1,2-halo shifts

In addition, MgCl2 exhibits active, or 5 forms, which can be obtained, e.g., by mechanical treatment of the a form, treatment of the a form with Lewis bases, or by chlorination of Mg-organic derivatives. With respect to the a form, the 5 forms are characterized by the broadening of the (104) reflection, forming a halo shifted with respect the position of the (104) reflection (Fig. 4). 

It is possible to synthesize alkylcobalamins containing halogenated alkyl groups. Of these, the compounds studied most extensively are the halo-methylcobalamins (745). For the various fluorine containing derivatives which have been prepared, 19F NMR spectra have been obtained and the results are shown in Table 6. Chemical shifts of a number of fluorome-thanes are included for comparison. 

H and13C NMR Data for Halofluoroalkanes. Scheme 3.13 provides some pertinent proton and carbon chemical shift and coupling constant data for fluorochloro- and fluorobromomethanes, whereas Scheme 3.14 contains relevant data for some typical halo fluoroalkanes. There does not appear to be anything unusual going on here. 

It is obvious that the semicrystalline material contains this amorphous feature as well - underneath the reflections. In the semicrystalline material the halo is shifted... 

Nevertheless, acetoxycarbenes are less reactive than analogous chlorocarbenes, as shown by the data in Table 5, where we compare 1,2-H shift rate constants for phenoxymethyl-, cyclobutyl-, and isopropyl halo and acetoxy carbenes. Decreased rates of 1,2-H shifts are observed, due to the influence of the acetoxy spectator substituents, with the kinetic suppression reaching a factor > 900 for the comparison of cyclobutylacetoxycarbene with cyclobutylchlorocar-bene.81... 

Table 5. Rate Constants for 1,2-H Shifts of Halo and Acetoxycarbenes in Hydrocarbon Solvents0...

Another feature of carbenoid-type reactivity is the cyclopropanation (reaction c). Again, this reaction does not only take place in vinylidene but also in alkyl carbenoids . On the other hand, the intramolecular shift of a /3-aryl, cyclopropyl or hydrogen substituent, known as the Fritsch-Buttenberg-Wiechell rearrangement, is a typical reaction of a-lithiated vinyl halides (reaction d) . A particular carbenoid-like reaction occurring in a-halo-a-lithiocyclopropanes is the formation of allenes and simultaneous liberation of the corresponding lithium halide (equation 3). ... 

In addition to MAK values, which are for healthy persons capable of earning a normal living, the DFG publication20 includes so-called BAT values (biological tolerance limits) for substances which show additional biological effects. These define maximum concentrations of a substance, or its metabolites, normally in the blood or urine of an employee. Only one fluorinated chemical was included in 1997. 2-bromo-2-chloro-l,l,l-trifluoroethane = Halo-thane, CAS-No. 151-67-7, with a BAT value for trifluoroacetic acid (its toxic metabolite) of 25 mg - L 1 in human blood determined after exposure/shift. 

Application of the equilibrium-shift procedure (addition of LDA to a mixture of a halo derivative and a carbonyl electrophile) to 5-bromopyrimidine (30) and benzaldehyde leads to formation of the 4-substituted product 33 (Scheme 32) (79JOC2081). Similarly, the reaction... 

That the plateau should be shifted to lower Teff in halo stars can be understood rather easily as due to a Z dependence of the depth of the convection zone at a given Teff (Michaud, Fontaine and Beaudet 1984). 

Oxidation of the heterocycles with common reagents such as MCPBA, sodium periodate or hydrogen peroxide cleanly affords the sulfoxides and sulfones, and it is clear that the sulfur atom is the principal centre of reaction for electrophiles. While the sulfone is a quite inert functionality, the sulfoxides may be reduced to the sulfides with phosphorus pen-tasulfide as for the tetrahydro systems (78CJC1423). Positive halogen sources likewise react at sulfur, and the intermediate sulfonium halide rearranges, usually by 1,2-shift to the a-halo product. 

Table 3.2. 13C Shift Increments Z = (5RX — (5RH (in ppm) Induced in Hexane by Halo-genation of a Terminal Hydrogen.

Alkyl carbon atoms attached in a position a, / , or y to a carboxy function give rise to tx, [1. and y effects which shift the carboxy carbon resonances by 10, 4 and — 1 ppm, respectively. This trend is illustrated by the 13C shift values collected for formic, acetic, propionic, and butyric acids among others in Table 4.34 [305-309], Further, carboxy carbons of x halo acids and dicarboxylic acids with closely spaced carboxy groups arc shielded relative to those of parent alkanoic acids (Table 4.34). On the other hand, the x, j3 and y carboxy increments Z, = hi(RCOon)- — krh) f°r the carbon shifts of an alkyl chain are... 

The 4H NMR spectra of some methyl-,79-83 halo-,81 mercapto-,84 nitro-,84 and methoxybenzo[6]thiophenes,85 and of some sulfonic acids, sulfonyl chlorides, and sulfonate esters86 have been recorded. Two groups of workers87,88 have independently studied the 4H NMR spectra of a range of benzo[6]thiophene derivatives in an attempt to correlate the chemical shifts of the protons with the substituents. Such a correlation helps to assign structures to new benzo[6]thiophene derivatives, and it also throws light on the influence of substituents on the NMR parameters of heteroaromatic systems in general. 

Attempts to correlate the position of the substituent with the UV spectrum have been largely unsuccessful, but some general comments may be made. The spectra of most monosubstituted derivatives resemble that of benzo [6]thiophene and the three distinct zones usually remain. Methyl or halo substituents cause an overall bathochromic shift relative to benzo [6]thiophene—zone B is most affected by 3-, 5-, or 6-substituents zone C by 5-substituents.134,159,162 3-Alkyl-benzo[6]thiophenes are characterized by zone-B bands of lower intensity than those of benzo [6]thiophene and its other alkyl derivatives.134 The UV spectra of 2-methylbenzo[6]thiophene and its selenium analog have been compared.182... 

The situation is different for c = 0.9, where the PDMS-enriched central part is stabilized and shifted away from the binodal. But now, the regions outside the central area, where PEMS accumulates, cross the phase boundary into the metastable range. The demixing by nucleation and growth is visible in the lower two micrographs in Fig. 16 in the form of a halo of dark droplets around the written structures. 

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