101-02-0Relevant articles and documents
The local structure of triphenyl phosphite studied using spallation neutron and high-energy X-ray diffraction
Mei, Qiang,Ghalsasi, Prasanna,Benmore, Chris J.,Yarger, Jeffery L.
, p. 20076 - 20082 (2004)
Spallation neutron and high-energy X-ray diffraction experiments have been performed to investigate the local structural changes in triphenyl phosphite (TPP) in the crystalline, glacial, glassy, and supercooled liquid phases. The hydrogen/deuterium first-order difference method shows a large increase in intensity due to additional hydrogen correlations in the crystalline spectra compared to the glass and supercooled liquid at a??3.0 and 3.4 Aì?. These features are shown to be largely due to inter-phenyl ring H-C/H interactions, which are probably associated in part with the formation of weak intermolecular hydrogen bonds. The high-energy X-ray diffraction data show a decrease in correlations at 3.12 Aì? which is attributed to changes in C-O/P intramolecular interactions between the glacial and crystalline forms. The structural evolution of the glacial state was also measured over time using total neutron diffraction. The largest structural differences between the early glacial and crystalline states are observed at 3.0 and 4.5 Aì?. Moreover, as the transformation progresses, the glacial spectra cannot be adequately described as a simple mixture of supercooled liquid and crystalline components. These results suggest that changes in molecular conformation and nearest-neighbor interactions are responsible for the existence of the glacial state.
LIGAND DISSOCIATION FROM MONO-SUBSTITUTED DERIVATIVES OF HEXACARBONYLCHROMIUM (Cr(CO)5L, L = P(C6H5)3, P(C4H9)3, P(OCH3)3, P(OC6H5)3, AND As(C6H5)3)
Wovkulich, Michael J.,Atwood, Jim D.
, p. 77 - 89 (1980)
The rates of dissociation of the unique ligand from Cr(CO)5L have been determined for L = P(C6H5)3, P(OC6H5)3, P(OCH3)3, and As(C6H5)3 by reaction with CO.The reactions were investigated from 80-140 deg C and activation parameters were determined.The rate
Ruthenium-catalyzed regio- And site-selective: Ortho C-H borylation of phenol derivatives
Homma, Yuki,Fukuda, Kazuishi,Iwasawa, Nobuharu,Takaya, Jun
, p. 10710 - 10713 (2020)
Efficient synthesis of o-borylphenols is achieved through the Ru-catalyzed regio- and site-selective sp2 C-H borylation of aryl diphenylphosphinites followed by removal of the phosphorus directing group. A successful application to aryl phosphites enables practical one-pot borylation of phenols, demonstrating high synthetic utility of this protocol.
Selective deoxygenation of aryl selenoxides by triaryl phosphites. Evidence for a concerted transformation
Stratakis, Manolis,Rabalakos, Constantinos,Sofikiti, Nikoletta
, p. 349 - 351 (2003)
Triaryl phosphites selectively reduce aryl selenoxides to selenides. The Hammett plot of the reactions of para-phenyl substituted triaryl phosphites with diphenyl selenoxide gave ρ=+2.3, whereas with bis(p-methoxyphenyl) selenoxide, ρ=-2.1. The results are consistent with a concerted mechanism for the oxygen transfer from Se to P.
Reactions of η2-Acyl Ligands in Tp'(CO)2Mo2-C(O)R> Complexes To Form Complexed Enolates and Enones, Allyls, and Alkyne Insertion Products
Rusik, C.A.,Collins, M.A.,Gamble, A.S.,Tonker, T.L.,Templeton, J.L.
, p. 2550 - 2560 (1989)
Elaboration of the η2-acyl ligand in hydridotris(3,5-dimethylpyrazolyl)borate (Tp') complexes of the type Tp'(CO)2Mo2-C(O)R> (R=Me, Et) has been accomplished by deprotonation to form enolates which react with electrophiles such as MeI, PhCH2Br, and PhCHO.Two enolate complexes, K and K, have been characterized by NMR spectroscopy.Photolysis of an acetonitrile solution of the achiral dicarbonyl reagent, Tp'(CO)2Mo2-C(O)R>, followed by addition of triphenyl phosphite forms racemic Tp'(CO)Mo.Excellent diastereoselectivity characterizes the addition of benzyl bromide (BzBr) to the enolate of Tp'(CO)Mo2-C(O)CH2CH3>; the Tp'(CO)Mo(η2-C(O)CHMeBz) product has been structurally characterized.Condensation of enolate complexes with benzaldehyde or benzophenone produces unsaturated η2-enone complexes.The structure of Tp'(CO)2Mo2-C(O)CH=CPh2> is reported.The η2-enone complexes undergo conjugate addition reactions to form saturated η2-acyl products, e.g., nucleophilic addition of MeLi to Tp'(CO)2Mo(η2-C(O)CH=CHPh) followed by acidification yields Tp'(CO)2Mo2-C(O)CH2CHMePh>.Heating Tp'(CO)2Mo(η2-C(O)CMe=CHPh) in toluene yields a ?-allyl complex, Tp'(CO)2Mo(η3-CH2CHCHPh).Insertion of alkynes (RCCR, R = Et or Ph) into the metal-carbon bond of the η2-acyl ligand in Tp'(CO)(CH3CN)Mo(η2-C(O)Et) under carbon monoxide forms oxametallacycles of the Tp'(CO)2Mo(CRCRC(O)Et) (R = Et or Ph).The structure of Tp'(CO)2Mo(CEtCEt(O)Et) has been determined.
