Method for catalyzing and synthesizing optically pure beta-nitramine derivative

A technology of derivatives and nitramines, applied in the field of synthesis of β-nitroamines

Inactive Publication Date: 2015-01-21
JINGCHU UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although this method has high yield and good selectivity, its catalyst contains rare earth precious metals, so it is expensive and difficult to industrialize production
Other known complex catalysts also have disadvantages such as high cost and poor selectivity

Method used

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  • Method for catalyzing and synthesizing optically pure beta-nitramine derivative
  • Method for catalyzing and synthesizing optically pure beta-nitramine derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Example 1: Synthesis of (S)-1-nitro-2-(4-nitrophenyl)-2-tert-butoxyamide ethane

[0034] Add 0.49 g (1 mmol) of chiral copper complex (catalyst) and 40 mL of absolute ethanol as a solvent into a 100 mL flask. Then add 4-nitrophenyl tert-butoxyimide 5.0 g (20 mmol) and nitromethane 3.66 g (commercially available industrial product 98%, 60 mmol) successively under stirring, after stirring at room temperature for 2 hours, reduce The solvent was removed by rotary evaporation. The obtained crude product was directly separated by silica gel column chromatography (eluent: 1:3 diethyl ether / petroleum ether), and the product was dried in vacuum for 24 hours to obtain a light yellow product, which was 5.72 g of β-nitroamine derivatives, yield: 92 %, purity HPLC: 98.5%, optically pure HPLC, ee: 95%. Characterization data: nuclear magnetic resonance spectrum (hydrogen spectrum) 8.32 (d, 2H, J = 8.4 Hz), 7.55 (d, 2H, J = 8.4 Hz), 5.57 (brs, 1H), 5.46 (brs, 1H), 4.91 (m, 1H...

Embodiment 2

[0035] Example 2: Synthesis of (S)-1-nitro-2-(4-cyanophenyl)-2-tert-butoxyamide ethane

[0036]Add 0.49 g (1 mmol) of chiral copper complex (catalyst) and 40 mL of absolute ethanol as a solvent into a 100 mL flask. Then add 4.60 g (20 mmol) of 4-cyanophenyl tert-butoxyimide and 3.66 g of nitromethane (commercially available industrial product 98%, 60 mmol) successively under stirring, and after stirring at room temperature for 4 hours, reduce The solvent was removed by rotary evaporation. The obtained crude product was directly separated by silica gel column chromatography (eluent: 1:3 diethyl ether / petroleum ether), and the product was dried in vacuum for 24 hours to obtain a light yellow product, which was 5.35 g of β-nitroamine derivatives, yield: 92 %, purity HPLC: 98%, optically pure HPLC, ee: 93%. Characterization data: nuclear magnetic resonance spectrum (hydrogen spectrum) 7.70 (d, 2H, J = 8.0 Hz), 7.56 (d, 2H, J = 8.0 Hz), 5.56-5.53 (brs, 2H), 4.59 (m, 1H), 4...

Embodiment 3

[0037] Example 3: Synthesis of (S)-1-nitro-2-(3-pyridyl)-2-tert-butoxyamide ethane

[0038] Add 0.49 g (1 mmol) of chiral copper complex (catalyst) and 40 mL of absolute ethanol as a solvent into a 100 mL flask. Then add 4.12 g (20 mmol) of 3-tert-butoxyimide pyridine and 3.66 g (commercially available industrial products, 60 mmol) successively under stirring, stir and react at room temperature for 2 hours, and then rotary evaporate under reduced pressure Remove solvent. The obtained crude product was directly separated by silica gel column chromatography (eluent: 5% methanol / dichloromethane), and the product was dried in vacuum for 24 hours to obtain a colorless oily product, namely β-nitroamine derivative 5.23g, the yield: 98%, purity HPLC: 98%, optically pure HPLC, ee: 93%. Characterization data: NMR spectrum (H spectrum) 8.66-8.61 (brs, 2H), 7.80 (d, 1H, J = 8.0 Hz), 7.37 (m, 1H), 5.56-5.53 (dd, 2H, J = 9.2, 2.8 Hz), 4.65 (m, 1H), 4.54 (dd, 1H, J = 13.2, 2.8 Hz...

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Abstract

The invention relates to an optically pure beta-nitramine derivative, which is characterized by comprising a general formula (I) as following, wherein R1 represents alkane group with carbon atoms being 2-8, cycloalkyl group with carbon atoms being 5-8, phenyl group, substituted phenyl group, heterocyclic radical or substituted heterocyclic radical. R2 represents aromatic base, tertbutyloxycarbonyl, benzyloxycarbonyl or methoxyphenyl. R3 represents H or methyl; R4 represents H or alkane group with carbon atoms being 1-6, or alkyl with carbon atoms being 2-6 and with functional group such as carboxyl and alkyl. The method has the advantages that a chiral copper complex is used as a catalyst, the optically pure beta-imine derivative is synthesized, preparation is convenient, price is low, and yield is high, large-batch synthesis can be carried out, and the method is suitable for industrial production and application.

Description

[0001] technical field [0002] The invention relates to the field of synthesis methods of β-nitroamine compounds, in particular to a method for synthesizing β-nitroamine derivatives through stereoselective catalysis of chiral copper complexes. [0003] Background technique [0004] β-Nitramine is a very important intermediate in organic synthesis and pharmaceutical chemical synthesis. By reducing the nitro group in β-nitroamine, it can be converted into very useful chiral ortho-diamine compounds in one step. β-nitroamines can also be peroxidized to give chiral α-amino acid derivatives. These compounds are widely used in drug synthesis. In particular, there are few synthetic methods for chiral ortho-diamine compounds, but their demand in the synthesis of pharmaceutical functional molecules and intermediates is very large. For example, chiral ortho-diamine is a key intermediate in the synthesis of some important raw materials such as Nemonapride. [0005] In...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B53/00C07C271/14C07C269/06C07D213/40
Inventor 刘娥刘金丽李立李立威杨成雄
Owner JINGCHU UNIV OF TECH
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