Preparation method of 2, 6-dioxabicyclo-(3.3.0)-octane-3,7-dione

A technology for dioxa and octane, which is applied in the field of preparation of 2,6-dioxabicyclo-octane-3,7-dione, can solve the problems of high price, unfavorable industrialized production, low yield and the like

Active Publication Date: 2021-03-19
浦拉司科技(上海)有限责任公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] There are few studies on this compound in the existing published patents or literature, and 2,6-dioxabicyclo-(3.3.0)-octane-3,7-diene is mainly synthesized by reacting adienedioic acid with TMSOTf and HMDS. Ketone, SU2017 / 335031A1 This method uses more expensive reagents, and the yield is low, which is not conducive to industrial production

Method used

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  • Preparation method of 2, 6-dioxabicyclo-(3.3.0)-octane-3,7-dione
  • Preparation method of 2, 6-dioxabicyclo-(3.3.0)-octane-3,7-dione
  • Preparation method of 2, 6-dioxabicyclo-(3.3.0)-octane-3,7-dione

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Experimental program
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Effect test

Embodiment 1

[0023]

[0024] Add 144g (1.0mol) hexa-3-enedioic acid, 2.1g sodium bromide and 500mL dichloromethane into the reaction flask, cool the reaction solution to 0°C and slowly add 168g (1.05mol) bromine and 200mL dichloromethane Mixed solution of methane, the dropwise addition process controlled the temperature at 0-10°C, after the dropwise addition was completed, the reaction was stirred overnight at room temperature. TLC detected that the reaction of raw materials was complete, quenched with saturated sodium bisulfite aqueous solution, washed with saturated brine, distilled the solvent under reduced pressure, filtered the precipitated solid, and rinsed with a small amount of ice water and n-heptane to obtain 257.1 g of 3,4-dibromoadipic acid. Yield 84.6%, HPLC 98.9%. 1 H NMR (400MHz, CDCl 3 ):11.23(s,2H),4.21-4.17(m,2H),2.71-2.66(m,4H).

Embodiment 2

[0026]

[0027] Add 144g (1.0mol) hexa-3-enedioic acid, 1.6g potassium bromide and 500mL chloroform into the reaction flask, cool the reaction solution to 0°C and slowly add 168g (1.05mol) bromine and 200mL chloroform mixed solution, During the dropwise addition, the temperature was controlled at 0-10°C. After the dropwise addition was completed, the reaction was stirred overnight at room temperature. TLC detected that the reaction of raw materials was complete, quenched with saturated sodium bisulfite aqueous solution, washed with saturated brine, distilled under reduced pressure to distill chloroform, solid precipitated, filtered, rinsed with a small amount of ice water and n-heptane to obtain 3,4-dibromoadipic acid 283.0 g, yield 93.1%, HPLC: 99.5%.

Embodiment 3

[0029]

[0030] Under nitrogen protection, 30.4g (0.1mol) 3,4-dibromoadipic acid and 210mL sulfolane were added to the reaction flask, and the material was cooled to 0°C, and 8.8g (0.22mol) 60% sodium hydride and 40mL tetrahydrofuran were slowly added After the dropwise addition is completed, stir and react at room temperature for 1 hour, add 4.4g of 15-crown-5, and then heat up to 90-95°C for reaction. During the reaction, the tetrahydrofuran solvent is distilled out under normal pressure, and then the heat preservation reaction is continued. After 6 hours, TLC detected that the reaction of the raw materials was complete. Then the temperature of the reaction solution was lowered, and distillation under reduced pressure (11 mmHg) was started, and the fraction at 77-83°C was collected to obtain 12.4 g of 2,6-dioxabicyclo-(3.3.0)-octane-3,7-dione. 87.6%, GC: 99.5%. 1 H NMR (400MHz, CDCl 3 ):5.04-4.98(m,2H),2.56-2.51(m,4H).

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Abstract

The invention discloses a preparation method of 2,6-dioxabicyclo-(3.3.0)-octane-3,7-dione, and belongs to the technical field of organic synthesis. The preparation method comprises the following steps: taking hexadienoic acid as a raw material, carrying out addition reaction with bromine under the action of a catalyst to obtain 3,4-dibromoadipic acid, then reacting with a deprotonation reagent toobtain dicarboxylate, and then carrying out heating reaction to obtain 2,6-dioxabicyclo(3.3.0)-octane-3,7-dione. The method has the advantages of simple and efficient post-treatment operation of eachstep, simple and easily available raw materials, short reaction steps and high product purity, and meets the requirements of large-scale production.

Description

technical field [0001] The invention relates to a preparation method of 2,6-dioxabicyclo-(3.3.0)-octane-3,7-dione, belonging to the technical field of organic synthesis. Background technique [0002] 2,6-dioxabicyclo-(3.3.0)-octane-3,7-dione, CAS 14116-72-4, English name 1β,5βH-2,6-dioxabicyclo[3.3.0]octan- 3,7-dione, as an important compound for the synthesis of natural products such as epoxy eicosatrienoic acid, lauryl diol, aidanol and egapeol, etc., is composed of two γ-lactones. [0003] 2,6-dioxabicyclo-(3.3.0)-octane-3,7-dione, as an intermediate with a specific structure, plays an important role in the discovery and development of functional substances such as new medicines in the synthesis of natural products Intermediates have broad application prospects in scientific fields such as medicine and health, life, materials and energy. [0004] There are few studies on this compound in the existing published patents or literature, and 2,6-dioxabicyclo-(3.3.0)-octane-3...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D493/04
CPCC07D493/04
Inventor 陆电云漆伟君蔡伟兵
Owner 浦拉司科技(上海)有限责任公司
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