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Preparation method of chiral five-membered ring sulfite with active functional groups on alpha-carbon in substituent

A technology of cyclic sulfites and active functional groups is applied in the field of preparation of chiral five-membered cyclic sulfites, which can solve problems such as environmental pollution, dehydration, troublesome separation, etc., and achieves high regioselectivity, high product yield, and operation simple effect

Inactive Publication Date: 2012-07-25
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the high reactivity of cyclic sulfite, side reactions such as ring opening and dehydration often occur during the deprotection process; this not only affects the expected yield of cyclic sulfite, but also brings trouble to the separation and causes environmental pollution.

Method used

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  • Preparation method of chiral five-membered ring sulfite with active functional groups on alpha-carbon in substituent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Cooled in an ice bath (2 R ,3 R 0.426 g (1 mmol) of )-1,1,4,4-tetraphenylbutanetetraol and 0.3 mL of pyridine were added to a mixture of 6 mL of tetrahydrofuran and 0.1 mL of thionyl chloride was added, followed by stirring for 2 hours. The resultant was treated with water, the organic layer was separated, the aqueous phase was extracted with ether, the extracts were combined, dried over anhydrous sodium sulfate, and 0.496 g of (4 R ,5 R )-4,5-bis(diphenylhydroxymethyl)cyclosulfite, m.p. 165-167 o C. [α] D 20 = +65.8 ( c 0.19, CHCl 3 ). 1 H-NMR (300 MHz, CDCl 3 ): δ 7.50 (d, J =7.5 Hz, 2H), 7.42 (d, J =7.2 Hz, 2H), 7.34-7.19 (m, 10H), 7.03 (s, 10H), 5.97 (d, J =2.1 Hz, 1H), 5.90 (d, J =2.1 Hz, 1H), 4.49 (s, 1H, disappears after adding water), 3.70 (t, J =6.0 Hz, 4H), 2.37 (s, 1H, disappears after adding water), 1.83 (t, J =6.0 Hz, 4H). 13 C-NMR (75 MHz, CDCl 3 ): δ 145.1, 143.3, 141.5, 141.0, 128.7, 128.5, 128.4, 128.0, 127.4, 127.1, 126.9, 125.9, 89....

Embodiment 2

[0022] According to the same operation as in Example 1, (4 S ,5 S )-4,5-bis(diphenylhydroxymethyl)cyclosulfite was obtained in 79% yield, m.p. 165-168 o C. [α] D 20 = -66.0 ( c 0.30, CHCl 3 ). 1 H NMR (300 MHz, CDCl 3 ): δ 7.50 (d, J =7.5 Hz, 2H), 7.43 (d, J =7.2 Hz, 2H), 7.35-7.13 (m, 8H), 7.04 (s, 8H), 5.97 (d, J =2.1 Hz, 1H), 5.91 (d, J =2.1 Hz, 1H), 4.48 (s, 1H, disappears after adding water), 3.75 (t, J =6.3 Hz, 4H, -CH 2 O of THF), 2.12 (s, 1H, disappears after adding weighted water), 1.85 (t, J =6.3 Hz, 4H, -CH 2 O of THF). 13 C NMR (CDCl 3 , 75 MHz): δ 144.7, 142.8, 141.1, 140.5, 128.4, 128.2, 128.0, 127.7, 127.4, 127.1, 126.7, 126.3, 125.7, 125.5, 89.3, 56.7, 678.4,

Embodiment 3

[0024] Cooled in an ice bath (2 R ,3 R 0.426 g (1 mmol) of )-1,1,4,4-tetraphenylbutanetetraol and 0.3 mL of pyridine were added to a mixture of 6 mL of dichloromethane and 0.1 mL of thionyl chloride was added, followed by stirring for 2 hours. The resultant was treated with water, the organic layer was separated, the aqueous phase was extracted with ether, the extracts were combined, dried over anhydrous sodium sulfate, and the solvent-free (4 R ,5 R )-4,5-bis(benzhydrylol)cyclosulfite.

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Abstract

The invention relates to a preparation method of chiral five-membered ring sulfite with active functional groups on alpha-carbon in substituent. 4,5-bifunctional (4R,5R)- or (4S,5S)-cyclic sulfite is obtained through selective 2,3-cyclic sulfidation reaction of enantiomerically pure 1,1,4,4-tetra-substituted butantetraol and thionyl chloride in the presence of organic alkali in aprotic polar organic solvent. The invented preparation method is obviously available in raw materials, convenient in operation, good in reaction selectivity, easy to dispose and high in yield.

Description

technical field [0001] The invention relates to a preparation method of a chiral five-membered ring sulfite with an active functional group on the α-carbon of a class of substituents, belonging to the field of chiral heterocyclic compound chemistry. Background technique [0002] Chiral cyclic sulfites themselves can be used as drugs [(a) Hardacre, C.; Messina, I.; Migaud, M. E.; Ness, K. A.; Norman, S. E. Tetrahedron 2009, 65 (32), 6341. (b) Yu, B.; Jiang, Z. X.; Xiao, N. WO 2008034095, 2008 . (c) Knapp, S.; Yang, C. H.; Pabbaraja, S.; Rempel, B.; Reid, S.; J. Org. Chem . 2005, 70 (19), 7715. (d) Yang, S. W.; Jang, Y. A.; Liou, Y. L. Taiwan 2001, TW 466226. (e) Yang, S. W.; Jang, Y. A.; Liu, Y. L. US 5977380. 1999. (f) Nandanan, E.; Phukan, P.; Sudalai, A. Ind. J. Chem., Sect B: Org. Chem. Incl. Med. Chem. 1999, 38B (8), 893. (g) Radisson, X. EP 515272, 1992. (h) Cyclic sulfate ester of glucose, D. L. Ingles, Chem. & Ind. (London, United Kingdom), 196...

Claims

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Application Information

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IPC IPC(8): C07D327/10
Inventor 单自兴胡晓允
Owner WUHAN UNIV
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