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Preparation method for 3-oxetanone

A technology of oxetanone and oxidant, which is applied in the direction of organic chemistry, can solve the problems of low reaction selectivity, difficult separation and purification, difficult industrial production, etc., and achieve the effect of short synthetic route, high purity and few by-products

Active Publication Date: 2018-12-07
EAST CHINA NORMAL UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] The method is long in route, cumbersome in operation, and the overall yield is not high; especially in step a, the reaction selectivity is not high, and more impurities are produced; and the product of each step of the route is liquid, and separation and purification are difficult
These disadvantages make it difficult to use in industrial production

Method used

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  • Preparation method for 3-oxetanone
  • Preparation method for 3-oxetanone
  • Preparation method for 3-oxetanone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] 1.1 Preparation of compound Ⅱ

[0024] Dissolve 5.0g o-bromobenzoic acid in 20mL N,N-dimethylformamide, add 2.76g epichlorohydrin, then add 0.40g benzyltriethylammonium chloride, and react at 80°C. After reacting for 5 hours, TLC detected that the reaction of raw materials was complete. Evaporate N,N-dimethylformamide to dryness, extract with ethyl acetate, wash with appropriate amount of saturated NaHCO 3 The solution was washed twice, and then washed twice with water, and the organic phase was separated, anhydrous Na 2 SO 4 After drying, the solvent was distilled off to obtain 4.75 g of brownish-yellow liquid, compound II, with a yield of 65%. 1 H NMR: (500MHz, CDCl 3 ):δ=7.82(dd,J=7.4,2.1Hz,1H),7.68(dd,J=7.7,1.4Hz,1H),7.42–7.33(m,2H),4.52–4.45(m,2H), 4.28–4.20 (m, 1H), 3.80–3.67 (m, 2H), 2.80 (d, J=5.4Hz, 1H).

[0025] 1.2 Preparation of compound Ⅱ

[0026] Dissolve 5.0g o-bromobenzoic acid in 20mL N,N-dimethylformamide, add 3.45g epichlorohydrin, then add 0.4...

Embodiment 2

[0038] 2.1 Preparation of compound III

[0039] Dissolve 5.0g of 3-chloro-2-hydroxypropyl-2-bromobenzoate in 25mL of dichloromethane, add 25mL of water, add 2.23g of potassium bromide, 0.72g of sodium bicarbonate, 53mg of 2,2 , 6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO), 14.6g of NaClO solution (13%) was slowly added dropwise at 20°C. After reacting for 2 hours, add Na equivalent to the oxidant to the system 2 SO 3 solution, stirred for 30min, extracted and separated, and the organic phase was washed successively with 1M HCl, saturated NaHCO 3 Solution, water wash once. Anhydrous Na for organic phase 2 SO 4 Dry and evaporate to dryness to obtain a crude product, which is beaten with petroleum ether: ethyl acetate = 3:1 to obtain 2.08 g of white solid, compound III, with a yield of 42%. 1 H NMR: (500MHz, CDCl 3 ):δ=7.87(dd,J=7.4,2.1Hz,1H),7.63(dd,J=7.6,1.5Hz,1H),7.37–7.27(m,2H),5.09(s,2H),4.18( s, 2H).

[0040] 2.2 Preparation of compound III

[0041] Dissolve 5...

Embodiment 3

[0051] Preparation of compound Ⅳ

[0052] Dissolve 40.0g of 3-chloro-2-oxopropyl-2-bromobenzoate in 200mL of methanol, add 12.07g of NaOH, and react at 80°C for 8h. The system was filtered, and the filtrate was distilled at atmospheric pressure first. After the solvent was distilled off, it was distilled under reduced pressure using a rectification column to collect fractions with stable boiling points to obtain 5.63 g of compound IV, a colorless oily liquid, with a yield of 57%. 1 H NMR: (500MHz, CDCl 3 ): δ=5.35(s, 4H).

[0053] 3.2 Preparation of Compound IV

[0054] Dissolve 40.0g of 3-chloro-2-oxopropyl-2-bromobenzoate in 200mL of methanol, add 16.90g of KOH, and react at 80°C for 8h. The system was filtered, and the filtrate was distilled at atmospheric pressure first. After the solvent was evaporated, it was distilled under reduced pressure using a rectification column to collect fractions with stable boiling points to obtain 6.72 g of a colorless oily liquid, namely...

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Abstract

The invention discloses a preparation method for 3-oxetanone and belongs to the technical field of medicinal chemical synthesis. The method includes: with a compound (I), o-bromobenzoic acid, being aninitial raw material, performing a nucleophilic substitution reaction under effect of a phase-transfer catalyst with epoxy chloropropane to obtain a compound (II); oxidizing the compound (II) under effect of an oxidant to prepare a compound (III); under alkaline condition, performing a hydrolysis reaction and an intramolecular nucleophilic substitution reaction on the compound (III) to obtain thetarget compound (IV), 3-oxetanone. The method can be used for preparing the target compound within three steps, employs controllable conditions and simple post-treatment, is less in side reactions and high in yield, can satisfy industrial production demands. Synthesis route is represented as the equations.

Description

technical field [0001] The invention belongs to the chemical synthesis of medicines in the field of organic chemistry, and relates to a preparation method of 3-oxetanone. Background technique [0002] 3-oxetanone is a commonly used drug synthesis intermediate, and its structural formula is: [0003] [0004] There are few reports in the literature about the synthetic method of 3-oxetanone. Regarding the synthetic method of 3-oxetanone, at present, there are mainly documents (Tetrahedron Letters, 2013, 54, 5849-5852) reporting its synthetic process route, and its reaction formula is as follows: [0005] [0006] The method has a long route, cumbersome operation, and low overall yield; especially in step a, the reaction selectivity is not high, and more impurities are produced; and the product of each step of the route is liquid, and separation and purification are difficult. These disadvantages make it difficult to be used in industrial production. Contents of the i...

Claims

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Application Information

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IPC IPC(8): C07D305/10
CPCC07D305/10
Inventor 罗宇何洋周朴张玉柳朱皓庭李晓林吴晓东刘郝敏
Owner EAST CHINA NORMAL UNIV
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