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Synthetic method for romatic carbamic acid ester

A technology for synthesizing carbamic acid and carbamic acid, which is applied to the preparation of carbamic acid derivatives, organic chemical methods, chemical instruments and methods, etc., can solve the problems of not being easy to obtain phenol and the small range of substrates, and achieve non-toxic raw materials and methods Simple, safe and simple effect

Active Publication Date: 2015-08-12
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] At present, there are few reports on the synthesis of aryl carbamate by non-phosgene method, and the most studied is the use of formamide and 2-carbonyl substituted phenol to generate oxidative coupling reaction under the catalysis of copper to synthesize aryl carbamate (G.S.Kumar, C.U.Maheswari, R.A.Kumar, M.L.Kantam, K.R.Reddy, Angew.Chem.Int.Ed.2011, 50, 11748-11751; N.T.S.Phan, T.T.Nguyen, P.H.L.Vu, ChemCatChem 2013, 5, 3068-3077), but the method The scope of applicable substrates is small, and 2-carbonyl substituted phenols are not easy to obtain
However, there is no report on the direct synthesis of aromatic carbamates using carbon dioxide as a raw material.

Method used

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  • Synthetic method for romatic carbamic acid ester
  • Synthetic method for romatic carbamic acid ester
  • Synthetic method for romatic carbamic acid ester

Examples

Experimental program
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Effect test

Embodiment 1

[0045]Add 0.25 mmol of bis(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, 2.5 mmol of diethylamine, 0.5 mmol of 1,8-diazabis Cyclo[5.4.0]undec-7-ene (DBU), 3 mL DMF, filled with 4 MPa of CO 2 , after stirring and reacting at 80°C for 12 hours, stop heating and stirring, cool to room temperature, and slowly vent unreacted CO 2 . The reaction solution was extracted with ethyl acetate, the solvent was removed by rotary evaporation under reduced pressure, and then separated and purified by column chromatography to obtain the target product. The column chromatography eluent used was a mixed solvent of petroleum ether:ethyl acetate with a volume ratio of 30:1 , yield 72%.

Embodiment 2

[0047] Add 0.25 mmol of bis(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, 2.5 mmol of diethylamine, 0.5 mmol of 1,4-diazabis Cyclo[2.2.2]octane (DABCO), 3 mL of acetonitrile, filled with 4 MPa of CO 2 , after stirring and reacting at 80°C for 12 hours, stop heating and stirring, cool to room temperature, and slowly vent unreacted CO 2 . The reaction solution was extracted with ethyl acetate, the solvent was removed by rotary evaporation under reduced pressure, and then separated and purified by column chromatography to obtain the target product. The column chromatography eluent used was a mixed solvent of petroleum ether:ethyl acetate with a volume ratio of 30:1 , yield 63%.

Embodiment 3

[0049] Add 0.25 mmol of bis(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, 2.5 mmol of diethylamine, 0.5 mmol of 1,8-diazabis Cyclo[5.4.0]undec-7-ene (DBU), 3 mL of acetonitrile, filled with 0.7 MPa of CO 2 , after stirring and reacting at 40°C for 12 hours, stop heating and stirring, cool to room temperature, and slowly vent unreacted CO 2 . The reaction solution was extracted with ethyl acetate, the solvent was removed by rotary evaporation under reduced pressure, and then separated and purified by column chromatography to obtain the target product. The column chromatography eluent used was a mixed solvent of petroleum ether:ethyl acetate with a volume ratio of 30:1 , yield 41%.

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Abstract

The invention relates to a synthetic method for romatic carbamic acid ester. The method comprises the following steps: adding diaryliodonium salt, amine, alkali and an organic solvent into a high-pressure reaction kettle, wherein diaryliodonium salt and amine are as raw materials, alkali is used as an accelerator and the organic solvent is used as a solvent; introducing carbon dioxide, and carrying out reaction under stirring at 40 to 150 DEGC for 2 to 24 hours; when the reaction is completed, carrying out cooling to room temperature, then slowly releasing unreacted carbon dioxide to normal pressure, filtering reaction liquid, and carrying out pressure reduced evaporation to remove the solvent so as to obtain a crude product; and carrying out purifying through column chromatography so as to obtain a series of romatic carbamic acid ester compounds. The synthetic method for the romatic carbamic acid ester provided by the invention avoids usage of phosgene or isocyanate, is simple and safe in operation and friendly to the environment, has wide substrate applicability and high yield, employs reusable raw materials, is beneficial for industrial production and has an extensive application scope in pesticides, medicines and natural product syntheses.

Description

technical field [0001] The invention relates to the technical field of pharmaceutical chemical synthesis, in particular to a method for synthesizing aromatic carbamate. Background technique [0002] Aromatic carbamate compounds are a class of compounds with the general formula RNHCOOAr, where R is hydrogen, aliphatic or aryl, and Ar is aryl or heteroaryl. Aryl carbamate is the basic skeleton of many natural products, such as physostigmine, which has important biological activities. Aromatic carbamates play a great role in agricultural production and are widely used as insecticides, acaricides, herbicides and fungicides (such as carbofuran, benomyl, oats, etc.); It has also been widely used in medicine. For example, Exelon, which is used to treat Alzheimer's disease, belongs to a carbamate aromatic ester compound. In addition, aromatic carbamate is also an important synthetic intermediate and chemical raw material, and has important uses in organic synthesis. [0003] Trad...

Claims

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Application Information

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IPC IPC(8): C07C271/44C07C269/04C07D295/205C07B43/00
Inventor 戚朝荣熊文芳江焕峰郭天佐
Owner SOUTH CHINA UNIV OF TECH
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