The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile

The aminolysis of aryl diphenylphosphinates, p-nitrophenyl diphenylphosphinothionate, -phosphinothioate, and -phosphinodithioate by n-butylamine, by the secondary amines piperidine, pyrrolidine, morpholine, and dipropylamine, as well as by a series of diamines, has been studied in acetonitrile. The...

وصف كامل

محفوظ في:
التفاصيل البيبلوغرافية
المؤلف الرئيسي: Kabbani, Ahmad (author)
مؤلفون آخرون: Cook, Robert D. (author), Samaha, Muna (author), Daouk, Wafa A (author), Hajj, Asaad N. (author), Shayban, Fuad (author), Tanelian, Ohannes V. (author)
التنسيق: article
منشور في: 1986
الوصول للمادة أونلاين:http://hdl.handle.net/10725/3329
http://www.nrcresearchpress.com/doi/abs/10.1139/v86-037#.V5mw3rh97y0
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author Kabbani, Ahmad
author2 Cook, Robert D.
Samaha, Muna
Daouk, Wafa A
Hajj, Asaad N.
Shayban, Fuad
Tanelian, Ohannes V.
author2_role author
author
author
author
author
author
author_facet Kabbani, Ahmad
Cook, Robert D.
Samaha, Muna
Daouk, Wafa A
Hajj, Asaad N.
Shayban, Fuad
Tanelian, Ohannes V.
author_role author
dc.creator.none.fl_str_mv Kabbani, Ahmad
Cook, Robert D.
Samaha, Muna
Daouk, Wafa A
Hajj, Asaad N.
Shayban, Fuad
Tanelian, Ohannes V.
dc.date.none.fl_str_mv 1986
2016-03-15T09:43:58Z
2016-03-15T09:43:58Z
2016-03-15
dc.identifier.none.fl_str_mv 0008-4042
http://hdl.handle.net/10725/3329
Cook, R. D., Daouk, W. A., Hajj, A. N., Kabbani, A., Kurku, A., Samaha, M., ... & Tanielian, O. V. (1986). The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile. Canadian journal of chemistry, 64(2), 213-219.
http://www.nrcresearchpress.com/doi/abs/10.1139/v86-037#.V5mw3rh97y0
dc.language.none.fl_str_mv en
dc.relation.none.fl_str_mv Canadian Journal of Chemistry
dc.rights.*.fl_str_mv info:eu-repo/semantics/openAccess
dc.title.none.fl_str_mv The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
dc.type.none.fl_str_mv Article
info:eu-repo/semantics/publishedVersion
info:eu-repo/semantics/article
description The aminolysis of aryl diphenylphosphinates, p-nitrophenyl diphenylphosphinothionate, -phosphinothioate, and -phosphinodithioate by n-butylamine, by the secondary amines piperidine, pyrrolidine, morpholine, and dipropylamine, as well as by a series of diamines, has been studied in acetonitrile. The general reactivity order is diamines > butylamine > sec-amines. Butylaminolysis follows a two-term rate law, one first order in amine and the other second order in amine. The second order in amine term predominates. sec-Amines and diamines follow a rate law which is first order in amine only. Leaving group effects, solvent effects, and activation parameters support a pathway which involves rate-determining collapse of a zwitterionic pentacoordinate intermediate. In the case of butylamine this collapse is general base catalyzed and for the diamines the reaction is intramolecularly general base catalyzed.
eu_rights_str_mv openAccess
format article
id LAURepo_4dbe5030a48b48db39d4f0d9611f3613
identifier_str_mv 0008-4042
Cook, R. D., Daouk, W. A., Hajj, A. N., Kabbani, A., Kurku, A., Samaha, M., ... & Tanielian, O. V. (1986). The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile. Canadian journal of chemistry, 64(2), 213-219.
language_invalid_str_mv en
network_acronym_str LAURepo
network_name_str Lebanese American University repository
oai_identifier_str oai:laur.lau.edu.lb:10725/3329
publishDate 1986
repository.mail.fl_str_mv
repository.name.fl_str_mv
repository_id_str
spelling The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrileKabbani, AhmadCook, Robert D.Samaha, MunaDaouk, Wafa AHajj, Asaad N.Shayban, FuadTanelian, Ohannes V.The aminolysis of aryl diphenylphosphinates, p-nitrophenyl diphenylphosphinothionate, -phosphinothioate, and -phosphinodithioate by n-butylamine, by the secondary amines piperidine, pyrrolidine, morpholine, and dipropylamine, as well as by a series of diamines, has been studied in acetonitrile. The general reactivity order is diamines > butylamine > sec-amines. Butylaminolysis follows a two-term rate law, one first order in amine and the other second order in amine. The second order in amine term predominates. sec-Amines and diamines follow a rate law which is first order in amine only. Leaving group effects, solvent effects, and activation parameters support a pathway which involves rate-determining collapse of a zwitterionic pentacoordinate intermediate. In the case of butylamine this collapse is general base catalyzed and for the diamines the reaction is intramolecularly general base catalyzed.PublishedN/A2016-03-15T09:43:58Z2016-03-15T09:43:58Z19862016-03-15Articleinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article0008-4042http://hdl.handle.net/10725/3329Cook, R. D., Daouk, W. A., Hajj, A. N., Kabbani, A., Kurku, A., Samaha, M., ... & Tanielian, O. V. (1986). The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile. Canadian journal of chemistry, 64(2), 213-219.http://www.nrcresearchpress.com/doi/abs/10.1139/v86-037#.V5mw3rh97y0enCanadian Journal of Chemistryinfo:eu-repo/semantics/openAccessoai:laur.lau.edu.lb:10725/33292016-08-24T08:22:19Z
spellingShingle The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
Kabbani, Ahmad
status_str publishedVersion
title The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
title_full The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
title_fullStr The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
title_full_unstemmed The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
title_short The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
title_sort The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
url http://hdl.handle.net/10725/3329
http://www.nrcresearchpress.com/doi/abs/10.1139/v86-037#.V5mw3rh97y0