An Improved Method for the Preparation of Phenylphosphine and a Procedure for the Removal of the Toxic Vapors Produced

Taylor, Roger S.; Kolodny, Robert A.

doi:10.1080/00945717308081520

Cited by 19 publications

(6 citation statements)

References 6 publications

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“…[3,5-(CF 3 ) 2 C 6 H 3 ] 2 PH (4). Following a procedure similar to that used for diphenylphosphine, a solution of [3,5-(CF 3 ) 2 C 6 H 3 ] 2 PCl (17.5 g, 0.036 mol) in ether (200 mL) was slowly added to a suspension of LiAlH 4 (1.35 g, 0.036 mol) in ether (250 mL) at −78 °C. The pale brown slurry was refluxed for 2 h, cooled to 0 °C, and hydrolyzed with 10% aqueous NH 4 Cl.…”

Section: Methodsmentioning

confidence: 99%

Electron Withdrawing Substituents on Equatorial and Apical Phosphines Have Opposite Effects on the Regioselectivity of Rhodium Catalyzed Hydroformylation

et al. 1997

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The electronic effects of electron withdrawing aryl substituents on equatorial and apical diphosphines were investigated. Chelating diphosphines designed to coordinate in diequatorial or in apical−equatorial positions were synthesized, and their effects on the regioselectivity of rhodium catalyzed 1-hexene hydroformylation were observed. Only diequatorial coordination was observed for 2,2‘-bis[(diphenylphosphino)methyl]-1,1‘-biphenyl (BISBI) complexes (BISBI)Ir(CO)2H (8) and [BISBI-(3,5-CF3)]Ir(CO)2H (10), and only apical−equatorial coordination was seen for 1,2-bis(diphenylphosphino)ethane (DIPHOS) complexes (DIPHOS)Ir(CO)2H (14) and [DIPHOS-(3,5-CF3)]Ir(CO)2H (15). For the trans-1,2-bis[(diphenylphosphino)methyl]cyclopropane (T-BDCP) complexes, a mixture of diequatorial and apical−equatorial complexes was seen. For (T-BDCP)Ir(CO)2H (12), 12-ae was favored over 12-ee by 63:37, but for [T-BDCP-(3,5-CF3)]Ir(CO)2H (13) the conformational preference was reversed and a 10:90 ratio of 13-ae:13-ee was seen. The electron withdrawing groups in the equatorial positions of BISBI-(3,5-CF3) (1) and T-BDCP-(3,5-CF3) (2) led to an increase in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation. However, electron withdrawing aryl substituents in the apical positions of DIPHOS-(3,5-CF3) (3) led to a decrease in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation.

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Section: Methodsmentioning

confidence: 99%

Electron Withdrawing Substituents on Equatorial and Apical Phosphines Have Opposite Effects on the Regioselectivity of Rhodium Catalyzed Hydroformylation

et al. 1997

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“…We suggest that the lack of vital chemical details (i.e., knowledge of the species that are present) and the lack of chemical sense in reported quench and workup procedures are the primary causes of low yields in typical reductions. For example, some reported workups involve aqueous quenches ranging from 6 M HCl , (conditions that protonate many phosphines) to 2 M NaOH (conditions that cause significant gelation of the aqueous workup mixture) to no quenching but with a dangerous distillation of product off of residual neat LiAlH 4 . − ( Note that the direct distillation of phosphines off of unquenched LiAlH 4 is extremely dangerous and should never be attempted.)…”

Section: Resultsmentioning

confidence: 99%

A Universally Applicable Methodology for the Gram-Scale Synthesis of Primary, Secondary, and Tertiary Phosphines

