6002-31-9

Usage

Uses

Used in Chemical Synthesis:
TERT-BUTYLPHENYLPHOSPHINE 97 is used as a reactant for [application type] in the following applications:
1. Reactant in the reaction with electron deficient boranes, which is crucial for the synthesis of various organic compounds.
2. Reactant in platinum-catalyzed asymmetric alkylation of secondary phosphines, a process that contributes to the production of chiral compounds with potential applications in pharmaceuticals and agrochemicals.
3. Reactant for the preparation of "chiral-at-Ru" secondary phosphine complexes, which are valuable in homogeneous catalysis and can be used to create enantioselective catalysts for asymmetric reactions.

Upstream product

• 507-20-0 tertiary butyl chloride 
• 644-97-3 Dichlorophenylphosphine 
• 108-86-1 bromobenzene 
• 67033-70-9 tert-butyl(trimethylsilyl)phosphine 
• 29949-69-7 tert-butylchlorophenylphosphane 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 1079-66-9 chloro-diphenylphosphine 
• 172487-18-2 ethyl Phenylphosphinate 
• 98976-30-8 tert-Butylphenylphosphine oxide 
• 62839-84-3 tert.-butyl-phenylthiophosphinic chloride 
• 32673-25-9 di(tertbutyl)phenylphosphine 

Downstream Products

• 66830-56-6 dimethylaminomethyl-tert-butylphenylphosphine 
• 7621-16-1 (+/-)-tert-butylmethylphenylphosphine 
• 142132-64-7 C₁₃H₂₁Br₂P 
• 142132-65-8 C₁₃H₂₁I₂P 
• 1125780-68-8 (rac)-3-[(tert-butyl)(phenyl)phosphinoyl]pyridine 
• 93634-81-2 (tert-butyl)(bromo)(phenyl)phosphine 
• 639463-05-1 (+/-)-tert-butylphenylphosphine borane 
• 1383686-35-8 (+/-)-2-(bromophenyl)(tert-butyl)phenylphosphine borane 
• 1144113-71-2 (t-Bu)(Ph)PH(C₆F₄)BF(C₆F₅)2 
• 215729-87-6 (C₅H₅)Fe(CO)2(PH(C₆H₅)(C(CH₃)3))⁽¹⁺⁾*BF₄^(1-)=[(C₅H₅)Fe(CO)2(PH(C₆H₅)(C(CH₃)3))]BF₄ 

Relevant academic research and scientific papers

Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl, and amino substituents

We present the comprehensive study of diphosphanes with diversified substituents regarding their syntheses, structures, and properties. To this end, we have synthesized a series of novel unsymmetrical alkyl, aryl and amino-substituted diphosphanes of the general formula R1R2P-PR3R4 (where R1, R2, R3, R4 = tBu, Ph, Et2N or iPr2N) via a salt metathesis reaction of halophosphanes with metal phosphides in high yield. We vastly expanded this group of compounds by obtaining the first mono- A nd tri-amino-substituted systems. The structures of the isolated compounds were characterized by NMR spectroscopy and X-ray diffraction. The isolated unsymmetrical diphosphanes have no tendency to rearrange to the corresponding symmetrical species. Additionally, we proposed the general classification of diphosphanes based on the number of different groups attached to phosphorus atoms and their distribution within a molecule. To investigate the impact of substituents on the properties of P-centers and a molecule as a whole, we conducted a DFT study on the electronic and steric properties of the obtained systems. The experimental and theoretical results can be very useful for designing P-P systems with desired properties.

Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes

Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.

Synthesis of building blocks for the development of the SUPRAPhos ligand library and examples of their application in catalysis

We have previously introduced the SUPRAPhos ligand library, which is based on components that are self-assembled through nitrogen-zinc interactions, and report here an extension of this library, which widens the scope for application in asymmetric homogeneous catalysis. For example, we report the synthesis of phosphorus amidite appended porphyrins and building blocks with stereogenic centers at the phosphorus. With the new building blocks described in this paper we can form a 450-membered SUPRAPhos library, which is based on 45 building blocks (30 pyridyl phosphorus ligands and 15 complementary porphyrin-appended phosphorus ligands). Examples of the use of members of the library in the rhodium-catalyzed asymmetric hydroformylation of styrene are included. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

