Unlock instant, AI-driven research and patent intelligence for your innovation.

A kind of preparation method of fully acylated sugar alkenes

A technique for acylating glycoalkenes and acylated disaccharides, which is applied in the field of fully acylated glycosylated organic synthesis intermediates, can solve the problems of poor catalytic effect, large amount of Zn powder, and high production costs, so as to avoid high toxicity The use of chemical raw materials, mild reaction conditions, and low production costs

Inactive Publication Date: 2016-01-20
EAST CHINA NORMAL UNIV
View PDF4 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] The above methods can effectively synthesize fully acylated sugar alkenes, but the disadvantages are: the raw material Ag in (1) above is more expensive; the reducing agent [Cp in (2) and (3) 2 TiCl] 2 , SmI 2 The synthesis is cumbersome and difficult; (4) the synthesis of the catalyst VO(salen) is cumbersome and expensive, and the heavy metals are not environmentally friendly; (5) the Co + The catalytic effect is not good, so the yield is not high, the amount of Zn powder is large (15eq), and the reaction time is long (1 ~ 4h)
[0014] In summary, the fully acylated glucoene prepared by the prior art has complex synthesis process, difficult operation, low yield, especially expensive raw materials, high production cost, and is toxic, harmful, easy to pollute the environment, and seriously restricts full acylation Wide application of glucoene

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • A kind of preparation method of fully acylated sugar alkenes
  • A kind of preparation method of fully acylated sugar alkenes
  • A kind of preparation method of fully acylated sugar alkenes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Under nitrogen protection, dissolve 206mg (0.5mmol) of 1-bromo-peracylated glucose in 5mL of acetonitrile, slowly add 195mg (3mmol) of Zn powder and 161mg (3mmol) of ammonium chloride under stirring, then heat to 60°C and stir Carry out the synthesis reaction of fully acylated glucoene, and the reaction is complete after 20 minutes as detected by TLC. After the reaction, the reaction system was filtered with suction, the filtrate was concentrated by rotary evaporation under reduced pressure and purified by column chromatography to obtain 131 mg of fully acylated glucosene as a white solid with a yield of 97%. The eluent separated by column chromatography For PE:EA=5:1.

[0023] The resulting product fully acylated glucosene is analyzed, and the test data are as follows:

[0024] 1 H-NMR (500MHz, CDCl3): δ (ppm) 6.47 (d, J=6.2Hz, 1H), 5.35 (dd, J=4.2Hz, 3.7Hz, 1H), 5.22 (dd, J=7.5Hz, 6.0 Hz,1H),4.85(dd,J=9.5Hz,3.3Hz,1H),4.40(dd,J=12.2Hz,5.8Hz,1H),4.26(m,1H),4.20(dd,J=...

Embodiment 2

[0026] Under nitrogen protection, dissolve 0.018 mmol of 1-bromo per-acylated glucose in 50 mL of acetonitrile, slowly add 0.137 mmol of zinc powder and 0.137 mmol of ammonium chloride under stirring, then heat to 82°C and stir to synthesize fully acylated glucosene The reaction was detected by TLC in 10 minutes and the reaction was complete. After the reaction, the reaction system was filtered with suction, the filtrate was concentrated by rotary evaporation under reduced pressure and purified by column chromatography to obtain 4.4 g of fully acylated glucosene as a white solid with a yield of 90%. The agent is PE:EA=2:1.

[0027] The obtained product fully acylated glucosene can be confirmed as a pure target product after detection and analysis. Example 3

Embodiment 3

[0028] Under nitrogen protection, 2.06g (5mmol) of 1-bromo acylated mannose was dissolved in 10mL of acetonitrile, and 4.88g (75mmol) of Zn powder and 4.0g (75mmol) of ammonium chloride were slowly added under stirring, and then heated to Stir at 82°C to carry out the synthesis reaction of fully acylated glucoene, and the reaction is complete in 60 minutes as detected by TLC. After the reaction was completed, the reaction system was filtered with suction, the filtrate was concentrated by rotary evaporation under reduced pressure and purified by column chromatography to obtain 1.32 g of fully acylated mannosene as a white solid with a yield of 98%. The removal agent is PE:EA=5:1.

[0029] The obtained product fully acylated mannosene can be confirmed as a pure target product after detection and analysis. Example 4

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a preparation method of fully-acylated glycal. The method is characterized by comprising the following steps: dissolving fully-acylated 1-bromine substituted monosaccharide or fully-acylated 1-bromine substituted disaccharide in acetonitrile in the presence of nitrogen; then performing a synthetic reaction of the fully-acylated glycal for 10 to 60 minutes at the temperature of 20 to 82 DEG C by adding zinc powder and ammonium chloridel; performing suction filtration and purification after the reaction, thereby obtaining the fully-acylated glycal as a product, wherein the molar volume ratio of the fully-acylated 1-bromine substituted monosaccharide or the fully-acylated 1-bromine substituted disaccharide to the acetonitrile to the zinc powder and the ammonium chloridel is 1 mmol (millimole):(1-10 mL):(3-15 mmol):(3-15 mmol). Compared with the prior art, the method is simple in process, convenient to operate, low in production cost, high in yield and more moderate in reaction condition; a high-toxic chemical raw material is effectively prevented from being used, so that the environment is not polluted. Thus, the preparation method is environmentally-friendly, economical, efficient and good in application prospect.

Description

technical field [0001] The invention relates to the technical field of chemical reagents, in particular to a method for preparing fully acylated glucoene as an organic synthesis intermediate. Background technique [0002] Fully acylated glucoene is an unsaturated sugar, which is mainly used as an intermediate in chemical industry, textile, medicine and organic synthesis. As an important intermediate in organic synthesis, fully acylated glycosides can be used to synthesize O-glycosides, C-glycosides, S-glycosides, oligosaccharides, oligosaccharides, and nucleosides. The application is also becoming more and more extensive. [0003] At present, the preparation of fully acylated glucoene is mainly to obtain the target product from the 1-position substitution of sugar as the reaction raw material, such as (1): Csuk, R; Fürstner, A.; Glanzer, B.I.; Weidmann, H.J.Chem..Soc ., Chem.Commun.1986:1149-1150, the equation of its reaction is as follows: [0004] [0005] Another ex...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07D309/30
Inventor 张剑波冼婷陈和善司文帅李娟张梅玉骆小胜
Owner EAST CHINA NORMAL UNIV