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Method for catalytically synthesizing beta-amino carboxylic ester through cooperation of pentamethyl titanocene trichloride and 4-hydroxybenzoic acid

A technology of pentamethyltrichlorotitanocene and hydroxybenzoic acid, which is applied in the field of synthesis of β-aminocarboxylates, can solve the problems of catalyst prefabrication, harsh reaction conditions, and low reaction efficiency, and achieve a wide range of biological activities and Medicinal value, mild reaction conditions, and high atom economy

Pending Publication Date: 2021-08-03
SHAANXI NORMAL UNIV
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Problems solved by technology

[0003] Although Lewis acids have great applications in catalyzing the synthesis of β-aminocarboxylates, they sometimes face problems such as harsh reaction conditions, poor reaction selectivity, low reaction efficiency, weak substrate appl

Method used

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  • Method for catalytically synthesizing beta-amino carboxylic ester through cooperation of pentamethyl titanocene trichloride and 4-hydroxybenzoic acid
  • Method for catalytically synthesizing beta-amino carboxylic ester through cooperation of pentamethyl titanocene trichloride and 4-hydroxybenzoic acid
  • Method for catalytically synthesizing beta-amino carboxylic ester through cooperation of pentamethyl titanocene trichloride and 4-hydroxybenzoic acid

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Synthetic structural formula following 2,2-dimethyl-3-phenyl-3-(2-hydroxyl) methyl phenylalanine

[0016]

[0017] Add 0.0545g (0.5mmol) o-aminophenol, 71μL (0.7mmol) benzaldehyde, 102μL (0.5mmol) silyl ketene acetal, 0.0125g (0.05mmol) titanocene dichloride, 0.0181g (0.1mmol) p-hydroxybenzoic acid, 0.5mL ethanol, stirred and reacted at room temperature for 12 hours, stopped the reaction, cooled to room temperature naturally, removed ethanol by rotary evaporation, and separated with a silica gel column (eluent was ethyl acetate and sherwood oil) The volume ratio of the mixture is 1:10) to obtain methyl 2,2-dimethyl-3-phenyl-3-(2-hydroxy)phenylalanine with a yield of 93%.

[0018] The resulting product was characterized by a Bruker Avance superconducting Fourier digital NMR spectrometer, and the characterization data were: 1 HNMR (400MHz, CDCl 3 )δ7.36–7.23(m,5H),6.78–6.48(m,3H),6.43(d,J=6.9Hz,1H),5.73(s,1H),4.98(s,1H),4.62(s ,1H), 3.73(s,3H), 1.29(s,3H), 1.26(s, 3...

Embodiment 2

[0020] Synthesis of 2,2-dimethyl-3-(4-nitro)phenyl-3-(2-hydroxyl) methyl phenylalanine with the following structural formula

[0021]

[0022] In Example 1, the benzaldehyde used is replaced with equimolar 4-nitrobenzaldehyde, and other steps are the same as in Example 1 to obtain 2,2-dimethyl-3-(4-nitro)phenyl- 3-(2-Hydroxy)phenylalanine methyl ester, the yield was 66%.

[0023] The resulting product was characterized by a Bruker Avance superconducting Fourier digital NMR spectrometer, and the characterization data were: 1 H NMR (400MHz, CDCl 3 )δ8.17(d, J=8.6Hz, 2H), 7.51(d, J=8.6Hz, 2H), 7.28(s, 1H), 6.72(d, J=7.6Hz, 1H), 6.64(t, J=7.5Hz, 1H), 6.56(t, J=7.4Hz, 1H), 6.29 (d, J=7.7Hz, 1H), 5.46(s, 1H), 5.14(s, 1H), 4.69(s, 1H), 3.73(s,3H), 1.32(s,3H), 1.28(s,4H), 1.26(s,4H).; 13 C NMR (101MHz, CDCl 3 )δ176.63, 147.36, 143.68, 134.96, 129.20, 123.2, 121.28, 118.15, 114.37, 113.00, 64.21, 52.40, 47.09, 29.66, 24.15, 20.61.

Embodiment 3

[0025] Synthetic structural formula following 2,2-dimethyl-3-p-chlorophenyl-3-(2-hydroxyl) methyl phenylalanine

[0026]

[0027] In Example 1, the benzaldehyde used was replaced with 4-chlorobenzaldehyde, and other steps were the same as in Example 1 to obtain 2,2-dimethyl-3-p-chlorophenyl-3-(2-hydroxy)benzene Methyl allanate, the yield was 89%.

[0028] The resulting product was characterized by a Bruker Avance superconducting Fourier digital NMR spectrometer, and the characterization data were: 1 H NMR (400MHz, CDCl 3 )δ7.27(t, J=3.2Hz, 4H), 6.72(d, J=7.5Hz, 1H), 6.66(t, J=7.4Hz, 1H), 6.56(t, J=7.3Hz, 1H) ,6.36(d,J=7.7Hz,1H),4.57(s,1H),3.72(s,3H),1.28(s,3H),1.24(s,3H); 13 C NMR (101MHz, CDCl 3 )δ177.38, 144.08, 137.78, 135.37, 133.24, 129.70, 128.24, 121.2, 118.07, 114.36, 113.68, 64.11, 52.33, 47.27, 24.29, 20.24.

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Abstract

The invention discloses a method for catalytically synthesizing beta-amino carboxylic ester by using pentamethyl titanocene trichloride in cooperation with 4-hydroxybenzoic acid, which comprises the following steps of: under the condition that pentamethyl titanocene trichloride is used as a catalyst, 4-hydroxybenzoic acid is used as a ligand and ethanol is used as a solvent, a benzaldehyde compound reacts with an aniline compound and silyl ketene acetal to generate beta-amino carboxylic ester. The method is mild in reaction condition, simple to operate, short in reaction time, single in reaction product and high in atom economy, the product only needs to be subjected to simple column chromatography separation after the reaction is finished, and the obtained beta-amino carboxylic ester has wide biological activity and medicinal value.

Description

technical field [0001] The invention belongs to the technical field of synthesis of beta-aminocarboxylates, in particular to a method for synthesizing beta-aminocarboxylates by catalyzing pentamethyltrichlorotitanocene and 4-hydroxybenzoic acid. Background technique [0002] β-Aminocarboxylate derivatives have rich pharmacological and biological properties and are widely found in natural products. In addition, they are useful and versatile synthetic intermediates in organic chemistry. Therefore, there have been extensive studies on the synthesis of β-aminocarboxylate derivatives. The classic method for preparing β-aminocarboxylate is the Mannich reaction synthesis method: a molecule of silyl ketene acetal is condensed with a molecule of aldehyde and a molecule of ammonia to obtain β-aminocarboxylate. Due to the medicinal and synthetic value of these compounds, many scientists around the world are striving to develop other synthetic methods using a variety of catalysts, incl...

Claims

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Application Information

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IPC IPC(8): C07C227/02C07C229/34B01J31/22
CPCC07C227/02B01J31/2295B01J31/2208B01J2531/46C07C229/34
Inventor 高子伟涂丽杨明明孙华明
Owner SHAANXI NORMAL UNIV
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