Benzyltrimethylammonium hydroxides

In their initial studies, Shechter and Wynstra had demonstrated that these catalysts could achieve high selectivity of the epoxy-phenol reaction in a solution of excess phenol. They later reversed the situation and studied the reaction selectivity in a solution of excess glycidyl ether in which the phenol was used as the limiting reagent. The excess of epoxide over phenol was measured until phenol had practically disappeared, and the results in all cases indicated high selectivity towards the epoxy-phenol reaction. The tertiary amine, ben ldimethylamine, was somewhat more effective than potassium hydroxide benzyltrimethylammonium hydroxide was even more powerful. First-order kinetics were observed for all reactions. Since it was postulated that the phenoxide ion was common to all these reactions, the observed diffCTences in reaction rates were linked to the cation. In was not determined, however, whether the cation effect is one of different degrees of dissociation of the phenol salts or of some other phenonomenon. 

Sodium hydroxide/benzyltrimethylammonium chloride NaOH/PhCH N Me Cl O-Methylation of alcohols OH OMe... 

Sodium hydroxide/benzyltrimethylammonium chloride NaOHIPhCH2N Me Cl Haloform condensation CO -> C(OH)CCl3... 

Cinnolin-3(2//)-one (7) is methylated with diazomethane or methyl sulfate to give 2-methylcinnolin-3(2H)-one. In a similar manner, benzylation with benzyl chloride, cyanoethylation with acrylonitrile in the presence of benzyltrimethylammonium hydroxide and glucosidation with tetra-O-acetyl-a-o-glucopyranosyl bromide in the presence of a base affords the corresponding 2-substituted cinnolin-3(2//)-ones. However, glucosidation of the silver salt of cinnolin-3(2//)-one produces the corresponding O-substituted compound. 

Benzyltrimethylammonium hydroxide (Triton B) [100-85-6] M 167.3, d 0.91. A 38% soln (as supplied) was decolorized (charcoal), then evaporated under reduced pressure to a syrup, with final drying at 75° and 1 mm pressure. Prepared anhydrous by prolonged drying over P2O5 in a vacuum desiccator. 

A solution of benzyltrimethylammonium hydroxide (Triton B, 10ml, 40% in MeOH) was treated with aqueous HF (ca. 8.6ml, 4.7%) until the pH reached 8-7. The solvent was removed in vacuo (ca. 1 mm), and the residue was dried at 50°C/0.5 mmHgfor 20 h. The resulting highly hygroscopic solid was powdered, and then stored in a desiccator over P205. 

A 500 mL round-bottom flask containing aqueous sodium hydroxide (25 or 50 wt%) and benzyltrimethylammonium bromide as the phase transfer agent (0.2 g, 0.0008 mole) was placed in a constant-temperature oil bath and heated to the reflux temperature of 165°C. Chopped nylon-4,6 fibers (6 g, 0.030 mol) were placed in the reaction flask. The reaction mixture was constantly stirred with a magnetic stirrer and the reaction was carried out at atmospheric pressure for a period of 24 or 36 h (see Table 10.3 for results). The aqueous sodium hydroxide solution containing products of depolymerization was concentrated by evaporation and 30 mL of 35% aqueous hydrochloric acid was added to the concentrate. The precipitate was filtered and washed with water. The product was dried in a vacuum oven at 120°C for 24 h. 

Note In the second spray potassium hydroxide solution can be replaced by sodium hydroxide solution or by a solution of 17 g benzyltrimethylammonium hydroxide in 100 ml 33 percent methanol [4]. The Kedde reagent [13] can also be applied very sue-... 

Tetrahydrocarbazole, Benzyltrimethylammonium hydroxide Anon., BCISC Quart. Safety Summ., 1968, 39, 36... 

See Benzyltrimethylammonium hydroxide, etc., and Bases, both above See other cyano compounds See related haloalkenes... 

In the first systematic study of the reaction between several different diary-loxalates, hydrogen peroxide, and fluorophores [3], it was recognised that the chemiluminescence reaction was highly sensitive to base catalysis by potassium hydroxide or benzyltrimethylammonium hydroxide, and that acidic conditions markedly diminished the light production. The addition of bases was noted to... 

