Highly stereoselective decarboxylation of (+)-1-Bromo-1-chloro-2,2,2-trifluoropropanoic acid gives (+)-1-Bromo-1-chloro-2,2,2-trifluoroethane ((+)-Halothane) with retention of configuration

The absolute configuration of the title acid (2) has been determined to be S by X-ray crystallography. Thus, decarboxylation of 2 produces (S)-(+)-halothane with 99% retention of configuration. This behavior is compared to other stereoselective decarboxylation reactions of ?-haloacids from the literature that also give high degrees of retention of configuration when in the form of their quaternary ammonium salts, which contain one proton. The proton of the ammonium salt is necessary to protonate the anionic intermediate formed from decarboxylation. In the absence of this relatively acidic proton, we had previously found that using triethylene glycol (TEG) as both solvent and proton source for the decarboxylation reaction of acid 2 caused poor stereoselectivity. This was in contrast to 1,2,2,2-tetrafluoro-1-methoxypropionic acid (6), which showed a high degree of retention of configuration in TEG. To rationalize this differing behavior we report DFT studies at PCM-B3LYP/6-31++G** level of theory (the results were additionally confirmed with 6-311++G** and aug-cc-pVDZ basis sets). The energy barrier to inversion of configuration of the anionic reaction intermediate of acid 2 (11) is 10.23 kcal/mol. However, we find that the anionic intermediate from acid 6 (10) would rather undergo ?-elimination instead of inversion of configuration. Thus the planar transition state required for inversion of configuration is never reached, regardless of the rate of proton transfer to the anion.

(Table 7) Fe**3+/Fe**2+ ratios in selected nontronite samples at DSDP Leg 70 Holes

Since its discovery in 1974 (Klitgord and Mudie, 1974), the Galapagos mounds hydrothermal field has received much attention. Sediment samples were taken during Leg 54 of the Deep Sea Drilling Project (DSDP) and by other expeditions to the area (e.g., Corliss et al., 1978). While a hydrothermal origin for the mounds sediments has been generally accepted, several different theories of origin for the mounds themselves have been proposed (e.g., Corliss et al., 1978; Natland et al., 1979; Williams et al., 1979). One of the aims of DSDP Leg 70 was to return to the mounds field and, using the new hydraulic piston cor er described elsewhere in this volume, to obtain more complete recovery of mounds sediments than had previously been possible. It was our hope that this would help in our understanding of the nature and origin of these deposits. In this chapter, we describe the results of chemical analysis of over 250 sediment samples taken during the course of Leg 70.