{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T04:40:39Z","timestamp":1760244039801,"version":"build-2065373602"},"reference-count":35,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2008,9,4]],"date-time":"2008-09-04T00:00:00Z","timestamp":1220486400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/3.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>The influence of carbon-carbon multiple bonds on the solvolyses of 3-chloro-3-methylbutyne (1), 2-chloro-2-phenylpropane (2), 2-bromo-2-methyl-1-phenylpropane (3), 4-chloro-4-methyl-2-pentyne (4) and 2-chloro-2-methylbutane (5) is critically evaluated through the extended Grunwald-Winstein equation. Substrates 1, 3 and 5 lead to correlations with unexpected negative sensitivity, h, to changes in the aromatic ring parameter, I. It is claimed that I is not a pure parameter, reflecting also some solvent nucleophilicity, NOTs, character. In substrates 2 and 4 the possibility of rearside solvation is reduced due to steric hindrance and\/or cation stabilization and the best found correlations involve only the solvent ionizing power, Y, and I.<\/jats:p>","DOI":"10.3390\/ijms9091704","type":"journal-article","created":{"date-parts":[[2008,10,2]],"date-time":"2008-10-02T12:45:09Z","timestamp":1222951509000},"page":"1704-1716","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["The Influence of Carbon-Carbon Multiple Bonds on the Solvolyses of Tertiary Alkyl Halides: a Grunwald-Winstein Analysis"],"prefix":"10.3390","volume":"9","author":[{"given":"Marina C.","family":"Reis","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry, Sciences Faculty, University of Lisbon, CQB, Campo Grande, 1749-016 Lisboa, Portugal"}]},{"given":"Ruben","family":"Elvas-Leit\u00e3o","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering, Lisbon Institute of Engineering, IPL, R. Conselheiro Em\u00eddio Navarro, 1, 1959-007 Lisboa, Portugal"}]},{"given":"Filomena","family":"Martins","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, Sciences Faculty, University of Lisbon, CQB, Campo Grande, 1749-016 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2008,9,4]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"913","DOI":"10.1039\/P29870000913","article-title":"Linear solvation energy relationships. 37. An analysis of contributions of dipolarity polarizability, nucleophilic assistance, electrophilic assistance, and cavity terms to solvent effects on tert-butyl halide solvolysis rates","volume":"2","author":"Abraham","year":"1987","journal-title":"J. Chem. Soc. Perkin"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"5741","DOI":"10.1021\/ja00385a031","article-title":"The SN2-SN1 spectrum. 4. The SN2 (intermediate) mechanism for solvolyses of tert-butyl chloride-a revised Y-scale of solvent ionizing power based on solvolyses of 1-adamantyl chloride","volume":"104","author":"Bentley","year":"1982","journal-title":"J. Am. Chem. Soc"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1061","DOI":"10.1002\/poc.816","article-title":"Solvation effects in the heterolyses of 3-X-3-methylpentanes (X = Cl, Br, I)","volume":"17","author":"Martins","year":"2004","journal-title":"J. Phys. Org. Chem"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"846","DOI":"10.1021\/ja01182a117","article-title":"The correlation of solvolysis rates","volume":"70","author":"Grunwald","year":"1948","journal-title":"J. Am. Chem. Soc"},{"key":"ref_5","unstructured":"Kevill, DN, and D\u2019Souza, MJ (1993). Additional Y(Cl) values and the correlation of the specific rates of solvolysis of tert-butyl chloride in terms of N(T) and Y(Cl) scales. J. Chem. Res.-S, 174\u2013175."