Reaction Of Diphenyl Research Articles

Tandem Cyclization Reaction of Diphenyl 3,5-Di-tert-butyl-p-quinone Phosphonate Catalyzed by Trifluoromethanesulfonic Acid: Introduce a Comprehensive Experiment of Organic Chemistry

Tandem Cyclization Reaction of Diphenyl 3,5-Di-tert-butyl-p-quinone Phosphonate Catalyzed by Trifluoromethanesulfonic Acid: Introduce a Comprehensive Experiment of Organic Chemistry

Heterobimetallic PtII–AgI complex supported by diphenyl(2-pyrimidyl)phosphine: Synthesis and thermochromic photoluminescence

The reaction of diphenyl(2-pyrimidyl)phosphine (L) derived complex [Pt(L)2Cl2] with AgNO3 (1:3 M ratio, respectively) results in assembly of heterobimetallic complex [AgPt(L)2(NO3)3], wherein Pt → Ag dative bond of 2.9088(2) Å is formed. This complex features thermochromic photoluminescence that appears as ~40 nm red-shift of an emission maximum upon cooling from 300 to 77 K. The related PdII/AgI complex, [AgPd(L)2(NO3)3], showing Pd → Ag dative bond of 2.9098(5) Å, has also been synthesized and structurally attested.

Reactions of [(3,5-Di-tert-butyl-4-oxocyclohexa-2,5-dien- 1-ylidene)methyl]phosphonates with Phenols

Dialkyl [(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phosphonates reacted with phenol and benzenediols in the presence of trifluoromethanesulfonic acid to give products of electrophilic substitution in the benzene ring, the corresponding diarylmethylphosphonates or [phenylenebis(arylmethylene)]- diphosphonates. The reaction of diphenyl [(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phosphonate with 2-methylbenzene-1,3-diol at a ratio of 1: 1 afforded 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-6-hydroxy-7-methyl-2-phenoxy-2,3-dihydro-1,2λ5-benzoxaphosphol-6-one.

Reactions of diphenyl- and diethylphosphinodithioic acids with N-alkyl-2-haloaldimines in the synthesis of new P,S- and N,P,S-containing organic compounds

Diphenyl- and diethylphosphinodithioic acids, unlike the stronger О,О-dialkyl phosphorodithioic acids, react with N-alkyl-2-chloroaldimines at a 1: 1 ratio, following two pathways: nucleophilic substitution of chlorine in the primary salt by the phosphinothioylthio group and reduction of the cation of the primary salt on the C–Cl bond. Nucleophilic substitution contributes more in the case of the stronger diphenylphosphinodithioic acid, as well as in the case of a large excess of the starting chlorimine. N-Alkyl-2-bromoaldimines react only by a single pathway, specifically, reducing the cation of the primary iminium salt on the C–Br bond. New iminium salts were synthesized and converted into the corresponding aldehydes and imines. The aldehydes synthesized were converted into acetals and five-membered heterocyclic compounds.

Chlorido{1-[(dimethylamino)methyl]ferrocenyl-κ2C2,N}(triphenylstibine-κSb)palladium(II)

In the title compound, [FePdCl(C5H5)(C8H11N)(C18H15Sb)], obtained by reaction of diphen­yl(N,N-di­methyl­amino­methyl­ferrocen­yl)stibine with sodium tetra­chlorido­palladate(II) in acetone, the PdII atom is coordinated in a slightly distorted square-planar geometry by a C atom of the ferrocenyl ring, and by N, Cl and Sb atoms. The Sb and N atoms are trans to each other.

β-Diphenylphosphorylated alkanones and related compounds: synthesis and structure

The reactions of diphenyl(diisopropyl)chlorophosphine with arylidene(heteroarylidene)-acetones and 3-benzylidenepentane-2,4-dione in the presence of acetic acid proceed at a high rate at room temperature to afford the corresponding β-diorganylphosphorylated alkanones and alkanediones in high yields. The reaction of diphenylchlorophosphine with 4-methoxybut-3-en-2-one and dibenzylideneacetone carried out under similar conditions at the equimolar reagent ratio can serve as a convenient method for the synthesis of unique β-diphenylphosphorylalkenones. The structures of compounds obtained were established by IR, Raman, and NMR spectroscopy and X-ray diffraction.

Synthesis and Electrophilic Cyclization Reactions of Diphenyl 3-Methylpenta-1,2,4-trienyl Phosphine Oxide

Diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide can be readily prepared via an atom-economical [2,3]-sigmatropic rearrangement of the mediated alkenynyl phosphinite formed in situ by reaction of 3-methylpent-1-en-4-yn-3-ol with diphenylchlorophosphine. Electrophilic cyclization reactions of the vinylallenyl phosphine oxide prepared were investigated as it was established that the reactions proceeded with formation of various heterocyclic or highly unsaturated compounds with participation of the allenic and/or 1,3-dienic part of the vinylallenic system with neighboring group participation of phosphoryl and/or vinylic group. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.

