Substituent effects on the nitrogen-15 and carbon-13 shieldings of some N-arylguanidinium chlorides.
The (13)C and (15)N chemical shifts of five N-arylguanidinium chlorides carrying polar substituents, ranging in character from 4-methoxy to 4-nitro groups, have been determined by NMR spectroscopy at the natural-abundance level of (13)C and (15)N in dimethyl sulfoxide solution. Comparison of the (13)C shifts of these salts with those of monosubstituted benzenes shows that the guanidinium group induces an average downfield shift of -5.8 ppm of the resonance of the aryl carbon to which it is attached (C1), an average upfield shift of +4.2 ppm for C2 and C6, and a small upfield shift of +1.9 ppm for C4. The shifts of C3 and C5 are small and erratic relative to the corresponding carbons in monosubstituted benzenes. The (15)N resonances of the guanidinium nitrogens are quite sensitive to electric effects resulting from substitution of polar groups at C4. The (15)N shift of the [unk]NAr nitrogen relative to that of the salts suggests that the predominant tautomer for N-arylguanidines is (H(2)N)(2)C[unk]NAr. The (15)N shifts of the (NH(2))(2) nitrogens correlate rather well with sigma(p) (-) parameters, whereas the shifts of the -NHAr nitrogens seem to correlate only with R values derived from the sigma(p) (-) substituent constants.
Gates and Crellin Laboratories of Chemistry, California Institute of Technology, Pasadena, California 91125.
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Botto
J H
JH
Schwartz
J D
JD
Roberts