ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHydrogen-bonding. Part 11. A quantitative evaluation of the hydrogen-bond acidity of imides as solutesMichael H. Abraham, Priscilla L. Grellier, David V. Prior, Jeffrey J. Morris, Peter J. Taylor, and Ruth M. DohertyCite this: J. Org. Chem. 1990, 55, 7, 2227–2229Publication Date (Print):March 1, 1990Publication History Published online1 May 2002Published inissue 1 March 1990https://pubs.acs.org/doi/10.1021/jo00294a045https://doi.org/10.1021/jo00294a045research-articleACS PublicationsRequest reuse permissionsArticle Views119Altmetric-Citations9LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

AbstractThe scale log K = LA log KH B + DA is given; LA and DA values characterise the acids while log KH B characterise the base.

AbstractUsing the solvatochromic indicator method, a scale of solvent hydrogen‐bond basicity, β1 (General), has been set up using a series of double regression equations, for 11 aniline‐type indicators. A similar solvent scale, β1 (Special), has been constructed by the homomorphic comparison method using only results by Laurence et al. on the indicators 4‐nitroaniline and 4‐nitro‐N,N‐dimethylaniline. Results are available from our previous work on a general solute scale, β, and we have also obtained a special solute scale, β2 (pKHB) from available log K values for hydrogen‐bond complexation of bases with 4‐fluorophenol in CCl4. However, the two solute β2 scales are virtually identical.It is shown that there is a general connection between β1(General) and β, with r = 0·9775 and s.d. = 0·05 for 32 compounds, and between β1(Special) and β, with r = 0·9776 and s.d. = 0·06 for the same 32 compounds. The latter correlation over 60 compounds yields r = 0·9684 and s.d. = 0·07. However, there are so many compounds in these regressions for which the differences in the solvent and solute β values are larger than the total expected error of 0·07 units that the use of β1 to predict β2 or vice versa is a very hazardous procedure. About 70 new β1 values obtained by the double regression method are also reported.

A thermodynamically-based scale of solute hydrogen-bond basicity, log KBH, has been set up, using log K values in the complexation of solutes against reference acids in tetrachloromethane. Values of log KBH have been obtained for over 500 solutes.

A scale of solute hydrogen-bond acidity has been constructed using equilibrium constants (as log K values) for complexation of series of acids (i) against a given base in dilute solution in tetrachloromethane, equation (A). Forty-five such equations have been solved to yield LB and DB, log Ki=LB log KAHI+DB(A) values characterising the base, and log KAH values that characterise the acid. In this analysis, use has been made of the novel observation that all the lines in equation (A) intersect at a given point where log K= log KAH=–1.1 with K on the molar scale. Some 190 log KAH values that constitute a reasonably general scale of solute hydrogen-bond acidity have been obtained. It is shown that there is no general connection between log KAH; and any proton-transfer quantities, although certain family dependences are obtained. A number of acid-base combinations are excluded from equation (A), and alternative log KAHE values have been determined for such cases. The general log KAH values may be transformed into α2H values suitable for use in multiple linear-regression analysis through the equation α2H=(log KAH+ 1.1)/4.636.

AbstractThe principal components factors F1 and F2 in the equation have been used to obtain S1 and S2 values for sets of hydrogen‐bond bases against 32 reference acid/solvent systems. The constants S1 and S2 define an angle θ = tan−1 S2/S1 that is a measure of the electrostatic:covalent bonding ratio in the hydrogen‐bond complex. It is shown that θ can vary from 53 (4‐fluorophenol in CH2Cl2)to 86 degrees (Ph2NH in CCl4) depending on the reference acid and solvent. This variation in θ can lead to family dependent behaviour in plots of log K for bases against a given reference acid system vs log K for bases against another reference acid system, and precludes the construction of any general scale of hydrogen‐bond basicity using log K values. Amongst a quite wide range of reference acid/solvent systems θ varies only from 64 to 73 degrees, and for bases against these reference systems a ‘reasonably general’ scale could be set up. Such a scale could be extended to bases against reference acid/solvent systems outside the 64–73 degree range provided that certain classes of base (e.g. pyridines, alkylamines) were excluded from the additional reference acid/solvent systems.

A scale of solute hydrogen-bond acidity has been constructed for over 150 solutes, based on logK values for the hydrogen-bond complexation of solutes with reference bases in CCl4 There is no general connection between quantities characteristic of full proton transfer, and our hydrogen-bond acidity scale, so that the latter represents a new solute acidity parameter.

