Benzyltriphenylphosphonium Chloride Research Articles

Benzyltriphenylphosphonium Dichromate as a Mild Reagent for Oxidation of Thiols and Sulfides

Oxidation of thiols and sulfides under non-aqueous and aprotic conditions uses benzyltriphenylphosphonium dichromate (1, PhCH2PPh3)2 Cr2O7) which is very easily prepared by mixing an aqueous solution of benzyltriphenylphosphonium chloride with CrO3 in 3N HCl at room temperature. This reagent, a stable orange powder which may be stored for a month without loss of activity, is soluble in acetonitrile, chloroform and dichloromethane and slightly soluble in carbon tetrachloride, ether and hexane.

SOLID-PHASE OXIDATION OF ORGANIC COMPOUNDS WITH BENZYLTRIPHENYLPHOSPHONIUM DICHROMATE

Benzyltriphenylphosphonium dichromate could be used for oxidation of organic compounds such as alcohols, thiols and sulfides to the corresponding carbonyl, disulfide and sulfoxide derivatives under solid-phase conditions. This reagent is very easily prepared from an aqueous solution of benzyltriphenylphosphonium chloride with CrO3 in 3 N HCI at room temperature. The reagent, is a stable orange powder, which may be stored for month without loss of its activity.

Crystal structure of benzyltriphenylphosphonium chloride, (C6H5)CH2P(C6H5)3Cl

Article Crystal structure of benzyltriphenylphosphonium chloride, (C6H5)CH2P(C6H5)3Cl was published on December 1, 1997 in the journal Zeitschrift für Kristallographie - New Crystal Structures (volume 212, issue 1).

Mercuriation of 3,4,5-trimethoxybenzoic acid. Synthesis of derivatives of the mercuriation product and crystal and molecular structure of PPh 3(CH 2Ph)][HgCl{C 6H(CO 2)-6-(OMe) 3-2,3,4}

The mercuriation of 3,4,5-trimethoxybenzoic acid has been re-investigated and the product [HgCl{C 6H(CO 2H)-6-(OMe) 3-2,3,4}] ( 1) characterized. It is deprotonated by Na 2CO 3 to give [Hg{C 6H(CO 2)-6-(OMe) 3-2,3,4}] n ( 2) which, in turn, reacts with benzyltriphenylphosphonium chloride or triphenylphosphine to give [PPh 3(CH 2Ph)][HgCl{C 6H(CO 2)-6-(OMe) 3-2,3,4}]( 3) or [Hg{C 6H(CO 2)-6-(OMe) 3-2,3,4}(PPh 3)] ( 4), respectively. The reaction of 2 with MeI in the presence of [NMe 4]Cl affords [Hg{C 6H(CO 2Me)-6-(OMe) 3-2,3,4} 2] ( 5), which reacts with HgCl 2 or HgCl 2 to give [HgX{C 6H(CO 2Me)-6-(OMe) 3-2,3,4}] [X  Cl ( 6), I ( 7)]. The crystal structure of 3 shows a linear geometry at the mercury atom [ClHgC 178.0(2)°, HgCl 2.315(2), HgC 2.060(5) Å], with an additional long Hg⋯O contact [2.573(4) Å].

Macrocycles containing tin. Solid complexes of anions encrypted in macrobicyclic Lewis acidic hosts

Abstract : Crystalline complexes of 1,10-dichloro-1,10-distannabicyclo.8. 8hexacosane and benzyltriphenylphosphonium chloride (complex 3) and of 1,8- dichloro-1,8-distannabicyclo-6.6.6eicosane and tetrabutylammonium fluoride (complex 4) have been studied by X ray crystallography and solid state 119 Sn NMR spectroscopy. The halide ions are encrypted within the cavities of the bicyclic hosts in both complexes. Complex 3 is a stannates stannane species wherein one of the Lewis acidic tins binds the chloride strongly and the other interacts with the chloride only weakly. Complex 4 is a bis-hemistannate species wherein the Lewis acidic tin atoms bind the guest fluoride simultaneously. Low temperature species wherein the Lewis acidic tin the two complexes in halogenated solvents were studied. A chloride jump from one tin to the other was observed in complex 3; the dynamic process has an activation energy of 5.3 kcal/ mol. Line broadening of the tin signals in complex 4 was consistent with a similar fluoride jump with an activation energy of 2.9 kcal/mol. The crystalline complexes were reasonable models for the solution complexes in both cases, and the structural features in the solid state can be used to rationalize the binding in solution.

