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Synthesis of alkyl-gem-dichlorocyclopropanes based on isoamylene fraction

https://doi.org/10.32362/2410-6593-2020-15-6-9-15

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Abstract

Objectives. The study aims to analyze the dichlorocarbenation of the isoamylene fraction, which is a mixture of 2-methyl-butene-1 and 2-methyl-butene-2, in order to obtain the corresponding alkyl-gem-dichlorocyclopropanes in quantitative yield, and also to determine their structure.

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

Results. Alkyl-gem-dichlorocyclopropanes were synthesized from an isoamylene fraction in the presence of catamine AB as a catalyst. Alternatively, isomeric alkenyl-gem-dichlorocyclopropanes were obtained on the basis of isoprene, and by reduction, the corresponding alkyl-gemdichlorocyclopropanes were synthesized. The synthesized substances were analyzed by gasliquid chromatography, mass spectrometry, and NMR spectroscopy, as previously mentioned above.

Conclusions. The results show that the dichlorocyclopropanation of the isoamylene fraction proceeds quantitatively with the formation of a mixture of 2-methyl-2-ethyl-1,1dichlorocyclopropane and 2,3,3-trimethyl-1,1-dichlorocyclopropane. Using isoprene, countersynthesis through successive dichlorocarbenation and hydrogenation was used to synthesize 2-methyl-2-ethyl-1,1-dichlorocyclopropane, one of the products of dichlorocarbenation of the isoamylene fraction.

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



Yu. G. Borisova
Ufa State Petroleum Technological University, Branch in Sterlitamak
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



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



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

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

2, Oktyabrya pr., Sterlitamak, 453118



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



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



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Supplementary files

1. Chromatogram of a mixture of alkyl-gem-dichlorocyclopropanes 3, 4.
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2. This is to certify that the paper titled Synthesis of alkyl-gem-dichlorocyclopropanes based on isoamylene fraction commissioned to us by Airat I. Musin, Yulianna G. Borisova, Gul’nаra Z. Raskil’dina, Rustem R. Daminev, Ruslan U. Rabaev, Simon S. Zlotskii has been edited for English language and spelling by Enago, an editing brand of Crimson Interactive Inc.
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  • The results show that the dichlorocyclopropanation of the isoamylene fraction proceeds quantitatively with the formation of a mixture of 2-methyl-2-ethyl-1,1-dichlorocyclopropane and 2,3,3-trimethyl-1,1-dichlorocyclopropane.
  • Using isoprene, countersynthesis through successive dichlorocarbenation and hydrogenation was used to synthesize 2-methyl-2-ethyl-1,1-dichlorocyclopropane, one of the products of dichlorocarbenation of the isoamylene fraction.

For citation:


Musin A.I., Borisova Yu.G., Raskil’dina G.Z., Daminev R.R., Rabaev R.U., Zlotskii S.S. Synthesis of alkyl-gem-dichlorocyclopropanes based on isoamylene fraction. Fine Chemical Technologies. 2020;15(6):9-15. https://doi.org/10.32362/2410-6593-2020-15-6-9-15

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ISSN 2410-6593 (Print)
ISSN 2686-7575 (Online)