Cross pyrazoline

Burger s criss-cross cycloaddition reaction of hexafluoracetone-azine (76S349) is also a synthetic method of the [CNN + CC] class. In turn, the azomethines thus produced, (625) and (626) (79LA133), can react with alkenes and alkynes to yield azapentalene derivatives (627) and (628), or isomerize to A -pyrazolines (629) which subsequently lose HCF3 to afford pyrazoles (630 Scheme 56) (82MI40401). 

Simple criss-cross cycloadditions described so far are in fact limited to aromatic aldazines and cyclic or fluorinated ketazines. Other examples are rather rare, including the products of intramolecular criss-cross cycloaddition. The criss-cross cycloadditions of hexafluoroacetone azine are probably the best studied reaction of this type. It has been observed that with azomethine imides 291 derived from hexafluoroacetone azine 290 and C(5)-C(7) cycloalkenes < 1975J(P 1)1902, 1979T389>, a rearrangement to 177-3-pyrazolines 292 competes with the criss-cross adduct 293 formation (Scheme 39). 

Although the cross-linked pyrazoline polymer is insoluble in common organic solvents by virtue of the crosslinks present, it was discovered that films of this material could be cast onto a variety of substrates from a suspension in a swelling solvent such as benzene. The ability to cast films is presumably related to the substantial change in polymer resin morphology after the coupling reaction has proceeded. The initial resin is hard, spherical and white in color, while the reacted bead is powdery, irregular in appearance and yellow, the color of the pyrazoline monomer. 

These differences in film morphology were also reflected as differences in film formation conditions, film adhesion, and in electrochemical properties. The pyrazoline beads readily formed films from solvents such as benzene. For the phenoxy TTF system, however, only CH2Cl2 was effective in forming films. In general, the TTF cross-linked polymers were found to be less adherent to the metallized substrates than the pyrazoline cross-linked polymers. Electro-chemically, it was found that the pyrazoline films showed complete activity after one potential sweep. The TTF polymer films, on the other hand, required from 5 to 20 cycles to reach full electrochemical activity as evidenced by a constant voltammogram with cycling. Furthermore, it was observed that the TTF polymer films were much less electroactive than the pyrazoline materials as shown by optical densities and total coulombs passed which were several times less for the TTF systems. 

Figure 9. Schematic of electron transport at metal-pyrazoline cross-linked polymer interfaces...

Deactivation processes competing with fluorescence are mainly nonradiative deactivation to the S0 state (IC) and nonradiative transition to a triplet state (intersystem crossing, ISC). Photochemical products are often formed from this triplet state. Important photochemical reactions are the E—yZ isomerization of ethylene, the oxidation of pyrazoline to pyrazole, and the dimerization of cou-marins. 

Their extensive kinetic study of the thermolysis of deuterated methylenepyra-zoline molecules at 170°C, and in particular the ratios of the differently labeled MCP molecules produced, led Crawford and Chang [40, 41] to reject reactive intersystem crossing of MP to TMM. They propose instead that, as in the case of 1-pyrazoline, initial rupture of one CN bond is followed by closure of the resulting diazenyl biradical to MCP with concomitant loss of N2. The rates of... 

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