Reaction of the N, N-dimethylamide and methyl ester of 3-phenyl-3-chloro-2-ketopropionic acid with triphenylphosphine

The dimethylamide of 3-phenyl-3-chloro-2-ketopropionic acid reacts with Ph3P to give α-(N,N-dimethyloxamoyl)benzyltriphenylphosphonium chloride. In the presence of methanol, this reaction gives dimethyl(phenylpyruvoyl)amide and Ph3PO.

KINETIC STUDY OF STILBENE SYNTHESIS VIA THE REACTION OF BENZYLTRIPHENYLPHOSPHONIUM CHLORIDE WITH BENZALDEHYDE IN A TWO PHASE SYSTEM

Abstract The kinetic study of the Wittig reaction of synthesizing stilbene is carried out by reacting benzaldehyde (C6H5CHO) with benzyltriphenylphosphonium chloride (BTPPC) in the NaOH (aq)/-CH2C12 two-phase system, the rate of reaction depends on the agitating speed, temperature, and the concentration of C6H5 CHO, BTPPC, and NaOH. When the agitating speed is less than 200 rpm, the reaction rate is controlled by diffusion. Uniform mixing of two phases is reached when the agitating speed is greater than 600 rpm. The kinetic data indicated that the reaction rate depends linearly on the concentrations of NaOH and BTPPC and asymptotically on C6H 5CHO concentration. The reaction is very rapid and is complete within a few minutes, even at 0°C. The yield of stilbene as high as 95% can easily be obtained. The cis- to trans-isomer ratio in the stilbene product is about 2, independent of reactant concentrations and temperature. A simplified reaction mechanism is proposed to rationalize the kinetic data.

Kinetic study of stilbene synthesis with benzyltriphenylphosphonium bromide as phase transfer catalyst

Abstract A kinetic study of the Wittig reaction for synthesizing stilbene is carried out by reacting benzaldehyde (C6H5CHO) with benzyltri‐phenylphosphonium bromide (BTPPB) in the NaOH(aq)/CH2Cl2(org) two‐phase reaction system. The rate of reaction depends on the agitation speed, the temperature and the concentrations of C6H5CHO, BTPPB, and NaOH. When the agitation speed is low, the reaction is highly affected by interface diffusion. The reactant rate constant, based on the SN 2 substitution mechanism and the activation energy are also determined. It is found that the activation energy obtained from the present study (Ea =11.97 kcal/mole) is less than that of the previously documented data (Ea =12.984 kcal/mole) in which benzyltriphenylphosphonium chloride (BTPPC) was used as a phase transfer catalyst.

Kinetic study of the substitution reaction of benzyl chloride with triphenylphosphine to synthesize benzyltriphenylphosphonium chloride. Solvent effects

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetic study of the substitution reaction of benzyl chloride with triphenylphosphine to synthesize benzyltriphenylphosphonium chloride. Solvent effectsMaw Ling Wang, Anhong Liu, and Jing Jer JwoCite this: Ind. Eng. Chem. Res. 1988, 27, 4, 555–559Publication Date (Print):April 1, 1988Publication History Published online1 May 2002Published inissue 1 April 1988https://doi.org/10.1021/ie00076a004RIGHTS & PERMISSIONSArticle Views431Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (553 KB) Get e-Alerts Get e-Alerts

Kinetic study of the reaction of benzyl chloride with triphenylphosphine to synthesize benzyl-triphenylphosphonium chloride under water extraction.

Kinetic study of the reaction of benzyl chloride with triphenylphosphine to synthesize benzyl-triphenylphosphonium chloride under water extraction.

