1769-51-3

Basic information

• Product Name: 4,4'-Phosphinediylbis(N,N-diMethylaniline)
• Synonyms: 4,4'-Phosphinediylbis(N,N-diMethylaniline)
• CAS NO: 1769-51-3
• Molecular Weight: 272.33
• Mol File: 1769-51-3.mol

Chemical Properties

• CAS DataBase Reference: 4,4'-Phosphinediylbis(N,N-diMethylaniline)(CAS DataBase Reference)
• NIST Chemistry Reference: 4,4'-Phosphinediylbis(N,N-diMethylaniline)(1769-51-3)
• EPA Substance Registry System: 4,4'-Phosphinediylbis(N,N-diMethylaniline)(1769-51-3)

Safety Data

• Hazardous Substances Data: 1769-51-3(Hazardous Substances Data)

Upstream product

• 7439-52-3 bis(p-(dimethylamino)phenyl)phosphonic acid 
• 120011-50-9 C₂₃H₂₇N₂P 
• 84127-06-0 bis[4-(N,N-dimethylaminephenyl)]phosphine oxide 
• 7353-91-5 4-dimethylaminophenylmagnesium bromide 
• 13190-50-6 4-dimethylaminophenyllithium 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 698-69-1 4-chloro-N,N-dimethylaniline 

Downstream Products

• 123135-89-7 (4R,5R)-4-diphenylphosphinomethyl-5-bis(4-N,N-dimethylaminophenyl)phosphinomethyl-2,2-dimethyl-1,3-dioxolane 
• 123135-90-0 C₃₇H₄₆N₂O₂P₂ 
• 122712-88-3 (-)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bisbutane 
• 694514-81-3 N,N-bis{2-[di-(4-dimethylaminophenyl)phosphino]ethyl}-N-tert-butylamine 
• 694514-80-2 N,N-bis{2-[di-(4-dimethylaminophenyl)phosphino]ethyl}-N-p-anisidine 
• 125653-57-8 (2S,4R)-N-tert.-butoxycarbonyl-2-bis(4-dimethylaminophenyl)phosphinomethyl-4-tosyloxypyrrolidine 
• 1370793-50-2 1,1,1-tris{[bis(4-dimethylaminophenyl)phosphino]methyl}ethane 

Relevant articles and documents

Synthesis and Characterization of Manganese(I) Carbonyl Complexes of the Type [(OC)4Mn{μ-P(R)Aryl}]2

Metalation of secondary phosphanes HPRR′ [R = R′ = C6H4-4-Me, C6H3-3,5-Me2 (3), C6H4-4-NMe2 (4); R/R′ = Ph/cHex] with Mn2(CO)10 in boiling xylene

Rapid Metal-Free Formation of Free Phosphines from Phosphine Oxides

A rapid method for the reduction of secondary phosphine oxides under mild conditions has been developed, allowing simple isolation of the corresponding free phosphines. The methodology involves the use of pinacol borane (HBpin) to effect the reduction while circumventing the formation of a phosphine borane adduct, as is usually the case with various other commonly used borane reducing agents such as borane tetrahydrofuran complex (BH3?THF) and borane dimethyl sulfide complex (BH3?SMe2). In addition, this methodology requires only a small excess of reducing agent and therefore compares favourably not just with other borane reductants that do not require a metal co-catalyst, but also with silane and aluminium based reagents. (Figure presented.).

Facile, Catalytic Dehydrocoupling of Phosphines Using β-Diketiminate Iron(II) Complexes

Catalytic dehydrocoupling of primary and secondary phosphines has been achieved for the first time using an iron pre-catalyst. The reaction proceeds under mild reaction conditions and is successful with a range of diarylphosphines. A proton acceptor is not needed for the transformation to take place, but addition of 1-hexene does allow for turnover at 50°C. The catalytic system developed also facilitates the dehydrocoupling of phenylphosphane and dicyclohexylphosphane. A change in solvent switches off dehydrocoupling to allow hydrophosphination of alkenes.

Selective dehydrocoupling of phosphines by lithium chloride carbenoids

The development of a simple, transition-metal-free approach for the formation of phosphorus-phosphorus bonds through dehydrocoupling of phosphines is presented. The reaction is mediated by electronically stabilized lithium chloride carbenoids and affords a variety of different diphosphines under mild reaction conditions. The developed protocol is simple and highly efficient and allows the isolation of novel functionalized diphosphines in high yields.

Selective formation of a polar incomplete coordination cage induced by remote ligand substituents

Instead of highly symmetrical T-symmetry cages common in self-assembly, the p-NMe2-substituted triphosphine CH3C{CH 2P(4-C6H4NMe2)3 gives open, polar C3 symmetry cages [Ag6(triphos) 4X3]3+ which lack one of the expected face-capping anions; despite its subtlety this difference occurs selectively in solution and two examples have been crystallographically characterised.

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 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).

Reductive cleavage of the carbon-phosphorus bond with alkali metals. II. Cleavage of mixed functionalized triarylphosphines; Birch reduction of arylphosphines

The reductive cleavage of mixed ortho- and para-functionalized triarylphosphines with Na/NH3 and Li/THF depends strongly on the nature and positions of the substituents.Reduction occurs readily with phosphines PhAr2P (4, 6 and 9) and Ph2ArP 19 when the corresponding phosphine Ar3P is not reduced.Cleavage of para-substituted compounds 7 and 9 leads to mixtures of secondary phosphines.By contrast, cleavage of mixed ortho-substituted triphenylphosphines is very selective.The functionalized phenyl group is split off in high yield when it carries CH3, (CH3)2N and CH3O substituents (2, 3, 5, 6, 8, 10, 11, 13, 14, 17, 19, 24, 25).Reaction of 4 is not selective due to loss of methoxy groups (1, 15, 16).The reactions of bis- and tris(diphenylphosphino)benzenes with Li/THF leads predominantly to cleavage of the diphenylphosphino group from the respective substrates.In a number of cases, the product of a Birch reduction with an isolated diene system is formed in NH3 (1, 9, 12, 21, 23) via a phosphino-stabilized cyclohexadienyl anion.This reduction does not occur in the aprotic solvent THF.Base-catalyzed isomerization leads to a conjugated double-bond system with a vinylphosphine moiety.We also report interesting large 4J(PP) couplings in 1,3-diphosphinobenzenes and complicated 13C resonances of para-substituted phosphines.

Chiral phosphines

Novel substituted diphenyl tertiary phosphines of a pyrrolidine carboxylic acid derivative and their use as catalysts in the enantioselective hydrogenation of α-keto-β,β-dimethyl-γ-butyrolactone.