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Method for reducing nitroxylbenzyl amine compound to amino-benzylamine hydrochloride

A technology of aminobenzylamine hydrochloride and nitrobenzylamine is applied in the field of reducing nitrobenzylamine compound to aminobenzylamine hydrochloride, and achieves the effects of mild reaction conditions, convenient post-processing and simple operation

Inactive Publication Date: 2006-11-22
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Since the Pd-C catalyst can reduce the nitro group and hydrogenolyze the benzyl group under almost the same conditions, so far, the method of Pd-C catalyzed hydrogenation from nitro-substituted N,N-dialkylbenzylamine cannot be effectively Amino-N, N-dialkylbenzylamines can be easily obtained (references: Shiraishi, M.; Aramaki, Y.; Seto, M. et al. J. Med. Chem., 2000, 43, 2049-2063.)

Method used

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Embodiment 1

[0053] Embodiment 1, use CHCl 3 Preparation of 4-amino-N,N-dimethylbenzylamine dihydrochloride (formula IX / a) as a source of HCl

[0054] At 25° C., 4-nitro-N, N-dimethylbenzylamine (formula VI / a, 450 mg, 2.5 mmol), 10% Pd / C (45 mg, 10% by weight) and CHCl 3 (2 mL) in methanol (30 mL) was hydrogenated at atmospheric pressure for 2 h, and the Pd / C catalyst was filtered off. The filtrate was distilled off of methanol under reduced pressure to obtain a crude product of yellow crystals. The yellow crystals were then washed with a small amount of ether to remove any non-salt-forming material. Finally by MeOH / Et 2 O was recrystallized to give pale yellow crystalline compound 4-amino-N,N-dimethylbenzylamine dihydrochloride (formula IX / a, 510 mg, 91%).

[0055] m.p.198-200℃(MeOH / Et 2 O);

[0056] 13 C NMR (CD 3 OH): δ133.7, 133.0, 130.5, 123.7, 60.1, 42.0;

[0057] Elemental analysis (C 9 h 16 N 2 Cl 2 ): C, 48.44; H, 7.23; N, 12.55; Found: C, 48.20; H, 7.24; N, 12.32.

Embodiment 2

[0058] Embodiment 2, use concentrated hydrochloric acid as the source of HCl to prepare 4-amino-N, N-dimethylbenzylamine dihydrochloride (formula IX / a)

[0059] At 25° C., 4-nitro-N, N-dimethylbenzylamine (formula VI / a, 450 mg, 2.5 mmol), 10% Pd / C (45 mg, 10% by weight) and 37% concentrated hydrochloric acid ( A suspension of 1 mL containing about 8 mmol of HCl) in methanol (30 mL) was hydrogenated at atmospheric pressure for 15 minutes, and hydrogen uptake ceased completely. The Pd / C catalyst was filtered off, and the filtrate was evaporated to remove methanol under reduced pressure to obtain a crude product of yellow crystals. The yellow crystals were then washed with a small amount of ether to remove any non-salt-forming material. Finally by MeOH / Et 2 O was recrystallized to give pale yellow crystalline compound 4-amino-N,N-dimethylbenzylamine dihydrochloride (formula IX / a, 550 mg, 98%). The physical data are the same as in Example 1.

Embodiment 3

[0060] Embodiment 3, preparation 4-amino-N, N-diethylbenzylamine dihydrochloride (formula IX / b)

[0061] Under the same conditions as in Example 2, the reaction was carried out with 4-nitro-N,N-diethylbenzylamine (formula VI / b), and hydrogen absorption was completely stopped after 15 minutes. The crude product was obtained from MeOH / Et 2 Recrystallization from O gave pale yellow crystalline compound 4-amino-N,N-diethylbenzylamine dihydrochloride (Formula IX / b, 100%).

[0062] m.p.180-182℃(MeOH / Et 2 O);

[0063] 13 C NMR (CD 3 OH): δ150.0, 132.2, 117.3, 115.1, 56.2, 46.4, 8.1;

[0064] Elemental analysis (C 11 h 20 N 2 Cl 2 ): C, 52.60; H, 8.03; N, 11.15; Found: C, 52.48; H, 8.03; N, 11.17.

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Abstract

This invention discloses a method for reducing the nitrabenzylamine compound to be nitrabenzylamine hydrochlorate whichreduces the nitrabenzylamine compound under hydrogen gas atmosphere by catalytic hydrogenation, using Pd-C / HCl catalytic system. This invention reduces the reaction activity of Pd-C catalyst by adding HCl or hydrochloric acid or CHCl3 which can produce HCl during the reaction to the reaction system, to entitle the Pd-C catalyst with the activity of catalyzing the nitro group of hydrogenated nitrobenzylamine compound to be amidol, without benzyl hydrogenolysis. This invention is characterized of simple operation, mild reaction condition, convenient treatment of post-production material, and broad application future.

Description

technical field [0001] The invention relates to a method for reducing nitrobenzylamine compound to aminobenzylamine hydrochloride. Background technique [0002] Pd-metal catalysts play a very important role in the transformation of functional groups in modern organic synthesis. Pd-metal catalysts with chemical functional group selectivity have very special application value, such as: Lindler catalyst [Pd-CaCO 3 -Pb(OAc) 2 ] can selectively reduce acetylenic bonds to cis-olefinic bonds; Rosenmund catalyst (Pd-BaSO 4 ) can selectively reduce acid chlorides to aldehydes. [0003] Pd-C catalyst is one of the most easily prepared Pd-metal catalysts, and it is also the most commonly used Pd-metal catalyst in organic synthesis. In the presence of Pd-C catalysts, the use of clean hydrogen not only enables efficient transformation of many organic functional groups, but also features high yields, simple post-processing, atom economy, and environmental friendliness. For example: u...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/36B01J21/18B01J23/44C07C211/49
Inventor 胡跃飞程传杰王歆燕邢立新
Owner TSINGHUA UNIV
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