5-ARYL- AND 5-ALKYL-1,2,3,4-THIATRIAZOLES: SYNTHETIC, SPECTROSCOPIC, AND DEGRADATIVE STUDIES

1963 ◽  
Vol 41 (4) ◽  
pp. 926-931 ◽  
Author(s):  
Eugene Lieber ◽  
C. N. R. Rao ◽  
R. C. Orlowski

A number of 5-(p-substituted)phenyl-1,2,3,4-thiatriazoles have been synthesized by the diazotization of p-substituted thiobenzhydrazides or by the reaction of sodium thiobenzoyl-thioglycollates with sodium azide. The thermal decomposition of these thiatriazoles yields nitriles, nitrogen, and sulphur. 5-Alkyl-1,2,3,4-thiatriazoles are very unstable and readily decompose to nitriles. Infrared and ultraviolet absorption spectra of 5-(p-substituted)phenyl-1,2,3,4-thiatriazoles have been studied. Infrared spectra of several thiohydrazides have also been studied and there appears to be no thiol–thione tautomerism in these derivatives. The thiatriazole ring is found to be electron withdrawing.

1954 ◽  
Vol 32 (9) ◽  
pp. 823-838 ◽  
Author(s):  
Paul E. Gagnon ◽  
Jean L. Boivin ◽  
Roderick MacDonald ◽  
Leo Yaffe

2-Monosubstituted-3-hydroxy-5-pyrazolones were prepared from diethyl malonate itself and diethyl malonates monosubstituted with methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, and benzyl groups by condensation of the esters with o-, m-, and p-chlorophenylhydrazines, and n-hexylhydrazine. By using diethyl n-hexyl malonate-2-C14 and o-, m-, and p-chlorophenylhydrazines, and n-hexylhydrazine as starting materials the corresponding pyrazolones labelled with C14 were obtained. Their specific activities were 7.0, 8.8, 9.0, and 8.8 µc./gm. respectively. Ultraviolet absorption spectra were determined in neutral and alkaline solution and the infrared spectra were also obtained. From the data it was possible to ascribe the tautomeric structures best suited for the compounds.


1961 ◽  
Vol 39 (1) ◽  
pp. 171-179 ◽  
Author(s):  
C. N. R. Rao ◽  
J. Ramachandran ◽  
A. Balasubramanian

The near-ultraviolet absorption spectra of polyphenyl derivatives of the IVb and Vb elements have been studied in detail. In the case of the triphenyl derivatives of the Vb elements, the unshared p-electrons on the central atoms interact strongly with the π-orbitals of the benzene rings. When the central atoms do not possess unshared electrons as in the case of the derivatives of the IVb and the pentavalent Vb elements, there appears to be no such resonance interaction. The Hammett reactivity constants of the para- and meta-trityl, triphenylsilyl, and triphenylgermanyl groups are estimated to be close to zero. However, the reactivity constant of the triphenylsilyl group in the para position of phenol is estimated to be about 0.30. The infrared spectra of the phenyl derivatives of the IVb and Vb elements show smooth trends due to mass effects of the central atoms, in the C=C skeletal, C—H out-of-plane, and other vibrations. The absorption frequencies which are assigned to the phosphorus-phenyl and silicon–phenyl bonds in the literature do not appear to be unique for these linkages.


2013 ◽  
Vol 779 (1) ◽  
pp. 40 ◽  
Author(s):  
Yu-Jong Wu ◽  
Hui-Fen Chen ◽  
Shiang-Jiun Chuang ◽  
Tzu-Ping Huang

1950 ◽  
Vol 187 (1) ◽  
pp. 299-312
Author(s):  
R.L. Sinsheimer ◽  
J.F. Scott ◽  
J.R. Loofbourow

1959 ◽  
Vol 37 (3) ◽  
pp. 563-574 ◽  
Author(s):  
Eugene Lieber ◽  
J. Ramachandran ◽  
C. N. R. Rao ◽  
C. N. Pillai

The ultraviolet absorption spectra of 5-(substituted)amino-1,2,3,4-thiatriazoles and the corresponding isomeric 1-substituted-tetrazoline-5-thiones have been studied. The spectra and the dipole moments of the 5-(substituted)amino-1,2,3,4-thiatriazoles eliminate the possibility of meso-ionic structures for these compounds. The dipole moments of 5-amino-, 5-methylamino-, and 5-dimethylamino-1,2,3,4-thiatriazole were all high but approximately of the same value (5.77 to 5.84 D). This suggests that the amino thiatriazoles are best represented by conventional covalent structures with significant ionic resonance contributions. The thiatriazole ring system exhibits a characteristic absorption maximum at 250–255 mμ and an electron-withdrawing effect approximately equal to the tetrazolyl ring system. The tetrazolinethionolyl ring system is similarly electron-withdrawing. The relative acidities of the 1-substituted-tetrazoline-5-thiones and the 5-alkylmercaptotetrazoles have also been studied and the results support the observations made on the basis of their ultraviolet absorption spectra.


1962 ◽  
Vol 8 (1-6) ◽  
pp. 257-275 ◽  
Author(s):  
Haruo Hosoya ◽  
Jiro Tanaka ◽  
Saburo Nagakura

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