Equatorial oxides

The type of data contained in Table 11 for the case of PF6, were also obtained for both isomers (27) and (27 ). The former (27), with equatorial oxide is more stable than the latter (27 ), with apical oxide, as indicated in Scheme 3. There is a difference of 0-0175 a.u. (1 a.u. =627-463 kcal mole-1) for the d-orbital contribution to the binding energy. Hence about 30% of the entire binding energy difference in these two isomers is due to d-orbital contribution. 

We shall describe a specific synthetic example for each protective group given above. Regiosdective proteaion is generally only possible if there are hydroxyl groups of different sterical hindrance (prim < sec < tert equatorial < axial). Acetylation has usually been effected with acetic anhydride. The acetylation of less reactive hydroxyl groups is catalyzed by DMAP (see p.l44f.). Acetates are stable toward oxidation with chromium trioxide in pyridine and have been used, for example, for protection of steroids (H.J.E. Loewenthal, 1959), carbohydrates (M.L. Wolfrom, 1963 J.M. Williams, 1967), and nucleosides (A.M. Micbelson, 1963). The most common deacetylation procedures are ammonolysis with NH in CH OH and methanolysis with KjCO, or sodium methoxide. 

The sulfoxide group tends to occupy an axial rather than an equatorial position in the thiane S-oxides. 

CP-1 was assembled in an approximately spherical shape with the purest graphite in the center. About 6 tons of luanium metal fuel was used, in addition to approximately 40.5 tons of uranium oxide fuel. The lowest point of the reactor rested on the floor and the periphery was supported on a wooden structure. The whole pile was surrounded by a tent of mbberized balloon fabric so that neutron absorbing air could be evacuated. About 75 layers of 10.48-cm (4.125-in.) graphite bricks would have been required to complete the 790-cm diameter sphere. However, criticality was achieved at layer 56 without the need to evacuate the air, and assembly was discontinued at layer 57. The core then had an ellipsoidal cross section, with a polar radius of 209 cm and an equatorial radius of309 cm [20]. CP-1 was operated at low power (0.5 W) for several days. Fortuitously, it was found that the nuclear chain reaction could be controlled with cadmium strips which were inserted into the reactor to absorb neutrons and hence reduce the value of k to considerably less than 1. The pile was then disassembled and rebuilt at what is now the site of Argonne National Laboratory, U.S.A, with a concrete biological shield. Designated CP-2, the pile eventually reached a power level of 100 kW [22]. 

Extensive research has established that axial cyclohexanols are more reactive than equatorial alcohols toward chromic acid oxidation. The basis for this effect can be seen... 

Because of the presence of alkali in Raney nickel, ketones are hydrogenated over this catalyst to yield the more stable, equatorial alcohol e.g. 59) as the predominant product, Similar results can be expected with platinum in basic media or with platinum oxide in an alcoholic solvent since this catalyst also contains basic impurities. 

The NMR spectrum of methyl kasugaminide in deuterium oxide at 100 Me is shown in Figure 3. The anomeric proton at C-l linking with methoxyl group is shown as a doublet at 4.57 p.p.m. indicating one proton at C-2. The weak coupling, 1.6 c.p.s., is possible between protons in cis relation (28) or in equatorial-equatorial relation (6) at C-l and C-2 of the six-membered ring. 

The power of the new spectrometer to reveal configurations of difficult cyclitols or sugars was first tested with mt/o-inositol (2), using deuterium oxide as solvent. At 60 or 100 MHz. the one equatorial and five axial protons appear to have different chemical shifts as shown by Lemieux in 1956 with a 40 MHz. instrument (14,15). However, since the five-proton axial signal could not be resolved, one could probably not have assigned the configuration 2 (which was already known from laborious chemical correlations extending over many years.)... 

The facile and selective oxidation of both primary and secondary hydroxy groups with certain nucleotides led Pfitzner and Moffatt (48) to explore the scope of the carbodiimide-methyl sulfoxide reagent with steroid and alkaloid alcohols. Relatively minor differences were apparent in the rate of oxidation of epimeric pairs of 3- and 17- hydroxy steroids whereas the equatorial lLx-hydroxyl group in several steroids was readily oxidized under conditions where the axial epimer was unreactive [cf. chromic oxide oxidation (51)]. 

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