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Hydroxyl bromine compound preparation method

A compound and catalyst technology, applied in the field of preparation of hydroxybromide compounds, can solve problems such as complex preparation process, and achieve the effects of easy availability of raw materials, mild reaction conditions and easy operation

Inactive Publication Date: 2015-10-07
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Optically active 1,2-hydroxy bromide compounds can be derivatized to obtain a series of natural product intermediates. The traditional method of synthesizing optically active hydroxy bromide compounds is to obtain ring-opening of epoxy intermediates by bromide anions, but often Using acids, alcohols, etc. as nucleophiles, further reactions are required to obtain the target product, and the preparation process is complicated

Method used

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  • Hydroxyl bromine compound preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Embodiment 1, preparation (S)-2-bromo-1-phenylethanol:

[0046] according to figure 1 The flowchart in the preparation:

[0047] In test tube add (DHQD) 2 PHAL (0.0389g, 0.05mmol) and N-bromobenzamide (0.120g, 0.6mmol), dissolved in 5mL of acetone and 1mL of water, stirred at -40°C for 15min, then added the compound shown in formula I-a (0.0521g, 0.5mmol), react at -40°C for 72h, add 10mL saturated sodium thiosulfate solution to quench, separate the layers, extract the aqueous phase with dichloromethane (10mL x 3), dry over anhydrous magnesium sulfate, filter, and concentrate by rotary evaporation , Purified by silica gel column chromatography, the yield is 64%, and it is known by HPLC test that one enantiomer in the product is 60% more than the other enantiomer (ie, the enantiomeric excess is 60%).

[0048] HPLC conditions: chiral OD-H column; the volume ratio of n-hexane: isopropanol is 95:5; flow rate: 1.0mL / min; absorption wavelength: 210nm.

[0049] The results...

Embodiment 2

[0051] Embodiment 2, preparation (S)-2-bromo-1-(2-methylphenyl)ethanol:

[0052] according to figure 2 The flowchart in the preparation:

[0053] Add in test tube (DHQD) 2PHAL (0.0389g, 0.05mmol) and N-bromobenzamide (0.120g, 0.6mmol), dissolved in 5mL acetone and 1mL water, stirred at -40°C for 15min, then added formula I-b (0.0591g, 0.5mmol) , reacted at -40°C for 72h, quenched by adding 10mL saturated sodium thiosulfate solution, separated the layers, extracted the aqueous phase with dichloromethane (10mL x 3), dried over anhydrous magnesium sulfate, filtered, concentrated by rotary evaporation, and silica gel column Purified by chromatography, the yield was 78%, and the enantiomeric excess (measured by HPLC) was 83%.

[0054] HPLC conditions: chiral OD-H column; n-hexane:isopropanol volume ratio of 95:5; flow rate: 1.0mL / min; absorption wavelength: 220nm.

[0055] The results of structural confirmation are as follows: 1 H NMR (400Hz, CDCl 3 )δ7.42-7.30 (m, 5H), 4.93...

Embodiment 3

[0057] Example 3, preparation of (S)-2-bromo-1-(2-ethylphenyl)ethanol:

[0058] according to image 3 The flowchart in the preparation:

[0059] In test tube add (DHQD) 2 PHAL (0.0389g, 0.05mmol) and N-bromobenzamide (0.120g, 0.6mmol), dissolved in 5mL acetone and 1mL water, stirred at -40°C for 15min, then added formula I-c (0.0661g, 0.5mmol) , reacted at -40°C for 72h, quenched by adding 10mL saturated sodium thiosulfate solution, separated the layers, extracted the aqueous phase with dichloromethane (10mL x 3), dried over anhydrous magnesium sulfate, filtered, concentrated by rotary evaporation, and silica gel column Purified by chromatography, the yield was 68%, and the enantiomeric excess (measured by HPLC) was 71%.

[0060] HPLC conditions: chiral AD-H column; n-hexane:isopropanol volume ratio of 95:5; flow rate: 1.0mL / min; absorption wavelength: 220nm.

[0061] The results of structural confirmation are as follows: 1 H NMR (400Hz, CDCl3) δ7.55-7.47 (m, 1H), 7.30-7....

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Abstract

The present invention discloses a hydroxyl bromine compound preparation method comprising the following steps: in the presence of a catalyst, a compound shown as the formula I and N-brombenzamide are reacted in a liquid mixture of an organic solvent and water to obtain a compound shown as the formula II, wherein R1 are hydrogen or C1-C3 alkyl group; R2 are hydrogen or C1-C3 alkyl group; and R3 are hydrogen or C1-C4 alkyl group. A styrene type substrate and the N-brombenzamide are used as raw materials for effectively synthesizing a series of hydroxyl bromine compounds in the effect of (DHQD) 2PHAL. The raw materials are simple and easy to get, the nucleophile water is non-toxic and harmless, reaction conditions are mild, operation is simple, the method is atomic economic, enantiomer excess can reach up to 88%, the yield can reach up to 94%, the compounds has regioselectivity completely different from that of epoxy ring opening products, meanwhile the introduced C-Br bond and C-O bond both can be further transformed, and the method has great value.

Description

technical field [0001] The present invention relates to a kind of preparation method of hydroxyl bromide compound. Background technique [0002] At present, many natural products and drug molecules contain halogens, and the halogenation reaction of alkenes is a very important method to introduce halogens. Optically active 1,2-hydroxy bromide compounds can be derivatized to obtain a series of natural product intermediates. The traditional method of synthesizing optically active hydroxy bromide compounds is to obtain ring-opening of epoxy intermediates by bromide anions, but often By using acids, alcohols, etc. as nucleophiles, further reactions are required to obtain the target product, and the preparation process is complicated. Contents of the invention [0003] The purpose of this invention is to provide a kind of preparation method of hydroxyl bromide compound. The method uses water as a nucleophile to prepare a hydroxyl bromide compound in one step. [0004] The pre...

Claims

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Application Information

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IPC IPC(8): C07C29/64C07C33/46C07C33/50
CPCC07C29/64C07C33/46C07C33/50C07C2602/10
Inventor 史一安张勋李静田华
Owner INST OF CHEM CHINESE ACAD OF SCI
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