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"4654","DOI":"10.1021\/jo980109d","article-title":"Solvolytic reactions in fluorinated alcohols. Role of nucleophilic and other solvation effects","volume":"63","author":"Bentley","year":"1998","journal-title":"J. Org. Chem"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"881","DOI":"10.1002\/poc.569","article-title":"Correlation of the rates of solvolysis of benzoyl chloride and derivatives using extended forms of the Grunwald-Winstein equation","volume":"15","author":"Kevill","year":"2002","journal-title":"J. Phys. Org. Chem"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"121","DOI":"10.1002\/9780470171967.ch5","article-title":"Yx scales of solvent ionizing power","volume":"17","author":"Bentley","year":"1990","journal-title":"Prog. Phys. Org. Chem"},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Kevill, DN, and D\u2019Souza, MJ (2008). Sixty years of the Grunwald-Winstein equation: development and recent applications. J. Chem. Res., 61\u201366.","DOI":"10.3184\/030823408X293189"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2700","DOI":"10.1021\/ja01150a078","article-title":"The correlation of solvolysis rates and the classification of solvolysis reactions into mechanistic categories","volume":"73","author":"Winstein","year":"1951","journal-title":"J. Am. Chem. Soc"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"4146","DOI":"10.1021\/ja01572a046","article-title":"Correlation of solvolysis rates .8. Benzhydryl chloride and bromide - comparison of mY and Swain\u2019s correlations","volume":"79","author":"Winstein","year":"1957","journal-title":"J. Am. Chem. Soc"},{"key":"ref_12","first-page":"1","article-title":"Medium effects on the rates and mechanisms of solvolytic reactions","volume":"14","author":"Bentley","year":"1977","journal-title":"Adv. Phys. Org. Chem"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"992","DOI":"10.1021\/ja00758a049","article-title":"Correlation of solvolysis rates with 3-parameter and 4-parameter relationships - scale of solvent nucleophilicities","volume":"94","author":"Bentley","year":"1972","journal-title":"J. Am. Chem. Soc"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"5174","DOI":"10.1021\/ja031828z","article-title":"Solvent nucleophilicity","volume":"126","author":"Minegishi","year":"2004","journal-title":"J. Am. Chem. Soc"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"973","DOI":"10.1039\/P29950000973","article-title":"Considerably improved Grunwald\u2013Winstein correlations for solvolyses of several secondary and tertiary benzylic derivatives upon inclusion of a term governed by the aromatic ring parameter (I)","volume":"2","author":"Kevill","year":"1995","journal-title":"J. Chem. Soc. Perkin"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1845","DOI":"10.1021\/jo00005a034","article-title":"An improved scale of solvent nucleophilicity based on the solvolysis of the s-methyldibenzothiophenium ion","volume":"56","author":"Kevill","year":"1991","journal-title":"J. Org. Chem"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"10877","DOI":"10.1021\/ja010600d","article-title":"Is the tert-butyl chloride solvolysis the most misunderstood reaction in organic chemistry? Evidence against nucleophilic solvent participation in the tert-butyl chloride transition state and for increased hydrogen bond donation to the 1-adamantyl chloride solvolysis transition state","volume":"123","author":"Gajewski","year":"2001","journal-title":"J. Am. Chem. Soc"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"5717","DOI":"10.1021\/ja00306a019","article-title":"Relative reactivity of bridgehead adamantyl and homoadamantyl substrates from solvolyses with heptafluorobutyrate as a highly reactive carboxylate leaving group - absence of SN2 character of solvolysis of tert-butyl derivatives","volume":"107","author":"Farcasiu","year":"1985","journal-title":"J. Am. Chem. Soc"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2225","DOI":"10.1021\/ol016103j","article-title":"What is the stabilizing interaction with nucleophilic solvents in the transition state for solvolysis of tertiary derivatives: Nucleophilic solvent participation or nucleophilic solvation?","volume":"3","author":"Richard","year":"2001","journal-title":"Org. Lett"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1360","DOI":"10.1021\/jo972169+","article-title":"B-strain and solvolytic reactivity revisited. Nucleophilic solvent participation and abnormal rate ratios for tertiary