Thermolytic behavior

The following examples describing the thermolytic behavior of di(ferf-butyl)phosphate complexes serve to demonstrate the utihty of the TMP approach for synthesis of various phosphate materials. 

Most 1,2,4-triazines are very stable thermally. Only a few data on their thermolytic behavior are therefore to be found in the literature. We observed a few years ago that triphenyl-1,2,4-triazine (349) can be refluxed in an open tube at 550 °C without extensive decomposition. When the tris(dimethylamino) compound (350) was heated at 650 °C the colorless starting material was isolated (76UP21900). 

The thermolytic behavior of triazolines formed by the addition of phosphoryl azides to norbornenes differs from related compounds imines (phosphoramidates) are the sole decomposition products.105,466,477,478 The rate of decomposition is described by two consecutive first-order reactions, formation of the betaine in the first step and nitrogen expulsion in the... 

Silyl- and germylorganyldiazenes are intermediate between azoalkanes and azosilanes and show thermolytic behavior resembling both classes of compounds. Thus, they decompose partly by dissociation and partly by disproportionation. They also show new types of decomposition pathways. 

TeffD. J., Minear C. D., Baxter D. V., Caulton K. G. Synthesis and thermolytic behavior of mixed-valence homo- and heterometallic group 14 aUcoxides. Inorg. Chem. 1998 37 2547... 

Gamard A., Babot O., Jousseaume B., Rascle M.C., Toupance T., Campet G. Conductive F-doped tin dioxide sol-gel materials from fluorinated beta-diketonate tin(IV) complexes. Characterization and thermolytic behavior. Chem. Mater. 2000 12 3419-3426 Gan F.X. Optical-properties of fluoride glasses—a review. J. Non-Cryst. Solids 1995 184 9-20... 

The preparation and investigation of the thietane oxide system (5a) is largely associated with stereochemical and conformational studies . The investigation of the thietane dioxides (5b) is substantially related to the chemistry of sulfenes , the [2 -I- 2] cycloaddition of which with enamines is probably the method of choice for the synthesis of 5b . The study of the thiete dioxide system (6) evolved, at least in part, from the recognition that the unstable thiete system 183 can be uniquely stabilized when the sulfur in the system is transformed into the corresponding sulfone , and that the thiete dioxide system is very useful in cycloadditions and thermolytic reactions. The main interest in the dithietane oxides and dioxides (7) appears to lie in the synthetic challenge associated with their preparation, as well as in their unique structural features and chemical behavior under thermolytic conditions . ... 

The suitability of ethers derived from 1,4-dihydroxy-1,2,3,4-tetrahydro-naphthalene (DHTN) in the design of polymers susceptible to catalyzed thermolytic cleavage is demonstrated by the behavior of its bis-p-nitrophenyl ether derivative upon treatment by a trace of acid. Figure 2, curve A, shows the H-NMR spectrum of the starting compound, while curve B shows the product which is obtained upon addition of triflic acid. It is readily seen from these spectra that quantitative cleavage into naphthalene and p-nitrophenol is obtained as elimination occurs easily to afford the aromatic product. The driving force in this reaction is the facile aroma-tization which produces naphthalene. 

Tetrachlorocyclopropene has been known for some time to be a reasonably reactive dienophile.4 Its thermal ring opening to perchlorovinyl carbene is in accord with the behavior of other cyclopropenes under thermolytic conditions,5 but the... 

Examples of carbene insertions into the carbon-silicon bond of SCBs have been known since 1967, when Seyferth studied the behavior of SCBs exposed to dichlorocarbene, which was generated by thermolytic activation of phenyl(bromodichloromethyl)mercury <1967JA1538>. The reaction produces a mixture of products arising from Si-C and C-H bond insertions, with the major products being the ring-expanded silacyclopentanes that result from Si-C bond insertions (Scheme 30). 

In contrast to the well-defined photochemical behavior of 2/f-azirines, the thermal reactions of these compounds have been studied less thoroughly. It was not until 1968 that the first report of a thermolytic reaction of a 2H-azirine was made by Taniguchi and coworkers. It should be noted that the products derived from the thermolysis of vinyl azides have, on occasion, been suggested to proceed via 2/f-azirines as transient intermediates. Since the first publication by Taniguchi in 1968, a large number of reports dealing with the thermal reactions of a variety of 2i/-azirines have appeared in the literature ov the past decade. 

Tiwari, S. K., Nema, S. K., and Agarwal, Y. K. 1998. Thermolytic degradation behavior of inorganic ion-exchanger incorporated Nafion-117. Thermochimica Acta 317 175-182. 

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