Triethylammonium chloride

The solution was cooled to 0°C in an ice-bath, and then the chloropho-sphine (2.2 g) was added dropwise via a syringe over 5 minutes with stirring. A white precipitate of triethylammonium chloride appeared. When the addition was complete, the ice-bath was removed and the stirring was continued at ambient temperature for 15 hours. 

There are relatively few reports of phase-transfer catalysed syntheses of phenols from activated haloarenes using quaternary ammonium salts, presumably because of the instability of the ammonium salts under the reaction conditions. A patented procedure for the conversion of, for example, 2,6-dichloropyridine into 6-chloropyrid-2-one (98%) using aqueous sodium hydroxide in the presence of benzyl-triethylammonium chloride at 120-150°C has been filed [32], A possible route to the phenols, however, comes from the observed reaction of phenols with potassium carbonateipotassium hydrogen carbonate to yield the aryl carbonates (80-85%) using the procedure described for the preparation of dialkyl carbonates (3.3.13) [50]. 

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. 

Finally, manganese carbonyl complexes also show potential for effecting interesting phase transfer catalyzed carbonylation reactions. Alkynes react with carbon monoxide and methyl iodide in methylene chloride, using 5N NaOH as the aqueous phase, benzyl-triethylammonium chloride as the phase transfer catalyst, and either bromopentacarbonylmanganese or dimanganese decacarbonyl to afford... 

The triethylamine is used to trap any hydrogen chloride present as the insoluble triethylammonium chloride which is collected in the glass wool filter. A reagent grade of triethylamine (b.p. 88°) was distilled from calcium hydride prior to use. 

Inhibitors have been used to investigate the biosynthesis of 1,2-dihydroneuro-sporene [l,2,7,8-tetrahydro-i/, i/f-carotene (143)] and related 1,2-dihydro-carotenoids in Rhodopseudomonas viridis, and possible alternative sequences are presented.The C-1,2 hydrogenation reaction is inhibited by CPTA [2-(4-chlorophenylthio)triethylammonium chloride], a compound known to inhibit cyclization and C-1,2-hydration in other systems, thus indicating possible similarity of the reactions involved. 

The Dervan group discovered that addition of ferf-butyl hypochlorite to a solution of l-amino-2,2,6,6-tetramethylpiperidine and triethylamine in ether at —78 °C produces triethylammonium chloride as an insoluble white precipitate and an intense purple solution. The purple coloration, which is stable for hours at —78 °C, fades in minutes at 0 °C and was assigned to the 1,1-diazene 64. " " " ... 

Triethylammonium chloride [554-68-7] M 137.7, m 257-260"(dec). Purified like the bromide above. 

Oxidative decyanation (6, 430). This reaction can be conducted under phase-transfer conditions with 50% NaOH in DMSO with catalytic amounts of benzyl-triethylammonium chloride (TEBA). The method fails with purely aliphatic nitriles. The highest yields (85-90%) are obtained with aromatic secondary nitriles. 

B. 2,4-Bis(trimethylsilyloxy)-5-methylpyriniidine. In an oven-dried, 1-L, round-bottomed flask Is placed thymine (12.6 g, 0.1 mol) (Note 1) and chlorotrimethylsilane (Note 7) in 300 mL of benzene (Note 8) under an argon atmosphere. To the stirred suspension is added triethylamine (20.2 g, 0.2 mol) (Note 9) dropwise via a dropping funnel over 1 hr. After the addition is complete, the reaction is stirred overnight. The precipitated triethylammonium chloride and unreacted thymine are removed by suction filtration (Note 10) and the solid is washed with dry benzene (2 x 30 mL). The solvent is then removed with a rotary evaporator. The resulting viscous oil is distilled... 

Heck intramolecular cyclization. Silver carbonate or nitrate was added originally to tandem Heck arylation reactions to depress alkene isomerization, but they also improve selectivity in the -elimination step. Grigg et al.1 have used a number of useful additives such as triethylammonium chloride, sodium formate (15, 248), phenylzinc chloride, as well as silver(l) and thallium(I) salts. In fact, thallium(I) salts... 

Z-Lys(Boc)-NH-(CH2)4-NH-Boc 7.0 g (31 mmols) of Boc-NH-(CH2)4-NH2-HCI and 4.2 ml (30 mmols) of triethylamine in 100 ml of dimethylformamide are stirred for 20 hours together with 16.8 g (30 mmols) of Z-Lys(Boc) OTCP. The product is filtered off the triethylammonium chloride and the filtrate is evaporated to dryness in vacuo. The residue is dissolved in ethyl acetate, thoroughly shaken at 0°C with 2 N citric acid, 1 N bicarbonate and H20 and dried over sodium sulfate. After distilling off the solvents, the residue is recrystallized two times from isopropanol/ether. Yield 14.1 g (83%), M.P. 83°-85°C. 

To a 10-mL round-bottomed flask fitted with a nitrogen balloon was added sulfide catalyst (0.2 equiv), anhydrous dioxane (4.0 mL), rhodium(II) acetate dimer (2 mg, 0.01 equiv), substrate (0.5 mmol), benzyl triethylammonium chloride (23 mg, 0.2 equiv), and tosylhydrazone sodium salt (1.5 equiv). The reaction mixture was stirred vigorously at 40 °C for 48 h. Work-up consisted of the sequential addition to the reaction mixture of water (5 mL) and ethyl acetate (5 mL). The aqueous layer was washed with ethyl acetate (2.5 mL) and the combined organic phases dried (MgSC ), filtered, and concentrated in vacuo. The crude products were analyzed by aH NMR to determine the diastereomeric ratio, and then purified by FC to afford the corresponding cyclopropane. 

DIB (diacetoxyiodo)benzene TEBA benzyl triethylammonium chloride... 

One mole of acetyl chloride is added to a liter of triethylamine, resulting in a vigorous exothermic reaction. Once the reaction mixture has cooled, 1 mole of ethanol is added. Another vigorous exothermic reaction results. The mixture is analyzed and found to contain triethylamine, ethyl acetate, and triethylammonium chloride. Propose mechanisms for the two exothermic reactions. 

Allyl bromides (14) react, at room temperature, with a stoichiometric quantity of Co2(CO)8, sodium hydroxide (5 N), benzene, and benzyl-triethylammonium chloride as the phase-transfer catalyst. Fine yields (Table II) of ir-allylcobalt tricarbonyl complexes (15) were obtained by use of short reaction times (15-60 min) (28). This simple and mild method is superior to conventional routes described in the literature (29-31). 

Alkylation of alcohols with 2-(methoxyethoxy)methyl chloride (MEMC1, bp 50-52 C/1.7 kPa) (HAZARD carcinogenic) under an assortment of conditions pioneered by Corey still retain favour. These include reaction of the lithium or sodium alkoxide (generated from sodium or potassium hydride) with ME MCI in THF or DME at 0 °C (10-60 min) and reaction of the alcohol with MEMCI in dichloromethane in the presence of /-Pr NEt at room temperature for 3 h. For hindered alcohols, sodium iodide can be added to generate the more reactive 2-methoxyethoxymethyl iodide in situ. Alternatively, reaction of the alcohol with [(2-methoxyethoxy)methyl]triethylammonium chloride (prepared from MEMO and trie thy lamine) in refluxing acetonitrile is recommended for acid-sensitive substrates such as tertiary alcohols [Scheme 4,271],500... 

CHLORINATION Chlorine oxide. N-Chloro-triethylammonium chloride. 

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)... 

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