Synthesis of novel phosphorus-containing sterically hindered phenols by the reaction of diphenyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methylphosphonate with phenols

Diphenyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate was oxidized to the corresponding methylidenequinonoid derivative. The addition of phenols to the exocyclic double bond of this compound gave phosphonates with two phenol moieties.

Reaction of diphenyl[2-(triethoxysilyl)ethyl]phosphine oxide with boron trifluoride etherate

Diphenyl[2-(trifluorosilyl)ethyl]phosphine oxide was synthesized by the reaction of diphenyl[2-(triethoxysilyl)ethyl]phosphine oxide with boron trifluoride etherate. As shown by the 1H, 13C, 19F, 31P, 29Si multinuclear NMR spectroscopy data, the silicon atom in the molecule is tetracoordinate. The absence of P=O→Si interaction in diphenyl[2-(trifluorosilyl)ethyl]phosphine oxide, as follows from the comparison of the calculated [GIAO B3LYP/6-311++G(2d,p)] and experimental δ(29Si) and δ(31P) values, is due to the formation of complex with BF3 by the phosphoryl oxygen.

ChemInform Abstract: Studies on PTC-Wittig Reaction of Diphenyl Ylids.

Abstract The phase transfer catalyzed (PTC) Wittig reaction has the advantage of not requiring additional catalyst due to the catalytic property of phosphonium salt itself. This report presents the studies on such a reaction of diphenyl-, di-alkyl- and methyl-2-butenyl phosphonium ylids which are produced in situ from the corresponding phosphonium salts.

Diphenyl (benzylamido)phosphate

The title compound, C19H18NO3P, was prepared by the reaction of diphenyl phospho­rochloridate and benzyl­amine. In the crystal structure, mol­ecules are linked via N—H⋯O=P hydrogen bonds into extended chains parallel to the c axis.

THE DIELS-ALDER REACTION OF DIPHENYL(1,2-PROPADIENYL)PHOSPHINE OXIDE AND DIPHENYL(1-PROPYNYL)PHOSPHINE OXIDE WITH CYCLOPENTADIENE

The Diels-Alder reaction of diphenyl(1,2-propadienyl)phosphine oxide 1 and diphenyl(1-propynyl)phosphine oxide 2 with cyclopentadiene is reported. 1 reacts smoothly at room temperature in the presence of one equivalent of aluminum trichloride to give the corresponding adducts endo 3a and exo 3b (90:10 ratio) whose structure was attributed on the basis of their 13C NMR spectra, whereas 2 is a poor dienophile, affording the corresponding adduct in low yield even under harsh conditions.

Reactions of alkyl- and aryl(ferrocenyl)phosphines with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

Reaction of diphenyl(ferrocenyl)phosphine ( 1), tri(ferrocenyl)phosphine ( 2) and tbutyl(diferrocenyl)phosphine ( 3) with one equivalent of 2,3-dichloro-4,5-dicyano-1,4-benzoquinone (DDQ) yields FcPPh 2 • DDQ ( 4), Fc 3P • DDQ ( 5) and Fc 2P tBu • DDQ ( 6), respectively. Infrared, UV–Vis and ESR spectra of 4– 6 are consistent with formation of DDQ − Mössbauer spectroscopy, however, reveals that 4– 6 all contain low spin Fe II suggesting that the radical cation is ligand centered rather than iron centered.

Reactions of -Aminoalkylphosphonates with Iso(thio)cyanatophosphates(phosphonates, phosphinates). Synthesis of 1,3,4-Diazaphospholidines and 1,3,4-Oxaza(thiaza)phospholines

Phenyl α-aminoalkylphosphonates add to phenyl iso(thio)cyanates to give saturated heterocycles, 1,3,4-diazaphospholidin-2-(thi)ones. The reaction of diphenyl (α-methylamino)benzylphosphonate with diethyl isothiocyanatophosphate involves initial formation of 1,3,4-tiazaphospholidine-2-thiones containing exo- and endocyclic phosphorus atoms. These products are readily hydrolyzed in air, yielding diethyl isothio- cyanatophosphate and phenyl hydrogen (α-methylamino)benzylphosphonate. The final products of the reaction of chloromethyl isocyanatophosphonates with aminoalkylphosphonates are 1,3,4-oxazaphospholines. Phenyl aminoalkylphosphonates react with chloromethyl isocyanatophosphonates to give saturated heterocycles, 1,3,4-diazaphospholidines, whereas with chloromethyl isothiocyanatophosphonates 1,3,4-thiazaphospholines are formed.