A METHOD FOR GENERATING SECONDARY PHOSPHINES

This invention provides a method for generating secondary phosphines from secondary phosphine oxides in the presence of a reducing agent, such as diisobutylaluminum hydride (DIBAL-H), triisobutyldialuminoxane, triisobutylaluminum, tetraisobutyldialuminoxane, or another reducing agent comprising: (i) an R1R2AIH moiety, wherein R1 and R2 are each an alkyl species or oxygen, and wherein at least one of R1 or R2 comprises at least 2 carbon atoms, or (ii) an R1R2R3AI moiety, wherein R1, R2, and R3 are not hydrogen, and wherein at least one of R1, R2, and R3 is an alkyl species comprising a β-hydrogen, not including triethylaluminum. Preferred reducing agents for the present invention include: diisobutylaluminum hydride, triisobutyldialiuminoxane, triisobutylaluminum, tetraisobutyldialuminoxane, and combinations thereof.

A superior method for the reduction of secondary phosphine oxides

(Chemical Equation Presented) Diisobutylaluminum hydride (DIBAL-H) and triisobutylaluminum have been found to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70°C. This new reduction has distinct advantages over existing technologies.

Reductive cleavage of the halogen-phosphorus and sulfur-phosphorus bonds with alkali metals

The reduction of thiophosphorus acid chlorides with alkali metals (Na, K) in liq. NH3/THF solution, potassium anthracenide, and potassium napththalenide was investigated. It was found that these types of phosphorus compounds easily undergo reduction to 〉P-S- anions. It was also demonstrated that 〉P-O- and 〉P-S- anions as well very efficiently undergo sulfurization with elementary sulfur in liquid ammonia to yield 〉P(O)S- and 〉P(S)S- anions, respectively.

Reductive cleavage of the carbon-phosphorus bond with alkali metals. III Reactions of arylalkylphosphines

The reductive cleavage of phenylalkylphosphines Ph2PR, PhPR2 (R = Bu, iPr) with Na/NH3 is unselective; both phenyl and alkyl groups can be cleavaged and Birch reduction may occur.Reaction of Ph2tBuP gives a high yield of diphenylphosphide.Polar groups (CO2Na, SO3Na) at the ω position of primary alkyl groups may lead to an increase in selectivity; Birch reduction is suppressed and a functionalised secondary phosphide is obtained.From diarylbenzyl- and diarylallylphosphines, the benzyl and allyl groups are selectively removed; Ar2PH and ArRPH are formed in high yield after hydrolytic work-up unless the aryl group bears F, CF3 or (CH3)2N substituents.From the reaction mixture of Ph2PCH2Ph we have isolated 1,2-diphenylethane. 2-Methoxyphenyl and 2,6-dimethoxyphenyl groups are selectively removed from Ar2BuP, ArPhBuP and Ar2P(CH2)3PAr2, forming ArBuPH, PhBuPH and ArP(H)(CH2)3(H)PAr, respectively.A double-cleavage reaction of Ar2RP may occur in low yield. 2,6-(dimethoxyphenyl-dibutylphosphine gives dibutylphosphine in moderate yield.When compounds with a 2,6-dimethoxyphenyl moiety are allowed to react with Li/THF, removal of a methyl group leads to novel phosphinophenols.It is concluded that cleavage of alkyl groups R selectively occurs when R radical is relatively stable (tBu, PhCH2> iPr > Bu).

SYNTHESIS OF ASYMMETRIC SECONDARY PHOSPHINES BY THE CROSS COUPLING OF ARYL HALIDES WITH SILYLPHOSPHINES

The cross coupling of aryl halides with alkyl(trimethylsilyl)phosphines catalyzed by zero-valent palladium complexes yields secondary alkylarylphosphoranes containing both electron-donor and electron-withdrawing substituents in the aromatic ring.The rever

A nuclear magnetic resonance investigation of the bonding in fourth-group phenylphosphines

The compounds (CH3)3MPHC6H5 where M = C, Si, and Sn have been synthesized, and J(31P-1H) values recorded. Infrared assignments in the region 4000-400 cm-1 are also presented. Controlled oxidation of the tin compound yields (CH3)3-SnOPHC6H5 as established by 31P couplings which also give information concerning the exchange of groups at phosphorus in mixtures of the two tin compounds. The one-bond 31P-1H couplings have been interpreted in terms of a pyramidal arrangement of bonds at phosphorus.