The preparation of FCIOl has been reported (1, 2), but spectral data are not available. The infrared and fluorine nuclear magnetic resonance spectra of fluori~ie perchlorate are reported below.Since tlie fluorine resonance appears to shift to low field with increasing electronegativity of an attached atoll1 or group (3, 4a and b), the fluorine chemical shift of fluorine perchlorate was ~neasured in order to deternline the extent of tlie displacement of the fluorine resonance to low field.The fluorine n.1n.r. spectruln of neat perchloryl fluoride has been reported (3). A lowfield fluorine chemical shift as well as fluorine-chlorine spin-spin coupling was observed in perchloryl fluoride (3).Since the method (3) of measuring the chemical shift and tlie standard used were different fro111 those used in this laboratory, a comparison among fluorine perchlorate, fluorine oxide, and perchloryl fluoride was made using CFC13 ( 5 ) as a standard and solvent.The fluorine n.m.r. spectrulil of fluorine perchlorate consisted of a single line, and a chemical shift of -225.9 p.p.m. relative to CFC13 was obtained. The chemical shift of fluorine perchlorate was not rneasured neat but as a 50% solutio~l in Freon-11. Although the perchlorate will detonate in the pure form, in solution fluorine perchlorate appears to be stable and the data was obtained without incident.A joyo solution of perchloryl fluoride in Freon-11 was studied in an effort to resolve the spcctru~n ol the proposed quartets (3). However, the use of a solvent did little t o help resolve the spectrum. The center of what appeared t o be a broad doublet was -287.0 p.p.nl. relative to CFCI?. The splitting between the peaks was 460 cycles.The fluorine chemical shift of fluorine oxide was measured as a gas under 5-atm pressure and relative to CFC1.I in a sealed capillar~. The side-band technique (6) was used to measure tlie chemical shifts. Since different techniques were used, comparison of presented and published (3) data would be difficult, but the chemical shifts of the three compounds FC104, FC1O3, and OFz, appear t o be of the right order of magnitude, and are in the order predicted by theory (4).The infrared spectrum of fluorine perchlorate was obtained in the sodiu~n chloride region only. As the spectruln of fluorine perchlorate has not previously been reported,
The determination of the relative geometry of substituents on the 5-membered indanone ring and the corresponding indanol derivatives involved the utilization of deuterium substitution, spin-spin decoupling, and the calculation of the theoretical spectra wherever applicable. The NMR spectra of a series of methylsubstituted 1-indanones and indanols were obtained and the stereochemistry was determined. The coupling constants were used as a criterion for the conformation of the 5-membered ring. Spin-spin decoupling experiments were used for further confirmation of the assignment of the ring protons. Theoretical spectra were obtained for the 2-and 3-methyl-l-indanones.The data indicate that the ring geometry and symmetry is dependent on the nature and the number of the substituents on the 5-membered ring.The preparation of indanone and indanone derivatives usually involves a series of reactions; however, the novel synthesis reported (J) has made possible a study of substituted 1indanones by proton nuclear magnetic resonance spectrometry. The elimination reactions of 2-bromo-2(a-bromobenzyl)-l-indanones and 2-bromo-2(a-bromobenzyl)-3,3 -dimethyl-1 -indanone have been studied, and infrared and ultraviolet spectral data were obtained (2). Elvidge and Foster (3) published nuclear magnetic spectral data for a series of indenes, whose structures were established by means of the proton resonance spectra of parent indanones and indanols. These authors demonstrated the presence of long range proton coupling in the series of indenes studied. Related work on 2-substituted indanes (4) has been reported. These authors utilized the formation of the indane complex with tricarbonyl chromium to obtain data concerning the geometry of the indane 5-membered ring. Recently, the NMR spectra of 1,2disubstituted indanes and related indanones have been obtained and the data reported by Rosen, Dorfman, and Linfield (5). Their discussions involved the dependence of the coupling constants of the protons of the 5-membered ring on ring planarity. However, a study of a series of 1-indanones has not been the subject of reported data thus far.The scope of this study includes the determination of the relative geometry of indanones and the corresponding indanol derivatives, as well as a discussion of interesting phenomena encountered. The stereochemistry of the compounds that were studied was determined by conversion of the indanones to indanols with sodium borohydride and by consideration of the
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