-methylbenzenesulfonamides
N-methylbenzenesulfonamide
Benzenesulfonamide (79mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 95 percent
1HNMR(500MHz,CDCl3)δ7.86(d,J＝7.8Hz,2H,ArH),7.59(t,J＝7.4Hz,1H,ArH),7.53(t,J＝7.6Hz,2H,ArH),3.41(br s,1H,NH),2.66(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ138.7,132.6,129.0,127.1,29.1.。
Example 24:
n, 4-dimethyl benzene sulfonamide
N,4-dimethylbenzenesulfonamide
P-toluenesulfonamide (86mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusette. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 94 percent of
1HNMR(500MHz,CDCl3)δ7.74(d,J＝8.2Hz,2H,ArH),7.31(d,J＝8.1Hz,2H,ArH),2.64(s,3H,CH3),2.43(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ143.4,135.7,129.6,127.2,29.2,21.4.。
Example 25:
n, 2-methylbenzenesulfonamides
N,2-dimethylbenzenesulfonamide
M-toluenesulfonamide (86mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusette. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 90 percent of
1HNMR(500MHz,CDCl3)δ7.96(d,J＝8.1Hz,1H,ArH),7.46(t,J＝7.3Hz,1H,ArH),7.33(t,J＝6.4Hz,2H,ArH),2.64-2.63(m,6H,CH3)；13C NMR(125MHz,CDCl3)δ137.0,136.7,132.7,132.5,129.6,126.0,28.9,20.2.。
Example 26:
3-chloro-N-methylbenzenesulfonamide
3-chloro-N-methylbenzenesulfonamide
M-chlorobenzenesulfonamide (96mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL K.tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 92 percent of
1HNMR(500MHz,CDCl3)δ7.86(s,1H,ArH),7.75(d,J＝7.5Hz,1H,ArH),7.56(d,J＝7.5Hz,1H,ArH),7.48(t,J＝7.7Hz,1H,ArH),2.69(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ140.5,135.2,132.8,130.4,127.2,125.2,29.2.。
Example 27:
4-bromo-N-methylbenzenesulfonamides
4-Bromo-benzenesulfonamide
Para-bromobenzenesulfonamide (118mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusel tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 92 percent of
1HNMR(500MHz,CDCl3)δ7.7(d,J＝8.9Hz,2H,ArH),7.6(d,J＝8.9Hz,2H,ArH),2.67(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ137.8,132.8,128.7,127.6,29.2.。
Example 28:
n-methyl-4-trifluoromethylbenzenesulfonamide
N-methyl-4-(trifluoromethyl)benzenesulfonamide
P-trifluoromethylbenzenesulfonamide (113mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL Kjeldahl tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 93 percent
1HNMR(500MHz,CDCl3)δ8(d,J＝8.2Hz,2H,ArH),7.7(d,J＝8.3Hz,2H,ArH),2.69(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ142.5,134.5,127.7,123.6,123.2,29.2.。
Example 29:
n-methyl-4-trifluoromethoxybenzenesulphonamide
N-methyl-4-(trifluoromethoxy)benzenesulfonamide
P-trifluoromethoxybenzenesulfonamide (120mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL K.tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 96 percent
Yellow oil；96％yield(122.41mg)；1H NMR(500MHz,CDCl3)δ7.90(d,J＝8.8Hz,2H,ArH),7.31(d,J＝8.7Hz,2H,ArH),4.01(br s,1H,NH),2.63(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ151.9,137.6,129.3,119.2(q,JC-F＝260.1Hz),29.2.。
Example 30:
n-methyl-2-naphthalenesulfonamides
N-methylnaphthalene-2-sulfonamide
Naphthalene-2-benzenesulfonamide (96mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL Kjeldahl tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 93 percent
1H NMR(500MHz,CDCl3)δ8.44(s,1H,ArH),7.97(d,J＝8.6Hz,2H,ArH),7.91(d,J＝8.2Hz,1H,ArH),7.84(d,J＝8.6Hz,1H,ArH),7.65(t,J＝7.2Hz,1H,ArH),7.61(t,J＝7.1Hz,1H,ArH),4.59(br s,1H,NH),2.69(d,J＝5.4Hz,3H,CH3)；13C NMR(125MHz,CDCl3)δ135.4,134.7,132.0,129.4,129.1,128.7,128.6,127.8,127.4,122.2,29.2.。
Example 31:
n-methylbenzenesulfonamide
N-methyl(phenyl)methanesulfonamide
Benethanamide (86mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusette tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 92 percent of
1HNMR(500MHz,CDCl3)δ7.37(s,5H,ArH),4.42(br s,1H,NH),4.41(s,2H,CH3),2.64(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ130.5,129.3,128.8,128.6,57.5,29.6.。
