• S J Shenoy

      Articles written in Journal of Chemical Sciences

    • Anomalous1H NMR spectra of 3,4-dihydroisoquinolines and related compounds

      S Narayanaswami S Rajeswari B R Pai K Nagarajan W J Richter S J Shenoy

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      Solutions of 3,4-dihydro-6,7-methylenedioxyisoquinoline (1) and analogues25 and9 as well as isoquinolines7 and8 in certain samples of CDCl3, CCl4, DMSO-d6 or acetone-d6 gave rise to anomalous1Hnmr spectra with extreme line broadening, signals due to protons at C-l and C-3 most often not being seen. The spectra of1 and3 were most striking in this respect.1Hnmr spectra of the quaternary salt10 and the model schiff base11 were normal. Several hypotheses for the observed line broadening have been considered and rejected, a slow equilibrium113 being one of them. NaBH4 reduction of1 and2 followed by mass spectrometric analysis of the crude tetrahydroisoquinolines16 and17 ruled out a slow equilibrium114 and215 as contributory cause for line broadening. The crude reduction products unexpectedly contained N-ethyl species22 and25. Their formation is rationalised

    • Spectral studies on 1-substituted-3-(1-oxo-3-hydroxy-2-cyclohexene-2-yl)-4-oxo-4, 5,6,7-tetrahydroindoles — an unexpected mass spectral fragmentation

      K Nagarajan S J Shenoy D R Müller W J Richterc L Kozerski V Pattabhi

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      IR, UV, NMR and mass spectral data for the title compounds are discussed. The EI mass spectra of4. and the analogues59 and1115 display major (M-Cn2H3O2)+ fragment ions that correspond to the loss of a structural element not present in the parent molecules. These (M-59)+ ions have no equivalent in the model compound l-phenyl-2,6,6-trimethyl-4-oxo-4, 5,6,7-tetrahydroindole (27). The unusual fragmentation is thought to be initiated by α-cleavage within the alicyclic 1,3-diketone moiety (ring C) under concomitant formation of a benzylic radical site. Reclosure of this ‘open’ intermediate to a lactone-type molecular ion provides two O-atoms in the proximity required for an ejection of a CH2COOH radical as the neutral species in question. The1H NMR spectra of4 and its methyl ether16 reveal restricted rotation of substituents at positions 1 and 3 of the pyrrole ring, the eight methylene protons becoming fully anisochronous at 500 MHz. X-ray studies on single crystals of8 confirmed its structure.

    • Condensed heterotricycles: Pyrido(1,2,3-de)(1,4)benzoxazines, pyrido(1,2,3-ef)(1,5)benzoxazepines and pyrido(1,2,3-fg)(1,6) benzoxazocines

      K Nagarajan A Nagana Goud V Ranga Rao R K Shah S J Shenoy

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      Cyclization of N-(2-haloacyl)-8-hydroxy-l,2,3,4-tetrahydroqumolines47 and9 with alkali affords pyridobenzoxazinones2124 and26 respectively and of the 4-chlorobutyramide13 with NaH, the benzoxazocinone31. Exposure of 3-chloropropionamide12 to NaH affords acrylamide15, benzoxazepinone28 or methyl benzoxazinone22 or mixtures thereof under various conditions.28 undergoes rapid base-catalysed ring contraction to22. NaH-catalysed ring closure of acrylamide15 affords mixtures of22 and28, while from the crotonamides16 and17, the methylbenzoxazepinones29 and30 are obtained preponderantly, the former amide yielding only traces of the ethyl benzoxazinone23.29 shows no propensity for ring contraction to give23. The cinnamoyl derivatives18,19 and20 are cyclized to benzyl benzoxazinones24,27 and25, respectively. The intermediacy of the phenyl benzoxazepinone39 in the formation of24 has been established by deuteration studies. Benzylidene benzoxazinone41 is obtained from dibromocinnamamide14 and propiolamide40. Dichloracetamides8 and10 undergo interesting ring closure to compounds4554 upon treatment with amines. The course of electrophilic reactions of the lactams depends upon the ring size.

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