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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 41, 2011 - Issue 22
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Original Articles

Polyethylene Glycol–Enhanced Chemoselective Synthesis of Organic Carbamates from Amines, CO2, and Alkyl Halides

, &
Pages 3298-3307 | Received 30 Dec 2009, Published online: 26 Jul 2011
 

Abstract

An efficient and environmentally benign method for the synthesis of organic carbamates was developed. Amines, CO2, and alkyl halides underwent a three-component reaction with the aid of K2CO3 and polyethylene glycol (PEG, MW = 400), affording the organic carbamates under ambient conditions. PEG could presumably act as a solvent and phase-transfer catalyst (PTC). Notably, the presence of PEG could also depress the alkylation of both the amine and the carbamate, thus resulting in enhanced selectivity toward the target carbamate.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.

ACKNOWLEDGMENTS

Financial support from the National Natural Science Foundation of China (Grant Nos. 20421202, 20672054 and 20872073), the 111 Project (B06005), and the Committee of Science and Technology of Tianjin is gratefully acknowledged.

Notes

a Reaction conditions: dibutylamine (2 mmol), 1-bromobutane (4 mmol), PEG400 (10 mL), base (4 mmol), CO2 (1 atm), and biphenyl (60 mg, as internal standard), rt, 24 h.

b Determined by GC using biphenyl as internal standard.

c 1,4-Diazabicyclo[2.2.2]octane.

a Reactions were conducted with dibutylamine (2 mmol), 1-bromobutane (4 mmol), solvent (10 mL), K2CO3 (4 mmol), CO2 (1 atm), and biphenyl (60 mg, as internal standard) at rt for 24 h.

b Determined by GC using biphenyl as internal standard.

c N-Methylpyrrolidone.

d 373 K for 6 h.

a Reactions were conducted with dibutylamine (2 mmol), 1-bromobutane (4 mmol), PEG400 (10 mL), biphenyl (60 mg, as internal standard), and K2CO3 (4 mmol).

b Determined by GC using biphenyl as internal standard.

a Reactions were conducted with amine (2 mmol), halide (4 mmol), PEG400 (10 mL), biphenyl (60 mg, as internal standard), K2CO3 (4 mmol), and CO2 (1 atm), at rt for 48 h.

b Conversion and yield were determined by GC using biphenyl as internal standard. Data in parentheses refer to the isolated yield.

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