Effect of Amines on the Kinetics of alkaline Decomposition of Benzyltriphenylphosphonium Chloride in Binary Solvent Mixtures

AbstractThe kinetics of decomposition of benzyltriphenylphosphonium chloride by sodium hydroxide was studied in binary aqueous solvent mixtures ranging from pure water to about 70% (v/v) of dipolar aprotic solvents such as DMSO or acetone in presence of a series of aliphatic and aromatic amines. The rate, which is directly proportional to the organic solvent content, was found to increase to a maximum at 0.1 M amine concentration and then to decrease. The small increase in rate due to the addition of amine is explained on the basis of an amine‐water interaction, where the concentration of OH− ions in the solution increases slightly due to the ability of the amines to abstract protons from water molecules in the medium. However, the decrease in rate beyond 0.1 M amine concentration is explained as due to the decrease of hydroxide ion concentration by formation of a weakly ionised quaternary ammonium hydroxide. The observed activation energies, thermodynamic parameters and radii of the activated complex for all solvent compositions are computed. The effect of the bulk dielectric constant on the reaction rate was investigated in the light of the available electrostatic theories.

CRYSTAL STRUCTURE AND PROPERTIES OF THE DBTTF SALT WITH A NOVEL CHLORIDE-BRIDGED TRIMERIZED DIMETHYLTIN(IV) DIANION. [DBTTF]3[Sn3(CH3)6Cl8]·C6H5CN

Abstract The title salt has been obtained By electrolysis of dibenzotetrathiafulvalene in a benzonitrile solution containing dichlorodimethyltin(IV) and benzyltriphenylphosphonium chloride. The X-ray crystal analysis has revealed the presence of a DBTTF columnar structure and a novel trimerized tin(IV) anion [Sn3(CH3)6Cl8]2−. Electrical and spectroscopic properties also are described.

Preparation of some polymer-supported crown ethers and their use as phase-transfer catalysts

Benzo-15-crown-5 and dibenzo-18-crown-6 have been formylated. The products were then bound to diol-containing crosslinked polystyrenes via acetalisation and to crosslinked polymers containing benzyltriphenylphosphonium chloride residues (obtained by treating chloromethylated polystyrenes with triphenylphosphine)via phase-transfer catalysed Wittig reactions. The various polymer-supported crown ethers have been found to be satisfactory phase-transfer catalysts for the reactions of n-octyl bromide in toluene with aqueous potassium iodide at 90 °C and with aqueous sodium p-methylthiophenolate at 80 °C, but not for the reaction of n-octyl bromide in toluene with aqueous potassium cyanide at 90 °C. The crosslinked polymers containing benzyltriphenylphosphonium chloride residues were also satisfactory catalysts for the first two reactions.

Component loss during evaporation—reconstitution of organic environmental samples for gas chromatographic analysis

Standard and sample solutions stored in borosilicate sample vials were allowed to evaporate to dryness at room temperature. The solutins were analyzed by gas chromatography—flame ionization detection before evaporaion and after reconstitution to the original volume to determine component losses due to evaporation. The standard solutions were also stored in sample vials which had been treated with a surface deactivating agent, benzyltriphenylphosphonium chloride. The standard solution contained n-hydrocarbons, l-alcohols, phthalates and polynuclear aromatic hydrocarbons. The sample solution was a benzene extrat of municipal incinerator fly-ash which contained over 200 components including n-hydrocarbons, phthalates, polynuclear aromatic hydrocarbons and polychlorinated dibenzo- p-dioxins. At the 95% confidence level, the differences among mean losses observed with the 100 ng/μl standard mixture were within random variations between untreated and deactivated vials. The random variations between mean losses of the 10 ng/μl mixture were significantly higher with the deactivated vials at the 99% confidence level. Large losses were observed for early-eluting components of the standard solutions and the benzene extract of incinerator fly ash. Losses for polychlorinated benzo- p-dioxins and polynuclear aromatic hydrocarbons averaged ca. 10%.

