ChemInform Abstract Title compounds such as (III) and (IV) are prepared via double Wittig reaction of the dicarbaldehydes (I). Some of these polyenes exist as sole isomers; the geometries of the double bonds can be determined by NMR. In other cases E,Z-mixtures are obtained. The 1H NMR spectra show that the methanothia-(17)-, -(19)-, -(23)-, and -(27)-annulenes sustain ring current, while the remaining title compounds do not. Dynamic NMR analysis of the methylene protons reveals the flipping of the methylene bridge above and below the average plane of the macrocycle.

The title thia-annulenes (9), (Il), ( 14), and ( 16) have been synthesized by Wittig reactions of (2€,4Z)-5-methylhepta-2,4-dien-6-ynal (6) and its vinylogous aldehydes ( 7 ) , (12) with bis-[ (triphenylphosphonio)methyl] sulphide dibromide (5), followed by intramolecular oxidative coupling of the resulting acyclic sulphides. The properties of the thia-annulenes are discussed on the basis of 'H NMR and electronic spectra and compared with those of their lower homologues.Although diatropicity or paratropicity in monocyclic conjugated systems reduces with increasing ring size,' a monocyclic 30-membered annulene, tetradehydro[30]annulene, has been reported to show diatropicity.2 The degree of dia-or paratropicity of an annulenone or a heteroannulene has been found to be much smaller than that of the corresponding carbocyclic annulene; similarly, benzene, the parent compound of annulenes, is more diatropic than tropone or heteroaromatics such as pyridine, pyrrole, furan, and thiophene. Thus, the limiting ring size to show dia-or para-tropicity is predicted to be smaller for annulenone and heteroannulene systems than the 30-membered ring observed in the carbocyclic annulene system. However, the alternation of the tropic nature between [4n + 2 3 ~-and [4n]~-electron systems, arising from polarization of carbonyl group of dimethyl-or trimethyltetradehydroannulenones of type (l), has been confirmed from 13to 25-membered ring In 1975, Sondheimer and co-workers reported the synthesis of diatropic dimethyltetradehydrothia-[ 131-and -[ 171-annulene [(2)6 and (3)' respectively] as well as that of paratropic 2.22, and 2.10 in 3 : 4 : 3 ratio.

Title compounds such as (III) and (IV) are prepared via double Wittig reaction of the dicarbaldehydes (I).

209ChemInform Abstract The components (II) + (Ia) + (Ib) are the starting compounds for the synthesis of the title annulene (IV)/(V) (= mixture of the "all-trans" and "di-cis" isomer). Similarly, the annulenes (VI)/(VIIa) and (VIIb) and (VIIc) are obtained using the starting compounds (II) and (Ib) or (Ib) + (Ic) or (Ic), respectively. The properties of the thia-annulenes are discussed on the basis of 1H NMR and electronic spectra and compared with those of their lower homologues.

ChemInform Abstract Starting with the annulenone (I), the dinitrile (IIIa) is prepared and converted into a series of derivatives such as (IIIb) by standard methods. From NMR and UV measurements it is shown that the paratropicity of the tridecafulvene system decreases with the decreasing electron-withdrawing inductive effect of the substituents in position 14.