Issue 18, 2024

From a humorous post to a detailed quantum-chemical study: isocyanate synthesis revisited

Abstract

Isocyanates play an essential role in modern manufacturing processes, especially in polyurethane production. There are numerous synthesis strategies for isocyanates both under industrial and laboratory conditions, which do not prevent searching for alternative highly efficient synthetic protocols. Here, we report a detailed theoretical investigation of the mechanism of sulfur dioxide-catalyzed rearrangement of phenylnitrile oxide into phenyl isocyanate, which was first reported in 1977. The DLPNO-CCSD(T) method and up-to-date DFT protocols were used to perform a highly accurate quantum-chemical study of the rearrangement mechanism. An overview of various organic and inorganic catalysts has revealed other potential catalysts, such as sulfur trioxide and selenium dioxide. Furthermore, the present study elucidated how substituents in phenylnitrile oxide influence reaction kinetics. This study was performed by a self-organized collaboration of scientists initiated by a humorous post on the VK social network.

Graphical abstract: From a humorous post to a detailed quantum-chemical study: isocyanate synthesis revisited

Supplementary files

Article information

Article type
Paper
Submitted
25 Sep 2023
Accepted
22 Feb 2024
First published
27 Feb 2024

Phys. Chem. Chem. Phys., 2024,26, 13850-13861

From a humorous post to a detailed quantum-chemical study: isocyanate synthesis revisited

O. B. Beletsan, I. Gordiy, S. S. Lunkov, M. A. Kalinin, L. E. Alkhimova, E. A. Nosach, E. A. Ilin, A. V. Bespalov, O. L. Dallakyan, A. A. Chamkin, I. V. Prolomov, R. A. Zaripov, A. A. Pershin, B. O. Protsenko, Y. V. Rusalev, R. A. Oganov, D. K. Kovaleva, V. A. Mironov, V. V. Dotsenko, A. M. Genaev, D. I. Sharapa and D. S. Tikhonov, Phys. Chem. Chem. Phys., 2024, 26, 13850 DOI: 10.1039/D3CP04654K

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