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Synthesis and reactions of alkenyl-gem-dichlorocyclopropanes obtained from piperylene

https://doi.org/10.32362/2410-6593-2020-15-5-16-25

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Abstract

Objectives. This study aims to obtain alkenyl-gem-dichlorocyclopropanes from piperylene. The products are then subjected to thermocatalytic isomerization and hydrogenation.

Methods. To determine the qualitative and quantitative composition of the reaction crudes, the following analytical methods were used: gas-liquid chromatography using the Crystal 2000 hardware complex, mass spectrometry using a Chromatec-Crystal 5000M device with the NIST 2012 database, and nuclear magnetic resonance (NMR) spectroscopy using a Bruker AM-500 device at operating frequencies of 500 and 125 MHz.

Results. Alkenyl-gem-dichlorocyclopropanes were synthesized in the presence of triethylbenzyl ammonium chloride as catalyst. Their isomerization and hydrogenation gave the corresponding gem-dichlorocyclopentene and isomers of alkyl-gem-dichlorocyclopropanes. The structure of synthesized substances were analyzed by gas-liquid chromatography, mass spectrometry, and NMR spectroscopy.

Conclusions. The results show that formation of four isomeric substituted gemdichlorocyclopropanes occurs in high yield during incomplete dichlorocyclopropanation of piperylene. The thermocatalytic isomerization of substituted gem-dichlorocyclopropanes in the presence of SAPO-34 zeolite leads to the formation of one product, i.e., gem-dichlorocyclopentene, and hydrogenation of substituted gem-dichlorocyclopropanes in the presence of Pd/C catalyst gives three isomeric alkyl-gem-dichlorocyclopropanes.

About the Authors

A. I. Musin
Ufa State Petroleum Technological University, Branch in Sterlitamak
Russian Federation

Airat I. Musin, Postgraduate Student, Department of General, Analytical and Applied Chemistry. ResearcherID R-9142-2016

2, Oktyabrya pr., Sterlitamak, 453118, Russia



Yu. G. Borisova
Ufa State Petroleum Technological University
Russian Federation

Yulianna G. Borisova, Cand. of Sci. (Chemistry), Teacher, Department of General, Analytical and Applied Chemistry. ResearcherID P-9744-2017, Scopus Author ID 56526865000

2, Oktyabrya pr., Sterlitamak, 453118, Russia



G. Z. Raskil’dina
Ufa State Petroleum Technological University
Russian Federation

Gul’nara Z. Raskil’dina, Cand. of Sci. (Chemistry), Associate Professor, Department of General, Analytical and Applied Chemistry. ResearcherID F-1619-2017, Scopus Author ID 56069888400

1, Kosmonavtov ul., Ufa, 450064, Russia



R. U. Rabaev
Ufa State Petroleum Technological University
Russian Federation

Ruslan U. Rabaev, Cand. of Sci. (Engineering), Vice Rector for Innovation and Scientific Work. Scopus Author ID 57207916610

1, Kosmonavtov ul., Ufa, 450064, Russia



R. R. Daminev
Ufa State Petroleum Technological University, Branch in Sterlitamak
Russian Federation

Rustem R. Daminev, Dr. of Sci. (Engineering), Professor, Director. Scopus Author ID 15026168000

2, Oktyabrya pr., Sterlitamak, 453118, Russia



S. S. Zlotskii
Ufa State Petroleum Technological University
Russian Federation

Simon S. Zlotskii, Dr. of Sci. (Chemistry), Professor, Head of Department of General, Analytical and Applied Chemistry. ResearcherID W-6564-2018, Scopus Author ID 6701508202

1, Kosmonavtov ul., Ufa, 450064, Russia



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Supplementary files

1. Schematic diagram of the installation for hydrogenation at atmospheric pressure. Valves (1–5), hydrogen generator (6), buffer tank (7), cylindrical vessel (8), pressure tank (9), hydrogenation reactor (10), stirring device (11).
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2. This is to certify that the paper titled Synthesis and reactions of alkenyl-gem-dichlorocyclopropanes obtained from piperylene commissioned to us by Airat I. Musin, Yulianna G. Borisova, Gul’nаra Z. Raskil’dina, Ruslan U. Rabaev, Rustem R. Daminev, Simon S. Zlotskii has been edited for English language and spelling by Enago, an editing brand of Crimson Interactive Inc.
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  • Alkenyl-gem-dichlorocyclopropanes were synthesized in the presence of triethylbenzyl ammonium chloride as catalyst.
  • Their isomerization and hydrogenation gave the corresponding gem-dichlorocyclopentene and isomers of alkyl-gem-dichlorocyclopropanes.
  • The results show that formation of four isomeric substituted gem-dichlorocyclopropanes occurs in high yield during incomplete dichlorocyclopropanation of piperylene. The thermocatalytic isomerization of substituted gem-dichlorocyclopropanes in the presence of SAPO-34 zeolite leads to the formation of one product, i.e., gem-dichlorocyclopentene, and hydrogenation of substituted gem-dichlorocyclopropanes in the presence of Pd/C catalyst gives three isomeric alkyl-gem-dichlorocyclopropanes.

For citation:


Musin A.I., Borisova Yu.G., Raskil’dina G.Z., Rabaev R.U., Daminev R.R., Zlotskii S.S. Synthesis and reactions of alkenyl-gem-dichlorocyclopropanes obtained from piperylene. Fine Chemical Technologies. 2020;15(5):16-25. https://doi.org/10.32362/2410-6593-2020-15-5-16-25

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