Triethylammonium fluoride

Chloromethoxy-1,2,2 2-tetrafluoroethane is converted by triethylammonium fluoride or piperidine hydrogen fluoride to fluoromethoxy 1 2,2,2-tetra-fluoroethane in greater than 60% yield Piperidine hydrogen fluoride or butyl-ammonium fluoride can convert methoxy-l-chloro-2,2,2-trifluoroethane to methoxy-1,2,2,2-tetrafluoroethane in 80% yield [79]... 

Copper(ll) acetylacetonate Copper, bis(2,4-pentanedionato-0,0 )- (9) (46369-53-3) Methyl diazoacetate Acetic acid, diazo-, methyl ester (8,9) (6832-16-2) Triethylammonium fluoride Triethylamine hydrofluoride (8) Elhanamine, N,N-diethyl-, hydrofluoride (9) (29585-72-6)... 

The process involves one technological step. Tetrabutyl- or triethylammonium fluorides can serve as reagents for the cleavage of cycloadducts (181). For this purpose, N-chlorosuccinimide in aqueous THF can also be used. 

Lead(IV) salts will a-oxygenate enol ethers as they do enols vide supra), although in this case the process involves bisoxygenation of the unsaturated Ullage and subsequent hydrolysis. For example, the combination of lead tetrabenzoate and triethylammonium fluoride at 0-25 C effects efficient a-benzoyl-oxylation, e.g. (68) to (69). 0, y-Unsaturated ketones are also successfully oxidized, e.g. (70) to (71). The correspon ng LTA a-acetoxylations are possible, but the benzoate salt remains the transition metal reagent of choice for these substrates.These reactions appear to be uniformly efficient and perluq)S deserve wider synthetic tq>plication. 

BU4NF, THF, 2 min. This group is less reactive toward triethylammonium fluoride than the TIPDS group. It is stable to 2 M HCl, aq. dioxane, overnight. Treatment with 0.2 M NaOH, aq. dioxane leads to cleavage of only the Si-O bond at the 5 -position of the uridine derivative. The TBDS derivative is 25 times more stable than the TIPDS derivative to basic hydrolysis. 

Reaction of enol silyl ethers with lead tetrabenzoate followed by treatment with triethylammonium fluoride leads to the a-benzoyloxyketones. In both cases, the sequence involves bisoxygenation of the double bond followed by hydrolysis. a-Acetoxylation is also possible, but the benzoate is the reagent of choice for that system. i In the cyclohexanone series, reaction of lead tetraacetate with cyclohexanone trimethylsilyl enol ether afforded also a-acetoxycyclohexanone after hydrolysis." When the same reaction was performed on the triethyltin enol ether, the main product was now a-acetoxycyclohexanone with a small amount of dimeric product. This latter result could be explained by a transmetallation followed by ligand coupling, in the major pathway. 

The nucleophilic addition-protonation mechanism is not confined to aqueous media. Reaction of phenylmethanesulfonyl-d2 chloride and triethylamine in the presence of triethylammonium fluoride gave PhCHDS02F132. Experiments with Et3NH + Cl and a mixture of the fluoride and chloride salts suggested that Cl was also capable of trapping the sulfene, but that the fluoride was more reactive toward sulfene by a factor of 4.6. 

Caution. Carbonyl fluoride is a poisonous gas. Carbon monoxide, which is highly poisonous, is a product of the reaction. The triethylammonium fluoride that is formed in the reaction should be placed in the solid waste container. The phosphorus compounds and amines are evil-smelling and harmful. These reactions should be carried out in a well-ventilated fume hood using safety shields. Gloves and other protective clothing should be worn. 

The (C6Hs)3CF and triethylammonium fluoride remain in the flask. The latter is removed by bulb-to-bulb distillation at 50°/1 torr. The residue, which is crude (CsH5)3CF, is purified by recrystallizing from benzene to give 0.32 g (1.25 mmol 60%). 

Oxidation of trimetkylsilyl enol ethers. The reaction of these enol ethers with lead tetrabenzoate in methylene chloride (20°) followed by treatment with triethylammonium fluoride affords a-benzoyloxy carbonyl compounds in high yield (equation I),... 

Perfluoroalkylation of cyanuric fluoride with perfluorocarbanions goierated in situ from perfiuoro-oleflns and alkali-metal fluorides or triethylammonium fluoride in acetonitrile or dimethylformamide has been reported in the patent literature similarly, details of the preparation of perfluoroisopropoxy-substituted sym-triazines via treatment of cyanuric chloride with hexa-fluoroacetone and potassium fluoride in diglyme have been disclosed. ... 

Sulfenyl fluorides are extremely unstable and therefore only few perhalosulfenyl fluorides have so far been reported122. The formal addition of the elements of methanesulfenyl fluoride to carbon-carbon double bonds has been obtained123 by a one-pot reaction with dimethyl(methylthio)sulfonium tetrafluoroborate and triethylammonium tris(hydrofluo-ride). With this system also the addition to double bonds is highly stereoselective, at least... 

E-2-bromomethyleneglutaric esters (>70%) have been obtained from the corresponding 2-bromo-2-bromomethylglutarates using a 25% excess tetra-n-butyl-ammonium fluoride in HMPA [24], A similar procedure converts dimethyl 2-bromo-2-bromomethylsuccinate into dimethyl Z-2-bromomethylenefumarate [25], whereas methyl 2,2-bis(bromomethyl)ethanoate yields the 2-bromomethyl-propenoate when reacted with aqueous sodium hydroxide in the presence of benzyl-triethylammonium chloride [26]. No hydrolysis of the ester is evident at 0°C, but becomes apparent at 25 °C. 

Triethylammonium hydrogen fluorides (Et,N - nHF complexes, n = 4 6) allow the fluorocyclization of unsaturated aldehydes such as 2,6-dimethylhcpt-5-enal (7) to livc-mem-bered cyclic fluoro alcohols, such as 8 and 9 (yields 55-81 %).39s... 

Figure 16. Inhibition of the reaction between p-nitrophenyl acetate and HSA by inorganic anions. Solutions of each anion, triethanolamine, and 3.5 X 10 5M HSA were prepared at the appropriate concentrations and pH 8.1. Logarithms of the observed pseudo-first-order rate constants are plotted vs. a function of ionic strength, jjl, for triethylammonium phosphate (O), fluoride (D), sulfate (%), chloride (M), iodide (A), and perchlorate ( A).

Alkanoyl chlorides and chloroformates can be treated with potassium fluoride and benzy[triethylammonium chloride to obtain the respective alkanoyl fluorides or fluoroformates [62], 2-Amino-6-chloro-9-(2,3,5-tri-0-acetyl-P-D-ribofurano-syl)purine is converted to the 2-amino-6-fluoro product with potassium fluoride and trimethylamine in dimethylforinamide under rigorously anhydrous conditions [65] (equation 37)... 

A simple one-pot conversion of phenols to arenes by the reaction of fluoroalkanesul-fonyl fluoride with phenols, i.e. without isolating aryl fluoroalkanesulfonates, in the presence of alkenes, alkynes or triethylammonium formate, can be accomplished in good yields139 (equation 119). 

---