Triphenylstibine Oxide Research Articles

ChemInform Abstract: Facile Esterification Promoted by the Triphenylstibine Oxide-Phosphorus Sulfide (Ph3SbO/P4S10) System.

Various esters are conveniently prepared by direct esterification of the corresponding carboxylic acids with alcohols catalyzed by a triphenylstibine oxide–phosphorus(V) sulfide combined system (Ph3SbO/P4S10) under mild conditions (25–80 °C).

Methylrhenium trioxide as a catalyst for oxidations with molecular oxygen and for oxygen transfer

Methylrhenium trioxide (MTO) was found to be a good catalyst for the oxidation of tertiary phosphines by molecular oxygen at room temperature. Evidence is given that an intermediate Re(V) compound — CH 3ReO 2, or the adduct CH 3ReO 2·OPPh 3 — is involved. The deoxygenation of epoxides, sulfoxides, N-oxides, triphenylarsine oxide and triphenylstibine oxide at room temperature was also catalyzed by MTO, with triphenylphosphine as the oxygen acceptor. A plausible reaction mechanism involves phosphine attack at a compound formed between MTO and the epoxide or other oxygen-donor compound.

Carbonylation of amines by carbon dioxide in the presence of an organoantimony catalyst

1,3-Dialkylureas (RNHCONHR; where R=Bu, i-Bu, s-Bu, t-Bu, allyl, Ph) and tetramethylurea were successfully prepared at 80 o C under an initial CO 2 pressure of 4.9 MPa, from the corresponding amines and carbon dioxide with catalysis by triphenylstibine oxide and assistance from tetraphosphorus decasulfide (Ph 3 SbO/P 4 S 10 ). Monitoring of the reaction by 13 C NMR revealed that the successive thiolation of carbamic acid to an intermediate antimony carbamate species and aminolysis of tha carbamothioic acid thus formed constitute the reaction course. Cyclic ureas can also be synthesized by similar carbonylations of diamines (RNHCH 2 CH 2 NHR': where R,R' = H, H; Me, H; Ph, H; HOCH 2 CH 2 , H; HOCHMeCH 2 , H; Me, Me). Furthermore, the Ph 3 SbO/P 4 S 1 0 catalyst system enabled the preparation of trisubstituted ureas such as 1-butyl-3,3-diethylurea by a selective cocarbonylation of butylamine and diethylamine

Facile esterification promoted by the triphenylstibine oxide‐phosphorus sulfide (Ph3SbO/P4S10) system

AbstractVarious esters are conveniently prepared by direct esterification of the corresponding carboxylic acids with alcohols catalyzed by a triphenylstibine oxide–phosphorus(V) sulfide combined system (Ph3SbO/P4S10) under mild conditions (25–80 °C).

ChemInform Abstract: Triphenylstibine Oxide‐Phosphorus(V) Sulfide as a Novel Condensation Catalyst System: Application to the Synthesis of Dipeptides.

Triphenylstibine oxide (Ph3SbO) and phosphorus(V) sulfide (P4S10) synergistically catalyzed the aminolysis of N-protected amino-acids with amino-acid esters in benzene. Ph3SbO accelerated both the initial conversion of carboxylic moieties into the corresponding thiocarboxylic moieties by P4S10 and the subsequent aminolysis of the resulting thiocarboxylic acids. Thus, dipeptides such as Z–A–A′–OEt (where Z = PhCH2OC(O)– and A,A′ = Ala,Gly; Gly,Gly; Leu,Gly; Phe,Gly; Phe,Leu;Ser,Gly; Val,Gly, respectively) were conveniently prepared even at 35°C.

Triphenylstibine oxide–phosphorus(V) sulfide as a novel condensation catalyst system: application to the synthesis of dipeptides

AbstractTriphenylstibine oxide (Ph3SbO) and phosphorus(V) sulfide (P4S10) synergistically catalyzed the aminolysis of N‐protected amino‐acids with amino‐acid esters in benzene. Ph3SbO accelerated both the initial conversion of carboxylic moieties into the corresponding thiocarboxylic moieties by P4S10 and the subsequent aminolysis of the resulting thiocarboxylic acids. Thus, dipeptides such as Z–A–A′–OEt (where Z = PhCH2OC(O)– and A,A′ = Ala,Gly; Gly,Gly; Leu,Gly; Phe,Gly; Phe,Leu;Ser,Gly; Val,Gly, respectively) were conveniently prepared even at 35°C.

Polymerization of oxiranes by polymeric organoantimony oxides

AbstractPolymeric arylantimony(V) oxides [poly(ArSbO2), Ar = phenyl, p‐chlorophenyl (CPh), and p‐methylphenyl (Tol)] were employed as catalysts for the polymerization of oxirane [ethylene oxide (EO)] and also substituted oxiranes [propylene oxide (PO), 1,2‐butylene oxide (BO), and epichlorohydrin (ECH)]. The polymerization of EO by ArSbO2s proceeded 3–60 times faster than that by the other organoantimony and ‐tin compounds such as triphenylstibine oxide (Ph3SbO) and arenestannoic acids (ArSnO2H), respectively. Apparent activation energy for the polymerization of EO was estimated as 13.7, 13.3, and 13.6 kcal/mol for PhSbO2, TolSbO2, and CPhSbO2, respectively. The results of the polymerization as well as 1H‐, 13C‐, and 17O‐NMR spectroscopy suggested that the polymerization was initiated by ArSbO2 or Ar2Sb2O4 fragments, which was derived from a nucleophilc solvation of the polymeric ArSbO2 by oxiranes in situ.

