0 CD3 CDs dc (3.3), di (0.2) 3.90 6.0 60.1 6.0 6.21 f 0.02 1.05 5.63 6.0 4.0 0.32 6.70 f 0.01 1.13 dlo (69.7), dg (25.0) 9.60-9.63 9.59 6.0 60.1 0.35 6.99 f 0.01 1.18 de (3.9), ds-7 (1.4) CDJ CDI Corresponding to the major constituent. Measurements were kindly performed by Mr. E. Miller, using a CEC type 21-103C instrument operated at 7-8 e.v. A = aromatic multiplet with center peak a t r = 2.8-2.9; B = methylene peak, T = 7.4; C = methyl singlet, T = 7.7-7.8. Measurements were made using a Varian A-60 spectrometer and -10% w./v. solutions in CDCll with TMS as internal standard. e Determined polarimetrically (X 435 mfi, 12 dm.) on benzene solutions (c 1-5) a t 42.0 * 0.1'. In each case the listed average and standard error were computed by a nonlinear least squares analysis of readings taken over a span of three half-lives. Determined by Mr. J. Nemeth, Urbana, Ill., using the falling drop method.
The 'H NMR and 13C NMR spectra of neopentyl and benzyl substituted disulfides, thiosulfinates, thiosulfonates, thiols, sulfides, sulfinic acids and sulfonic acids are reported. The deshielding electron withdrawing effects of -SO, -SO,, -SOz-, -SO,H, -SO,-, S 0 , H and S03CH3 on or-ðylene and benzylic protons are observed. The 'H NMR spectra show, except for two dialkylthiosulfinates, that the a'-protons of thiosulfinates absorb farther downfield than those of the thiosulfonates. Although the "C NMR spectra show that orso effects are deshielding and are smaller than the aso, effects, the aso values are more shielding than the ago, values for some compounds. The effects on 13C NMR spectra which result from substituting a phenyl group for a neopentyl or benzyl group are discussed. The or-methylene carbon shifts for neopentanesulfinic acid and or-toluenesulfinic acid are further downfield than those for the corresponding sulfonic acids.
not afford the expected dimer l 4 of tri-tert-butylcyclobutadiene. Rather, the exclusive product in essentially quantitative yield was cyclopropenyl ketone 6.The fact that 6 was also formed from the solvolysis of 1 suggests that cationic intermediate^'^ may be involved in the oxidation of 2 as well. Details of the mechanism of this latter transformation remain obscure at the present time. Efforts to provide information in this area are in progress.Acknowledgments. Acknowledgment is made to the Research Corporation for financial support of this work. We thank Mr. J. G. Henkel for the use of his computer program and Mr. S. Cichanowski for the dipole moment determination. (14) We have obtained a compound which possesses the expected analytical and spectroscopic data for a dimer of tri-tert-butylcyclobutadiene, namely 1,3,4,5,7,8-hexa-tert-butyltricyclo[4.2.O,O~~~]octa-3,7diene (IO) by reaction of 1 with lithium amalgam in ether. This dimer may be formed by a stcpwise double Wurtz reaction. Cf. discussion in ref 6.
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