Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 1. Preparation of aliphatic and terminal alkynes

Aitken, R. A.; Atherton, J. Ian

doi:10.1039/p19940001281

Cited by 45 publications

(40 citation statements)

References 27 publications

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“…The phosphorus ylide Ph3PdCHC(dO)-4-MeC6H4 was prepared by the one-step method of Atherton 26 by reaction of Ph3PMe . 27 The ylide ligands were obtained by neutralization of the resulting zwitterion with aqueous solutions of sodium hydroxide and hexadecyltrimethylammonium hydroxide to a phenolphthalein end point.…”

Section: Methodsmentioning

confidence: 99%

Aqueous Homo- and Copolymerization of Ethylene by Neutral Nickel(II) Complexes

2001

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Aqueous coordination polymerization of ethylene by different neutral nickel(II) complexes [(X∧O)NiR(L)] (X ) P: type 1; X ) N: type 2) was investigated. With catalyst precursors of type 1, productivities and molecular weights were reduced by comparison to conventional polymerization in organic solvents. This effect results to a large extent from a lowering of the chain growth rate due to a low concentration of ethylene at the catalytically active centers in the aqueous polymerization. The catalysts are stable in water for hours. Stable latices of low-molecular-weight linear polyethylene were obtained with a hydrophilic complex of type 1 in an emulsion-type polymerization (Mw ca. 3 × 10 3 g mol -1 , Mw/Mn 2-3; solids content of polymer dispersions up to 10%). With complexes of type 2, productivities in aqueous ethylene polymerization were also reduced by comparison to polymerization in organic solvents. However, moderately branched semicrystalline polymers of high molecular weight are accessible (Mn > 10 4 g mol). Employing norbornene as a comonomer, high-molecular-weight amorphous copolymers were obtained in water as a reaction medium. Ethylene solubility in water-acetone mixtures was estimated experimentally.

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Section: Methodsmentioning

confidence: 99%

Aqueous Homo- and Copolymerization of Ethylene by Neutral Nickel(II) Complexes

2001

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“…Flash vacuum pyrolysis was performed using the set-up previously described. 18 Compounds 4, 4 5, 5 and 11 8,9 were prepared by the published methods.…”

Section: Methodsmentioning

confidence: 99%

New reactions and reactive intermediates in the pyrolysis of cyclic phosphonium ylides

Aitken¹,

Bjørnstad²,

Massil³

et al. 2017

Arkivoc

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Pyrolysis, either neat or in diphenyl ether solution, results in the conversion of both 4-triphenylphosphoranylidenetetrahydrofuran-2,3,5-trione and 4-triphenylphosphoranylidenetetrahydrothio--phene-2,3,5-trione into 3,5-bis(triphenylphosphoranylidene)cyclopentane-1,2,4-trione. These reactions involve extrusion of CO 2 or COS to give 3-triphenylphosphoranylidenecyclopropane-1,2-dione which further loses CO to give triphenylphosphoranylideneketene. The precise way in which these two reactive phosphorus compounds combine to give the observed product has been examined by chemical and isotopic labelling studies. Cyclotrimerization of triphenylphosphoranylideneketene upon thermolysis in diphenyl ether has also been observed for the first time. The erroneous literature interpretation of the 13 C NMR spectrum for triphenylphosphoranylideneketene is corrected.

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“…12 All pyrolyses were conducted at pressures in the range 10 -2 -10 -1 Torr. Under these conditions the contact time in the hot zone was estimated to be ≈10 ms.…”

Section: Flash Vacuum Pyrolysis Of Acetylenic Estersmentioning

confidence: 99%

Pyrolytic decomposition of simple acetylenic esters

Aitken¹,

Morrison²

2008

Arkivoc

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The mechanism of thermal decomposition of nine acetylenic esters has been examined under conditions of flash vacuum pyrolysis. The products formed may be explained by a series of wellprecedented steps involving such processes as ene reactions, alkyne to vinylidene rearrangements, carbene CH insertions, and fragmentation of 2,3-dihydrofuran-2-ones or 5,6-dihydropyran-2-ones with extrusion of CO and CO 2 respectively.

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Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 1. Preparation of aliphatic and terminal alkynes

Cited by 45 publications

References 27 publications

Aqueous Homo- and Copolymerization of Ethylene by Neutral Nickel(II) Complexes

Aqueous Homo- and Copolymerization of Ethylene by Neutral Nickel(II) Complexes

New reactions and reactive intermediates in the pyrolysis of cyclic phosphonium ylides

Pyrolytic decomposition of simple acetylenic esters

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