Linear free energy equations, log L=c+sπ*2+aαH2+bβH2+l log L16 log L=c+sµ22+aαH2+bβH2+l log L16 have been used to analyse the solvation of a series of gaseous non-electrolytes in a given bulk solvent as log L values where L is the Ostwald solubility coefficient. The parameters π*2, αH2, βH2, log L16 and µ2 characterise the solutes and the constants c, s, a, b and l are obtained by multiple linear-regression analysis. It is shown that for solvation in the bulk solvents ethyl acetate, acetonitrile, ethanol and methanol, the contribution of hydrogen-bonding terms to solvation is quite small, the main contributing terms being an endoergic cavity term and an exoergic solute–solvent dispersion interaction term. Even with bulk water as the solvent, hydrogen-bonding interactions of the type solute (base)–water (acid) and solute (acid)–water (base) are not more than ca. -15 or -11 kJ mol–1, respectively, for DMSO (base) and ethanol (acid). It is shown also that linear free energy equations can be used for the correlation and prediction of the solubility of gaseous solutes in a given liquid phase, even when the latter is polymeric in nature.

ChemInformVolume 19, Issue 24 Article ChemInform Abstract: A Quantitative Measure of Solvent Solvophobic Effect M. H. ABRAHAM, M. H. ABRAHAM Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this authorP. L. GRELLIER, P. L. GRELLIER Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this authorR. A. MCGILL, R. A. MCGILL Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this author M. H. ABRAHAM, M. H. ABRAHAM Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this authorP. L. GRELLIER, P. L. GRELLIER Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this authorR. A. MCGILL, R. A. MCGILL Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this author First published: June 14, 1988 https://doi.org/10.1002/chin.198824065Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume19, Issue24June 14, 1988 RelatedInformation

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA general treatment of hydrogen bond complexation constants in tetrachloromethaneMichael H. Abraham, Priscilla L. Grellier, David V. Prior, Robert W. Taft, Jeffrey J. Morris, Peter J. Taylor, Christian. Laurence, Michel. Berthelot, Ruth M. Doherty, and . et al.Cite this: J. Am. Chem. Soc. 1988, 110, 25, 8534–8536Publication Date (Print):December 1, 1988Publication History Published online1 May 2002Published inissue 1 December 1988https://pubs.acs.org/doi/10.1021/ja00233a034https://doi.org/10.1021/ja00233a034research-articleACS PublicationsRequest reuse permissionsArticle Views440Altmetric-Citations106LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Gibbs energies of transfer of argon, alkanes, and alkane-like compounds from water to numerous aqueous–organic mixtures and to pure solvents are tabulated. It is shown that these ΔGt° values can be correlated through a set of equations, where ΔGt° refers to transfer of a series of solutes from water to a ΔGt°(to solvent)=MRT+D given solvent, RT is a solute parameter, and M and D characterise the solvent. For 20 solutes in 51 solvent systems, 375 ΔGt° values are thus correlated with a standard deviation of 0.078 kcal mol–1. The M values in the above equation are then used to define a solvent solvophobic effect so that Sp values are scaled Sp= 1 –M/M(hexadecane) from unity (water) to zero (hexadecane). The Sp values so obtained agree with the qualitative series reported by Sinanoglu and Abdulnur for pure solvents, and are shown to be quantitatively related to h.p.l.c. capacity factors.

Solvent effects on a number of different processes have been surveyed, and results of the application of multiple linear regression analysis are discussed. The processes examined include examples of solubility of gases or vapours, distribution coefficients of solutes between water and a series of solvents, and solvent effects on conformational equilibria, on keto–enol tautomerism, and on reaction rates. It is shown that two particular equations, that due to Koppel and Palm and extended by Makitra and Pirig, and that due to Abraham, Kamlet, and Taft, can cope quite satisfactorily with solvent effects on these various processes. It is pointed out that interpretation of parameters obtained from equations that involve macroscopic quantities such as ΔG≠ or ΔG0 is not necessarily straightforward, and that some model is needed in order to interpret these macroscopic quantities in terms of microscopic quantities that can characterise, for example, solute–solvent interactions.