N,N,o-trimethyl-, 34, 61 N-Benzylaniline, 36, 22 Benzyl chloride, 34, 65 Benzyl cyanide, 31, 53 32, 64, 65, 92 N-Benzylidenemethylamine, 34, 65 Benzyl isocyanide, 31, 54 Benzylmagnesium chloride, 34, 65 3-Benzyl-3-methylpentanenitkile, 35, 8 3-BENZYL-3-METHYLPENTANOIC ACID, 35, 6 /S-Benzyl-/ -methylvaleric acid, 35, 6 Benzylthiosulfuric acid, 32, 103 Benzyltrimethylammonium hydroxide,... 

Temperature Effects. The oxidation of 9,10-dihydroanthrafcene to anthraquinone in anhydrous pyridine solvent with benzyltrimethylammo-nium hydroxide as the base occurs over a wide temperature range (Table I). Some oxidation takes place at a temperature as low as — 20°C., but maximum anthraquinone conversions (about 70%) occur between 50° and 70°C. Above 70°C., the conversion decreases, probably as a result of thermal decomposition of the benzyltrimethylammonium hydroxide. 

Reaction mixture and conditions anhydrous pyridine, 50 ml., benzyltrimethylammonium hydroxide, dihydroanthracene, 9.0 grams, 50 mmoles reaction time, 2 hrs. 

Table VI. Oxidation of Various Compounds" in Pyridine with Benzyltrimethylammonium Hydroxide Catalyst...

Mechanism for Base-Catalyzed Autoxidation of 9,10-Dihydroanthracene. The autoxidation of 9,10-dihydroanthracene in pyridine as the solvent and in the presence of benzyltrimethylammonium hydroxide, a strong base, is believed to involve the reaction of a carbanion and molecular oxygen. Indirect evidence of the existence of the carbanion of dihydroanthracene in pyridine solution comes from the color that forms in the presence of the base. When dihydroanthracene is added to a pyridine solution of the base, a deep blood-red color develops immediately. This color is not completely attributable to carbanions since a trace of anthra-quinone alone will produce it. However, under an inert atmosphere (nitrogen) in which no anthraquinone can be formed, a deep red color is also formed. 

A sample of the monohydroperoxide, previously reported by Bickel and Kooyman (2), was obtained by autoxidation of 9,10-dihydroanthra-cene in benzene under ultraviolet irradiation. When this compound was treated under nitrogen with benzyltrimethylammonium hydroxide, it decomposed to give a mixture of anthracene and anthrone. (Under acidic conditions, it decomposed entirely to anthracene.) A fresh sample of the hydroperoxide was then oxidized. The physical appearance of the reaction mixture was similar to that in the oxidation of anthrone. The product was analyzed, and the conversion to anthraquinone was only 59%. Again, other oxidation products or anthrone may have contributed to the anthraquinone estimate. 

No systematic study is available on other parameters in triphase alkylation of phenylacetonitrile, but the following isolated observations may be significant. Both dilution of the organic phase with benzene or cyclohexane and use of 10% NaOH in place of 50% NaOH greatly reduced the rate 101). The benzyltrimethylammonium ion is attacked by hydroxide ion under the conditions of phenylacetonitrile alkylation. Repeated use of either Dowex ion exchange resins101) or 2 % CL, 16-50 % RS resins 103) gave reduced activity. 

Compounds derived from indole have been extensively investigated as potential psychoactive dmgs. The construction of a tricyclic indole derivative starts by benzyltrimethylammonium hydroxide catalyzed Michael addition of 2-carbethoxy-indole (70-1) to acrylonitrile to give the adduct (70-2). In one of several alternatives... 

The phase transfer catalyzed alkylation reaction of dodecyl phenyl glycidyl ether (DPGE) with hydroxyethyl cellulose (HEC) was studied as a mechanistic model for the general PTC reaction with cellulose ethers. In this way, the most effective phase transfer catalysts and optimum reaction concentrations could be identified. As a model cellulose ether, CELLOSIZE HEC11 was chosen, and the phase transfer catalysts chosen for evaluation were aqueous solutions of choline hydroxide, tetramethyl-, tetrabutyl-, tetrahexyl-, and benzyltrimethylammonium hydroxides. The molar A/HEC ratio (molar ratio of alkali to HEC) used was 0.50, the diluent to HEC (D/HEC) weight ratio was 7.4, and the reaction diluent was aqueous /-butyl alcohol. Because some of the quaternary ammonium hydroxide charges would be accompanied by large additions of water, the initial water content of the diluent was adjusted so that the final diluent composition would be about 14.4% water in /-butyl alcohol. The results of these experiments are summarized in Table 2. 

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