Reductive activation of arenes - 22. Reactions of the terephthalonitrile radical anion and dianion with alpha,omega-dibromoalkanes. New evidence for the charge transfer complex as a key intermediate in the reactions of the dianion

Reductive activation of arenes - 22. Reactions of the terephthalonitrile radical anion and dianion with alpha,omega-dibromoalkanes. New evidence for the charge transfer complex as a key intermediate in the reactions of the dianion Full article

Journal

Russian Chemical Bulletin
ISSN: 1066-5285 , E-ISSN: 1573-9171

Output data

Year: 2007, Volume: 56, Number: 6, Pages: 1110-1118 Pages count : 9 DOI: 10.1007/s11172-007-0168-z

Tags

terephthalonitrile; radical anion; dianion; alpha,omega-dibromoalkanes; 4-(omega-bromoalkyl) benzonitriles; alpha,omega-bis(4-cyanophenyl) alkanes; charge transfer complexes; reaction mechanisms

Authors

Panteleeva E.V. ^1,2 , Lukyanova M.Yu. ¹ , Pokrovsky L.M. ¹ , Shteingarts V.D. ¹

Affiliations

1	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 9 prosp. Akad. Lavrent'eva
2	Novosibirsk State University, 2 ul. Pirogova

The major products of reactions of the terephthalonitrile radical anion with alpha,omega-dibromoalkanes Br(CH2)(n)Br (n = 3-5) were 4-(omega-bromoalkyl) benzonitriles. Analogous reactions of the terephthalonitrile dianion mainly yielded alpha,omega-bis(4-cyanophenyl) alkanes. Both transformations are convenient one-step routes to otherwise not easily accessible compounds that are valuable as versatile building blocks. The results of alkylation allow one to suggest that reactions of the dianion with intermediate 4-(omega-bromoalkyl) benzonitriles proceed more rapidly than those with the starting alpha,omega-dibromoalkanes. This was confirmed by competitive reactions of the dianion with 4-(omega- bromoalkyl) benzonitriles and the corresponding alkyl bromides. To explain such a ratio of the reaction rates, a mechanism was proposed for the reaction of the dianion with 4-(omega-bromoalkyl) benzonitriles. According to this mechanism, a charge transfer complex is a key reaction intermediate.

Panteleeva E.V. , Lukyanova M.Y. , Pokrovsky L.M. , Shteingarts V.D.
Reductive activation of arenes - 22. Reactions of the terephthalonitrile radical anion and dianion with alpha,omega-dibromoalkanes. New evidence for the charge transfer complex as a key intermediate in the reactions of the dianion
Russian Chemical Bulletin. 2007. V.56. N6. P.1110-1118. DOI: 10.1007/s11172-007-0168-z WOS Scopus РИНЦ

Пантелеева Е.В. , Лукьянова М.Ю. , Покровский Л.М. , Штейнгарц В.Д.
Восстановительная активация аренов. сообщение 22. взаимодействие анион-радикала и дианиона терефталонитрила с α,ω-дибромал-канами. новое свидетельство в пользу комплекса с переносом заряда как ключевого ин-термедиата в реакциях дианиона
Известия Академии наук. Серия химическая.(RUSS CHEM B+). 2007. №6. С.1069-1077. РИНЦ

Published print:

Jun 1, 2007

Web of science	WOS:000251971700003
Scopus	2-s2.0-36949037580
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