<b>Ylid Intermediate in the Reaction of Triphenylphosphine with Carbon Tetrachloride</b>

Rabinowitz, Robert; Marcus, R. A.

doi:10.1021/ja00866a056

Cited by 144 publications

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“…9-Dichloroniethylenefluorene, C,,H,Cl,, was prepared by the reaction between 9-fluorenone, carbon tetrachloride and triphenylphosphine. 20 The product was recrystallized from methanol; m.p. 134°C.…”

Section: O N C L U S I O Nmentioning

confidence: 99%

The mass spectra of some chlorinated aromatic pesticidal compounds

Sphon

Damico

1970

Org. Mass Spectrom.

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Mass spectral studies of some chlorinated aromatic pesticidal compounds are reported. The compounds studied include substituted diphenyl derivatives of methane, ethene and methanol.The diphenylmethanes are characterized by a relatively intense peak at m/e 165. Comparison of their low voltage spectra with 9-dichloromethylfluorene indicates that this ion has a fluorenyl ion structure.The structure of the base peak (m/e 246) of the diphenylethenes was investigated by comparing competitive metastable transitions with 9-dichloromethylenefluorene and utilizing defocusing metastables. Additional studies of model compounds suggest that the m/e 246 ion is very complex and is probably comprised of a number of structures.The mass spectra of the diphenylmethanols are significantly different from the other two groups. The hydroxyl group markedly affects the fragmentation process for these compounds; the characteristic peak is presumably the chlorobenzoyl ion and is probably precursor for other fragment ions.Mass spectral correlations of pesticidal compounds of similar structure are needed to obtain enough background to facilitate interpretation of the mass spectra of their metabolites. Furthermore, such studies make feasible the identification of characteristic product ions formed by rearrangement processes during ionization of organic molecules in the gas phase. This information can be a nucleus for correlating the other significant mass spectral data of an unknown compound. Intensive studies of carbamates,' organophosphorus2 and bridged polycyclic chlorinated pesticida13 compounds were invaluable in identifying metabolites of the aforementioned pesticide^.'.^.^ The compounds in this

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Section: O N C L U S I O Nmentioning

confidence: 99%

The mass spectra of some chlorinated aromatic pesticidal compounds

Sphon

Damico

1970

Org. Mass Spectrom.

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“…methylene phosphorus compound 2, by analogy with the triphenylphosphine system (17). Extended boiling of the red phosphole -carbon tetrachloride system in the presence of benzaldehyde, a Wittigtype substrate added to trap any potential phosphorane, only returned unchanged starting materials.…”

Section: Electron Spin Resonance Experimentsmentioning

confidence: 99%

Thermochromism of 1,2,5-triphenylphosphole and the formation of 1,1,2,2-tetrachloro-1,2-diphenylethane from α,α,α-trichlorotoluene

Hocking¹,

Smyth²

1982

Can. J. Chem.

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MARTIN B. HOCKING and TREVOR A. SMYTH. Can. J. Chem. 60, 138 (1982). On boiling a yellow solution of 1.2.5-triphenylphosphole in carbon tetrachloride the colour changes to red, reverting to yellow on cooling. This reversible colour change has been conducted in the presence of various additives in an attempt to determine the cause of the colour change. Boiling 1,2,5-triphenylphosphole in a,a,a-trichlorotoluene similarly showed a colour change and gave a coupling product of the solvent, 1, I ,2,2-tetrachloro-1-2-diphenylethane. From this evidence and related synthetic, nmr, and esr experiments it is proposed that the colour change of the former system arises from the incipient formation of a phospholetrichloromethide salt with carbon tetrachloride. With trichlorotoluene the phosphole undergoes more substantive formation of dichlorophenylmethide and possibly chloride salts which undergo further reaction to the observed coupling product. MARTIN B. HOCKING et TREVOR A. SMYTH. Can. J. Chem. 60, 138 (1982). Une solution de triphenyl-l,2,5-phosphole dans le tetrachlorure de carbone portee a ebullition devient rouge, et la couleur passe du rouge au jaune lors du refroidissement. On a realise ce changement reversible de couleur en presence de plusieurs additifs dans le but d'en determiner la cause. Le triphenyl-l,2,5-phosphole dans le trichloro-a,a,a-toluene porte a ebullition presente les m h e s caracteristiques et donne un produit de couplage avec le solvant; le tetrachloro-1,1,2,2 diphenyl-l,2-ethane. A partir de ces observations et apartir des experiences de synthese, de rmn et de rpe, on propose que le changement de couleur du premier systeme provient de la formation d'un sel phosphole-trichloromethylure par reaction avec le tetrachlorure de carbone. Dans le cas du trichlorotoluene. le phosphole conduit a la formation plus appreciable de dichlorophenylmethylure et eventuellement de chlorures qui, par des reactions subsequentes, conduisent au produit de couplage observe.[Traduit par le journal] Introduction Thermochromism, or a reversible colour change obtained on heating (or cooling) a substance from room temperature, has been relatively recently reviewed (1-3). More recently than these summaries and related to this study, the thermochromism demonstrated by solutions of highly arylated pyr-

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“…Compound 7-d6 was prepared from 5-dG by a reaction with carbon tetrachloride and triphenylphosphine according to the method of Rabinowitz and Marcus (29). Thus, a solution of 0.48 g of 5-dG (3 mmol) and 1.6 g of triphenylphosphine in 30 ml of carbon tetrachloride was heated to 80°C for 10 h. After work-up (29), 0.35 g of crude product was obtained.…”

Section: Preparation Of 6-d6 and 7-d6 (Sclzeme I )mentioning

confidence: 99%

Nuclear magnetic resonance investigation of the conformational dynamic properties of benzocycloheptenones and related compounds

Bodennec¹,

St‐Jacques²

1977

Can. J. Chem.

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Free energy barriers for ring inversion were determined from dnmr studies of 3,4-benzo-cycloheptenone (4) and for deuterated derivatives 6 and 7 of 4,5-benzocycloheptenone (5). The investigation of 2,3-benzocycloheptenone (3) revealed negative results. The magnitude of ΔG≠ for 4 and the trend observed for 5, 6, and 7 strongly suggest that the chair conformation of these molecules interconverts through a wagging motion of the C(5) end of the benzocycloheptene seven-membered ring.

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Ylid Intermediate in the Reaction of Triphenylphosphine with Carbon Tetrachloride

Cited by 144 publications

References 0 publications

The mass spectra of some chlorinated aromatic pesticidal compounds

The mass spectra of some chlorinated aromatic pesticidal compounds

Thermochromism of 1,2,5-triphenylphosphole and the formation of 1,1,2,2-tetrachloro-1,2-diphenylethane from α,α,α-trichlorotoluene

Nuclear magnetic resonance investigation of the conformational dynamic properties of benzocycloheptenones and related compounds

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