Pyrolysis acetonitrile

Photolysis and p5Tolysis of 4-phenyltriazole gives mainly phenyl-acetonitrile pyrolysis of 4,5-diphenyltriazole in solution gives 2,3,5,6-tetraphenylpyrazine, which is formally derived from the triazole by loss of nitrogen, dimerization, and oxidation (Scheme 58). ... 

Matter, P.H., Wang, E., Aries, M, Biddinger, E.J., and Ozkan, U.S. (2006) Oxygen reduction reaction catalysts prepared from acetonitrile pyrolysis over alumina-supported metal particles. J. Phys. Chem. B, 110, 18374-18384. 

Reversed-phase hplc has been used to separate PPG into its components using evaporative light scattering and uv detection of their 3,5-dinitroben2oyl derivatives. Acetonitrile—water or methanol—water mixtures effected the separation (175). Polymer glycols in PUR elastomers have been identified (176) by pyrolysis-gc. The pyrolysis was carried out at 600°C and produced a small amount of ethane, CO2, propane, and mostiy propylene, CO, and CH4. The species responsible for a musty odor present in some PUR foam was separated and identified by gc (Supelco SP-2100 capillary column)... 

Acetonitrile oxide was generated from 3,4-dimethylfuroxan oxide by flash vacuum pyrolysis and trapped at -40 °C where its and NMR spectra were examined. Warming to room temperature in the presence of propane produced 3,5-dimethyl-2-isoxazoline (Scheme 108) (79TL2443). The oxide could also be generated by photolysis of furoxan (68CC977). 

For more volatile compounds in soils, such as aromatic hydrocarbons, alcohols, aldehydes, ketones, chloroaliphatic hydrocarbons, haloaromatic hydrocarbons, acetonitrile, acrylonitrile and mixtures of organic compounds a combination of gas chromatography with purge and trap analysis is extremely useful. Pyrolysis gas chromatography has also found several applications, heteroaromatic hydrocarbons, polyaromatic hydrocarbons, polymers and haloaromatic compounds and this technique has been coupled with mass spectrometry, (aliphatic and aromatic hydrocarbons and mixtures of organic compounds). 

Thuren [1] determined phthalates in sediment using solvent extraction (acetonitrile, petroleum ether), clean-up with deactivated Florisil, and quantitative analysis by gas chromatography. The detector response was linear between 0.5 and lOOng. The detection limit (signahnoise ratio 2 1) was O.lng for dimethylphthalate, dibutylphthalate and di(2-ethylhexyl) phthalate, and 0.05ng for benzoylbutylphthalate. Recovery was between 30% and 130% depending on the ester. Low recovery for dimethylphthalate (30%) was probably due to pyrolysis in the detector (detector temperature was 320°C). 

CH4, and H2 while minor products such as HCCCN, H2C=CHCN, C2H4 and C4H2 were also detected. Ab initio chemical calculations revealed that the pyrolysis of acetonitrile is initiated by CH bond fission, forming a cyanomethyl radical. Products such as HCCN and H2C=CHCN have been shown to arise from the decomposition of succinonitrile, that forms by the recombination of two cyanomethyl radicals. The kinetics of thermocyclization of 2,3-diethynylquinoxaline (109) (Bergman cyclization) have been studied in various solvents. Non-polar solvents give shorter half-lives and better yields. The cyclization rates observed were found to be solvent dependent. ... 

The compound Os3(CO)j j(C5H5N) is very soluble in acetonitrile, dichl-oromethane, acetone, and methanol, and its solutions are stable to air. It is sparingly soluble in hydrocarbons. Its purity can be checked by IR spectroscopy (dichloromethane solution) v(CO)cm 1 2106(w), 2052(s), 2035(vs), 2008 (s), 1976 (m). Other physical properties have been reported.2 The vacuum pyrolysis of this compound provides a high-yield route to the carbido-dianion [Os10C(CO)24]2-.5... 

There are also not very many data on the photolysis of 1,2,4-triazines. Many 1,2,4-triazines are not only stable to irradiation but they increase the photolytic stability of other systems. Meier tried to prepare trimethylazete (356) by matrix photolysis of trimethyl-1,2,4-triazine (355) but observed only the formation of 2-butyne, acetonitrile and nitrogen (80LA798). Photolysis of tris(heptafluoroisopropyl)-l,2,4-triazine (329) afforded tris(heptafluoroisopropyl)-l,3,5-triazine (357), nitrogen, perfluorobutyronitrile and bis(heptafluoroisopropyl)acetylene. The last three products are the same as in the pyrolysis of (329) <80JCS(P1)2254). 

The first pathway, followed by 1,3,4-oxathiazolones (X = S Y = Z = O) and 1,4,2-dithiazolones (X = Y = S Z = 0), affords nitrile sulfides 53, a class of transient 1,3-dipolar species, which in the absence of suitable dipolarophiles decompose further affording nitriles and sulfur. However, under flash vacuum pyrolysis (FVP) conditions, 5-methyl 1,3,4-oxathiazolone 8 (R = Me X = S Y = Z = 0) does not produce acetonitrile sulfide but instead carbon dioxide, acetonitrile, and sulfur <2001PCA6258>. 

In its utilization of acetonitrile, the oxazoline synthesis shown in Scheme 56 resembles a Ritter reaction.The procedure is convenient, but yields are variable the pyrolysis gives starting alkene plus acetamide as by-products. Another oxazoline synthesis and subsequent conversion to a cif-amino alcohol is discussed later (Scheme 85). A recent y-hydroxy-a-amino acid synthesis incorporates the following type of transformation (Scheme 57).If a three-day equilibration with anhydrous HBr was introduced iMtween stages i and ii, almost pure trans product was obtained. The paper has many usefol references. Yet another modified Ritter reaction is shown in Scheme 58. ... 

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