Chemical, Electrochemical, and Structural Aspects of the Ruthenium Complexes Ru(η-arene)Cl2(P) (Where Arene = Benzene, [2.2]Paracyclophane and P = Triphenylphosphine, rac-[2.2]Paracyclophanylphosphine)

Reaction of diphenyl[2.2]paracyclophanylphosphine, rac-PPh2(C16H15) (1), with [Ru(η-arene)Cl2]2 (where arene = C6H6, [2.2]paracyclophane (C16H16)) in a 2:1 ratio affords the half-sandwich complexes Ru(η-arene)Cl2{PPh2(C16H15)} (arene = C6H6 (2), C16H16 (3)) in high yield. In solution, the structures of 2 and 3 have been probed and assigned using 2D NMR spectroscopy and the structure of the [2.2]paracyclophane derivative, 3, has been established in the solid-state by single-crystal X-ray diffraction. Cyclic voltammetry and steady-state voltammetry of 2 in 0.25 M [nBu4N][PF6]/CH2Cl2 shows that the complex undergoes a chemically reversible, one-electron oxidation and an irreversible, two-electron reduction. The voltammetry of the related complex [Ru(η6-C6H6)Cl2(PPh3)] (4), recorded under analogous conditions, is similar both in terms of the processes displayed and the potentials at which they occur.

Reactions of Diorganyl Disulfides with Dihaloalkanes in Basic Reductive Media. Synthesis of Bis(organylthio)alkanes

A convenient preparative synthesis of bis(organylthio)alkanes was developed. It is based on alkylation with dihaloalkanes of solutions of diorganyl disulfides in the basic reductive system hydrazine hydrate-alkali. The generation of organylthiolate anions from disulfides and the subsequent reaction of the anions with dihaloalkanes are performed in one reaction vessel without isolation of intermediate alkali metal thiolates. At the same time, the reactions of diphenyl or dithienyl disulfides with dihaloalkanes result in substitution with the thiolate anions of only one halogen atom to give the corresponding unsymmetrical sulfides. In certain cases in the presence of excess alkali the latter sulfides are dehalogenated to form alkyl vinyl sulfides.

Reinvestigation of the 31P NMR evidence for the formation of diorganyl phosphoropyridinium intermediates

A 31P NMR study on the reactions of diphenyl and diethyl chlorophosphates/bromophosphates with pyridine showed that equilibria of these reactions are heavily shifted to the left and thus concentrations of the putative diorganyl phosphoropyridinium chlorides/bromides are usually below the detection level of this spectroscopic method. However, when diphenyl iodophosphate was subjected to reaction with pyridine, we were able for the first time to observe the formation of a diorganyl phosphoropyridinium intermediate by 31P NMR spectroscopy.

The structures of [Ph 2XSNSPh 2NH] + cations (XNH, O)

Diphenyl(diphenylsulfodiimidoyl)(nitrido)sulfur(VI) ( 2) and diphenyl(diphenylsulfoximidoyl)(nitrido)sulfur(VI) ( 3) (Ph 2XSNSNPh 2N, X=NH, O) were prepared by the reaction of diphenyl(fluoro)(nitrido)sulfur(VI) (Ph 2FSN) with sodium salts of diphenyl-sulfodiimide (Ph 2S(NH) 2) and -sulfoximide (Ph 2OSNH). The nitrido-sulfur complexes 2 and 3 are considerably basic (p K a=7.86 and 7.60, respectively). Treatment of 2 and 3 with perchloric acid afforded quantitatively the corresponding μ- aza-bis[diphenyl(imido)sulfur(V)] perchlorate ( 4) and μ- aza-[diphenyl(imido)]-[diphenyl(oxo)]disulfur(V) perchlorate ( 5) ([Ph 2XSNSPh 2NH] +[ClO 4] −, X=NH, O). The crystal structures of 4 and 5 were determined by X-ray crystallographic analysis. The former has essentially C 2 symmetry with an SNS bond angle of 120.3(2)°, bridging SN bond lengths of 1.595(3) and 1.604(3) Å, and terminal SN bond lengths of 1.509(3) and 1.497(3); the latter cation is an unsymmetrically substituted oxygen analog with an SNS bond angle of 123.1(2)°, and bridging SN bond lengths of 1.607(4) and 1.568(4) Å, terminal SN and SO bond lengths of 1.501(3) and 1.438(2) Å. Single-point ab initio calculations were also carried out using the data from the crystal structures of 4 and 5.

Reaction of diphenyl(trimethylsilyl)phosphine with α-oxo phosphonates

Reaction of diphenyl(trimethylsilyl)phosphine with α-oxo phosphonates

A novel carbon leaving group in the reaction of organometallic compounds with phosphine oxides

The reaction of diphenyl(methoxymethyl)phosphine oxide 1 with organometallic reagents was found to lead to substitution of the methoxymethyl group. The P-phenyl substituent showed a lower propensity to undergo a displacement.