Pyridine ring, stability

The cleavage of fused pyrazines represents an important method of synthesis of substituted pyrazines, particularly pyrazinecarboxylic acids. Pyrazine-2,3-dicarboxylic acid is usually prepared by the permanganate oxidation of either quinoxalines or phenazines. The pyrazine ring resembles the pyridine ring in its stability rather than the other diazines, pyridazine and pyrimidine. Fused systems such as pteridines may easily be converted under either acidic or basic conditions into pyrazine derivatives (Scheme 75). 

The methyl groups on the pyridine ring result in a major difference in the reactivity of lutidines. In 3,5-lutidine the methyl groups act as electron donors tending to increase the stability of the tt-bonds, and activating the ring for electrophilic attack at the a-positions. The MOs in 3,5-lutidine show the it-levels pushed to lower energy... 

Tyrl52 (145), mediates the formation of ACC from SAM via a catalytic mechanism involving a quinoid intermediate (according to Li et aC) and stabilizes the pyridine ring of PLP ... 

The rather high basic strength of 3,5-diazaindole [91] (p/sTa = 6T) is not due to the protonation of the imidazole ring (for benzimidazole p g = 5-53), but rather of the pyridine ring. Cation [92] is formed and this is stabilized by the same kind of resonance as... 

PADP (171), an explosive synthesized from the reaction of 3,5-dinitro-2,6-bis-(hydrazino)pyridine with picryl chloride in DMF followed by oxidation with nitric acid, also exhibits high thermal stability. 2,4,6-Tris(picrylamino)-3,5-dinitropyridine (172) exhibits much lower thermal stability than both PYX (170) and PADP (171), a consequence of increased steric crowding around the pyridine ring. ° ... 

Tropicamide has p Ta appropriate for a pyridine ring. The second nitrogen is part of an amide group, and is thus a very weak base. Amides are stabilized through resonance, a stabilization that is not possible in the conjugate acid. 

Through the eoordinated water molecule to the terminal tin atoms of the polymer, the polymers are assoeiated with eaeh other via hydrogen bonds to the pendant 0 atoms of earboxyl groups and the N atoms derived of the pyridine ring, so that a 2-D network is formed. The distances of hydrogenbonding, 0(5)-H 0(2 1 ), 0(5)-H—0(4 1 ) and 0(5)-H—N(l l ), separations are 2.759, 2.792, and 2.876 A, respectively. This eonfirms that the water molecules play an important role in the stabilization of the polymer. ... 

The one-electron reduction of diquaternary salts of 2,2 -bipyridine has attracted much attention. When an aqueous solution of diquat dibromide (75) is treated with a one-electron reducing agent, such as zinc dust, the solution acquires an intense green color. This is due to the formation of the stable radical cation 87. The one-electron transfer is completely reversed by air. In theory the radical cation 87 can take up another electron to form the neutral species 88. The stability of the radical cation 87 is due to the ability of the odd electron to be located at any of the nuclear positions because of the near coplanarity of the two pyridine rings. The potential 0 of the first one-electron transfer occurs at — 0.35 V in aqueous solution... 

Two modifications of the well-known benzothiazole preparation have been employed to prepare unusual heteropoly cycles. Konig et al.ils treated l-thiocarbamoyl-l,2,3,4-tetrahydroquinoline (236) with bromine in chloroform to give the thiazolo[3,4,5-J,i]quinoline derivative 237. In a process which requires disruption of the resonance stabilization of the pyridine ring, Harris416 reported that treatment of l-(2-pyridyl)-2-thiourcas with sulfuryl chloride or with bromine gives the hydrohalide salts of 2-imino-2//-[l,2,4]thiadiazolo[2,3-a]pyridines (238). 

The enthalpy and entropy of complex formation between Zn11 and picolinate and dipicolinate anions in aqueous solution have been determined by calorimetry and from formation constant data. The greater stability of the dipicolinate complex compared to the picolinate complex reflects an entropy effect, and Ais actually less favourable. These anions are well known to have a low basicity to H+ compared to their complexing ability to metals. In the present case, this probably reflects the coplanarity of the carboxylate anions and the pyridine ring, so that the oxygen atoms are in a favourable position to coordinate.800... 

Each one of the groups around the chiral carbon of the amino acid may be cleaved, forming an anion that is stabilized by the Schiff base with the pyridine ring. (See Chapter 8, section FI, for a stereochemical explanation of why a particular bond is cleaved.)... 

The principles of the above reactions form the basis of a series of important metabolic interconversions involving the coenzyme pyridoxal phosphate (structure 2.41). This condenses with amino acids to form a Schiff base (structure 2.42). The pyridine ring in the Schiff base acts as an electron sink which very effectively stabilizes a negative charge. 

An essential feature of such stabilization is that the atoms in the tt system are planar. The extended molecular orbital is constructed from atomic orbitals that are perpendicular to the plane. Thus, for the electrons involved in any bond making or breaking processes to be stabilized by delocalization, the bonds that are being made or broken must also be perpendicular to the plane. This criterion may be used by pyridoxal phosphate-utilizing enzymes in choosing which bond jp cleave, as may be seen when the intermediate 8.44 is redrawn so that it is perpendicular to the plane of the paper (structures 8.45 the pyridine ring is represented as a solid bar). In each case, the bond that is broken is the one at the top, so that the electrons may be fed into the tt system. 

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