Benzyltriethylammonium chloride oxidations

For example, direct treatment of red phosphorus with potassium hydroxide in a mixture of dioxane and water with a phase-transfer catalyst (benzyltriethylammonium chloride) allows direct reaction with primary haloalkanes to form the trialkylphosphine oxide in moderate (60-65%) yield.1415 Allylic and benzylic halides are similarly reported to generate the corresponding tertiary phosphine oxides. When the reaction is performed with a,(o-dihalides, cyclic products are generated only with four- and five-carbon chains the third site... 

Efficient cleavage of A.A-dimethylhydrazones to yield the parent ketones (>90%) is effected under neutral conditions with tetra-n-butylammonium persulphate [40], The procedure is particularly useful for compounds with acid-sensitive substituents, e.g. vinyl or ketal groups. Similarly, reaction times for the oxidative cleavage of semicarbazones with sodium nitrite or nitrate/trimethylsilyl chloride are reduced by the addition of benzyltriethylammonium chloride [41]. 

Sulphoximes are obtained by a facile oxidation of sulphilimines [20], The reaction, which can be conducted in ethyl acetate and/or dichloromethane, is best catalysed by tetra-n-butylammonium bromide or Adogen. Benzyltriethylammonium chloride has no significant catalytic activity. 

The addition of benzyltriethylammonium chloride promotes the perborate-mediated Baeyer-Villiger oxidation of water-immiscible ketones [20]. 

In conjunction with a ruthenium oxide co-catalyst, sodium periodate has been used as a mild oxidizing agent in the presence of benzyltriethylammonium chloride... 

The metal-catalysed autoxidation of alkenes to produce ketones (Wacker reaction) is promoted by the presence of quaternary ammonium salts [14]. For example, using copper(II) chloride and palladium(II) chloride in benzene in the presence of cetyltrimethylammonium bromide, 1-decene is converted into 2-decanone (73%), 1,7-octadiene into 2,7-octadione (77%) and vinylcyclohexane into cyclo-hexylethanone (22%). Benzyltriethylammonium chloride and tetra-n-butylammo-nium hydrogen sulphate are ineffective catalysts. It has been suggested that the process is not micellar, although the catalysts have the characteristics of those which produce micelles. The Wacker reaction is also catalysed by rhodium and ruthenium salts in the presence of a quaternary ammonium salt. Generally, however, the yields are lower than those obtained using the palladium catalyst and, frequently, several oxidation products are obtained from each reaction [15]. 

The silver oxide oxidation of aldehydes to carboxylic acids is aided by the addition of benzyltriethylammonium chloride the active agent is thought to be TEBA-Ag(OH) [16]. 

Barbier reaction Samarium(II) iodide, 270 Benzoannelation Chromium carbene complexes, 82 Dicarbonylcyclopentadienylcobalt, 96 Ethyl (Z)-3-bromoacryIate, 130 Grignard reagents, 138 Methyl acrylate, 183 Methyllithium, 188 Ruthenium(III) chloride, 268 Benzoin condensation Benzyltriethylammonium chloride, 239 3-EthyIbenzothiazolium bromide, 130 Benzoylation (see also Acylation) Cadmium, 60 Dibutyltin oxide, 95 Birch reduction Birch reduction, 32... 

Morris Jr. and Kiely37 in 1987 noted a great acceleration in the oxidation of alcohols, with catalytic Ru04 in a biphasic system, upon addition of 1% molar benzyltriethylammonium chloride (BTEAC) as a phase-transfer catalyst. 

Oxidation of l,2 5,6-di-0-isopropylidene-a-D-glucofuranose (217) with ruthenium tetraoxide, using a phase-transfer catalyst, gave the 3-ulose derivative 218, which by further hydrolysis afforded D-n Zw-hexos-3-ulose 219. Benzyltriethylammonium chloride (BTEAC) was used as the catalyst. Using the same oxidant and conveniently derivatized starting materials, a-D-xy/o-hexofuranos-5-ulose, a-D-n Zw-hexofuranos-5-ulose, and /f-L-arabino-hexofuranos-5-ulose derivatives were obtained.436... 

Oxidation of aikenes. KMn04 can be solubilized in CH2CI2 by an equimolar amount of benzyltriethylammonium chloride. This solution can be used for homogeneous oxidation of aikenes to intermediates that can be decomposed either to dialdehydes or to s-l,2-diols. In two-phase oxidations with KMnOa and phase-transfer catalysts, diols or carboxylic acids are obtained. ... 

In situ formation of an oxaziridine is possible using a reagent combination of chloramine-M, benzaldehyde, and benzyltriethylammonium chloride <2000JA4039>. While the oxidation of /ra t-alkenes generates /ra t-oxiranes, the corresponding reaction of air-alkenes produces /ra t-oxiranes as major products. 

