title: Kinetic studies that evaluate the solvolytic mechanisms of allyl and vinyl chloroformate esters.
abstract: At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term) Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (NT) and solvent ionizing power (YCl). Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability.
authors.affiliation: Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA. dsouzama@wesley.edu.
authors.forename: Malcolm J
authors.initials: MJ
authors.lastname: D'Souza
authors.forename: Aaron F
authors.initials: AF
authors.lastname: Givens
authors.forename: Peter A
authors.initials: PA
authors.lastname: Lorchak
authors.forename: Abigail E
authors.initials: AE
authors.lastname: Greenwood
authors.forename: Stacey L
authors.initials: SL
authors.lastname: Gottschall
authors.forename: Shannon E
authors.initials: SE
authors.lastname: Carter
authors.forename: Dennis N
authors.initials: DN
authors.lastname: Kevill
mesh_terms: D002412:Cations; D004952:Esters / Q000737:chemistry*; D005561:Formates / Q000737:chemistry*; D021621:Imaging, Three-Dimensional; D007700:Kinetics; D012997:Solvents / Q000737:chemistry*; D013696:Temperature; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D002412:Cations; D004952:Esters; D005561:Formates; D012997:Solvents; D014753:Vinyl Compounds; C042113:allyl chloroformate
references.citation: Eur J Chem. 2011 Jun;2(2):130-135
references.pmid: 21881623
references.citation: Int J Mol Sci. 2012;13(1):665-82
references.pmid: 22312278
references.citation: Int J Mol Sci. 2011;12(8):4805-18
references.pmid: 21954326
references.citation: Int J Mol Sci. 2011 Feb 15;12(2):1161-74
references.pmid: 21541050
references.citation: J Org Chem. 2005 Oct 28;70(22):8963-70
references.pmid: 16238334
references.citation: Int J Mol Sci. 2008 Nov;9(11):2231-42
references.pmid: 19330071
references.citation: J Coll Teach Learn. 2012 Oct 1;9(4):245-252
references.pmid: 24273464
references.citation: J Mod Hist. 1975;47(3):460-8
references.pmid: 11614782
references.citation: J Org Chem. 2003 May 2;68(9):3425-32
references.pmid: 12713342
references.citation: ISRN Org Chem. 2011;2011:
references.pmid: 21666878
references.citation: Beilstein J Org Chem. 2011;7:543-52
references.pmid: 21647255
references.citation: J Org Chem. 1999 Jun 25;64(13):4817-4820
references.pmid: 11674555
references.citation: Counc Undergrad Res Q. 2011 Winter;32(2):41-45
references.pmid: 22303090
references.citation: Acc Chem Res. 2002 Jan;35(1):12-8
references.pmid: 11790084
references.citation: Nat Biotechnol. 2012 Sep;30(9):868-875
references.pmid: 22885723
references.citation: Chem Rev. 2005 Aug;105(8):3095-165
references.pmid: 16092827
references.citation: Org Chem Int. 2010 Jan 1;2010:1-9
references.pmid: 21552456
references.citation: Int J Mol Sci. 2011;12(11):7806-17
references.pmid: 22174633
references.citation: Int J Mol Sci. 2009 Mar;10(3):862-79
references.pmid: 19399225
references.citation: J Org Chem. 2008 Aug 15;73(16):6251-7
references.pmid: 18630963
references.citation: J Org Chem. 2002 Jan 11;67(1):182-7
references.pmid: 11777457
references.citation: J Org Chem. 2000 Apr 21;65(8):2548-54
references.pmid: 10789470
references.citation: J Org Chem. 2000 Nov 17;65(23):8051-8
references.pmid: 11073616
references.citation: J Org Chem. 2004 Oct 15;69(21):7044-50
references.pmid: 15471451
references.citation: J Drug Deliv. 2012;2012:103973
references.pmid: 22645686