Deuterated

Fig. XI-7. Volume fraction profile of 280,000-molecular-weight poly(ethylene oxide) adsorbed onto deuterated polystyrene latex at a surface density of 1.21 mg/m and suspended in D2O, from Ref. 70.

A unique but widely studied polymeric LB system are the polyglutamates or hairy rod polymers. These polymers have a hydrophilic rod of helical polyglutamate with hydrophobic alkyl side chains. Their rigidity and amphiphilic-ity imparts order (lyotropic and thermotropic) in LB films and they take on a F-type stmcture such as that illustrated in Fig. XV-16 [182]. These LB films are useful for waveguides, photoresists, and chemical sensors. LB films of these polymers are very thermally stable, as was indicated by the lack of interdiffusion up to 414 K shown by neutron reflectivity of alternating hydrogenated and deuterated layers [183]. AFM measurements have shown that these films take on different stmctures if directly deposited onto silicon or onto LB films of cadmium arachidate [184]. 

Nordhoim S 1989 Photoisomerization of stiibene—a theoreticai study of deuteration shifts and iimited internai vibrationai redistribution Chem. Phys. 137 109-20... 

Two of the most important functions in the application of neutron scattering are the use of deuterium labelling for the study of molecular confomiation in the bulk state and the use of deuterium solvent in polymer solutions. In the following, we will consider several different applications of die general fomuda to deuteration. 

Let us first consider two identical polymers, one deuterated and the other not, in a melt or a glassy state. The two polymers (degree of polymerization d) differ from each other only by scadermg lengths and b. If the total number of molecules is N, x is the volume fraction of the deuterated species x = N- / N, with Aq -t = A). According to equation (B1.9.116), we obtain... 

Let us take two polymers (one deuterated and one hydrogenated) and dissolve them in a solvent (or another polymer) having a scattering length b. The coherent scattered intensity can be derived from (B 1.9.117), which gives... 

Benzyl bromide can be converted into ethylbenzene (731) by the reaction of Me4Sn. The use of HMPA as a solvent is important. Overall inversion of configuration takes place at the chiral center of deuterated benzyl bro-mide[598]. The cyanomethyiation[599] and methoxymethyiation[600] of aromatic rings are carried out by the reaction of cyanomethyltributyltin (732) and methoxymethyltributyltin. 

Hydrogenolysis of aryl and alkenyl halides and triflates proceeds by the treatment with various hydride sources. The reaction can be explained by the transmetallation with hydride to form palladium hydride, which undergoes reductive elimination. Several boro hydrides are used for this purpose[680], Deuteration of aromatic rings is possible by the reaction of aryl chlorides with NaBD4681]. 

Highly regio- and stereoselective 4a-deuteration in steroids is possible by the hydrogenolysis of the cyclic allylic /3-carbonate 628 with NaBD4. the extent of 6a-deuteration is only 3%[393],... 

The mechanism of the PdCh-catalyzed Cope rearrangement has been studied by use of the partially deuterated 1.5-diene 53[46], The coordination of Pd(II) activates the alkene, and cyclization (carbopalladation) takes place to... 

Infrared absorption properties of 2-aminothiazole were reported with those of 52 other thiazoles (113). N-Deuterated 2-aminothiazole and 2-amino-4-methylthiazo e were submitted to intensive infrared investigations. All the assignments were performed using gas-phase studies of the shape of the vibration-rotation bands, dichroism, isotopic substitution, and separation of frequencies related to H-bonded and free species (115). With its ten atoms, this compound has 24 fundamental vibrations 18 for the skeleton and 6 for NHo. For the skeleton (Cj symmetry) 13 in-plane vibrations of A symmetry (2v(- h, 26c-h- Irc-N- and 7o)r .cieu.J and... 

Hydrogen exchange, in thiazole, especially deuteration, has been quantitatively investigated (379,380), but the mechanism of the reaction carried out at acidic or neutral pH corresponds to a protonation-deprotonation process (380), different from electrophilic substitution and is discussed in section I.3.E. 

More recently, the use of phase-transfer catalysis to promote the deproto-deuteration of thiazole and various alkylthiazoles enabled Spil-lane and Dou (435) to increase considerably the rate of H/D exchange and afforded the possibility of labeling alkylthiazoles in preparative quantities and at positions otherwise difficult to label. 

A primary isotope effect /ch/ d of 6.4 (extrapolated for 35 C) is observed for the metalation and the methylation of 171b when the C-5 position is deuterated. This value is in excellent agreement with the primary isotope effect of 6.6 reported for the metalation of thiophene (392) and it confirms that the rate-determining step is the abstraction by the base of the acidic proton. 

Reactions with substituted aryl- and alkylthiazoles and deuterated thiazoles (98) gave evidence of the general pathway of the rearrangement (Scheme 2). 

The general mechanism of the rearrangement of aryl and diaryl-thiazoles seems to exclude the zwitterion route. Instead it takes place through bending of thiazoles bonds (98.213). Moreover, tricyclic sul-fonium cation intermediates, after irradiation of deuterated phenyl-thiazoles, have been suggested by several workers (98). 

Deuterolysis of the organolithium compounds was used to characterize the three deuterated thiazoles corresponding to the three lithium derivatives. 

The 2-bromothiazole can also be reduced to thiazole by zinc (18) in CH3COOH, or by electrolytic reduction (68). The deuterated thiazoles can also be obtained starting from the corresponding halogenothiazoles, by Zn/Cu in CH3COOD (18). 

Table 7.48 Solvent Positions of Residual Protons in Incompletely Deuterated...

Table 7.60 Carbon-13 Chemical Shifts of Deuterated Solvents 7.110...

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