Tetrahydrothiophene dipole

The electric dipole moments in units 1 X 10 18 e. s. u. of these molecules and their derivatives by hydrogenation measured19 in benzene solution are the following furan, 0.670 2,5-di-hydrofuran, 1.53 tetrahydrofuran, 1.68 pyrrole, 1.80 pyrroline, 1.42 pyrrolidine, 1.57 thiophene, 0.54 and tetrahydrothiophene, 1.87. We now give a very rough interpretation of these quantities based on the bond moments given... 

Cycloadditions tetrahydrothiophenes.1 The reaction of 1 with CsF in CH,CN generates a 1,3-dipole (a), which undergoes [3 + 2]cycloadditions with alkenes to give tetrahydrothiophenes in 65-85% yield. 

The desilylation methodology for the generation of 1,3-dipoles, developed by Vedejs and West (29) with regard to azomethine ylides, was successfully applied by Achiwa and co-workers (30) to the field of thiocarbonyl ylides. This approach allowed the generation of the parent thioformaldehyde (5)-methylide (la) and its use for preparative purposes (31,32). Generation of la in the presence of C=C dipolarophiles led to tetrahydrothiophenes (19) in high yield (Scheme 5.4). 

The reaction of the sterically crowded thiocarbonyl ylide 69 with highly electron-deficient alkenes such as 2,3-dicyano fumarate and maleate, tetracya-noethene, a-cyano cinnamates, and l,2-bis(trifluoromethyl)ethene-l,2-dicarboni-trile occurred in a nonstereospecific manner (27,89,96,97,136-138). The formation of a mixture of cis/trans tetrahydrothiophenes of type 82 is the result of a stepwise reaction involving zwitterionic intermediates of type 81 (Scheme 5.29). Ylide 69 fulfills the fundamental requirements for a two-step reaction with electron-deficient alkenes. This species corresponds to an electron-rich 1,3-dipole that also contains a bulky substituent at one terminus (89). 

Vanadium trichloride or tribromide reacts with thioethers giving [VX3L2] (X = C1 or Br L = SMe2, tetrahydrothiophene or SEt2).288,289 The complex with di-n-propyl sulfide could not be isolated.288 These compounds are oxidized very easily. Solubility, molecular weights and conductance show that they are monomeric and non-ionic. Dipole moments, IR and electronic spectra are consistent with trans trigonal bipyramidal structures. 

The dipole moments of furan (0.72 D) and thiophene (0.53 D) are smaller than those of the corresponding saturated heterocycles (tetrahydrofuran, 1.68 D tetrahydrothiophene, 1.87 D.) Many authors35-38 seem to believe that, also in these cases, the direction of the dipole is from the heteroatom (positive pole) to the ring (negative pole) others, however, are of a different opinion.12, 32, 39, 40... 

The fact that the lone pair on sulfur contributes to the aromaticity is seen in the lower dipole moment of thiophene as compared to its saturated analogue tetrahydrothiophene (0.52 D vs. 1.90 D) <1972JA8854>. In thiophene, the dipole is directed from the ring toward the heteroatom. 

In contrast, dipolar aprotic solvents possess large relative permittivities (sr > 15), sizeable dipole moments p > 8.3 10 ° Cm = 2.5 D), and average C.f values of 0.3 to 0.5. These solvents do not act as hydrogen-bond donors since their C—H bonds are not sufficiently polarized. However, they are usually good EPD solvents and hence cation sol-vators due to the presence of lone electron pairs. Among the most important dipolar aprotic solvents are acetone, acetonitrile [75], benzonitrile, A,A-dimethylacetamide [76, 77], A,A-dimethylformamide [76-78], dimethylsulfone [79], dimethyl sulfoxide [80-84], hex-amethylphosphoric triamide [85], 1-methylpyrrolidin-2-one [86], nitrobenzene, nitro-methane [87], cyclic carbonates such as propylene carbonate (4-methyl-l,3-dioxol-2-one) [88], sulfolane (tetrahydrothiophene-1,1-dioxide) [89, 90, 90a], 1,1,3,3-tetramethylurea [91, 91a] and tetrasubstituted cyclic ureas such as 3,4,5,6-tetrahydro-l,3-dimethyl-pyr-imidin-2-(l//)-one (dimethyl propylene urea, DMPU) [133]. The latter is a suitable substitute for the carcinogenic hexamethylphosphoric triamide cf. Table A-14) [134]. 

Addition of electron deficient aUcenes, such as tetracyanoethylene to the dipole 20, generated by addition of diazomethane to methyl [(diaIkoxy)phosphinyl]dithioformates, gave the tetrahydrothiophene 21 in good yield. The application of cyclic dipolarophiles, such as maleic anhydride or A -phenylmaleimide in similar cycloadditions, provided access to the corresponding fused tetrahydrothiophene systems <05HCA2582>. 

The role of heteroatoms in ground- and excited-state electronic distribution in saturated and aromatic heterocyclic compounds is easily demonstrated by a comparison of a number of heteroaromatic systems with their perhydro counterparts. In Jt-excessive heteroaromatic systems, because of their resonance structures, their dipole moments are less in the direction of the heteroatom than in the corresponding saturated heterocycles furan (1, 0.71 D) vs. tetrahydrofliran (2, 1.68 D), thiophene (3, 0.52 D) vs. tetrahydrothiophene (4, 1.87 D), and selenophene (5, 0.40 D) vs. tetrahydroselenophene (6, 1.97 D). In the case of pyrrole (7, 1.80 D), the dipole moment is reversed and is actually higher than that of pyrrolidine (8, 1.57 D) due to the acidic nature of the pyrrole ring (the N-H bond) In contrast, the dipole moment of n-deficient pyridine (9, 2.22 D) is higher than that of piperidine (10, 1.17 D). In all these compounds, with the exception of pyrrole (7), the direction of the dipole moment is from the ring towards the heteroatom [32-34]. 

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