Studies on amphiprotic compounds. 2. Experimental determination of the hydrogen bond acceptor basicities of monomeric alcohols

Abboud, José‐Luis M.; Sraidi, Khadija; Guiheneuf, Georges; Negro, A.; Kamlet, Mortimer J.; Taft, Robert W.

doi:10.1021/jo00216a013

Cited by 47 publications

(18 citation statements)

References 2 publications

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“…This is of interest since a recent analysis showed that "monomeric" and "oligomeric" alcohols differ in their abilities as hydrogen-bond acceptors. 20 For comparison of our K^oc values we searched in ref lib, which covers the 1960-1973 period for data on systems RCOH, which are the closest analogues to our system, as well as for ROH systems with the same R's.…”

Section: Discussionmentioning

confidence: 99%

Association of .alpha.-alkyl-.beta.,.beta.-dimesitylethenols with hydrogen-bond-accepting solvents

Rappoport¹,

Nugiel²,

Biali³

1988

J. Org. Chem.

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an unrelated development, we had an occasion to reinvestigate the e x p e r i m e n t a l conditions for the hydroboration-oxidation of 2-methyl-2-butene with BHBr2.SMe2 and correct the regiochemistry to 99.3:0.7 at the secondary and tertiary carbons, r e s p e~t i v e 1 y . l~ The corrected regiochemistry does n o t call for an alternate m e c h a n i s m at all. Our independent studies on the various dialkylborane dimers20 and BH3.Lewis base complexes7 have shown that t h e y dissociate prior to hydroboration as well. T h u s , we are now convinced that the dissociation m e c h a n i s m is generally applicable to all of the hydroborating agents. Experimental SectionGeneral procedures for the manipulation of boron reagents have been described.21 All glassware, syringes, and needles were oven-dried at 140 "C for several hours. The glassware was assembled hot and cooled under a stream of dry nitrogen. Syringes were assembled and fitted with needles while hot and cooled as assembled units.Materials. BHBr2.SMe2 was prepared from BH3-SMe2 and BBr3.SMe2 by using a reported precedure, and was subsequently recrystallized12 from CHzC12 at -78 "C. The alkenes were purified by distillation over LAH in a nitrogen atmosphere. The alkynes were purified by distillation in a nitrogen atmosphere. Me2S was purified by distillation over 9-borabicyclo[ 3.3.llnonane in nitrogen atmosphere. CHzClz (Baker, analytical reagent grade) was stored over molecular sieves under nitrogen and used as such.(19) Brown, H. C.; Racherla, U. S.The 6(OH) values for a-alkyl-P,P-dimesitylethenols (Mes2C=C(OH)R, 2, R = Me, Et, i-Pr, t-Bu) were measured in eight solvents and in several binary CC14-DMSO-d8 mixtures. Large shifts to a lower field were observed on increasing the hydrogen bond accepting ability of the solvent or the mixture. The 6(OH) value for 2 in the various solvents were linear with 6(OH) for MeszC==CHOH (1) and approximately linear (with slopes C) with Kamlet-Taft's hydrogen bond accepting parameter P of the solvent. Long-range couplings 4J(HCCOH) were observed for 2, ~ ~~ (1) Part 20 is in the series "Stable Simple Enols". For part 19, see Biali, S. E.; Nugiel, D. A,; Rappoport, Z., submitted to J . Am. Chem. SOC. for publication. 0022-3263/88/1953-4814$01.50/0 mesityl-a-aryl-(and a -H ) ethenoh2 The most extensively studied compound was 2,2-dimesitylethenol (1) for which it was concluded from t h e changes of the coupling constant 3 J ( H C O H ) and the chemical shift of t h e enolic proton d(OH) with t h e solvent that the conformation of the C=COH moiety around the C-0 bond is syn planar ( l a ) (2) Biali, S. E.; Rappoport, Z. Alkali-metal reduction of a series of diaryl sulfides shows that, if both aryl moieties possess aromatic stabilization energies less than that of the phenyl group (i.e., able to generate relatively more stable radical anions), the diaryl sulfide forms an episulfide intermediate via regiospecific coupling of the aryl moieties at the stage of a reactive intermediate. The formation of the episulfide intermediat...

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Section: Discussionmentioning

confidence: 99%

Association of .alpha.-alkyl-.beta.,.beta.-dimesitylethenols with hydrogen-bond-accepting solvents

Rappoport¹,

Nugiel²,

Biali³

1988

J. Org. Chem.

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“…For such solvents, H-bond parameters derived from molecular properties are not sufficient to account for the behavior of the bulk solution. 4 , 5 , 18 In order to dissect the equilibria that determine the solvation properties of self-associating solvents, a series of experiments was carried out using a molecular recognition probe in mixtures of a self-associating polar solvent and a non-polar co-solvent. Typical results obtained from such a mixed solvent study are illustrated in Fig.…”

Section: Introductionmentioning

confidence: 99%

Polarisation effects on the solvation properties of alcohols

et al. 2018

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“…The concept of cooperativity implies that the hydrogen bonding energy in multi-particle complex is not equal to the sum of energies of pair-wise interactions [21]. The cause of the cooperative effect as follows from [22,23] is a change in the basicity and acidity of alcohols associative species in comparison with free molecules. Luck et al [24] revealed by FTIR-spectroscopy, that in ternary complex (ROH) 2 Á Á ÁB (B -proton acceptor) both hydrogen bonds are strengthened and the value of the cooperative effect does not depend on the base nature.…”

Section: Introductionmentioning

confidence: 99%

Enthalpy of cooperative hydrogen bonding in complexes of tertiary amines with aliphatic alcohols: Calorimetric study

Zaitseva

Varfolomeev

Novikov

et al. 2011

The Journal of Chemical Thermodynamics

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Studies on amphiprotic compounds. 2. Experimental determination of the hydrogen bond acceptor basicities of monomeric alcohols

Cited by 47 publications

References 2 publications

Association of .alpha.-alkyl-.beta.,.beta.-dimesitylethenols with hydrogen-bond-accepting solvents

Association of .alpha.-alkyl-.beta.,.beta.-dimesitylethenols with hydrogen-bond-accepting solvents

Polarisation effects on the solvation properties of alcohols

Enthalpy of cooperative hydrogen bonding in complexes of tertiary amines with aliphatic alcohols: Calorimetric study

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