Chip-based on-line nanospray MS method enabling study of the kinetics of isocyanate derivatization reactions.
The reaction of propyl isocyanate (2), benzyl isocyanate (3), and toluene-2,4-diisocyanate (4) with 4-nitro-7-piperazino-2,1,3-benzoxadiazole (1) to yield the corresponding urea derivatives 5 was carried out in a continuous flow glass microfluidics chip. Real-time monitoring of the derivatization reactions was done by electrospray ionization mass spectrometry, making use of a recently reported modular chip-MS interface. Rate constants of 1.5 x 10(4), 5.2 x 10(4), and 2.4 x 10(4) M(-1) min(-1) were determined for 2, 3, and 4, respectively. Using macroscale batch conditions, the rate constants are 3-4 times lower. The faster on-chip kinetics is attributed to the more efficient molecular diffusion in the micrometer-sized channel.
Brivio
Monica
M
Laboratory of Supramolecular Chemistry and Technology, University of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands.
Liesener
Andre
A
Oosterbroek
R Edwin
RE
Verboom
Willem
W
Karst
Uwe
U
van den Berg
Albert
A
Reinhoudt
David N
DN