Method for preparing deuterated amino-acid esters by photocatalysis

A technology for the preparation of catalysis and amino acids, which is applied in organic chemical methods, cyanide reaction preparation, chemical instruments and methods, etc. It can solve the problems of uncontrollable sites, high cost and energy consumption, and restrict development, and achieve short reaction time and environmental protection. Good, the effect of reducing the cost of deuterium

Active Publication Date: 2022-07-15
安徽贵朋功能材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the preparation of deuterated amino acids has disadvantages such as cumbersome steps, low deuterated rate, high cost and energy consumption, and uncontrollable sites (J.Biol.Chem, 1937, 120, 531-536; BBA-Gen Subject, 1977, 497, 1-13; Biochim Biophys Acta, 1976, 446, 479-485.)
And / or the preparation of the deuterated amino acid ester of prior art often needs to be prepared in advance to obtain corresponding imidate (CN113214099A, CN114436871A, CN111004076A, CN110885294A etc.) or dehydrogenated amino acid ester (CN113200895A, CN112358412A etc.), subsequently It can only be carried out under the conditions of an expensive reaction system, which greatly restricts its development, and the method of directly using amino acid ester as a raw material to perform deuterium at a specific position has not been reported.

Method used

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  • Method for preparing deuterated amino-acid esters by photocatalysis
  • Method for preparing deuterated amino-acid esters by photocatalysis
  • Method for preparing deuterated amino-acid esters by photocatalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043]

[0044] (1) Dissolve 500 mmol of the above-mentioned amino acid ester compound in 25 mol of deuterium water, and add a composite catalyst (ferric chloride: 0.025 mmol, tetraphenyl phosphine chloride: 0.025 mmol, sodium tetraphenyl boron: 0.5 mmol, Na 2 B 12 H 12 : 0.5mmol, Al 2 O 3 : 0.25 mmol), N 2 Stir well under protection;

[0045] (2) Under the irradiation of a UV lamp with a power of 5W and a wavelength of 365nm, at room temperature (25°C) for a full reaction for 8h;

[0046] (3) after the reaction finishes, remove the catalyst by filtration, extract with ethyl acetate / water=1:1, and get the organic phase;

[0047] (4) The deuterated amino acid ester compound of the following formula can be obtained by separation by column chromatography. The isolated yield was 91% according to 1 The H NMR spectrum calculated the deuterium incorporation of this compound to be 97%.

[0048] 1 H NMR (400 MHz, D6-DMSO): δ 3.68 (m, 3H), 1.34 (m, 9H), 1.29-1.27 (m, 3H). ...

Embodiment 2

[0050]

[0051] (1) Dissolve 10 mmol of the above amino acid ester compound in 500 mmol of deuterium water, and add a composite catalyst (HCl: 0.1 mmol, tetraphenylphosphonium chloride: 0.1 mmol, potassium tetraphenylboron: 0.1 mmol, Cs 2 B 10 H 10 : 0.05mmol, Al 2 O 3 : 0.1 mmol), N 2 Stir well under protection;

[0052] (2) Under the irradiation of a UV lamp with a power of 25W and a wavelength of 265nm, fully react for 4h at room temperature (25°C);

[0053] (3) after the reaction finishes, the catalyst is removed by filtration, extracted with butyl acetate / water=1:1, and the organic phase is taken;

[0054] (4) The deuterated amino acid ester compound of the following formula can be obtained by separation by column chromatography. The isolated yield was 88% according to 1 The H NMR spectrum calculated the deuterium incorporation of this compound to be 95%.

[0055] 1 H NMR (400 MHz, D6-DMSO): δ 3.63 (m, 3H), 2.06-1.93 (m, 1H), 1.3 (m, 9H), 0.88-0.85 (m, 6H). ...

Embodiment 3

[0057]

[0058] (1) Dissolve 1 mol of the above-mentioned amino acid ester compound in 100 mol of deuterium water, and add a composite catalyst (AgNO 3 : 0.05mmol, Tetraphenylphosphonium chloride: 0.05mmol, Sodium tetraphenylboron: 0.5mmol, C 2 B 3 H 7 : 0.05mmol, Al 2 O 3 : 0.5 mmol), N 2 Stir well under protection;

[0059] (2) Under the irradiation of a UV lamp with a power of 50W and a wavelength of 395nm, fully react for 24h at room temperature (30°C);

[0060] (3) after the reaction finishes, the catalyst is removed by filtration, extracted with butyl acetate / water=1:1, and the organic phase is taken;

[0061] (4) The deuterated amino acid ester compound of the following formula can be obtained by separation by column chromatography. The isolated yield was 89% according to 1 The deuterium incorporation of this compound was calculated to be 96% from the H NMR spectrum

[0062] : 1 H NMR (400MHz, D6-DMSO): δ 7.37-7.36 (m, 2H), 7.34-7.32 (m, 2H), 7.31-7.30 (m...

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Abstract

The invention discloses a method for preparing deuterated amino-acid esters by photocatalysis, which is characterized in that in deuterium water which is cheapest and easy to obtain, amino-acid esters are taken as a raw material, and direct deuteration of the amino-acid esters is realized under mild conditions by synergistic catalysis of a plurality of catalysts, so that a target product, namely a deuterated amino-acid ester compound, is obtained. The invention provides a preparation method of deuterated amino-acid esters, which is simple to operate, mild, green, cheap and high in deuteration rate.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a novel photocatalytic method for preparing deuterated amino acid esters. Background technique [0002] The isotope of hydrogen (H) deuterium (D or 2 H), also known as deuterium, consists of a proton, a neutron and an electron. The abundance on Earth is 0.015%, mostly deuterium water D 2 O exists in seawater. In chemistry, especially in the field of medicinal chemistry, the research and synthesis of deuterated compounds has become one of the current research hotspots. Compared with C-H bonds, C-D bonds have higher bond energy, so breaking C-D requires more energy than breaking C-H bonds, and the breaking of C-H bonds is the most important step in the metabolic process of drug compounds. Deuterated compounds can reduce the rate of drug metabolism. Compared with ordinary drug molecules, deuterated drug molecules have the following advantages: prolonging the half-l...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B59/00C07C269/06C07C271/22C07C227/16C07C229/36C07D333/24C07D207/24
CPCC07B59/001C07B59/002C07C269/06C07C227/16C07D333/24C07D207/24C07B2200/05C07C271/22C07C229/36
Inventor 张海波漆斌陆静刘霁
Owner 安徽贵朋功能材料科技有限公司
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