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Preparation method of five-membered cyclic sulphate

A technology of cyclic sulfate and cyclic sulfite, which is applied in the field of preparation of five-membered cyclic sulfate, can solve the problems of easy generation of metals, many side reactions, expensive reagents, etc., and achieves easy control and high product yield. , the effect of avoiding the use of chlorine-containing reagents

Active Publication Date: 2013-04-03
ZHEJIANG APELOA TOSPO PHARMA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0010] The second oxidizing agent used was ruthenium trichloride and sodium periodate (Paddon-Jones, G.C.; McErlean, C.S.P.; Hayes, P. et al. J. Org. Chem. 2001, 66, 7487-7495; ShaoH. ; Rueter, J.K.; Goodman, M.J.Org.Chem.1998, 63, 5240-5244; Zhang L.; Luo, S.; Mi, X.et al.Organic & Biomolecular Chemistry 2009, 74, 6819-6824.), Reagents using this method are expensive and prone to metal residues
[0011] The third method uses potassium permanganate oxidation, which has low yield, many side reactions, and poor compatibility to other functional groups (Berridge, M.S.; Franceschini, M.P.; Rosenfeld, E.et al.J.Org.Chem. 1990, 55, 1211-1217.)

Method used

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  • Preparation method of five-membered cyclic sulphate
  • Preparation method of five-membered cyclic sulphate
  • Preparation method of five-membered cyclic sulphate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] In this example, OXONE was used as the oxidant, and (2S,3R,4R)-4,5-O-isopropylidene-2,3-cyclosulfinyl-2,3,4,5-tetrahydroxy -Ethyl 2-methylpentanoate (abbreviated as sulfite, according to the method in Wang, P.; Chun, B.; Rachakonda, S. et al. J. Org. Chem. 2009, 74, 6819-6824. prepared) as a raw material, sodium bicarbonate as an additive, and OXONE as an oxidizing agent, wherein OXONE is dissolved in an appropriate amount of water and added, and the amount of water has little influence and can be dissolved. The feeding amount is as follows: sulfite 5g (17mmol), 1,4-dioxane 25mL, sodium bicarbonate 7.5g (89mmol), OXONE 17.8g (29mmol), the order of addition is raw material sulfite, 1,4- Dioxane, sodium bicarbonate, and OXONE aqueous solution, among them, the OXONE aqueous solution was added slowly, and the addition was completed in about 20 minutes. The reaction temperature was 85°C, and the reaction pH was about 6.0. The reaction was quenched with 15 mL of saturated aq...

Embodiment 2

[0037]The raw materials and reagents used in this example are the same as those in Example 1. The feeding amount is as follows: sulfite 5g (17mmol), 1,4-dioxane 25mL, sodium bicarbonate 7.2g (85mmol), OXONE 17.8g (29mmol), the order of addition is raw material sulfite, 1,4- Dioxane, sodium bicarbonate, and OXONE aqueous solution, among them, the OXONE aqueous solution was added slowly, and the addition was completed in about 20 minutes. The reaction temperature was 85°C, and the reaction pH was about 6.0. The reaction was quenched with 15 mL of saturated aqueous sodium bisulfite solution, and extracted with 100 mL of isopropyl acetate. Concentrate after adding diisopropylethylamine to give 4.59g of crude product, yield 87%, GC purity 96%, EI: m / z310.1 (M + ), the effect is better.

Embodiment 3

[0039] The raw materials and reagents used in this example are the same as those in Example 1. The feeding amount is as follows: sulfite 5g (17mmol), 1,4-dioxane 25mL, sodium bicarbonate 7.7g (92mmol), OXONE 17.8g (29mmol), the order of addition is raw material sulfite, 1,4- Dioxane, sodium bicarbonate, and OXONE aqueous solution, among them, the OXONE aqueous solution was added slowly, and the addition was completed in about 20 minutes. The reaction temperature was 85°C, and the reaction pH was about 6.4. The reaction was quenched with 15 mL of saturated aqueous sodium bisulfite solution, and extracted with 100 mL of isopropyl acetate. Concentrate after adding diisopropylethylamine to obtain 4.80 g of crude product, yield 91%, GC purity 96%, EI: m / z 310.1 (M + ), the effect is better.

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Abstract

The invention discloses a preparation method of five-membered cyclic sulphate, which comprises the following steps that: in the presence of an organic solvent and sodium bicarbonate, five-membered cyclic sulphite and OXONE are subjected to oxidation reaction; after reacting, treatment is carried out to obtain the five-membered cyclic sulphate. When the method disclosed by the invention is adopted for synthesizing the five-membered cyclic sulphate, the operation process is safe, simple and easy to control; the process cost is low; use of a chlorine-containing oxidant is avoided; the chlorine content and the metal content in a product are controlled; the yield of the product is high; and the prepared five-membered cyclic sulphate is an important drug synthetic midbody and has important application implications.

Description

technical field [0001] The invention belongs to the field of medicine synthesis, and in particular relates to a preparation method of five-membered cyclic sulfuric acid ester. Background technique [0002] Five-membered cyclic sulfuric acid ester (structure shown in formula I) is a class of important organic synthesis intermediates, and has the following characteristics: (1) has higher nucleophilic reactivity than epoxides to many nucleophiles; (2 ) The selectivity of the nucleophilic substitution reaction is higher; (3) the intermediate product of the nucleophilic substitution is easy to purify, and is generally separated from the organic phase in the form of monobasic sulfate ester salt. [0003] [0004] For example, ethyl (2S,3R,4R)-4,5-O-isopropylidene-2,3-cyclosulfonyl-2,3,4,5-tetrahydroxy-2-methylpentanoate (structure Shown in formula II) is a kind of important five-membered cyclic sulfuric acid ester, molecular formula is C 11 h 18 o 8 S, the appearance is a l...

Claims

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Application Information

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IPC IPC(8): C07D411/04
Inventor 唐志勇阳学文李光超
Owner ZHEJIANG APELOA TOSPO PHARMA
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