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

Autor: Beletsan OB; Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia., Gordiy I; ChemU Corporation Ltd, 17 17 Gr. Xenopoulou St., 3106 Limassol, Cyprus., Lunkov SS; Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia.; N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, 119991 Moscow, Russia., Kalinin MA; Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia., Alkhimova LE; Center for Nature-Inspired Engineering, University of Tyumen, 625003 Tyumen, Russia.; School of Natural Sciences, University of Tyumen, 625003 Tyumen, Russia., Nosach EA; Department of Fundamental Physical and Chemical Engineering, Lomonosov Moscow State University, 119234 Moscow, Russia., Ilin EA; Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia.; N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, 119991 Moscow, Russia., Bespalov AV; Department of Chemistry and High Technologies, Kuban State University, 149 Stavropolskaya St., 350040 Krasnodar, Russia., Dallakyan OL; Computational Material Science Laboratory, Department of Physics, Yerevan State University, 0025 Yerevan, Armenia., Chamkin AA; A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119334 Moscow, Russia., Prolomov IV; D. Mendeleev University of Chemical Technology of Russia, 125047 Moscow, Russia.; N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, 119991 Moscow, Russia., Zaripov RA; Skolkovo Institute of Science and Technology, 121205 Moscow, Russia., Pershin AA; Samara Branch of Lebedev Physical Institute, 443011 Samara, Russia.; Department of Physics, Samara University, 443086 Samara, Russia., Protsenko BO; The Smart Materials Research Institute, Southern Federal University, 344090 Rostov-on-Don, Russia., Rusalev YV; The Smart Materials Research Institute, Southern Federal University, 344090 Rostov-on-Don, Russia., Oganov RA; Department of Biochemistry, Lomonosov Moscow State University, 119991 Moscow, Russia., Kovaleva DK; Department of Biochemistry, Lomonosov Moscow State University, 119991 Moscow, Russia., Mironov VA; A. M. Butlerov Chemistry Institute, Kazan Federal University, 420008 Kazan, Russia., Dotsenko VV; Department of Chemistry and High Technologies, Kuban State University, 149 Stavropolskaya St., 350040 Krasnodar, Russia.; Faculty of Chemistry and Pharmacy, North-Caucasus Federal University, 355017 Stavropol, Russia., Genaev AM; N.N. Vorozhtsov Institute of Organic Chemistry, 630090 Novosibirsk, Russia. genaev@nioch.nsc.ru., Sharapa DI; Independent researcher, Germany. gess87@mail.ru., Tikhonov DS; Independent researcher, Germany. gess87@mail.ru.
Jazyk: angličtina
Zdroj: Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2024 May 08; Vol. 26 (18), pp. 13850-13861. Date of Electronic Publication: 2024 May 08.
DOI: 10.1039/d3cp04654k
Abstrakt: 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.
Databáze: MEDLINE