Preparation method of dithioerythritol (DTE)

A technology of dithioerythritol and dibutanol, which is applied in the field of compound preparation and achieves the effects of high yield, easily controllable conditions and easy industrial production

Inactive Publication Date: 2017-10-10
EAST CHINA NORMAL UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] It is one of the difficulties in the synthesis of DTE to construct the dihydroxyl group in the e

Method used

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  • Preparation method of dithioerythritol (DTE)
  • Preparation method of dithioerythritol (DTE)
  • Preparation method of dithioerythritol (DTE)

Examples

Experimental program
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Effect test

Embodiment 1

[0043] Dissolve 10g of cis-1,4-dichloro-2-butene (Sinopharm Group Shanghai Chemical Reagent Company, chemically pure) in 60mL of acetone and 20mL of water in a three-necked flask, and drop it into ice water until the internal temperature of the system is 0°C- 5°C, add 15.16 g of potassium permanganate (Sinopharm Group Shanghai Chemical Reagent Company, chemically pure) in three batches. React for 5 hours, use TLC to monitor the complete reaction of the raw materials, remove the solids by suction filtration, add an appropriate amount of activated carbon to stir and then suction filter, distill off acetone under reduced pressure, add ethyl acetate, wash with saturated sodium chloride solution, separate the organic phase, anhydrous Dry over sodium sulfate, evaporate to dryness, and use ethyl acetate to petroleum ether volume ratio of 1:6 to raise temperature and reflux for beating and purification. 8.5 g of the product formula (I) 1,4-dichloro-2,3-dibutanol was obtained, with a y...

Embodiment 2

[0054] Dissolve 2g of formula (I) 1,4-dichloro-2,3-dibutanol in 20mL of dichloromethane in a one-mouth bottle, add 1.27g of triethylamine (Shanghai Chemical Reagent Company, Sinopharm Group, chemically pure), Add 2.8 mL of acetic anhydride (Sinopharm Shanghai Chemical Reagent Company, chemically pure) and heat to reflux (70° C.) for reaction under nitrogen protection. After 8 hours of reaction, TLC detected that the reaction of the raw materials was complete. Evaporate acetic anhydride, add ethyl acetate, wash with saturated sodium bicarbonate solution, wash with aqueous solution, separate the organic phase, dry over anhydrous sodium sulfate, evaporate to dryness, and use ethyl acetate and petroleum ether at a volume ratio of 1:5. Purification by beating. 2.15 g of 1,4-dichloro-2,3-diacetate of formula (II) was obtained with a yield of 71%.

[0055] 1 H NMR (400MHz, CDCl 3 ):δ=2.07(s,6H),3.61(dd,J=12.0,4.0Hz,2H),3.75(dd,J=12.0,4.0Hz,2H),5.25(s,2H).MS(ESI) :calculated for[...

Embodiment 3

[0063] Dissolve 5g of formula (II) 1,4-dichloro-2,3-diacetate in 20mL of N,N-dimethylformamide in a single-necked bottle, add 0.2g of sodium iodide (Sinopharm Shanghai Chemical Reagent Company, chemically pure), and then add 5.85g of potassium thioacetate (Sinopharm Shanghai Chemical Reagent Company, chemically pure), and heat to reflux (80-90° C.) for reaction. The reaction was carried out for 3 to 5 hours, and TLC detected that the reaction of the raw materials was complete. Add ethyl acetate, wash with water, separate the organic phase, decolorize with activated carbon for 1 hour, filter with suction, add anhydrous sodium sulfate to dry, and evaporate to dryness. 4.65 g of 1,4-dithioacetyl-2,3-acetate of formula (III) was obtained with a yield of 70%.

[0064] 1 H NMR: (500MHz, CDCl 3 ):δ=2.07(s,6H),2.36(s,6H),3.07(dd,J=14.0,6.5Hz,2H),3.11(dd,J=14.0,3.0Hz,2H),5.15(s, 2H).MS(ESI):calculated for [C 12 h 18 o 6 S 2 H] + (M+H) + requires m / z=323.06, found: 323.05.

...

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Abstract

The invention discloses a method for preparing dithioerythritol (DTE). The method comprises the following steps: (a) performing a cis-dihydroxylation reaction on the initial raw material cis-1,4-dichloro-2-butene and potassium permanganate under low temperature conditions to obtain 1,4-dichloro-2,3-butanediol disclosed as Formula (I); (b) adding the 1,4-dichloro-2,3-butanediol disclosed as Formula (I) into an organic alkali, and performing an esterification reaction with acetic anhydride to obtain 1,4-dichloro-2,3-diacetate disclosed as Formula (II); (c) performing a nucleophilic substitution reaction on the 1,4-dichloro-2,3-diacetate disclosed as Formula (II) and potassium thioacetate under the catalytic action of sodium iodide to obtain 1,4-dithioacetyl-2,3-acetate disclosed as Formula (III); and (d) hydrolyzing the 1,4-dithioacetyl-2,3-acetate disclosed as Formula (III) under acidic conditions to obtain the target product DTE disclosed as Formula (IV). The method has the advantages of low synthesis cost, short synthesis route, high safety, high product quality and high yield, is simple to operate, and conforms to the industrial production requirements.

Description

technical field [0001] The invention relates to the technical field of compound preparation, in particular to a preparation method of dithioerythritol. Background technique [0002] Dithioerythreitol (DTE) is a stereoisomer of dithiothreitol (DTT). The two hydroxyl groups of DTT are in the threo configuration, and the two hydroxyl groups in DTE are in the erythro configuration. DTE can be used as a reducing agent and deprotecting agent for sulfhydrylated DNA, and is also commonly used for the reduction of disulfide bonds in proteins to prevent the intramolecular or intermolecular disulfide bonds of proteins formed between cysteines in proteins. Its structural formula is: [0003] [0004] It is one of the difficulties in the synthesis of DTE to construct the dihydroxyl group in the erythroic configuration, and there are few literature reports on the synthesis method of dithioerythritol. The present invention performs cis-addition on cis-alkenes to obtain erythro-config...

Claims

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Application Information

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IPC IPC(8): C07C319/06C07C321/04
CPCC07C319/06C07C29/48C07C67/08C07C319/14C07C321/04C07C321/14C07C69/63C07C31/42
Inventor 占莉周朴赵超尤东磊伍彦仟张婧怡朱勇吕敏杰
Owner EAST CHINA NORMAL UNIV
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