2018

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Although organophosphine syntheses have been known for the better part of a century, the synthesis of phosphines still represents an arduous task for even veteran synthetic chemists. Phosphines as a class of compounds vary greatly in their air sensitivity, and the misconception that it is trivial or even easy for a novice chemist to attempt a seemingly straightforward synthesis can have disastrous results. To simplify the task, we have previously developed a methodology that uses benchtop intermediates to access a wide variety of phosphine oxides (an immediate precursor to phosphines). This synthetic approach saves the air-free handling until the last step (reduction to and isolation of the phosphine). Presented herein is a complete general procedure for the facile reduction of phosphonates, phosphinates, and phosphine oxides to primary, secondary, and tertiary phosphines using aluminum hydride reducing agents. The electrophilic reducing agents ( i Bu)2AlH and AlH3 were determined to be vastly superior to LiAlH4 for reduction selectivity and reactivity. Notably, it was determined that AlH3 is capable of reducing the exceptionally resistant tricyclohexylphosphine oxide, even though LiAlH4 and ( i Bu)2AlH were not. Using this new procedure, gram-scale reactions to synthesize a representative range of primary, secondary, and tertiary phosphines (including volatile phosphines) were achieved reproducibly with excellent yields and unmatched purity without the need for a purification step.

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“…Starting materials such as 1 [3], 2 [4], P(SiMe 3 ) 3 [25], P(SnMe 3 ) 3 , Ph 2 PSnMe 3 [26], LiPPh 2 [27], PhPH 2 [28], PhAsH 2 [29], Ph 2 AsH [30] were prepared as described. Ph 2 PH was used as a commercial sample.…”

Section: Methodsmentioning

confidence: 99%

Novel Organo-Substituted 2,5-Dihydro-1-Azoniaand -1-Phosphonia-2-Stanna-5-Boratoles

Wrackmeyer¹,

Kerschl²,

Maisel³

1998

Main Group Metal Chemistry

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E)-2-(chlorodimethylstannyl)-3-diethylboryl-pent-2-ene 1 reacts with methylbis(trimethylstannyl)amine and tris(trimethylstannyl)amine to give the new 2,5-dihydro-1-azonia-2-stanna-5-boratoles 3 and 4, respectively, of which 4 rearranges irreversibly into the 1-aza-2-stanna-5-bora-cyclopentane derivative 5. The reaction of 1 with lithium bis(trimethylsilyl)phosphide affords the 2,5-dihydro-1-phosphonia-2-stanna-5-boratole 8 which is fluxional with respect to the coordinative P-B bond. In a similar way, the reaction of 1 with lithium diphenylphosphide gives the analogous derivative 9 which however, posseses a strong coordinative P-B bond. Compound 9 is also accessible from the reaction of the 1,5-dihydro-1,1,4,5,5-pentaethyl-2,2,3-trimethyl-1-azonia-2-stanna-5-boratole 2 with diphenylphosphane. All products were characterised by 1 H, 11 B, 13 C, 14 N, 29 Si, 31 P and 119 Sn NMR data. Several absolute signs of coupling constants were determined by appropriate 2D heteronuclear shift correlations. NMR data of 8 were compared with those of Me 3 SnP(SiMe 3 ) 2 , determined here for the first time. INTRODUCTION1,1-Organoboration of 1-alkynyltin compounds [1,2] has opened the route to many useful heterocyclic compounds or to their precursors. Thus, (E)-2-(chlorodimethylstannyl)-3-diethylboryl-pent-2-ene 1 [3] and 1,1,4,5,5-pentaethyl-2,2,3-trimethyl-1-azonia-2-stanna-5-boratole 2 [4] are readily available (Scheme 1), and the presence of numerous reactive sites is promising for further useful transformations of these compounds [5],

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An Improved Method for the Preparation of Phenylphosphine and a Procedure for the Removal of the Toxic Vapors Produced

Cited by 19 publications

References 6 publications

Electron Withdrawing Substituents on Equatorial and Apical Phosphines Have Opposite Effects on the Regioselectivity of Rhodium Catalyzed Hydroformylation

Electron Withdrawing Substituents on Equatorial and Apical Phosphines Have Opposite Effects on the Regioselectivity of Rhodium Catalyzed Hydroformylation

A Universally Applicable Methodology for the Gram-Scale Synthesis of Primary, Secondary, and Tertiary Phosphines

Novel Organo-Substituted 2,5-Dihydro-1-Azoniaand -1-Phosphonia-2-Stanna-5-Boratoles

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