Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate

A. V. Nemtarev, V. F. Mironov, A. S. Aniskin, D. S. Baranov, E. V. Mironova, D. B. Krivolapov, R. Z. Musin, S. F. Vasilevskii, N. O. Druzhkov, V. K. Cherkasov

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The reactions of 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole and its benzo-substituted derivatives with arylacetylenes containing strong +M-donors and -M-acceptors afford benzo[e]-1,2-oxaphosphinine 2-oxides (phosphacoumarins) in high yields. Studies by the competitive reaction method showed that the reaction rate is sensitive to the electronic nature of the substituent in arylacetylene. Thus, the introduction of +M-donors into the phenyl ring of arylacetylene leads to an increase in the reaction rate, whereas the introduction of -M-acceptors results in its substantial decrease. The molecular and supramolecular structures of selected 2-hydroxyphosphacoumarins and substituted vinylphosphonate, which is generated by the cleavage of the P-heterocycle, were studied by X-ray diffraction.

Original languageEnglish
Pages (from-to)55-70
Number of pages16
JournalRussian Chemical Bulletin
Volume62
Issue number1
DOIs
Publication statusPublished - 1 Jan 2013
Externally publishedYes

Fingerprint

Alkynes
Reaction rates
Oxides
Derivatives
X ray diffraction

Keywords

  • 2,2,2-trichloro-5-methylbenzo-1,3,2-dioxaphosphole
  • 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole
  • 4,7-bis(tert-butyl)-2,2,2- trichlorobenzo-1,3,2-dioxaphosphole
  • arylacetylene
  • benzo[e]-1,2-oxaphosphorinine 2-oxides
  • chlorination of the aromatic ring
  • electronic effect of the substituent
  • ipso-substitution of oxygen
  • reaction rate
  • vinylphosphonate

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Nemtarev, A. V., Mironov, V. F., Aniskin, A. S., Baranov, D. S., Mironova, E. V., Krivolapov, D. B., ... Cherkasov, V. K. (2013). Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate. Russian Chemical Bulletin, 62(1), 55-70. https://doi.org/10.1007/s11172-013-0008-2

Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate. / Nemtarev, A. V.; Mironov, V. F.; Aniskin, A. S.; Baranov, D. S.; Mironova, E. V.; Krivolapov, D. B.; Musin, R. Z.; Vasilevskii, S. F.; Druzhkov, N. O.; Cherkasov, V. K.

In: Russian Chemical Bulletin, Vol. 62, No. 1, 01.01.2013, p. 55-70.

Research output: Contribution to journalArticle

Nemtarev, AV, Mironov, VF, Aniskin, AS, Baranov, DS, Mironova, EV, Krivolapov, DB, Musin, RZ, Vasilevskii, SF, Druzhkov, NO & Cherkasov, VK 2013, 'Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate', Russian Chemical Bulletin, vol. 62, no. 1, pp. 55-70. https://doi.org/10.1007/s11172-013-0008-2
Nemtarev, A. V. ; Mironov, V. F. ; Aniskin, A. S. ; Baranov, D. S. ; Mironova, E. V. ; Krivolapov, D. B. ; Musin, R. Z. ; Vasilevskii, S. F. ; Druzhkov, N. O. ; Cherkasov, V. K. / Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate. In: Russian Chemical Bulletin. 2013 ; Vol. 62, No. 1. pp. 55-70.
@article{8bf6d4b839104a349e08088bd1ebf43b,
title = "Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate",
abstract = "The reactions of 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole and its benzo-substituted derivatives with arylacetylenes containing strong +M-donors and -M-acceptors afford benzo[e]-1,2-oxaphosphinine 2-oxides (phosphacoumarins) in high yields. Studies by the competitive reaction method showed that the reaction rate is sensitive to the electronic nature of the substituent in arylacetylene. Thus, the introduction of +M-donors into the phenyl ring of arylacetylene leads to an increase in the reaction rate, whereas the introduction of -M-acceptors results in its substantial decrease. The molecular and supramolecular structures of selected 2-hydroxyphosphacoumarins and substituted vinylphosphonate, which is generated by the cleavage of the P-heterocycle, were studied by X-ray diffraction.",
keywords = "2,2,2-trichloro-5-methylbenzo-1,3,2-dioxaphosphole, 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole, 4,7-bis(tert-butyl)-2,2,2- trichlorobenzo-1,3,2-dioxaphosphole, arylacetylene, benzo[e]-1,2-oxaphosphorinine 2-oxides, chlorination of the aromatic ring, electronic effect of the substituent, ipso-substitution of oxygen, reaction rate, vinylphosphonate",
author = "Nemtarev, {A. V.} and Mironov, {V. F.} and Aniskin, {A. S.} and Baranov, {D. S.} and Mironova, {E. V.} and Krivolapov, {D. B.} and Musin, {R. Z.} and Vasilevskii, {S. F.} and Druzhkov, {N. O.} and Cherkasov, {V. K.}",
year = "2013",
month = "1",
day = "1",
doi = "10.1007/s11172-013-0008-2",
language = "English",
volume = "62",
pages = "55--70",
journal = "Russian Chemical Bulletin",
issn = "1066-5285",
publisher = "Springer New York",
number = "1",

