Deutero dimethyl sulfoxide

In a subsequent study, the synthesis of urea and thiourea derivatives of types 3a and 3b were undertaken in an attempt to obtain new hosts that might yield more stable complexes with glutamic acid (of types 4a and 4b) and that might, in fact, hold together in polar solvents. The rationale for the design was based on the previously documented observation that both 1,3-dimethylurea and 1,3-dimethyl-thiourea form stable host-guest complexes with acetate in deutero-dimethyl sulfoxide the K values for the latter are 45 dm moF and 340 dm moF , respectively. 

In contrast to 2, the above derivatives incorporate four hydrogen bond donors. As a consequence, a favourable bonding situation is present in which the four secondary amine protons of each host can interact with the two charged carboxylate groups of the guest - see 4a and 4b. The proposed structure of the complex of the bis-urea derivative was supported by the existence of large NMR downfield shifts for both the inner and outer urea NH resonances in deutero-dimethyl sulfoxide and the observation of intramolecular H NOEs between the receptor aryl and the guest CH2 resonances in this solvent. A Job s plot confirmed the 1 1 stoichiometry of the product. 

The above results indicate that there is little difference between the rates of formation of the three rotaxanes (with R equal to H, CH3 or CjH ), suggesting that the steric hindrance to slippage is similar in all three cases. When the rotaxane with R = H was heated in deutero-dimethyl sulfoxide, there was loss of the crown component from the assembly - at 60 °C, the loss was less than 25% after six hours. 

Of course, you don t have to use either of the above standards at all. In the case of samples run in deutero chloroform/methanol and dimethyl sulfoxide, it is perfectly acceptable, and arguably preferable, to reference your spectra to the residual solvent signal (e.g., CD2HOH) which is unavoidable and always present in your spectrum (see Table 2.2). These signals are perfectly solid in terms of their shifts (in pure solvent systems) though the same cannot be said for the residual HOD signal in D2O and for this reason, we would advise adhering to TSP for all samples run in D20. 

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