Synthesis of methyl(ethyl) pyrazolo[4,3-b]pyridine-6-carboxylates and their conversion to tert-butyl 4,5,6,7-tetrahydropyrazolo-[4,3-b]pyridine-6-carboxylates

Georgiy G. Yakovenko ◽  
Lesya N. Saliyeva ◽  
Eduard B. Rusanov ◽  
Il’ya S. Donchak ◽  
Mykhailo V. Vovk
1980 ◽  
Vol 58 (23) ◽  
pp. 2592-2599 ◽  
Frederick J. Brown ◽  
Ian J. Massey ◽  
Carl Djerassi

The 3α,5-cyclo-6β-methoxy (i-methyl ether) moiety is a common protective grouping in steroid partial synthesis. Therefore, the mass spectrometric behavior of 6β-hydroxy-3α,5-cyclo-5α-cholestane, the corresponding methyl, ethyl, and tert-butyl ethers, the analogous ketone, and the parent hydrocarbon has been investigated in order to determine the mechanisms of the characteristic fragmentations of these compounds. Such knowledge is essential for unequivocal structure elucidation by mass spectrometry and also bears on the current interest in the stereospecificity of electron impact induced eliminations. Deuterium labeling of carbon atoms 1,2,3,4,7,8,9, and 19 of 6β-methoxy-3α,5-cyclo-5α-cholestane established the course of methanol extrusion and the identity of the highly diagnostic A ring cleavage ion [Formula: see text] Mechanisms are proposed for these key fragmentations. The mass spectra of the methyl, ethyl, and tert-butyl ethers of cholesterol are analyzed, and the features distinguishing these compounds from the isomeric 3,5-cyclosteroids are noted.

1993 ◽  
Vol 47 (6) ◽  
pp. 677-686 ◽  
R. A. Nyquist ◽  
C. W. Puehl

The νasym.NCS frequencies for alkyl isothiocyanates occur at higher frequency in CHCl3 or CDCl3 solution than in CCl4 solution. The νasym.NCS mode increases in frequency as the mole % CHCl3/CCl4 increases. The νasym.NCS mode for butyl isothiocyanate occurs at an exceptionally high frequency, and this result is explained in terms of the formation of a pseudo-six-membered intramolecularly hydrogen-bonded ring. The νasym.NCS modes for the alkyl isothiocyanates are corrected for Fermi resonance (FR), with the exception of the propyl analog. The propyl analog appears to have three other modes in FR with νasym.NCS, and an equation has not yet been developed to correct for FR in this case. The unperturbed νasym.NCS frequencies for alkyl isothiocyanates decrease in the alkyl order: methyl, butyl, ethyl, and tert-butyl. The decrease in frequency of νasym.NCS in the order methyl, ethyl, and tert-butyl isothiocyanate is attributed to weakening of the N=C=S bonds due to σ electron donation of each alkyl group. In the case of the butyl analog, the σ electron donation is partially compensated for by the postulated existence of a pseudo-six-membered hydrogen-bonded ring.

2003 ◽  
Vol 33 (15) ◽  
pp. 2709-2717 ◽  
Issa Yavari ◽  
Mohammad R. Hosseini-Tabatabaei ◽  
Azizollah Habibi

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