The Synthesis and Mechanistic Considerations of a Series of Ammonium Monosubstituted H-Phosphonate Salts
Lee, Keng Lung,Feld, Joey,Hume, Paul,S?hnel, Tilo,Leitao, Erin
, p. 815 - 824 (2021)
A series of ammonium monosubstituted H-phosphonate salts were synthesized by combining H-phosphonate diesters with amines in the absence of solvent at 80 °C. Variation of the ester substituent and amine produced a range of ionic liquids with low melting points. The products and by-products were analyzed by spectroscopic and spectrometric techniques in order to get a better mechanistic picture of the dealkylation and formal dearylation observed. For dialkyl H-phosphonate diesters, (RO)2P(O)H (R=alkyl), the reaction proceeds via direct dealkylation with the reactivity increasing in the order R=iPr?1. For the diphenyl H-phosphonate diesters, (PhO)2P(O)H, the dearylation was found to proceed via phenol-assisted formation of a 5-coordinate intermediate, (PhO)3PH(OH), from which P(OPh)3 and water were eliminated. The presence of an equivalent of water then facilitated the formation of P(OH)2OPh and the amine, R'NH2, subsequently abstracted a proton from it to yield [(PhO)PH(O)O]-[R'NH3]+.
Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates
Hernández, Javier,Goycoolea, Francisco M.,Zepeda-Rivera, Denisse,Juárez-Onofre, Josué,Martínez, Karla,Lizardi, Jaime,Salas-Reyes, Magali,Gordillo, Bárbara,Velázquez-Contreras, Carlos,García-Barradas, Oscar,Cruz-Sánchez, Samuel,Domínguez, Zaira
, p. 2520 - 2528 (2006)
Six tris(aryloxy)phosphorothionates substituted in the para position of the aromatic rings were synthesized and studied by 31P NMR, X-ray diffraction techniques and ab initio calculations at a RHF/6-31G** level of theory, in order to find the main structural factors associated with the δ31P in these compounds. As the electron-withdrawing (EW) ability of the substituents was increased, an 'abnormal' shielding effect on δ31P of the arylphosphorothionates was observed. The analyses of the geometrical properties obtained through both experimental and theoretical methods showed that a propeller-type conformation is preferred for the arylphosphorothionates, except in the case of the tris(O-4-methylphenyl) phosphorothionate, since one of the aromatic rings is not rotated in the same direction as the other two in the solid state. The main features associated with the δ31P NMR of compounds 1-6 were a decrease of the averaged O-P-O angle and mainly the shortening of the PS bond length, which is consistent with an increase of the thiophosphoryl bond order as δ31P values go upfield. On the other hand, comparison of the experimental and calculated bond lengths and bond angles involving α bonded atoms to phosphorus of the six compounds suggested that stereoelectronic interactions of the type nπO-σ*PS, nπO- σ*P-OAr and nπS-σ* P-OAr could be present in the arylphosphorothionates 1-6.
ELECTROCHEMICALLY INDUCED PROCESSES OF FORMATION OF PHOSPHORUS ACID DERIVATIVES. 4. SYNTHESIS OF TRIALKYL PHOSPHATES FROM WHITE PHOSPHORUS
Budnikova, Yu. G.,Kargin, Yu. M.,Zaripov, I. M.,Romakhin, A. S.,Ignat'ev, Yu. A.,et al.
, p. 1585 - 1588 (1992)
The products of electrolysis in dipolar aprotic solvents on the background of tetraethylammonium iodide in the presence of white phosphorus are trialkyl phosphite (the primary product after splitting of all the P - P bonds in the phosphoric oligomers) and triaryl phosphate.It was found that the formation of triaryl phosphate from white phosphorus proceeds by way of electrochemical reduction of pentaaroxyphosphorane - an intermediate product of the reaction of triaryl phosphite with iodine and phenol.A strong dependence of the yields and distribution of the products on the composition of the electrolyte has been observed. Keywords: white phosphorus, electrosynthesis, triaryl phosphate.
A novel mild deprotection method for phosphine-boranes
Schroeder, Marc,Nozaki, Kyoko,Hiyama, Tamejiro
, p. 1931 - 1932 (2004)
Treatment of phosphine-boranes with molecular sieves 4A in a mixture of an ethereal solvent and an alcohol provided deprotected free phosphines in quantitative yields. The phosphines can be obtained by a simple filtration/crystallization procedure in most cases. It should be noted that the current method is successfully applied to the deprotection of a phosphite-borane for the first time.
Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus
Zhang, Yue,Cai, Ziman,Chi, Yangyang,Zeng, Xiangzhe,Chen, Shuanghui,Liu, Yan,Tang, Guo,Zhao, Yufen
supporting information, p. 5158 - 5163 (2021/07/20)
Industrially important triaryl phosphites, traditionally prepared from PCl3, have been synthesized by a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen- and transition metal-free way to these compounds. Subsequent oxidation of triaryl phosphites produces triaryl phosphates and triaryl thiophosphates. Phosphorotrithioates are also prepared efficiently from aromatic thiols and aliphatic thiols.