Synthese und Kristallstruktur von (E)‐α‐(Trifluormethyl)stilben

Synthesis and X‐Ray Structure of (E)‐α‐(Trifluoromethyl)stilbeneStarting from benzyltriphenylphosphonium chloride and ω,ω,ω‐trifluoroacetophenone α‐(trifluoromethyl)stilbene was prepared with 91% yield with a phase transfer‐catalyzed Wittig reaction with solid KF but without bases. The isolated isomer was found by X‐ray structure analysis to have the thermodynamic preferred (E)‐configuration. For this configuration it was determined a torsion angle of 71.3° between the two cis‐configurated phenyl rings because of steric hindrance. AH ⃜F hydrogen bridge (distance: 223.8 pm) stabilizes the (E)‐isomer.

Polydentate phosphonium salts for the deactivation of wall-coated open-tubular columns : Comparison of temperature stability with other deactivation methods

The deactivation of glass capillary columns by polydentate phosphonium bromides has been demonstrated and compared with other methods of deactivation in the temperature range of 150 to 325°. Glass capillary columns treated with tetradentate phosphonium bromides proved to be considerably more stable than columns treated with benzyltriphenylphosphonium chloride (BTPPCl), toasted Carbowax or silanizing agents. Columns deactivated with the polyphosphonium bromides and subsequently coated with a liquid phase showed excellent peak symmetry for highly polar compounds even after having been heated to 275° for 16 h. A column deactivated with BTPPCl and similarly coated showed a considerable loss of resolution when subjected to the same conditions.

Formation of Benzyl Radicals by Pulse Radiolysis of Benzyltriphenylphosphonium Chloride in Aqueous Solutions

Abstract The reaction of benzyltriphenylphosphonium ion (PhCH2P+Ph3) with eaq− has been studied. The benzyl radical and triphenylphospine are formed by the reaction: PhCH2P+Ph3+eaq−→PhCH2·+Ph3P, with the rate constant (2.7±0.3)×1010 M−1 s−1. The benzyl radical decays in a bimolecular reaction with 2k=(2.7±0.4)×109 M−1 s−1.

Interactions between large organic ions of opposite charge: VI. Coacervation in mixtures of sodium dodecyl sulfate and benzyltriphenylphosphonium chloride

The coacervation of benzyltriphenylphosphonium chloride in solutions of sodium dodecyl sulfate has been studied at different temperatures and in the presence of added electrolyte. A complex coacervate is formed between the two species. Solubilization of the coacervate in sodium dodecyl sulfate micelles is also considered.

Interactions between large organic ions of opposite charge: V. The effect of substituted ureas on the interaction between sodium dodecyl sulfate and benzyltriphenylphosphonium chloride

Sodium dodecyl sulfate (SDDS) and benzyltriphenylphosphonium chloride interact in aqueous solution to form an insoluble complex. The solubility of this complex can be increased by the addition of urea or alkyl ureas. The longer chain length ureas, N-n-propyl and N-n-butyl ureas are less effective than N-methyl and N-ethyl ureas. In contrast the critical micelle concentration of SDDS is increased by added urea and N-methylurea and decreased by the higher chain length homologs. The results are discussed in terms of the effects of the various ureas on water structure and hydrophobic interaction, the formation of mixed complex coacervates and mixed micelles.

Activity and structural changes of purified kallikrein with detergent treatment

The esterase activity of rat urinary kallikrein is increased up to fourfold by the anionic detergent, deoxycholate and the nonionic detergents, Triton X-100, Lubrol PX, and Brij 58. The cationic detergents, benzyltriphenylphosphonium chloride and cetyltri-methylammonium bromide, inhibit kallikrein activity. Certain trypsin inhibitors stimulate kallikrein activity but this stimulation is not observed when kallikrein is preincubated with deoxycholate. In addition, deoxycholate weakens the inhibition of kallikrein activity by Trasylol. Deoxycholate-induced conformational changes of kallikrein are noted by a change in circular dichroism spectra in the far and near ultraviolet region. A maximal change of ellipticity at 275 nm suggests binding of deoxycholate to kallikrein at or around the tyrosine residue(s) or changes in the microenvironment of these residue(s).