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 language | English |
|---|---|
| Pages (from-to) | 55-70 |
| Number of pages | 16 |
| Journal | Russian Chemical Bulletin |
| Volume | 62 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 1 Jan 2013 |
| Externally published | Yes |
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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
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 journal › Article
}
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 -