Preparative flash vacuum thermolysis. Selective elimination of 6-chloro-1-hexene from esters of 6-chloro-1-hexanol with Schoenberg rearrangement of the S-methyl xanthate

Jenneskens, Leonardus W.; Hoefs, C. A. M.; Wiersum, U. E.

doi:10.1021/jo00285a030

Cited by 17 publications

(3 citation statements)

References 2 publications

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“…The benzoic acid sublimed onto the glass as white crystals immediately after coming out of the hot part of the apparatus. [17,18,23] The volatile product 1 was collected in a cold trap cooled with liquid nitrogen, in 96% yield.…”

Section: Discussionmentioning

confidence: 99%

Specific13C Isotope Enrichment of Isoprene

2000

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Section: Discussionmentioning

confidence: 99%

Specific13C Isotope Enrichment of Isoprene

2000

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“…The substrate is contained in the inlet, and is heated under a vacuum of 10-2-10-3 Tom (1 Torr = 133.322 Pa= 1. 31 x bar) until it sublimes (or distils) into the furnace tube.…”

Section: Apparatusmentioning

confidence: 99%

Synthetic applications of flash vacuum pyrolysis

McNab¹

1996

Contemp. Org. Synth.

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“…Study on the pyrolytic behavior of micromolecule and speculation on the mechanism of the reaction might be helpful in its GC quantitative determination and the structural analysis of the relative polymers . One type of pyrolyisis mechanism involves unimolecular gas-phase elimination through a cyclic transition state, such as pyrolysis of carboxylates, xanthates, amine oxides, phosphate esters, β-hydroxy alkenes, etc. The second one involves free radical reaction, which occurs in pyrolysis of halides, alkanethiols, and certain carboxylic esters …”

Section: Introductionmentioning

confidence: 99%

The Pyrolytic Reaction of Ketonic Hydrazones fromS-Methyl Dithiocarbazate: A Combined Online GC-MS Pyrolysis and DFT Study

et al. 2009

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The gas-phase pyrolysis of ketonic hydrazones from S-methyl dithiocarbazate R(1)R(2)C=N-NHC(=S)SCH(3) (R(1), R(2) = alkyl or aryl) was investigated by online GC-MS pyrolysis and theoretical calculation. Both of these pyrolytic products, ascribed to methanethiol and the corresponding N-isothiocyanate imines, were detected in the total ion chromatography (TIC) of GC-MS. Calculation results exhibit two stable configurational structures for reactants (Re), which can interconvert with relatively low barriers (<78 kJ/mol). DFT calculations showed that the two unimolecular pyrolytic processes, a direct 1,2-elimination of CH(3)SH for syn-Re and a two-step reaction pathway for trans-Re involving tautomer interconversion followed by decomposition of CH(3)SH, are competitive in the reaction. Both syn-Re and trans-Re exhibit lower critical energies in the propagation step of the radical pyrolysis than that in the unimolecular pyrolysis process (187.76 kJ/mol via 131.91 kJ/mol for syn-Re, and 159.15 kJ/mol via 98.92 kJ/mol for trans-Re). However, much more energy is needed to excite the compound to produce the methylthio radical, with 262.03 and 253.60 kJ/mol for syn-Re and trans-Re, respectively. Therefore, the unimolecular pyrolysis rather than the radical one occurs in the condition of this study.

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Preparative flash vacuum thermolysis. Selective elimination of 6-chloro-1-hexene from esters of 6-chloro-1-hexanol with Schoenberg rearrangement of the S-methyl xanthate

Cited by 17 publications

References 2 publications

Specific13C Isotope Enrichment of Isoprene

Specific13C Isotope Enrichment of Isoprene

Synthetic applications of flash vacuum pyrolysis

The Pyrolytic Reaction of Ketonic Hydrazones fromS-Methyl Dithiocarbazate: A Combined Online GC-MS Pyrolysis and DFT Study

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