Tetrabutylphosphonium acetate

In addition to tetrabutylphosphonium chloride, typical phosphonium salts that can be produced include tetraoctylphosphonium bromide [23906-97-0], tetrabutylphosphonium acetate [17786-43-5] (monoacetic acid), and tetrabutylphosphonium bromide [3115-68-2]. Inmost cases, these compounds can be prepared with alternative counterions. 

Reactions conducted in molten quaternary phosphonium salts require no other solvent (199). This material serves as both promoter and reaction medium. Care must be exercised in choosing the salt in such a reaction, since any decomposition could lead to products such as trialkylphosphines and alkyl halides which are expected to be deleterious to catalyst performance. Tetrabutylphosphonium bromide is reported to provide a stable catalyst medium which can be recycled (199, 200), but other related salts show evidence of thermal decomposition during catalytic reactions. Experiments in tetrabutylphosphonium acetate, for example, are found to produce large amounts of methyl and ethylene glycol acetate esters (199). 

McCloskey [4] prepared high molecular weight polymer carbonates consisting of bis(methyl salicyl) carbonate, bisphenol A, and an oligomeric carbonate of methyl salicylate using the transesterification catalyst, tetrabutylphosphonium acetate. 

Benzyl trimethyl ammonium hydroxide Cetrimonium bromide Dimethyl diallyl ammonium chloride Laurtrimonium bromide Laurtrimonium chloride Methyl tributyl ammonium chloride Tetrabutyl ammonium bromide Tetrabutyl ammonium chloride Tetrabutyl ammonium fluoride Tetra-n-butyl ammonium hydrogen sulfate Tetra-n-butyl ammonium hydroxide Tetrabutyl ammonium iodide Tetrabutylphosphonium acetate, monoacetic acid Tetrabutylphosphonium bromide Tetrabutylphosphonium chloride Tetraethylammonium bromide Tetraethylammonium hydroxide Tetrakis (hydroxymethyl) phosphonium chloride Tetramethylammonium bromide Tetramethylammonium chloride Tetramethylammonium hydroxide Tetramethyl ammonium iodide Tetraphenyl phosphonium bromide Tetrapropyl ammonium bromide Tetrapropyl ammonium iodide Tributylamine Tributyl phosphine Tributyl (tetradecyl) phosphonium chloride Trioctyl (octadecyl) phosphonium iodide catalyst, phase-transfer Tetraethylammonium chloride Tetraoctylphosphonium bromide Tri-n-butyl methyl ammonium chloride Tri methyl phenyl ammonium hydroxide catalyst, phenolics Triethylamine... 

Sulfur dioxide Tall oil N-Tallow-1,3-diaminopropane dioleate Tallow nitrile Tetrabromophthalate diol Tetra-n-butoxysilane Tetrabutylphosphonium acetate, monoacetic acid Tetrabutylphosphonium bromide Tetrabutylphosphonium chloride 1,1,1,2-Tetrachloroethane... 

It is known that tr-allylpalladium acetate is converted into allyl acetate by reductive elimination when it is treated with CO[242,243]. For this reason, the carbonylation of allylic acetates themselves is difficult. The allylic acetate 386 is carbonylated in the presence of NaBr (20-50 mol%) under severe conditions, probably via allylic bromides[244]. However, the carbonylation of 5-phenyl-2,4-pentadienyl acetate (387) was carried out in the presence of EtiN without using NaBr at 100 °C to yield methyl 6-phenyl-3,5-hexadienoate (388)[245J. The dicarbonylation of l,4-diacetoxy-2-butene to form the 3-hexenedioate also proceeds by using tetrabutylphosphonium chloride as a ligand in 49% yield[246]. 

Data in Table I illustrate the production of acetic acid from 1/1 syngas catalyzed by ruthenium-cobalt halide bimetallic combinations dispersed in tetrabutylphosphonium bromide (m.p. 100°C). 

The ruthenium(111) acetylacetonate-cobalt(II) iodide couple, for example, when dispersed in tetrabutylphosphonium bromide (ex. 1) and treated with 1/1 CO/H2 at 220°C, generates a liquid product containing 76 wt % acetic acid plus 1.1 wt % propionic acid (111 mmol total acid). The liquid yield increase is 66% and the estimated carbon selectivity to acetic plus propionic acids and their esters is 84%. There is normally no metallic residue at this stage, ruthenium and cobalt recovery is essentially quantitative at the end of the run, and the product acids may be recovered in >90% purity by fractional distillation. Methane and water are the major by-products (4). 

It is clear that ruthenium-cobalt-iodide catalyst dispersed in low-melting tetrabutylphosphonium bromide provides a unique means of selectively converting synthesis gas in one step to acetic acid. Modest changes in catalyst formulation can, however, have profound effects upon liquid product composition. 

Decarboalkoxylation Palladium(II) acetate, 232 Tetrabutylphosphonium bromide, 288 Decarbonylation (see also Elimination reactions)... 

A considerable amount of effort has already been devoted to producing dimethyl carbonate (DMC) from methanol and CO2, and some of the reactions have been catalyzed by organotin alkoxides. However, the catalytic activities so far obtained have been very low due to the decomposition of the catalysts by water generated during the reaction. The supercritical C02 reaction with trimethyl orthoacetate leads to the desired reaction and gives DMC and methyl acetate. Although di- -butyltin dimethoxide is less effective, the addition of tetrabutylphosphonium iodide substantially enhances the catalytic activity of the system (Equation (96)).261 262... 

Data in Table V illustrate the production of acetic acid from 1/1 syngas. A variety of ruthenium-containing precursors - coupled with cobalt halide, carbonate and carbonyl compounds - at different initial Co/Ru atomic ratios, have been found to yield the desired carboxylic acid when dispersed in tetrabutylphosphonium bromide. In a more detailed examination of the ruthenium-cobalt-iodide melt catalyst system, we have followed the generation of acetic acid and its acetate esters as a function of catalyst composition and certain operating parameters, and examined the spectral properties of these reaction products, particularly with regard to the presence of identifiable metal carbonyl species. 

Potassium acetate, tetrabutylphosphonium bromide, (chloro-methyl)methoxydimethylsilane, diphenyl ether or Hydroseal G 400 H (high-temperature boiling solvent). 

Potassium acetate 84.6 g (0.86 mol, 1.18equiv) and tetrabutylphosphonium bromide 4.96 g (14.6 mmol, 0.02 equiv) were suspended in (chloromethyl)methoxydimethylsilane 10.1 g (0.73 mmol, 1.00 equiv) and 100 mL Hydroseal G 400 H or diphenyl ether. The mixture was heated at 110°C with vigorous stirring for 4—8h. The (acetoxymethyl)methoxydimethylsilane was isolated by fractionated distillation imder reduced pressure (105 g, 0.65 mol, 89%). 

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