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	A theoretical model study on the cyclic reaction of 4-hydroxybutanal catalyzed by bronsted acid
	Meng, Qingyong; Zhang, Chenggen; Huang, Ming-Bao
刊名	Canadian journal of chemistry-revue canadienne de chimie
	2009-11-01
卷号	87期号:11页码:1610-1619
关键词	Cyclic reaction of 4-hydroxybutanal Catalyzed by bronsted acid B3lyp Self-consistent isodensity polarized continuum model (scipcm) model study
ISSN号	0008-4042
DOI	10.1139/v09-126
通讯作者	Huang, ming-bao()
英文摘要	For a theoretical model study on the cyclic reaction of 4-hydroxybutanal (4-oh-bl). we have examined five assumed reaction pathways (i-v) by performing the b3lyp calculations in the gas phase and self-consistent isodensity polarized continuum model (scipcm)-b3lyp calculations in aqueous solution. pathways ii (4-oh-bl + h(+)), iii (4-oh-bl + h(3)o(+)), and iv (4-oh-bl, + h(3)o(+) + h(2)o) represent three models for the cyclic reaction catalyzed by bronsted acids. the present study leads to the following conclusions concerning the five pathways (mainly on the basis of the calculation results in the solution) the high barrier along pathway i (with no catalyst) implies that the reaction does not occur without a catalyst, and the extremely large stabilization energy of the intermediate implies that pathway ii is not a realistic model for the reaction catalyzed by bronsted acid. along pathway iii, there are two intermediates and a transition state in between. and they are 10-16 kcal/mol lower in energy than the reactants (4-oh-bl + h(3)o(+)). along pathway iv. there is only one intermediate, and it is 20.6 kcal/mol lower in energy than the reactants (4-oh-bl + h(3)o(+) + h(2)o). pathways iii and iv are predicted to be feasible. energetically, pathway iv is more favourable than pathway iii and it is considered as a rational model for the cyclic reaction of 4-oh-bl, catalyzed by bronsted acid. our calculations for pathway v (catalyzed by h(2)o) indicate that the water molecule may also serve as a catalyst for the cyclic reaction the transition state along pathway v is 20.0 kcal/mol higher in energy than the reactants (4-oh-bl + h(2)o), and one can clearly see the "proton wire" in its structure. our calculations show strong solvent effects on energetics of the charged intermediates along pathways ii, iii and iv.
WOS关键词	GAS-PHASE ; NUCLEOPHILIC-SUBSTITUTION ; CARBONYL GROUP ; COOPERATIVE MECHANISM ; NEUTRAL HYDROLYSIS ; S(N)2 REACTIONS ; METHYL ACETATE ; AB-INITIO ; HYDRATION ; ENERGY
WOS研究方向	Chemistry
WOS类目	Chemistry, Multidisciplinary
语种	英语
出版者	NATL RESEARCH COUNCIL CANADA-N R C RESEARCH PRESS
WOS记录号	WOS:000272840800005
内容类型	期刊论文
URI标识	http://www.corc.org.cn/handle/1471x/2398867
专题	中国科学院大学
通讯作者	Huang, Ming-Bao
作者单位	Chinese Acad Sci, Grad Univ, Coll Chem & Chem Engn, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Meng, Qingyong,Zhang, Chenggen,Huang, Ming-Bao. A theoretical model study on the cyclic reaction of 4-hydroxybutanal catalyzed by bronsted acid[J]. Canadian journal of chemistry-revue canadienne de chimie,2009,87(11):1610-1619.
APA	Meng, Qingyong,Zhang, Chenggen,&Huang, Ming-Bao.(2009).A theoretical model study on the cyclic reaction of 4-hydroxybutanal catalyzed by bronsted acid.Canadian journal of chemistry-revue canadienne de chimie,87(11),1610-1619.
MLA	Meng, Qingyong,et al."A theoretical model study on the cyclic reaction of 4-hydroxybutanal catalyzed by bronsted acid".Canadian journal of chemistry-revue canadienne de chimie 87.11(2009):1610-1619.

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