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Method for synthesizing di-tert-butyl dicarbonic acid ester

A technology of di-tert-butyl dicarbonate and synthesis method, which is applied to the preparation of carbon dioxide or inorganic carbonate, organic chemistry, reagents, etc., and can solve the problems of large specificity of methanesulfonyl chloride, reduced reactivity, and difficult separation of products , to achieve the effects of easy separation, improved solubility, and cost reduction

Inactive Publication Date: 2008-05-07
上海中远化工有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0013] The advantage of this route is that the reaction steps are reduced and the reaction toxicity is reduced, but the reactivity is reduced and the reaction time is relatively long
European patent EP 468404 proposes to use methylsulfonyl chloride (MesylCloride) instead of tosyl chloride (TosylCloride) to improve the reactivity. The patent claims that the yield and product quality can be improved, but the proportion of methylsulfonyl chloride (MesylCloride) is extremely large, causing Special mass transfer and stirring problems, and MesylCloride (MesylCloride) is easy to form +O-SO2-Me with +O-Na, and the boiling point of DIBOC is very similar, and the product is not easy to separate

Method used

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  • Method for synthesizing di-tert-butyl dicarbonic acid ester
  • Method for synthesizing di-tert-butyl dicarbonic acid ester
  • Method for synthesizing di-tert-butyl dicarbonic acid ester

Examples

Experimental program
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Effect test

Embodiment 1

[0037] Add 400g (460ml) of toluene to 50g (0.52mol) sodium tert-butoxide, heat to 60°C to dissolve sodium tert-butoxide, cool down to 50°C, feed carbon dioxide at a flow rate of 0.2-0.3L / min, until the solution is flooded White, about 2.5hr; add 100g of tert-butanol; add catalyst N,N,N',N'-tetramethylethylenediamine (TMEDA) 0.15g, cool down to 0-20℃, drop diphosgene (Cl 3 COCOCl) 27g (0.136mol) of toluene solution 80 grams, add dropwise for 2-3 hours, continue to stir for 2.5 hours after the end, add 100 grams of anhydrous sodium carbonate solution for alkali washing, 150 grams of citric acid solution for acid washing, and 100 grams of water for washing When the pH of the washing water was equal to 5-7, the reaction liquid was distilled under reduced pressure to obtain 47.51 g of DIBOC with a yield of 83.73%.

Embodiment 2

[0039] Add 400g (238ml) of heptane to 50g (0.52mol) of sodium tert-butoxide, heat to 60°C to dissolve sodium tert-butoxide, cool down to 50°C, and feed carbon dioxide at a flow rate of 0.2-0.3L / min for 2.5hr; Supplement 100g (116ml) of toluene, 90g of tert-butanol, add 0.06g of catalyst triethylenediamine, lower the temperature to 0-20°C, add diphosgene (Cl 3 COCOCl) 25g (0.126mol) of toluene solution 80g, stirred for 2.5 hours, washed with anhydrous sodium carbonate alkali, washed with water until the washing water pH4.63, conductivity 24.6μs, the reaction solution was distilled under reduced pressure to obtain DIBOC43.19g, yield 76.12 %.

Embodiment 3

[0041] Add 400g (460ml) of toluene to 50.3g (0.52mol) sodium tert-butoxide, heat to 60°C to dissolve sodium tert-butoxide, cool down to 50°C, feed carbon dioxide at a flow rate of 0.2-0.3L / min, 2.5hr; Tetrahydrofuran 150ml; add catalyst N,N,N',N'-tetramethylethylenediamine 0.2g, cool down to 0-20°C, add diphosgene (Cl 3 COCOCl) 28.9g (0.146mol) of toluene solution 80g, stirred for 2.5 hours, washed with water until the pH of the washing water was 5.04, the conductivity was 77.1μs, and the reaction solution was distilled under reduced pressure to obtain 44.66g of DIBOC with a yield of 78.71%.

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Abstract

The invention relates to a method for synthetizing di-tert-butyl bicarbonic ester, comprising the steps as follows: tertiary butyl alcohol natrium is used as the raw material, toluol or heptane is used as the solvent, the raw material and the solvent are heated and mixed to dissolve, carbon dioxide gas is inlet under 40 to 80 DEG C, the additive latent solvent of tertiary butyl alcohol or tetrahydrofuran are additionally added to reduce the viscosity of the solution, the temperature is reduced to 0 to 40 DEG C, the catalyst N, N, , -tetramethyl quadrol and cocatalyst of crownether are added in, toluene solution containing diphosgene is dripped in for reacting for 2 to 3 hours, the acquired oil phase liquid is cleaned in alkali and water, decompressed and distilled to produce the di-tert-butyl bicarbonic ester. The method of the invention is characterized in low production cost, short reaction period, stable product quality and good applicability for industrialized production.

Description

technical field [0001] The present invention relates to the synthetic method of di-tert-butyl dicarbonate. Background technique [0002] Di-tert-butyl dicarbonate (hereinafter referred to as DIBOC) is an important amino-protecting agent formed by tert-butoxycarbonylation. DIBOC plays an important role in the chemical synthesis of amino acids, peptide groups and proteins. It has the characteristics of good reactivity and simple post-treatment, and the by-products of tert-butanol and carbon dioxide will not cause new pollution, so it is still important for the research and development of DIBOC. [0003] The route of synthetic DIBOC reported in the literature is mainly: [0004] (1) Phosgene method (Chem.Abstracts, 1941 35: 4351) reaction equation is as follows: [0005] <chemistry num="0001"> <chem file="200610117788_CML001.XML" / > < / chemistry> [0006] This route, the first intermediate product tert-butyl chloroformate is extremely unstable (begins to ...

Claims

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Application Information

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IPC IPC(8): C07C68/04C07C69/96
CPCY02P20/141
Inventor 袁爱萍
Owner 上海中远化工有限公司
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