}

TY - JOUR

T1 - Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate

AU - Nemtarev, A. V.

AU - Mironov, V. F.

AU - Aniskin, A. S.

AU - Baranov, D. S.

AU - Mironova, E. V.

AU - Krivolapov, D. B.

AU - Musin, R. Z.

AU - Vasilevskii, S. F.

AU - Druzhkov, N. O.

AU - Cherkasov, V. K.

PY - 2013/1/1

Y1 - 2013/1/1

N2 - The reactions of 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole and its benzo-substituted derivatives with arylacetylenes containing strong +M-donors and -M-acceptors afford benzo[e]-1,2-oxaphosphinine 2-oxides (phosphacoumarins) in high yields. Studies by the competitive reaction method showed that the reaction rate is sensitive to the electronic nature of the substituent in arylacetylene. Thus, the introduction of +M-donors into the phenyl ring of arylacetylene leads to an increase in the reaction rate, whereas the introduction of -M-acceptors results in its substantial decrease. The molecular and supramolecular structures of selected 2-hydroxyphosphacoumarins and substituted vinylphosphonate, which is generated by the cleavage of the P-heterocycle, were studied by X-ray diffraction.

AB - The reactions of 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole and its benzo-substituted derivatives with arylacetylenes containing strong +M-donors and -M-acceptors afford benzo[e]-1,2-oxaphosphinine 2-oxides (phosphacoumarins) in high yields. Studies by the competitive reaction method showed that the reaction rate is sensitive to the electronic nature of the substituent in arylacetylene. Thus, the introduction of +M-donors into the phenyl ring of arylacetylene leads to an increase in the reaction rate, whereas the introduction of -M-acceptors results in its substantial decrease. The molecular and supramolecular structures of selected 2-hydroxyphosphacoumarins and substituted vinylphosphonate, which is generated by the cleavage of the P-heterocycle, were studied by X-ray diffraction.

KW - 2,2,2-trichloro-5-methylbenzo-1,3,2-dioxaphosphole

KW - 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole

KW - 4,7-bis(tert-butyl)-2,2,2- trichlorobenzo-1,3,2-dioxaphosphole

KW - arylacetylene

KW - benzo[e]-1,2-oxaphosphorinine 2-oxides

KW - chlorination of the aromatic ring

KW - electronic effect of the substituent

KW - ipso-substitution of oxygen

KW - reaction rate

KW - vinylphosphonate

UR - http://www.scopus.com/inward/record.url?scp=84887112913&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84887112913&partnerID=8YFLogxK

U2 - 10.1007/s11172-013-0008-2

DO - 10.1007/s11172-013-0008-2

M3 - Article

VL - 62

SP - 55

EP - 70

JO - Russian Chemical Bulletin

JF - Russian Chemical Bulletin

SN - 1066-5285

IS - 1

ER -