α-alkoxy-α-nitroxyacetic acid ester derivatives and their synthesis methods and applications

A technology for nitroxyl acetate and a synthesis method, which is applied in the directions of drug combination, organic chemistry, antitumor drugs, etc., can solve the problems of lack of catalyst, cumbersome operation, low yield and the like, and achieves efficient atom economy, simple and safe operation , the effect of high region selectivity

Active Publication Date: 2020-12-22
EAST CHINA NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Due to the low activity of the substrate, the lack of catalysts, and the difficulty in controlling the selectivity, the existing synthetic methods have the disadvantages of high cost, low yield, and complicated operation.

Method used

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  • α-alkoxy-α-nitroxyacetic acid ester derivatives and their synthesis methods and applications
  • α-alkoxy-α-nitroxyacetic acid ester derivatives and their synthesis methods and applications
  • α-alkoxy-α-nitroxyacetic acid ester derivatives and their synthesis methods and applications

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0076]

[0077] Nitrosobenzene (0.2mmol), Benzyl Alcohol (0.3mmol), [PdCl(allyl)] 2 (0.05mmol) and Molecular sieves (0.2g) were dissolved in dichloromethane (1.5mL), then methyl phenyldiazoacetate (0.3mmol) dissolved in dichloromethane (1ml) was added dropwise to the reaction system within one hour, and the reaction Carried out at room temperature, after the dropwise addition was complete, stirred for ten minutes. Its structure is shown in formula (2-1). The crude product was subjected to column chromatography (ethyl acetate:petroleum ether=1:30~1:20) to obtain a pure product with a yield of 82%. nuclear magnetic resonance 1 HNMR, 13 C NMR spectrum as figure 1 , 2 Shown, 1H NMR (400MHz, CDCl 3 )δ7.84–7.63(m,2H),7.52–7.16(m,10H),7.01-6.98(m,J=7.1Hz,3H),6.72(s,1H),4.61(dd,J=56.0, 12.0Hz, 1H), 4.48(dd, J=56.0, 12.4Hz, 1H), 3.65(s, 3H); 13C NMR (101MHz, CDCl 3 )δ168.76, 146.87, 138.08, 135.77, 129.48, 128.76, 128.67, 128.07, 127.92, 126.89, 123.03, 116.15, 105.16, 65.8...

Embodiment 2

[0079]

[0080] Nitrosobenzene (0.2mmol), m-methoxybenzyl alcohol (0.3mmol), [PdCl(allyl)] 2 (0.05mmol) and Molecular sieves (0.2g) were dissolved in dichloromethane (1.5mL), then methyl phenyldiazoacetate (0.3mmol) dissolved in dichloromethane (1ml) was added dropwise to the reaction system within one hour, and the reaction Carried out at room temperature, after the dropwise addition was complete, stirred for ten minutes. Its structure is shown in formula (2-2). The crude product was subjected to column chromatography (ethyl acetate:petroleum ether=1:30~1:20) to obtain a pure product with a yield of 70%. nuclear magnetic resonance 1 HNMR, 13 C NMR spectrum as image 3 , 4 Shown, 1HNMR (400MHz, CDCl 3 )δ7.75-7.74(m,2H),7.43-7.41(m,3H),7.26-7.23(m,3H),7.10–6.92(m,5H),6.85-6.84(m,2H),4.57( dd, J=48.0, 12.5Hz, 1H), 4.46 (dd, J=48.0, 12.5Hz, 1H), 3.76(s, 3H), 3.64(s, 3H); 13C NMR (101MHz, CDCl 3 )δ168.73,159.89,146.94,139.61,135.82,129.71,129.49,128.78,128.66,126.90,12...

Embodiment 3

[0082]

[0083] Nitrosobenzene (0.2mmol), m-bromobenzyl alcohol (0.3mmol), [PdCl(allyl)] 2 (0.05mmol) and Molecular sieves (0.2g) were dissolved in dichloromethane (1.5mL), then methyl phenyldiazoacetate (0.3mmol) dissolved in dichloromethane (1ml) was added dropwise to the reaction system within one hour, and the reaction Carried out at room temperature, after the dropwise addition was complete, stirred for ten minutes. Its structure is shown in formula (2-3). The crude product was subjected to column chromatography (ethyl acetate:petroleum ether=1:30~1:20) to obtain a pure product with a yield of 55%. nuclear magnetic resonance 1 HNMR, 13 C NMR spectrum as Figure 5 , 6 Shown, 1HNMR (400MHz, CDCl 3 )δ7.76-7.67(m,2H),7.56-7.55(m,1H),7.48–7.36(m,4H),7.35–7.14(m,4H),7.08-7.06(m,2H),7.02- 6.98 (m, 2H), 4.49 (dd, J = 16.0, 12.0Hz, 1H), 4.45 (dd, J = 16.0, 12.0Hz, 1H), 3.65 (s, 3H); 13C NMR (101MHz, CDCl 3 )δ168.52, 146.84, 140.21, 135.52, 130.90, 130.73, 130.17, 129.6...

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Abstract

The invention discloses an alpha-alkoxy-alpha-nitroxyacetate derivative, and a synthesis method and an application thereof. A diazonium compound, benzyl alcohol and nitrosobenzene which are used as raw materials undergo a one-step reaction at room temperature with allylpalladium chloride as a catalyst, an organic solvent as a solvent and 4A molecular sieve as an additive to obtain the alpha-alkoxy-alpha-nitroxyacetate derivative. The synthesis method of the alpha-alkoxy-alpha-nitroxyacetate derivative has the advantages of high atomic economy, high selectivity, low dosage of the catalyst, andsimplicity and safety in operation, and the alpha-alkoxy-alpha-nitroxyacetate derivative synthesized in the invention is an important organic synthesis intermediate. The alpha-alkoxy-alpha-nitroxyacetate derivative prepared in the invention can be used as an important intermediate for medicines and chemical industry, and has wide application prospects in the field of medicines.

Description

technical field [0001] The invention belongs to the fields of synthetic medicine and chemical industry, and mainly relates to an α-alkoxy-α-nitrogen acetate derivative and its synthesis method and application. Background technique [0002] Nitrogen oxides have good oxidation resistance because they can form stable nitrogen oxide free radicals. α-Alkoxy-α-Nitroxyacetate derivatives are important intermediates in organic synthesis and pharmaceutical synthesis. α-Alkoxy-α-Nitroxyacetate derivatives can also be used to synthesize many anti-breast cancer drugs, anti-liver cancer, antibiotics and anti-lymphoma drugs, etc. Due to low substrate activity, lack of catalyst, and difficult control of selectivity, the existing synthetic methods have the disadvantages of high cost, low yield, and cumbersome operation. Therefore, the rapid and efficient construction of biologically active α-alkoxy-α-nitroxyacetic acid ester scaffolds from relatively simple substrates has become a very me...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C291/04C07D333/16C07D307/42A61P35/00
CPCA61P35/00C07C291/04C07D307/42C07D333/16
Inventor 刘顺英余杰康正辉吴逸欣胡文浩董素珍
Owner EAST CHINA NORMAL UNIV
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