The Role of an Acid in the Decomposition of Mixed Benzoyl-Substituted Phosphonium-Iodonium Ylide

被引：6

作者：

Nekipelova, T. D. ^{[1
]}

Podrugina, T. A. ^{[2
]}

Vinogradov, D. S. ^{[2
]}

Dem'yanov, P. I. ^{[2
]}

Kuzmin, V. A. ^{[1
]}

机构：

[1] Russian Acad Sci, Emanuel Inst Biochem Phys, Moscow 119334, Russia

[2] Moscow MV Lomonosov State Univ, Chem Fac, Moscow 119991, Russia

来源：

KINETICS AND CATALYSIS | 2019年 / 60卷 / 01期

关键词：

phosphonium-iodonium ylides; acid catalysis; radical decomposition; theoretical thermochemical analysis; NUCLEOPHILIC-SUBSTITUTION; PHENYLACETYLENE; RADICALS;

D O I：

10.1134/S0023158419010105

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Mixed phosphonium-iodonium ylides allow the synthesis of not easily accessible and novel heterocyclic compounds. Photoinitiated reactions of phosphonium-iodonium ylides with acetylenes proceed with induction time and are catalyzed by acids, the acids formed in the reaction among them. The kinetic peculiarities of the reaction between the benzoyl-substituted phosphonium-iodonium ylide and trifluoroacetic acid were studied by UV-visible spectrophotometry. The kinetic parameters of the reaction were determined. The mechanism of the autocatalysis by acids has been proposed, which involves the formation of a protonated form of the ylide active in the decomposition into radical cations. The more active decomposition of the protonated ylide is confirmed by theoretical thermochemical calculations.

引用

页码：44 / 51

页数：8

共 32 条

[1] The Role of an Acid in the Decomposition of Mixed Benzoyl-Substituted Phosphonium–Iodonium Ylide
T. D. Nekipelova
T. A. Podrugina
D. S. Vinogradov
P. I. Dem’yanov
V. A. Kuzmin
Kinetics and Catalysis, 2019, 60 : 44 - 51
[2] Radical intermediates in the photolysis of the mixed benzoyl-substituted phosphonium-iodonium ylide in different solvents
Potapov, I. D.
Motyakin, M. V.
Nekipelova, T. D.
Podrugina, T. A.
RUSSIAN CHEMICAL BULLETIN, 2024, 73 (03) : 523 - 528
[3] Spin Adducts in Photolysis of Mixed Benzoyl Phosphonium-Iodonium Ylide in Dichloromethane
Potapov, I. D.
Motyakin, M. V.
Podrugina, T. A.
Nekipelova, T. D.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B, 2024, 18 (06) : 1501 - 1510
[4] Synthesis and structure of mixed phosphonium-iodonium ylide
Matveeva, ED
Podrugina, TA
Grishin, YK
Tkachev, VV
Zhdankin, VV
Aldoshin, SM
Zefirov, NS
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY, 2003, 39 (04) : 536 - 541
[5] Synthesis and Structure of Mixed Phosphonium-iodonium Ylide
E. D. Matveeva
T. A. Podrugina
Yu. K. Grishin
V. V. Tkachev
V. V. Zhdankin
S. M. Aldoshin
N. S. Zefirov
Russian Journal of Organic Chemistry, 2003, 39 : 536 - 541
[6] Radicals in Annulation of Mixed Benzoyl Phosphonium-Iodonium Ylide and Acetylenes Explored by EPR-ST Spectroscopy
Potapov, Ilia D.
Levina, Irina I.
Motyakin, Mikhail V.
Podrugina, Tatyana A.
Nekipelova, Tatiana D.
ASIAN JOURNAL OF ORGANIC CHEMISTRY, 2024, 13 (12)
[7] Photosensitization of the Reaction of Mixed Phosphonium-Iodonium Ylide with 9-Ethynylphenanthrene
Nekipelova, T. D.
Potapov, I. D.
Pogonin, V. I.
Podrugina, T. A.
Kuzmin, V. A.
HIGH ENERGY CHEMISTRY, 2020, 54 (06) : 480 - 482
[8] Mechanism and remarkable features of photoinduced cycloaddition of phenylacetylene to mixed phosphonium-iodonium ylide
Nekipelova, T. D.
Taranova, M. A.
Matveeva, E. D.
Podrugina, T. A.
Kuzmin, V. A.
Zefirov, N. S.
DOKLADY CHEMISTRY, 2012, 447 : 262 - 265
[9] Mechanism and remarkable features of photoinduced cycloaddition of phenylacetylene to mixed phosphonium-iodonium ylide
T. D. Nekipelova
M. A. Taranova
E. D. Matveeva
T. A. Podrugina
V. A. Kuzmin
N. S. Zefirov
Doklady Chemistry, 2012, 447 : 262 - 265
[10] Photocyclization of a Mixed Phosphonium-Iodonium Ylide with Phenylacetylene: A Formal Kinetic Approach to the Mechanistic Study
Nekipelova, T. D.
Taranova, M. A.
Matveeva, E. D.
Kuz'min, V. A.
Zefirov, N. S.
KINETICS AND CATALYSIS, 2015, 56 (04) : 403 - 411

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