Pyrolysis, high-vacuum

High vacuum pyrolysis, heating in organic bases, contact with acidic adsorbents and reaction at room temperature with perchloric acid or boron trifluoride etherate cleaves the pyrazoline to give a 45-60% yield of the cyclopropane derivative (13) as well as 9 % of the unsaturated methyl compound (14). ° ... 

High-vacuum pyrolysis of 2,5-dimercapto-l,3,4-thiadiazole 34 and 2-mercapto-5-methyl-l,3,4-thiadiazole 9 performed between ambient and 800 °C gave products that were trapped by matrix-isolation techniques and characterized by IR spectroscopy. Pyrolysis of the dimercaptothiadiazole 34 gave HNCS, CS2, and HCN (Equation 2), whereas the thiadiazolethione 9 showed a more complex fragmentation pattern forming HNCS, CH3NCS, HCN, and CS2 (Equation 3) <2002J(P2)1620>. 

Subsequent structure determination studies involving high-vacuum pyrolysis (3) HNMR (4) and infrared (4) spectroscopy indicated 70% unrearranged... 

High vacuum pyrolysis of (2) gives mainly the 16-methyl-A16-steroid (3) besides a small quantity of the 16a, 17a-methylene product (4).188,189... 

Infrared analysis of the liquid fractions obtained by high vacuum pyrolysis in the authors laboratory confirmed the conclusion reached from quantitative gas chromatographic results. Significantly, cationic... 

The first synthesis of unsubstituted silacyclopropene 8 was achieved recently, along with a novel route to obtain this class of substances. High vacuum pyrolysis of l,l,l-trimethyl-2-vinyldisilane 80 produces the corresponding silacyclopropene by elimination of trimethylsilane (Scheme 23). A ring-opening reaction of the silacyclopropene produces the other product <1995AGE1439>. 

The preparation of pure di-imine by high-vacuum pyrolysis of the sulphon-amide salt (54) has been reported (Scheme 128) it is a yellow liquid, unstable above — 150°C. 

Thermochemical Liquefaction. Most of the research done since 1970 on the direct thermochemical Hquefaction of biomass has been concentrated on the use of various pyrolytic techniques for the production of Hquid fuels and fuel components (96,112,125,166,167). Some of the techniques investigated are entrained-flow pyrolysis, vacuum pyrolysis, rapid and flash pyrolysis, ultrafast pyrolysis in vortex reactors, fluid-bed pyrolysis, low temperature pyrolysis at long reaction times, and updraft fixed-bed pyrolysis. Other research has been done to develop low cost, upgrading methods to convert the complex mixtures formed on pyrolysis of biomass to high quaHty transportation fuels, and to study Hquefaction at high pressures via solvolysis, steam—water treatment, catalytic hydrotreatment, and noncatalytic and catalytic treatment in aqueous systems. 

While it is possible to obtain a stoiehiometric Na,BogB,4 sodium boride when operating under Na pressure, the pyrolysis of the compound at low T and in high vacuum leads to Na,B(,gBi4 sodium-deficient phases where x can reach a value of 0 without the collapse of the boron skeleton". 

Methyl radicals were produced by pyrolysis of azomethane (CH3N2CH3). Azomethane was synthesized as describe earlier [18]. It was purified periodically by fteeze-pump cycles at 77 K, and the gas purity verified by RGA. The methyl radical source was similar to that developed by Stair and coworkers. [10, 11] The source was made of a quartz tube with 3 mm OD and 1 mm ID, resistive heating was supplied by means of a 0.25 mm diameter tantalum wire wrapped outside the quartz tube. The len of the heating zone was 4 cm, recessed from the end of the tube by 1 cm. An alumina tube around the outside of the heating zone served as a radiation shield. Azomethane was admitted to the hot tube at a pressure of 1x10-8 to 1x10-7 Torr via a high-vacuum precision leak valve. The pyrolysis tube was maintained at about 1200 K, adequate to decrease the major peaks in the mass sp trum of the parent azomethane at 58 and 43 amu by at least a factor of 100. 

A few routes to new silenes, usually involving flash vacuum pyrolysis at high temperatures, have been reported. Silenes were proposed as the result of the thermal expulsion of trimethylmethoxysilane, or a similar volatile fragment, from the starting material but frequently, proof that the silenes proposed to account for the observed products were in fact formed was not provided.116 119 The other thermal route employed was the retro-Diels-Alder regeneration of a silene from an adduct with an aromatic compound—often a 9,10-anthracene or 1,4-naphthalene adduct or, in some cases, a 1,4-benzene adduct, as illustrated in Eq. (19).120... 

It is fairly stable as an ethereal solution, but the isolated acid is explosively unstable, and sensitive to heat, shock or friction [1], In a new method of preparation of the acid or its salts, pyrolysis of 4-oximato-3-substituted-isoxazol-5(4//)-ones or their metal salts must be conducted with extreme care under high vacuum to prevent explosive decomposition [2],... 

Methylene cyclopropene (5), the simplest triafulvene, is predicted to be of very low stability. From different MO calculations5 it has been estimated to possess only minor resonance stabilization ranging to 1 j3. Its high index of free valency4 at the exocyclic carbon atom causes an extreme tendency to polymerize, a process favored additionally by release of strain. Thus it is not surprising that only one attempt to prepare this elusive C4H4-hydrocarbon can be found in the literature. Photolysis and flash vacuum pyrolysis of cis-l-methylene-cyclopropene-2,3-dicarboxylic anhydride (58), however, did not yield methylene cyclopropene, but only vinyl acetylene as its (formal) product of isomerization in addition to small amounts of acetylene and methyl acetylene65 ... 

Upon flash vacuum pyrolysis or under silver nitrate catalysis, a variety of 2-ethenyl-sub-stituted cydopropylamines 146 cleanly undergo a vinylcyclopropane to cyclopentene rearrangement [129] and afford high yields (up to 95%) of 4-aminocyclopent-l-enes 147, some of which have unprecedented substitution patterns (Scheme 11.37) [130],... 

Another method to prepare allenyl ketones uses flash vacuum pyrolysis of the heterocycles 121 (Scheme 7.19) [163], This elimination of carbon monoxide is at least formally a cheletropic reaction. Highly reactive allenes such as esters and nitriles of type 124 or unsubstituted butadienal can be generated if retro-Diels-Alder reaction of 123 or similar precursors, respectively, is performed by flash vacuum pyrolysis [164]. 

When pyrolysis of coal is carried out in the mass spectrometer in high vacuum of its ion source compartment, volatilization of broken fragments is likely to occur, unless they are of large molecular size. However, a large molecular size of a fragment would also reduce its rotational ability. 

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