chloroalkanes","volume":"63","author":"Liu","year":"1998","journal-title":"J. Org. Chem"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"717","DOI":"10.1002\/(SICI)1099-1395(199710)10:10<717::AID-POC941>3.0.CO;2-Y","article-title":"Structural effects on the Grunwald-Winstein correlations in the solvolysis of some simple tertiary alkyl chlorides","volume":"10","author":"Takeuchi","year":"1997","journal-title":"J. Phys. Org. Chem"},{"key":"ref_22","first-page":"1104","article-title":"Solvent effects on localized and delocalized cationic charges in solvolysis","volume":"16","author":"Lee","year":"1995","journal-title":"Bull. Kor. Chem. Soc"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"6303","DOI":"10.1021\/jo00100a036","article-title":"Solvolysis of the (p-methoxybenzyl)dimethylsulfonium ion\u2013development and use of a scale to correct for dispersion in Grunwald-Winstein plots","volume":"59","author":"Kevill","year":"1994","journal-title":"J. Org. Chem"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"3973","DOI":"10.1016\/S0040-4039(98)00739-4","article-title":"Application of the aromatic ring parameter (I) to solvolyses of extremely crowded alkyl derivatives","volume":"39","author":"Kevill","year":"1998","journal-title":"Tetrahedron Lett"},{"key":"ref_25","unstructured":"Kevill, DN, and D\u2019Souza, MJ (1996). Incorporation of a term governed by the aromatic ring parameter (I) into Grunwald-Winstein correlations of the solvolyses of diarylmethyl, naphthylmethyl and arylmethyl bromides. J. Chem. Res.-M, 1646\u20131654."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1039\/p29960000327","article-title":"Comments on the utility of aromatic ring parameters in the correlation analysis of solvolytic reactivities for benzylic substrates","volume":"2","author":"Liu","year":"1996","journal-title":"J. Chem. Soc. Perkin"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"2387","DOI":"10.1021\/jo00034a035","article-title":"Solvation effects adjacent to the reaction site - differences in solvation between alkyl, alkenyl, or alkynyl and aryl groups in binary aqueous mixtures","volume":"57","author":"Bentley","year":"1992","journal-title":"J. Org. Chem"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1905","DOI":"10.1080\/00268970600665104","article-title":"Solvent and temperature effects on ion association and mobility of 2,6-lutidinium chloride in non-aqueous solvents","volume":"104","author":"Moreira","year":"2006","journal-title":"Mol. Phys"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"153","DOI":"10.1007\/BF00647061","article-title":"Linear solvation energy relations","volume":"14","author":"Taft","year":"1985","journal-title":"J. Solution Chem"},{"key":"ref_30","unstructured":"Moreira, L, Martins, F, and Leitao, RE (2005). Communication to ESORX."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"122","DOI":"10.1002\/poc.610060209","article-title":"Nucleophilic solvent intervention in the solvolysis of 2-aryl-2-chloropropanes - an example to demonstrate the advantage of using the YBnCl scale in correlation-analysis","volume":"6","author":"Liu","year":"1993","journal-title":"J. Phys. Org. Chem"},{"key":"ref_32","first-page":"349","article-title":"Solvent effects on the solvolysis of 2-aryl-1,1-dimethylethyl bromides","volume":"19","author":"Hwang","year":"1998","journal-title":"Bull. Kor. Chem. Soc"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"87","DOI":"10.3390\/i6010087","article-title":"Application of the extended Grunwald-Winstein equation to solvolyses of n-propyl chloroformate","volume":"6","author":"Kyong","year":"2005","journal-title":"Int. J. Mol. Sci"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1181","DOI":"10.1246\/bcsj.53.1181","article-title":"A convenient method for the preparation of highly pure tert-alkyl bromides and iodides","volume":"53","author":"Masada","year":"1980","journal-title":"Bull. Chem. Soc. Jpn"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1879","DOI":"10.1021\/ed083p1879","article-title":"Design of an excel spreadsheet to estimate rate constants, determine associated errors, and choose curve\u2019s extent","volume":"83","author":"Moreira","year":"2006","journal-title":"J. Chem. 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