Toluene, a-bromo

Benzyl bromide Toluene, a-bromo- (8) Benzene, (bromomethyl)- (9) (100-39-0)... 

Benzyl bromide Toluene, a-bromo- (8) Benzene, (bromomethyl)- (9) (100-39-0) (S)-2-(N,N-Dlbenzylamino)-3-phenyl-1-propanol Benzenepropanol, p-[bis(phenylmethyl)amino]-, (S)- (12) (111060-52-7)... 

In a 500 ml. bolt-head flask provided with a thermometer (reaching almost to the bottom) and a calcium chloride (or cotton wool) guard tube, place 100 g. of a-bromo-wo-valerj l bromide and 50 g. of dry, finely-divided urea. Start the reaction by warming the flask on a water bath the temperature soon rises to about 80°. Maintain this temperature for about 3 horns the mass will liquefy and then resolidify. Transfer the sticky reaction product to a large beaker containing saturated sodium bicarbonate solution, stir mechanically and add more saturated sodium bicarbonate solution in small quantities until effervescence ceases. Filter at the pump, suck as dry as possible and dry the crude bromural upon filter paper in the air. RecrystaUise the dry product from toluene. Alternatively, recrystaUise the moist product from hot water (ca. 700 ml.). The yield of pure brommal, m.p. 154-155°, is 28 g. 

Feuer and co-workers also nitrated ring-substituted toluenes to the corresponding arylnitromethanes with potassium amide in liquid ammonia. Sulfonate esters and NJ -dialkylamides undergo similar nitration the latter isolated as their a-bromo derivatives. Alkaline nitration of ethyl and ferf-butyl carboxylic esters with potassium amide in liquid ammonia yields both the a-nitroester and the corresponding nitroalkane from decarboxylation. ... 

Thionyl chloride, 55, 27 Thiophenol, 58, 144 Thiophenol, copper(I) salt, 55, 123 Thiophenol, lithium salt, 55, 122 Toluene, 56,86,58,125 Toluene, p-bromo-, 56, 86 Toluene, 4-bromo-, 55,49 Toluene, p-chloro-, 56, 86 Toluene, a-cyclohexyhdene-, 56, 105 Toluene, a (2 hydroxycyclohexyhdene)-, 56,105... 

Allylic bromides 383 and 384 were the relais substances for the synthesis of coriamyrtin (9) (Scheme 43). The allylic bromides were eliminated with potassium ferf-butoxide in toluene affording diene 387. 1,4-Addition with W-bromosuccini-mide in polar solvent at room temperature yielded the unsaturated a-bromo-5-hydroxy unit of 388, which formed the unsaturated epoxide 389 by base treatment. Epoxidation with peracid occurred as expected from the convex face. The cyclic ether moiety of bisepoxide 390 was oxidized to the lactone 368 with ruthenium... 

The success of the reaction depends largely on the use of finely ground aluminum chloride and freshly prepared cyanogen bromide. Aromatic hydrocarbons—benzene, toluene, anthracene, and acenaphthene—and phenolic ethers respond favorably. However, phenanthrene gives none of the anticipated nitrile. As might be expected, a by-product is the aryl bromide. Indeed, thiophene and furan are converted largely to the a-bromo derivatives. 

Pyridine-N-oxide [1, 966]. a-Bromo and a-chloro carboxylic acids are oxidatively decarboxylated by treatment with pyridine-N-oxide (4 equiv.) in refluxing benzene or toluene.3 Cohen et at. note that, since pivalic acid is completely inert to pyridine-N-oxide, an u-hydrogen atom appears to be essential, for example in the reaction of phenylacetic acid. They suggest that an a-pyridinium ion is an intermediate ... 

Furanes. In a furane synthesis described recently the a-bromo acetal (1) and silyl enol ethers (2) react, in the presence of TiCU, to form alkoxy-7-bromoketones (3). The products undergo dehydrohalogenation and loss of CH3OH when heated in toluene for 5-8 hr. to form furanes (4). The furanes (4) are sometimes accompanied by (5), formed by elimination of only CH3OH. 

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