The influence of 20–30 solvents on ΔG‡, ΔH‡, and ΔS‡ for the solvolysis of t-butyl chloride and t-butyl bromide has been dissected into initial-state and transition-state contributions. Using the unified method in which the general equation (i) is applied to both these contributions, it is shown that the decrease in ΔG‡ due to solvent dipolarity (π1*) and to solvent hydrogen-bond acidity (α1) is primarily a transition-state effect, that there is little effect of solvent hydrogen-bond basicity (β1) on either initial-state or transition-state, and that large effects of solvent Hildebrand solubility parameter (δH) on initial-state and transition-state partly cancel out. XYZ = XYZ0+s(π1*+dδ)+aα1+bβ1+hδ2H/100 (i)A similar analysis carried out on the transition-state transfer quantities, ΔHt0 and ΔSt0, yields the surprising results that the influence of solvent π1* and α1 values on the transition-state is primarily an entropic effect and that there is a very large influence of solvent hydrogen-bond basicity in increasing both ΔHt0 and ΔSt0 for the transition-state in an almost exactly compensatory way. It is suggested that this latter effect, previously unsuspected, may arise through solute/solvent lone pair/lone pair repulsions.

ChemInformVolume 18, Issue 40 Article ChemInform Abstract: Determination of Olive Oil-Gas and Hexadecane-Gas Partition Coefficients, and Calculation of the Corresponding Olive Oil-Water and Hexadecane-Water Partition Coefficients M. H. ABRAHAM, M. H. ABRAHAM Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this authorP. L. GRELLIER, P. L. GRELLIER Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this authorR. A. MCGILL, R. A. MCGILL Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this author M. H. ABRAHAM, M. H. ABRAHAM Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this authorP. L. GRELLIER, P. L. GRELLIER Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this authorR. A. MCGILL, R. A. MCGILL Dep. Chem., Univ. Surrey, Guildford, Surrey GU2 5XH, UKSearch for more papers by this author First published: October 6, 1987 https://doi.org/10.1002/chin.198740056Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume18, Issue40October 6, 1987 RelatedInformation

Henry's constants at zero solute pressure have been determined by the gas chromatographic peak shape method for twenty-two soluts on four adsorbents (Rohm and Haas Ambesorb® XE-348F carbonaceous adsorbent at 323 and 373 K, Sutcliffe Speakman 207A and 207C at 323 K, and Calgon Filtrasorb® activated carbon at 323 K). The limiting values of log KH have been analysed in terms of solute dipolarity(π*2), solute hydrogen-bond acidity (α2), and basicity (β2), and a new solute parameter (log L16), the solute Ostwald absorption coefficient on n-hexadecane. The multiple linear regression equation. SP = SP0 + l · logL16 + s(π*2 + dδ2) + aα2 + bβ2 where in this instance SP = −log KH, can be used to identify the nature of the solute-adsorbent interactions, and to predict further values of log KH. For the solutes and solids we have studied, only the l · logL16 term is statistically significant, and hence − KH is proportional to l · log L16. It is concluded that interactions between the gaseous solutes (that include alcohols and amines) and the four adsorbents involve just general dispersion forces.

A general equation SP=SP0+l log L16+s(π2∗+dδ2) + aα2 + bβ2 has been used to describe solubility properties of a wide range of gaseous solutes in polymers. The property, SP, may be a log VG value, an enthalpy of solution, etc., and the explanatory variables are solute parameters: L16 is the Ostwald solubility coefficient of the solute on hexadecane at 25°C, π∗2 is the solute dipolarity, δ2 a polarizability correction term, α2 the solute hydrogen-bond acidity, and β2 the solute hydrogen-bond basicity. Solubilities may then be discussed in terms of the various solute-solvent interactions that are reflected by the coefficients of the various terms. These are cavity effects and dispersion forces (l), dipole-dipole and dipole-induced-dipole interactions (s), and hydrogen-bonding between solute acid and polymer base (a) or between solute base and polymer acid (b). For non-dipolar solutes in all non-aqueous solvent phases, and for weakly dipolar solutes in weakly dipolar phases, the general equation reduces to a more specific equation that includes only the term due to cavity effects and dispersion forces SP=SP0+l log L16

Chemischer InformationsdienstVolume 17, Issue 13 Reviews ChemInform Abstract: Heterolytic Cleavage of Main Group Metal- Carbon Bonds M. H. ABRAHAM, M. H. ABRAHAMSearch for more papers by this authorP. L. GRELLIER, P. L. GRELLIERSearch for more papers by this author M. H. ABRAHAM, M. H. ABRAHAMSearch for more papers by this authorP. L. GRELLIER, P. L. GRELLIERSearch for more papers by this author First published: April 1, 1986 https://doi.org/10.1002/chin.198613354Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume17, Issue13April 1, 1986 RelatedInformation