Preparation of N-9-fluorenylmethoxycarbonylamino acid chlorides from mixed anhydrides by the action of hydrogen chloride.
N-9-Fluorenylmethoxycarbonyl-(Fmoc) amino-acid chlorides have been prepared by reaction of hydrogen chloride on purified mixed Fmoc-amino acid-monoalkyl carbonic acid anhydrides in dichloromethane. The products partially undergo subsequent conversion to the corresponding esters due to the presence of the liberated alcohol, the extent depending on the nature of the alkyl group. Esterification occurred to 5-20% when the alkyl group was isopropyl. Anhydrides of monoisopropenyl carbonic acid which liberate acetone instead of an alcohol gave products uncontaminated with ester. The three components in a reaction mixture could be determined as the reaction progressed by normal phase high-performance liquid chromatography of aliquots, which had been freed of excess hydrogen chloride, on a mu Porasil (underivatized silica) column using tert.-butanol-hexane (1.5:98.5) as solvent.
Chen
F M
FM
Department of Biochemistry, University of Ottawa, Ontario, Canada.
Lee
Y C
YC
Benoiton
N L
NL
D000215:Acylation; D000596:Amino Acids / Q000138:chemical synthesis*; D000812:Anhydrides; D002851:Chromatography, High Pressure Liquid; D004951:Esterification; D005449:Fluorenes / Q000138:chemical synthesis*; D006851:Hydrochloric Acid / Q000737:chemistry; D008956:Models, Chemical; D010455:Peptides / Q000138:chemical synthesis; D013237:Stereoisomerism
D000596:Amino Acids; D000812:Anhydrides; D005449:Fluorenes; D010455:Peptides; D006851:Hydrochloric Acid