Example 32:
n-methylcyclopropanesulfonamide
Cyclopropanesulfonic acid amide
Cyclopropanesulfonamide (60mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 89 percent
1HNMR(500MHz,CDCl3)δ2.84(s,3H,CH3),2.44-2.44(m,1H),1.17(m,2H),1(m,2H)；13C NMR(125MHz,CDCl3)δ29.3,28.4,4.8.。
Example 33:
n-methylmethanesulfonamide
N-methylmethanesulfonamide
Methylsulfonamide (48mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL krusel tube. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developing solvent: petroleum ether/ethyl acetate) to give the pure title compound in the following yields: 90 percent of
1H NMR(500MHz,CDCl3)δ2.95(s,3H,CH3),2.84(s,3H,CH3)；13C NMR(125MHz,CDCl3)δ38.5,29.2.。
Comparative example 1:
aniline (46mg,0.5mmol), cat 2(4.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The nuclear magnetic yield was 93%.
Comparative example 2:
aniline (46mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (16mg,0.05mmol,0.1equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The nuclear magnetic yield was 81%.
Comparative example 3:
aniline (46mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), cesium carbonate (49mg,0.05mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 110 ℃ the reaction mixture was cooled to room temperature. The nuclear magnetic yield is 52%.
Comparative example 4:
aniline (46mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), potassium carbonate (21mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL gram-vial. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The nuclear magnetic yield is 84%.
Comparative example 5:
aniline (46mg,0.5mmol), cat 1(3.2mg,0.005mmol,1 mol%), sodium carbonate (16mg,0.15mmol,0.3equiv.), and methanol (1mL) were added sequentially to a 25mL kreb. After 12 hours of reaction at 120 ℃ the reaction mixture was cooled to room temperature. The nuclear magnetic yield is 79%.
Claims (9)
- A metal iridium catalyst I of a 2, 2' -bis-benzimidazole ligand is characterized by having the following structure:
- 2. a process for preparing the iridium metal catalysts I as claimed in claim 1, comprising reacting dichloro (pentamethylcyclopentadienyl) iridium dimer II[Cp*IrCl2]2IIA step of carrying out metal complex reaction with the benzimidazole III,
- 3. the process according to claim 2, characterized in that the reaction is carried out in the presence of N, N-dimethylformamide as solvent.
- 4. The method according to claim 2, characterized in that the reaction is carried out under nitrogen protection; the amount of the bis-benzimidazole III is 2.2 equivalents of dichloro (pentamethylcyclopentadienyl) iridium dimer II; the reaction temperature is 60 +/-10 ℃; the reaction time is not less than 12 hours.
- 5. A process for the synthesis of N-methylated primary amines IV,
which comprises reacting an amine V
With methanol VI in the presence of a metal iridium catalyst I of a 2, 2' -bisbenzimidazole ligand and a base, with MeOHVI
Wherein R is1Comprises a compound selected from the group consisting of methylphenyl, methoxyphenyl, trifluoromethylphenyl, halophenyl, pyridyl, pyrazinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, methylphenylsulfonyl, methoxyphenylsulfonyl, trifluoromethylphenylsulfonyl, and halophenylsulfonyl. - 6. The method of claim 5, wherein the base is selected from cesium carbonate.
- 7. The process according to claim 5, wherein the iridium metal catalyst of the 2, 2' -bibenzimidazole ligand is used in a molar ratio of 1.0 mol% with respect to the amine.
- 8. The process according to claim 5, characterized in that the molar ratio of base to amine is between 0.3 and 0.5 equivalents.
- 9. The process according to claim 5, wherein the reaction is carried out at 120 ± 10 ℃; the reaction time is more than 12 hours.
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