252

5 Solvent Eects on the Rates of Homogeneous Chemical Reactions

Table 5-18. A selection of twenty-one organic dipolar non-HBD solvents in order of increasing dipole moment (cf. also Appendix, Table A-1). Structure ( !)a) Name m=1030 Cm) tmp / C tbp / C References

Acetone

9.0

94.7 1.2 28.6

56.1 175.3 [602, 603]

Tetramethylurea (Temur) 11.6

Nitromethane

12.0

101.2

[604]

1,3,2-Dioxathiolane-2oxide (Ethylene sulte) N,N-Dimethylacetamide (DMAC) N,N-Dimethylformamide (DMF) 1-Methylpyrrolidin-2-one

12.3

170171 (dec.) 20.1 166.1

[605]

12.4

[606]; N,NDiethylacetamide: [633] [606608]

12.7

60.4 24.4

153.1

13.6

202

[609]; 1-Ethylpyrrolidin-2-one: [633] [603]

1,3-Dimethylimidazolidin- 13.6 2-one (N,N 0 -Dimethylethylene urea, DMEU)

8.2

225.5

3-Methyloxazolidin-2-one 13.7 Acetonitrile Dimethyl sulfoxide 3,4,5,6-Tetrahydro-1,3dimethyl-2(1H)pyrimidinone (N,N 0 Dimethylpropylene urea, DMPU) 1-Methyl-hexahydroazepin-2-one, N-Methyl-e-caprolactam Dimethylsulfone 13.0 13.5 14.1

15.9 43.8 18.5 23.8

8790 [610, 611] (1.3 mbar) 81.6 189.0 246.5 [296, 608, 612] [608, 613616] [603, 617618]

14.1

12 (25 mbar)

14.2

110

238

[619]

5.5 Specic Solvation Eects on Reaction Rates Table 5-18. (Continued) Structure ( !)a) Name m=1030 Cm) tmp / C tbp / C References

253

S,S-Dimethylsulfoximine (DMSOI) Tetraethylsulfamide (TES) Tetrahydrothiophene-1,1dioxide (Sulfolane) 1,3-Dioxolan-2-one (Ethylene carbonate) Methylphosphonic acid bis(dimethylamide) 4-Methyl-1,3-dioxolan2-one (Propylene carbonate) Hexamethylphosphoric acid triamide (HMPT) 14.6b)

5253 100 [620] (6.5mbar) 249251 [621]

16.0 16.0 16.0

28.4 36 3.2

287.3 156 6263 (4 mbar) 241.7

[608, 622624] [625, 626] [627, 628]

16.5

54.5

[608, 625, 629, 630]

18.5

7.3

233

[608, 617, 618, 631]

a) All formulae are oriented in such a way that the dipole moment of the solvent molecule is approximately in a parallel direction with this arrow. b) Value for tetramethylsulfamide; H. Noth, G. Mikulaschek, and W. Rambeck, Z. Anorg. Allg. Chem. 344, 316 (1966).

The observation that bimolecular reactions of anions are often much faster in dipolar non-HBD solvents than in protic solvents of comparable relative permittivity is of great practical signicance, not only for substitution reactions but also for elimination, proton abstraction, and addition reactions [6]. Reduced solvation of commonly used E2 bases (HOm , ROm ) in dipolar nonHBD solvents may elevate their reactivities to such an extent that E2 reactions of quite inert substrates occur [306]. Halide ions in dipolar non-HBD solvents are suciently strong bases to promote dehydrohalogenations of haloalkanes [73, 74]. Even the uoride ion is the most ecient in this reaction [307, 308, 600]; the elimination rates decrease in the order Fm > Clm > Brm > Im . A shift from CH3 Om /CH3 OH to tert-C4 H9 Om /CH3 SOCH3 can produce dramatic increases in rates (up to a factor of 10 9 ) of reactions which depend on proton abstraction from a CaH bond [31, 304]. The subsequent reaction of the carbanion may involve isomerization, elimination, oxidation, and condensation, hence demonstrating the importance of the potassium tert-butoxide/dimethyl sulfoxide system in organic syntheses. The base-catalyzed alkene isomerization reaction (double bond migration) has been used to investigate the ecacy of a wide variety of base/dipolar non-HBD solvent systems [309, 310].