Acetic triphenyl

Tributyl amine, palladium acetate, triphenyl phosphine from Fluka AG and N,N-dimethylformamide and formic acid from Farmitalia Carlo Erba Chemicals were used without further purification. 

Lithium methoxyacetylide, 166 Methyl bis(trifluoroethoxy)phos-phinylacetate, 186 Palladium(II) acetate-Triphenyl-phosphine, 233... 

Vinyl iodides are considerably more reactive than bromides in the vinylations. It may be presumed that chlorides are not generally useful, with one exception noted below, since they have not been employed in the reaction. The bromides are usually reacted with a palladium acetate-triphenyl- or tri-o-tolyl-phos-phine catalyst at about 100 C. The reaction will occur without the phosphine if a secondary amine is present. Vinyl iodides will react in the absence of a phosphine even with only a tertiary amine present.48 37 The iodides are so reactive, in fact, that reactions occur even at room temperature if potassium carbonate is the base and tetra-zi-butylammonium chloride is used as phase transfer agent in DMF solution when palladium acetate is the catalyst.88... 

TINESTAN TINESTAN 60 WP TIN TRIPHENYL ACETATE TPTA TPZA TRIFENYLTINACETAAT (DUTCH) TRIPHENYLACETO STANNANE TRIPHENYL-TIN ACETATE TRIPHENYL-ZINNACETAT (GERMAN) TUBOTIN VP 1940... 

Keywords 1,2-Diaza-l,3-dienes, trimethylsililazide, copper(II) acetate, triphenyl phosphine, isocyanates/isothiocyanates, dichloromethane, room temperature, sequential foiu-component aza-Michael, Staudinger and aza-Wittig reactions, one-pot synthesis, 1,2-diaminoimidazoles... 

Acetyl chlotide is reduced by vatious organometaUic compounds, eg, LiAlH (18). / fZ-Butyl alcohol lessens the activity of LiAlH to form lithium tti-/-butoxyalumium hydtide [17476-04-9] C22H2gA102Li, which can convert acetyl chlotide to acetaldehyde [75-07-0] (19). Triphenyl tin hydtide also reduces acetyl chlotide (20). Acetyl chlotide in the presence of Pt(II) or Rh(I) complexes, can cleave tetrahydrofuran [109-99-9] C HgO, to form chlorobutyl acetate [13398-04-4] in about 72% yield (21). Although catalytic hydrogenation of acetyl chlotide in the Rosenmund reaction is not very satisfactory, it is catalyticaHy possible to reduce acetic anhydride to ethylidene diacetate [542-10-9] in the presence of acetyl chlotide over palladium complexes (22). Rhodium trichloride, methyl iodide, and ttiphenylphosphine combine into a complex that is active in reducing acetyl chlotide (23). 

Triphenyl phosphate [115-86-6] C gH O P, is a colorless soHd, mp 48—49°C, usually produced in the form of flakes or shipped in heated vessels as a hquid. An early appHcation was as a flame retardant for cellulose acetate safety film. It is also used in cellulose nitrate, various coatings, triacetate film and sheet, and rigid urethane foam. It has been used as a flame-retardant additive for engineering thermoplastics such as polyphenylene oxide—high impact polystyrene and ABS—polycarbonate blends. 

The production of triphenyl tin hydroxide [76-87-9] and triphenyl tin acetate [900-95-8] start with triphenyl tin chloride, which is prepared by the Kocheshkov redistribution reaction from tetraphenyltin and tin tetrachloride. The hydroxide is prepared from the chloride by hydrolysis with aqueous sodium hydroxide. The acetate can be made directiy from the chloride using sodium acetate or from the hydroxide by neutrali2ation with a stoichiometric quantity of acetic acid. 

Ethyl (triphenylphosphoranylidene)acetate is available from FIuka AG and Trldom Chemical Inc. under the name (ethoxycarbonylmethylene)triphenyl-phosphorane and from Aldrich Chemical Company, Inc. under the name (carbethoxymethylene)triphenylphosphorane. The reagent may be prepared from triphenyl phosphine and ethyl bromoacetate by the following procedure. ... 

Although many plasticisers have been suggested for cellulose acetate very few have been used in practice. The most important of these are dimethyl phthalate (8 = 21.4), triacetin (8 = 20.3) and triphenyl phosphate (8 = 20.0), each of which have a solubility parameter within one unit of that of cellulose diacetate (-22.0). (All in units ofMPa. )... 

Triphenyl phosphate is a crystalline solid which has less compatibility with the polymer. This may be expected from solubility parameter data. It is often used in conjunction with dimethyl phthalate and has the added virtues of imparting flame resistance and improved water resistance. It is more permanent than DMP. Triacetin is less important now than at one time since, although it is compatible, it is also highly volatile and lowers the water resistance of the compound. Today it is essential to prepare low-cost compounds to allow cellulose acetate to compete with the synthetic polymers, and plasticisers such as ethyl phthalyl ethyl glycollate, which are superior in some respects, are now rarely used. 

A ( )-Enol-l 1-acetates are formed by distillation of acetic anhydride in the presence of / -toluenesulphonic acid. Another procedure employed for the synthesis of enol benzoates involves treatment with benzoic anhydride and triphenyl methyl sodium or ethynyl sodium. Suitable procedures utilizing a diluent have been developed for the enol esterification of a 20-ketone without affecting an 11-ketone. 

The spectra and halochromism of thiophene analogs of triphenyl and diphenyl carbinol, " the spectra of anilides of 2- and 3-thenoyl-acetic acid, " and the fluorescence of some thiophene compounds have been investigated. 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

A solution of 1.5 mol equiv of butyllithium in hexane is added to 1.5 mol equiv of a 1 M solution of hexabutylditin in THF at 0 C under nitrogen, and the mixture is stirred for 20 min. The solution is cooled to — 78 °C and a solution of 1.5 mol equiv of diethylaluminum chloride in toluene is added. After stirring for 1 h at — 78 °C, a solution of 0.05 mol equiv of [tetrakis(triphenyl)phosphine]palladium(0) in THF is added followed by a solution of the allyl acetate in THF. The mixture is warmed to r.t., and stirred until the allyl acetate has reacted (TLC). The solution is cooled to 0°C, and an excess of aq ammonia slowly added. After an aqueous workup, the products arc isolated and purified by flash chromatography on silica gel using 1 % triethylamine in the solvent to avoid acid-induced loss of stannane. 

The primary OH group can be selectively blocked by the bulky triphenyl-methyl (trityl) moiety, followed by esterification at the secondary OH groups and removal of the protecting trityl group. Thus 2,3-di-O-acetyl cellulose has been obtained by this procedure. Moreover, regioselectively substituted mixed cellulose esters, acetate/propionate, were prepared by subsequent acy-... 

Tricyclohexyltin hydroxide is metabolized in vivo to inorganic tin via di- and monocyclohexyltin derivatives (502), and in vitro studies suggested that the major, metabolic reaction is carbon-hydroxylation of the cyclohexyl group (503). Studies in vivo using either tri-phenyl[ Sn]tin acetate (467) or triphenyl[" Sn]tin chloride (504) in rats showed that these compounds are metabolized to yield substantial amounts of di- and monophenyltin derivatives, although no significant quantities of hydroxylated metabolites have been identified (503) in this case. 

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