An organoantimony catalyst for peptide synthesis; preparation and aminolysis of triphenylantimony bis(aminoacylate)s

AbstractTriphenylantimony bis(aminoacylate)s [Ph3Sb(OA)2, A = ZGly, ZPhe, ZLeu, BzPhe] were prepared by direct condensation between triphenylstibine oxide and N‐protected amino‐acids in acetone. The aminolysis of these antimony aminoacylates by amino‐acid esters gave corresponding dipeptides, which lead to a catalytic dipeptide synthesis using triphenylstibine oxide as a catalytic precursor of the antimony aminoacylate in situ.

ChemInform Abstract: Preparation of Cyclic Ureas from Carbon Dioxide and Diamines Catalyzed by Triphenylstibine Oxide.

AbstractThe diamines (Ia) ‐ (Ie) are treated with CO2 (II) in the presence of triphenylstibine oxide, forming the cyclic ureas (III).

Preparation of cyclic ureas from carbon dioxide and diamines catalyzed by triphenylstibine oxide

Synthese d'alkyl- et hydroxyalkyl-1 imidazolidones-2 et -perhydro pyrimidones-2 par carbonylation en presence de Ph 3 SbO de N-alkyl- et N-hydroxyalkyl ethylenediamines et -propanediamines-1,3; la carbonylation se fait sur la partie aminoalcool dans le cas d'ω-aminobutylamino-3- et ω-aminohexylamino-3 propanols-1 et on obtient des ω-aminoalkyl-3 oxazolidones-2

Second determination of the structure of dimeric triphenylstibine oxide

C 36 H 30 O 2 Sb 2 cristallise dans le systeme triclinique du groupe d'espace P1. Affinement de la structure jusqu'a 0,024. Elle se compose de molecules dimeriques (Ph 3 SbO) 2 . Chaque atome Sb a une coordination rhomboedrique bipyramidale reguliere par 3 atomes C et 2 atomes O

Synthesis and characterization of novel macrocyclic antimony car☐ylates containing disulfide bonds

Novel 18- and 22-membered ring cyclic antimony car☐ylates which contained two S S bonds were synthesized in the one-pot oxidative-coupling/condensation reaction of triphenylstibine oxide with thioglycolic or β-thiopropionic acids, respectively.

Aminolysis of Triphenylantimony Dicarboxylates and Its Application to Catalytic Amidation

Abstract Triphenylantimony dicarboxylates (Ph3Sb(O2CR)2, where R=Me, CF3, Ph and CH2NH-Z) readily reacted with amines (R′NH2, where R′=n-C6H13, s-Bu, C6H11, and Ph) to afford corresponding amides and triphenylstibine oxide in fairly good yields. The amidation of RCO2H with R′NH2 was also catalyzed by the orgnoantimony compounds.

ChemInform Abstract: PREPARATION AND REACTIONS OF NOVEL μ‐OXO‐BISANTIMONY AMINOALKOXIDE

AbstractAuf dem angegebenen Weg kann die Bis‐antimon‐Verbindung (III) leicht dargestellt werden.

Improvement of the process in the synthesis of 2-oxazolidinones from 2-amino alcohols and carbon dioxide by use of triphenylstibine oxide as catalyst

Improvement of the process in the synthesis of 2-oxazolidinones from 2-amino alcohols and carbon dioxide by use of triphenylstibine oxide as catalyst

PREPARATION AND REACTIONS OF NOVEL μ-OXO-BISANTIMONY AMINOALKOXIDE

Abstract Novel μ-oxo-bis(diphenylhydroxyantimony) di[2-(methylamino)ethoxide] (1) was obtained in the reaction of triphenylstibine oxide and 2-(methylamino)ethanol. Cyclic urethane derivatives were obtained by the reaction of 1 with CO2 or CS2 in good yields.

Polymerization of ethylene oxide catalyzed by triphenylstibine oxide

AbstractPolymerization of ethylene oxide (EO) and propylene oxide (PO) catalyzed by two types of triphenylstibine oxide ((C6H5)3SbO, TPSO) was investigated. The polymeric and high melting point triphenylstibine oxide (TPSOa) was found to be active, but it shows a long induction period in the polymerization at 80°C. During the induction period, TPSOa is probably cleaved into an active antimony species by interaction with EO. TPSOa is activated by addition of some O‐containing compounds such as ethanol, 1,4‐dioxane, or water. Monomeric and low melting point triphenylstibine oxides (TPSOb and TPSOc) were found to be inactive. Their activity markedly increases by addition of Lewis bases such as triphenylphosphine. The difference in the activity of TPSOa and TPSOb or TPSOc is considered to result from differences in aggregation.

Complex formation between iodine and triphenylstibine oxide

The thermodynamic characteristics of the complex between iodine and triphenylstibine oxide have been studied in dichloromethane by u.v. and i.r. spectroscopy and they are compared with other iodine–organic oxo-base complexes.

Preparation, properties and structure of poly(triphenylstibine oxide

Our results indicate that the best method for the preparation of poly(triphenylstibine oxide)_is the oxidation of triphenylstibine in acetone with 30% hydrogen peroxide, followed by the removal of water and excess peroxide with refluxing benzene. A less preferred alternative method involves the hydrolysis of triphenylstibine dichloride with alcoholic potassium hydroxide and the subsequent heating of the isolated solid (C 6H 5) 3Sb(OH) 2 until no hydroxyl bands can be detected by infrared spectroscopy. Solubility, PMR, infrared, Raman, thermal (DTA and TGA), mass spectral, and X-ray powder data are reported. The products are readily identified by characteristics infrared and Raman absorptions in the region between 800 and 400 cm -1. The mass spectral data, although inconclusive when trying to indentify impurities in the samples, corroborate the polymeric nature of triphenylstibine oxide.