Metal iridium catalyst with 2, 2'-bis-benzimidazole ligand and method for synthesizing N-methylated primary amine

A technology of bisbenzimidazole and synthesis method, applied in the directions of organic compound/hydride/coordination complex catalyst, chemical instrument and method, physical/chemical process catalyst, etc., can solve problems such as long reaction time, and achieve reaction conditions Mild, broad development prospects, high reaction atom economy effect

Active Publication Date: 2019-03-05
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this type of catalytic synthesis requires high temperature (150°C), long reaction

Method used

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  • Metal iridium catalyst with 2, 2'-bis-benzimidazole ligand and method for synthesizing N-methylated primary amine
  • Metal iridium catalyst with 2, 2'-bis-benzimidazole ligand and method for synthesizing N-methylated primary amine
  • Metal iridium catalyst with 2, 2'-bis-benzimidazole ligand and method for synthesizing N-methylated primary amine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] [Cp*Ir(BiBzImH2)Cl][Cl]

[0034]

[0035] Dichloro(pentamethylcyclopentadienyl) iridium dimer (100mg, 0.126mmol), bisbenzimidazole (65mg, 0.277mmol, 2.2equiv) and N,N-dimethylformamide (3mL ) into a 25mL Kirschner tube in turn. Under nitrogen protection, react at a temperature of 60° C. for 12 hours, and then cool to room temperature. Filtration and washing with petroleum ether gave the target product as a yellow solid. Yield: 65%

[0036] 1 H NMR (500MHz, CDCl 3 )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); 13 C NMR (125MHz, CDCl 3 )δ144.1,138.9,134.2,126.2,125.1,116.5,115.0,87.6,10.2.HRMS-EI(70eV)m / zcalcd for C 24 h 25 ikB 4 [M+H] + 597.1392, found 597.1397.

[0037] Its single crystal structure is as follows:

[0038]

[0039] Single crystal structure: bond length (10 -10 m), 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...

Embodiment 2

[0041] N-Methylaniline

[0042] N-methylbenzonamine

[0043]

[0044] Aniline (46 mg, 0.5 mmol), cat 1 (3.2 mg, 0.005 mmol, 1 mol%), cesium carbonate (49 mg, 0.15 mmol, 0.3 equiv.) and methanol (1 mL) were sequentially added to a 25 mL Kirschner tube. After reacting at a temperature of 120° C. for 12 hours, it was cooled to room temperature. Rotary evaporation removes solvent, then obtains pure target compound by column chromatography (developing solvent: sherwood oil / ethyl acetate), productive rate: 92%

[0045] 1HNMR (500MHz, CDCl 3 )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,CH 3 ); 13 C NMR (125MHz, CDCl 3 ) δ149.2, 129.1, 117.1, 112.3, 30.6.

Embodiment 3

[0047] 4-Chloro-N-methylaniline

[0048] 4-chloro-N-methylbenzonamine

[0049]

[0050] p-Chloroaniline (71 mg, 0.5 mmol), cat 1 (3.2 mg, 0.005 mmol, 1 mol%), cesium carbonate (49 mg, 0.15 mmol, 0.3 equiv.) and methanol (1 mL) were sequentially added to a 25 mL Kirschner tube. After reacting at a temperature of 120° C. for 12 hours, it was cooled to room temperature. Rotary evaporation removes solvent, then obtains pure target compound by column chromatography (developing solvent: sherwood oil / ethyl acetate), productive rate: 90%

[0051] 1 HNMR (500MHz, CDCl 3 )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, CH 3 ); 13 C NMR (125MHz, CDCl 3 ) δ 147.8, 128.8, 121.5, 113.5, 30.6.

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Abstract

The invention discloses a metal iridium catalyst with a 2, 2'-bis-benzimidazole ligand and a method for synthesizing N-methylated primary amine, an iridium metal complex containing the bis-benzimidazole ligand is used as a catalyst to activate methylation reaction of wide-source and low-toxicity methanol and an aromatic primary amine. Compared with the prior art, the method disclosed by the invention has the advantages that only a weak alkali needs to be added in the reaction process, the reaction temperature is 120 DEG C, and nitrogen protection, high temperature and high pressure, long-timereaction and other harsh conditions are not needed; meanwhile, a by-product only comprises water, and cause no environment pollution; therefore, the method has a wide development prospect.

Description

technical field [0001] The invention belongs to the technical field of organometallic chemistry and organic synthetic chemistry, and specifically relates to a metal iridium catalyst and a synthesis method of N-methylated primary amine thereof. Background technique [0002] N-methylation of primary amines is an important class of organic synthesis reactions, widely used in the 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.; .2004, 104, 5823-5846.). For example, pariparib hydrochloride has significant inhibitory effects on platelet-derived growth factor receptors and vascular endothelial cell growth factor receptors, and has inhibitory effects on non-small cell lung cancer, renal cell carcinoma, sarcoma and other types of tumors. [0003] The main synthesis method of N-methylated pr...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07F17/02C07C209/18C07C211/48C07C211/52C07C213/08C07C217/84C07C221/00C07C225/22C07C227/18C07C229/60C07C253/30C07C255/58C07C315/04C07C317/36C07C211/58C07D213/74C07D241/20C07D235/30C07D277/82C07C303/40C07C311/03C07C311/14C07C311/13C07C311/29C07C311/16
CPCB01J31/1815B01J31/2295B01J2231/4283B01J2531/0225B01J2531/0238B01J2531/827C07C209/18C07C213/08C07C221/00C07C227/18C07C253/30C07C303/40C07C315/04C07D213/74C07D235/30C07D241/20C07D277/82C07F17/02C07C211/48C07C211/52C07C217/84C07C225/22C07C229/60C07C255/58C07C317/36C07C211/58C07C311/16C07C311/29C07C311/13C07C311/14C07C311/03
Inventor 李峰梁然
Owner NANJING UNIV OF SCI & TECH
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