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Process for phase-transfer catalytic synthesis of alpha, beta-epoxy ketone compound

A technology of phase transfer catalysis and phase transfer catalyst, applied in the α field, can solve problems such as easy decomposition and poor stability, and achieve the effect of easy to obtain raw materials, easy to separate, and mild conditions

Inactive Publication Date: 2005-06-22
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although these oxidizing agents can be successfully used in the epoxidation reaction of α, β-unsaturated ketones, the oxidizing agents such as hydrogen peroxide, sodium hypochlorite, potassium hypochlorite and tert-butyl hydroperoxide generally have the disadvantages of poor stability and easy decomposition, while oxygen acts as oxygen source, requires the use of stoichiometric diethylzinc

Method used

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  • Process for phase-transfer catalytic synthesis of alpha, beta-epoxy ketone compound
  • Process for phase-transfer catalytic synthesis of alpha, beta-epoxy ketone compound
  • Process for phase-transfer catalytic synthesis of alpha, beta-epoxy ketone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Example 1 Synthesis of trans-2,3-epoxy-1,3-diphenylpropan-1-one by solid-liquid two-phase phase transfer catalysis

[0017] In a 100ml round bottom flask, add chalcone (2.08g, 10mmol), tetrabutylammonium bromide (322mg, 1mmol) and 30ml toluene, cool to 10°C, add solid trichloroisocyanuric acid (2.32g, 10mmol ), solid KOH (3.36, 60 mmol) was added. After the dropwise addition was completed, stirring was continued at 10° C. for 4 hours, and the end point of the reaction was detected by TLC. Warming up to room temperature, adding 15ml of diethyl ether to the reaction solution, filtering, washing the filtrate with water, anhydrous MgSO 4 dry. The solvent was distilled off, separated by column chromatography (silica gel, eluent: petroleum ether / ethyl acetate: 50 / 1), and the solvent was distilled off to obtain white crystals with a yield of 92%.

Embodiment 2

[0018] Example 2 Synthesis of trans-2,3-epoxy-1,3-diphenylpropan-1-one by solid-liquid two-phase phase transfer catalysis

[0019] The embodiment under the existence of different phase transfer catalysts is summarized as follows in tabular form: (reaction condition and step are with embodiment 1)

[0020]

[0021] Table 1. Effect of different phase transfer catalysts and dosage on epoxidation reaction

[0022] No. Catalyst Catalyst dosage [%] Base Reaction time [hours] Yield [%]

[0023] 1 PEG-4600 10 KOH 24 37

[0024] 2 PEG-400 10 KOH 24 71

[0025] 3 TBPB 10 KOH 24 71

[0026] 4 TBPC 10 KOH 24 48

[0027] 5 CTMAB 10 KOH 24 70

[0028] 6 TBABS 10 KOH 3 91

[0029] 7 TBAB 10 KOH 4 92

[0030] 8 TBAB 5 KOH 4 91

[0031] 9 TBAB 1 KOH 24 42

[0032] 10 TBAB 0.1 KOH 48 40

[0033] catalyst:

[0034] PEG-4600: polyethylene glycol-4600 (polyethylene glycol-4600),

[0035] PEG-400: polyethylene glycol-400 (polyethylene glycol-400),

[0036] TBPB: Tetrabutyl pho...

Embodiment 3

[0041] Example 3 Synthesis of trans-2,3-epoxy-1,3-diphenylpropan-1-one by solid-liquid two-phase phase transfer catalysis

[0042] The embodiment under different reaction solvent, the kind and consumption of alkali, temperature condition is summarized as follows in tabular form: (reaction condition and step are with embodiment 1)

[0043]

[0044] Table 2. Effect of reaction solvent, type and amount of base, TCCA amount, temperature on epoxidation reaction

[0045] ring

[0046] No. Solvent Base / [%] TCCA[%] Temperature Reaction time Yield

[0047] [℃] [hour] [%]

[0048] 11 Dichloromethane KOH / 600 100 0 24 73

[0049] 12 Xylene KOH / 500 90 0 5 78

[0050] 13 Toluene KOH / 600 100 0 4 91

[0051] 14 Toluene KOH / 200 50 0 24 63

[0052] 15 Toluene LiOH / 600 90 0 24 38

[0053] 16 Toluene NaOH / 600 90 0 24 53

[0054] 17 Toluene CsOH / 600 90 0 24 45

[0055] 18 Toluene KOH / 600 67 20 24 67

[0056] ...

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Abstract

The invention provides a process for phase-transfer catalytic synthesis of alpha, beta-epoxy ketone compound which comprises, at the presence of phase shift catalyst, using trichloroisocyanuric acid (TCCA) as oxidant, using alkali metal hydroxide as alkaline regulator, using alpha, beta unsaturated ketone as raw material, reacting in pure organic solvent, organic solvent - water or water, wherein the reaction formula is disclosed in the specification, wherein replaced R1, R2 can be alkyl or aryl groups, when R1 and / or R2 is aryl replaced group, one or more electron supply and / or electron absorption groups can be carried. The product by the invention can be obtained through disintegrating through the conventional methods.

Description

technical field [0001] The invention relates to the synthesis of α, β-epoxy ketone compounds, in particular to a method for synthesizing α, β-epoxy ketone compounds by phase transfer catalysis. Background technique [0002] α, β-epoxy ketone compounds are the most widely used intermediates in organic synthesis, and both carbonyl and propylene oxide groups can be functionalized [Document: Tetrahedron: Asymmetry, 2001, 12, 2359-2383, etc.] . The carbonyl functionalization includes reduction to α, β-epoxy alcohol, reductive amination reaction, Bayer-Villiger reaction, Melwein-Pondorf-Weilay reaction, etc. And the ring-opening of the propylene oxide group by nucleophilic reagents such as sulfur, oxygen, and halogen can be used to synthesize a wide variety of compounds. [0003] α, β-epoxy ketone building blocks can be used to synthesize bioactive compounds, such as leukotriene receptor antagonist SK&F104353 [Document: J.Org.Chem.1993, 58, 6247-6254, etc.], diltiazem and paclit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D303/32
Inventor 叶金星王永灿张国富梁鑫淼陈吉平
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI