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Method for preparing 3,4,-O-isopropylidene-3,4-dihydroxy butyraldehyde

A technology of isopropylidene and hydroxybutyraldehyde, applied in the direction of organic chemistry, can solve the problems of low yield and inability to oxidize raw materials, and achieve the effect of small dosage, low price and stable properties

Inactive Publication Date: 2008-12-31
SHANGHAI INST OF PHARMA IND CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In this method, the molar ratio of alcohol and oxidizing agent is the ratio of about 1: 1 to 1: 1.25 (based on active chlorine), because one molecule TCCA contains three active chlorines, the molar ratio converted into alcohol and TCCA molecule should be 1 : between 0.33 and 1:0.42, but when we refer to this method for oxidation, the raw material cannot be oxidized completely, and the yield is too low

Method used

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  • Method for preparing 3,4,-O-isopropylidene-3,4-dihydroxy butyraldehyde
  • Method for preparing 3,4,-O-isopropylidene-3,4-dihydroxy butyraldehyde
  • Method for preparing 3,4,-O-isopropylidene-3,4-dihydroxy butyraldehyde

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Add 120ml of dichloromethane and 10.0g of (S)-1,2-O-isopropylidene-1,2,4-butane in sequence to a 250ml four-necked bottle equipped with electromagnetic stirring, a thermometer and a calcium chloride drying tube Triol (II), 11.23g sodium acetate and 11mg TEMPO were cooled in an ice-water bath to an internal temperature of 0-5°C, and then 7.07g TCCA (trichloroisocyanuric acid, content: 90%, the same below) was added, and the ice-water bath was removed. After reacting at room temperature for 15 minutes, the reaction solution was filtered, and the obtained filtrate was subjected to saturated Na 2 CO 3 Aqueous solution, saturated brine washing, anhydrous MgSO 4 Dry and distill under reduced pressure to obtain 7.73g colorless transparent liquid product (S)-3,4-O-isopropylidene-3,4-dihydroxybutyraldehyde (I) [GC: 98.0%; bp: 56- 57℃ / 3mmHg; 1 H-NMR (CDCl 3, 400MHZ): 1.36(3H, s), 1.41(3H, s), 2.60-2.85(2H, m), 3.58(1H, dd), 4.17(1H, dd), 4.52(1H, m), 9.79( 1H, s); ESI-MS m / z...

Embodiment 2

[0035] Add 120ml methylene chloride, 8.42g sodium acetate, 10.0g (S)-1,2-O-isopropylidene-1 successively in a 250ml four-necked bottle equipped with electromagnetic stirring, a thermometer and a calcium chloride drying tube, 2,4-butanetriol (II) and 10.61g TCCA, cool in an ice-water bath to an internal temperature of 0-5°C, add dropwise a solution of 0.11g TEMPO in 5ml of dichloromethane, remove the ice-water bath, react at room temperature for 15 minutes, and then filter The reaction solution, the resulting filtrate was successively subjected to saturated Na 2 CO 3 Aqueous solution, saturated brine washing, anhydrous MgSO 4 After drying, the solvent was distilled off under reduced pressure to obtain 8.71 g of a colorless and transparent liquid product (S)-3,4-O-isopropylidene-3,4-dihydroxybutyraldehyde (I).

Embodiment 3

[0037] Add 120ml of dichloromethane and 10.0g of (R)-1,2-O-isopropylidene-1,2,4-butane in sequence to a 250ml four-necked bottle equipped with electromagnetic stirring, a thermometer and a calcium chloride drying tube Triol (II), 11.23g sodium acetate and 7.07g TCCA, cool in an ice-water bath to an internal temperature of 0-5°C, add 40mg TEMPO, remove the ice-water bath, react at room temperature for 10 minutes, and filter the reaction solution, and the obtained filtrate is saturated in turn Na 2 CO 3 Aqueous solution, saturated brine washing, anhydrous MgSO 4 Drying, solvent removal under reduced pressure obtains 8.56g colorless transparent liquid product (R)-3,4-O-isopropylidene-3,4-dihydroxybutyraldehyde (I) [ 1 H-NMR (CDCl 3 , 400MHZ): 1.35(3H, s), 1.41(3H, s), 2.57-2.85(2H, dd), 3.58(1H, m), 4.17(1H, m), 4.51(1H, m), 9.77( 1H,t)].

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Abstract

The invention provides a preparation method for 3,4-O-isopropylidene-3,4-dihydroxy butyraldehyde. In the method ,1,2-O-isopropylidene -1,2,4 - tromethamine (II) is oxidated with TCCA (trichloroisocyanuric acid) serving as oxidant in the presence of alkali and catalyst (III) to generate 3,4-O-isopropylidene -3,4-dihydroxy butyraldehyde (I). Compared with the prior art, the method disclosed in the invention is moderate and fast and is simple to operate, which has high yield; the oxidant used in the method is environmentally friendly, cheap and available, which is suitable for large-scale production.

Description

technical field [0001] The invention relates to a preparation method of a drug synthesis intermediate 3,4-O-isopropylidene-3,4-dihydroxybutyraldehyde. Background technique [0002] 3,4-O-isopropylidene-3,4-dihydroxybutyraldehyde (I) is an important synthon in the total synthesis of many natural products, such as the antibiotics griseoviridin and madumycin (Griseoviridin and Madumycin ; J.Org.Chem., 1986,51 (26): 5111-5123), macrolide MacrolactinA (Tetrahedron Lett., 2000, 41: 3463-3466), polyacetyl Callystatin A (J.Org.Chem ., 2005, 70 (12): 4762-4773) etc., its synthetic method according to the raw material of bibliographical report mainly contains following two kinds of preparation methods: [0003] One is 1,2-O-isopropylidene-1,2-dihydroxybutyric acid methyl ester or ethyl ester (IV) as raw material through DIBAL-H (diisobutyl aluminum hydride) [Chem.Lett. , 1984, 8: 1389-1392; Tetrahedron: Asym., 1998, 9 (8): 1359-1368;] reduced to 3,4-O-isopropylene at low temperature...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D317/26
Inventor 张福利邱友春张椿年
Owner SHANGHAI INST OF PHARMA IND CO LTD
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