Kinetics of the thermal decomposition of tetrakis(dimethylamino)ethylene in the vapor phase

Abstract

The thermal decomposition of the chemiluminescent compound tetrakis(dimethylamino)ethylene (TMAE) has been investigated in a static system between 283 and 323 "C over initial pressures from 6.0 to 45 mmHg. The order of the reaction was first, as was the order for the formation of methane and dimethylamine, the major decomposition products. The Arrhenius parameters for the TMAE decomposition are given as k¡ = 9.0(±1.0) X 10ue-39 900(±2ooo)/flr g_i wjjjje those for CH4 and DMA are &ch4 = 4.3(±0.03) X 10ne-39 300(±300)/rt s-i an¿ feDMA = 2.5(±0.01) X 10loe-36 5oo(±2O0)/fiT g-i¡ respectively. The effect of certain foreign gases indicated that the decomposition was free radical in nature. A mechanism is suggested which accounts for the predominant gaseous products and calculations from experimental data are offered in support of the proposed mechanism.

Palladium-Catalyzed Tetrakis(dimethylamino)ethylene-Promoted Reductive Coupling of Aryl Halides

“…TDAE has been used as a potent reductant of organofluorine compounds, and a radical generator. , TDAE forms a ferromagnetic charge-transfer complex with fullerene (C 60 ) . In previous papers, we have reported cross-coupling of aldehyde with alkenyl halide27a and allyl halide 27b using a combination of TDAE and nickel and chromium catalysts.…”

Near‐Infrared‐Absorbing Chiral Open [60]Fullerenes

“…The thus-formed cyclic polysulfides (ii) are regarded as carbene synthons since they could regenerate the carbene by the release of polysulfides. Otherwise, it undergoes CÀ N bond cleavage [31,34] followed by the ringopening of the dithiacyclopropane ring (iii) [35,36] to afford dithiocarbamic acid (iv) which further reacts with dimethylamine (v), generated from TDAE in an independent pathway, [37] consequently giving…”

Tetrakis(dimethylamino)ethylene: identification of impurities and compatibility with common metal, polymer, and ceramic laboratory materials

“…Tetrakis(dimethylamino)ethylene (TMAE), first reported by Pruett et al (1), is well-known for its strong electron-donor properties (2,3) and its ability to chemiluminesce on reaction with oxygen (1,4,5). Kinetic studies have shown that the thermal decomposition (6) and light-producing reactions (7,8) of TMAE are complex; chemiluminescence requires catalysis by protonic materials (9). Indeed, pure TMAE in the absence of a few parts per million of .protonic activators such as water and alcohols will not react to any appreciable degree with oxygen (9).…”

“…DMA was not tested because of its high vapor pressure and expected low electron capture detector (BCD) response. Samples of oxygen (6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25) ppm in helium) were analyzed by the GC from a 1-cm3 gas sampling loop. The linear detection range of the BCD was determined from measurements of different oxygen and TMAE impurity concentrations.…”