Burgess reagent

Structural formula
General
Surname	Burgess reagent
other names	Methyl N - (triethylammonium sulfonyl) carbamate, inner salt
Molecular formula	C 8 H 18 N 2 O 4 S
Brief description	colorless, needle-shaped crystals
External identifiers / databases
CAS number 29684-56-8 EC number 629-648-8 ECHA InfoCard 100.157.812 PubChem 9566069 Wikidata Q410969
properties
Molar mass	238.30 g mol −1
Physical state	firmly
Melting point	70-72 ° C
safety instructions
GHS labeling of hazardous substances Caution H and P phrases H: 315-319-335 P: 261-305 + 351 + 338
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

The Burgess reagent is a very mild and syn -selective dehydration reagent .

Extraction and presentation

The methyl derivative described here , which is now also commercially available under the name Burgess reagent , was first produced by Crabbé and Léon in 1970. However, the synthesis was carried out according to a working procedure that was published by Burgess in 1968 for the ethyl derivative. The reagent described here is prepared from chlorosulfonyl isocyanate with methanol and triethylamine in benzene . For the ethyl derivative, an analogous process is used with ethanol instead of methanol.

use

The Burgess reagent is used for the Burgess water separation. This name reaction is a dehydration of secondary and tertiary alcohols in order to specifically synthesize the corresponding olefins in a syn- elimination .

Other uses for the Burgess reagent were later described.

Synthesis of isonitriles

But other compounds can also be converted with the Burgess reagent. For example, formamides react in a reaction with the Burgess reagent to form isonitriles with formal dehydration :

Synthesis of nitriles

In the second half of the 1980s, the Burgess reagent was also used for the dehydration of primary amides and oximes to form the corresponding nitriles at room temperature :

Synthesis of nitrile oxides

If primary nitroalkanes react with the Burgess reagent, nitrile oxides can be synthesized:

Synthesis of carbamates

Primary alcohols react with the Burgess reagent to form the corresponding carbamates , which in turn react to primary amines through the subsequent hydrolysis :

Individual evidence

1. ↑ ^{a b} Khapli, S .; Dey, S .; Mal, D. "Burgess reagent in organic synthesis." J. Indian Inst. Sci. 2001 , 81 , 461-476 PDF .
2. ↑ ^{a b} Data sheet Burgess reagent from Sigma-Aldrich , accessed on March 14, 2011 ( PDF ).
3. ↑ Crabbé, P .; Léon, C. "A Novel Dehydration Reaction of Steroidal Alcohols" J. Org. Chem. 1970 , 35 , 2594-2596.
4. ↑ Atkins, GM; Burgess, EM "The Reactions of an N-Sulfonylamine Inner Salt" J. Am. Chem. Soc. 1968 , 90 , 4744-4745.
5. ^ Burgess, EM; Penton, HR, Jr .; Taylor, EA "Thermal Reactions of Alkyl N-Carbomethoxysulfamate Esters" J. Org. Chem. 1973 , 38 , 26-31.
6. ^ Burgess, EM; Penton, HR, Jr .; Taylor, EA; Williams, WM "Conversion of primary alcohols to urethanes. Methyl n-sulfonylurethane triethylamine complexes." Org. Synth. 1973 , 53 , 1857.
7. ↑ O'Grodnick, JS; Ebersole, RC; Wittstruck, T .; Caspi, E. "Trans dehydration of alcohols with methyl (carboxysulfamoyl) triethylammonium hydroxide inner salt." J. Org. Chem. 1974 , 39 , 2124-2126.
8. ^ Burgess, EM; Penton, HR, Jr .; Taylor, EA; Williams, WM "Conversion of primary alcohols to urethanes via the inner salt of methyl (carboxysulfamoyl) triethylammonium hydroxide: methyl n-hexylcarbamate." Org. Synth. 1977 , 56 , 40-43.
9. ^ Edward M. Burgess, Harold R. Penton, Edward Alan. Taylor: Synthetic applications of N-carboalkoxysulfamate esters . In: Journal of the American Chemical Society . tape 92 , no. 17 , 1970, pp. 5224-5226 , doi : 10.1021 / ja00720a041 .
10. ^ Siobhan M. Creedon, H. Kevin Crowley, Daniel G. McCarthy: Dehydration of formamides using the Burgess Reagent: a new route to isocyanides . In: Journal of the Chemical Society, Perkin Transactions 1 . No. 6 , 1998, pp. 1015-1018 , doi : 10.1039 / a708081f .
11. ↑ David A. Claremon, Brian T. Phillips: An efficient chemoselective synthesis of nitriles from primary amides . In: Tetrahedron Letters . tape 29 , no. 18 , 1988, pp. 2155-2158 , doi : 10.1016 / S0040-4039 (00) 86697-6 .
12. ↑ Mild and Efficient Dehydration of Oximes to Nitriles Mediated by the Burgess Reagent . In: Synlett . tape 2000 , no. 08 , 2000, p. 1169-1171 , doi : 10.1055 / s-2000-6752 .
13. ↑ Nathalie Maugein, Alain Wagner, Charles Mioskowski: New conditions for the generation of nitrile oxides from primary nitroalkanes . In: Tetrahedron Letters . tape 38 , no. 9 , 1997, pp. 1547-1550 , doi : 10.1016 / S0040-4039 (97) 00101-9 .
14. ↑ Edward M. Burgess, Harold R. Penton, E. Alan Taylor, W. Michael Williams: Conversion of Primary Alcohols to Urethanes via the Inner Salt of Methyl (Carboxysulfamoyl) Triethylammonium Hydroxide: Methyl n -Hexylcarbamate: Carbamic acid, hexyl-, methyl ester . In: Organic Syntheses . John Wiley & Sons, Inc., Hoboken, NJ, USA 2003, ISBN 978-0-471-26422-4 , pp. 40-40 , doi : 10.1002 / 0471264180.os056.10 .