Cyclic amines are oxidized to lactams using a mixture of RuCls and NaI04. Lactams are also formed using KMn04 with benzyltriethylammonium chloride. Tertiary amines are converted to amides and cyclic tertiary amines can be converted to lactams by oxidation with Hg -EDTA complex in basic solution. Lactams, which need not be A-substituted, can be converted to cyclic imides by oxidation with a hydroperoxide or peroxyacid and an Mn(II) or Mn(III) salt. Lactams are oxidized to cyclic imides with oxygen and Co(OAc)2 in the presence A-hydroxysuccinimide. ... 

The reaction of alkenes with alkaline potassium permanganate proceeds rapidly via formation of a cyclic manganese ester, which is hydrolyzed to the 1,2-diol. To avoid overoxidation to an acyloin (a-ketol), the pH of the reaction medium has to be monitored. Although the yields of cA-diols obtained are usually modest ( 50%), the procedure is less hazardous and much less expensive than using osmium tetroxide and thus is well suited for large-scale preparations. Improved yields of diols are obtained when the oxidation is carried out in water in the presence of a phase transfer agent such as benzyltriethylammonium chloride. 

The oxidation of c/.r-cyclooctene with basic permanganate illustrates the new method. The octene (0.1 mole) in methylene chloride is treated with a 40% aqueous solution of sodium hydroxide and I g. of benzyltriethylammonium chloride. The mixture is cooled to 0° and KMn04 (0.1 mole) is added in small portions over 2 hr. with vigorous stirring after standing overnight at 0°, the precipitated MnOz is dissolved by S02. The cis-1,2-cyclooctanediol is isolated by ether extraction and crystallization in 50% yield. The yield of diol obtained without a phase-transfer catalyst is 7%.22... 

ALKYLATION Benzyltriethylammonium chloride. n-Butyl mercaptan. Dialkylcar-bonium fluoroborates. Diethoxycarboni-um fluoroborate. Dimethylcopperhthium. Ethyl vinyl ether. Dimethylformamide dimethyl acetal. Dimethyl sulflde. Dimeth-ylsulfonium methylide. Ethyl chlorofor-mate. Hexamethylphosphoric triamide. Lithium diisopropylamide. Lithium N-iso-propylcydohexylamide. O-Methyldiben-zofuranium fluoroborate. Methyl fluoro-sulfonate. Naththalene-Sodium. Palladi-um(II) chloride. 1,2,2,6,6-Pentamethyl-piperidine. Potassium hydroxide. Silver oxide. Sodium bis-2-methoxyethoxyalu-minum hydride. Sodium hydride. Thal-lous ethoxide. 

A mixture of l-(dihalomethyl)alkyne and an alkene is treated with potassium tert-hwi-oxide/ or powdered potassium hydroxide in the presence of benzyltriethylammonium chloride as a catalyst, to give 1-alkynyl-l-halocyclopropanes 1 in reasonable to good yields (Table 35). 

ALKYLATION Benzyltriethylammonium chloride. 9-Borabicyclo [ 3.3.1 ] nonane. Dimethylcopperlithium. 1,3-Dithiane. Hexamethyl-phosphoric triamide. Lithiumdi-isopropylamide. Lithium diisopropylamide Methyl fluorosulfonate. Naphthalene -Lithium. Phenacylsulfonyl chloride. Polyphosphate ester Silver oxide. Triethylaluminum. Triethyl-oxonium fluoroborate. 

Oxidations. Oxidation of benzyl ethers with KMn04 in the presence of benzyltriethylammonium chloride gives alkyl benzoates in refluxing dichloromethane," and under similar conditions, (V-phenyl azacycles afford lactams. ... 

SoHd-liguid phase-transfer catalysis. Crown ethers have commonly been used as catalysts for reactions between a solid-liquid interface, and quaternary ammonium and phosphonium salts have been used only as catalysts for reactions in two-phase liquid liquid reactions. However, several laboratories have reported that the latter catalysts are also satisfactory for two-phase solid liquid reactions. Thus dichlorocarbene can be generated from chloroform and solid sodium hydroxide under catalysis from benzyltriethylammonium chloride in yields comparable to those of the classical Makosza method. Another example of this type of catalysis is the oxidation of terminal and internal alkynes by solid potassium permanganate in CH2CI2 with Adogen 464 as catalyst. Aliquat 336 has been found to be as satisfactory as a crown ether for certain displacement reactions with NaOAc, KSCN, KNOa, and KF in CH3CN or CHaCla. ... 

The two-phase permanganate oxidation of olefins generally affords products of oxidative cleavage. Weber and Shepherd found that when benzyltriethylammonium chloride was used as catalyst and the temperature was maintained near 0°C, internal olefins were oxidized by basic permanganate in dichloromethane to the corresponding czs-glycols in moderate yields (Eq. 11.3) [6]. Cyclohexene, c/s-cyclooctene and trans-cyclododecene were dihydroxylated by this method in 15%, 50%, and 50% yields... 

Benzyltriethylammonium permanganate has also been used for the mild oxidation of sulphoxides to sulphones at — 10 °C in methylene chloride in the presence of keto, amino and ester groups in > 65% yields142. 

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