Acetals bromination

The formation of intermediate enol ethers has long been recognised to occur in the mechanism of cyclic and acyclic acetal bromination or isotope exchange (54) (Marquet et al., 1961 Marquet and Jacques, 1962 Gaudry and Marquet,... 

The reaction of 26 with bromine in carbon tetrachloride yields325-327 a mixture of exo and endo bromo derivatives (27) in the ratio of 3 2 (see also, Section 11,7). The supposed intermediate of this acetal bromination into the 2-position is326 3,4-dihydro-2H-pyran-2-methanol (25) however, direct conversion of 25 into 27 was not demonstrated. 

Acetal Bromination and Formation. The bromination of an acetal by NBS under radical conditions does not require the presence of an aromatic group (eq 41). ... 

Silver acetate/potassium acetate/bromine Replacement of iodine by acetoxy groups with ring contraction... 

Related Reagents. Bromine-r-Butylamine Bromine Chloride Bromine-l,4-Diazabicyclo[2.2.2]octane Bromine-1,4-Dioxane Bromine-Silver(I) Oxide Bromine-Triphenyl Phosphite iV-Bromosuccinimide A7-Bromosiiccinimide-Dimethylformamide 7V-Bromosuccinimide-Dimethyl Sulfide Al-Bromosuccinimide-Sodium Azide Copper(II) Bromide Hy-drobromic Acid Mercury(II) Oxide-Bromine Phosphoms(III) Bromide Pyridinium Hydrobromide Perbromide Sodium Bromide Thallium(III) Acetate-Bromine. 

After combustion add an excess (5 to 10 ml) of acetic-bromine solution and allow to stand for two minutes. Remove the excess bromine by addition of formic acid (about 0 5 to 1 0 ml), wash down the sides of the flask with water and sweep out any bromine vapours above the liquid with a current of air. Add 1 g of potassium iodide and titrate with 0 02N sodium thiosulphate, using starch mucilage as indicator. 

Acetic-bromine solution Dissolve 100 g of potassium acetate in glacial acetic acid, add 4 ml of bromine and dilute to 1 litre with glacial acetic acid. 

Related Reagents. Mercury(II) Oxide-Bromine Thallium(I) Carbonate Thallium(III) Acetate-Bromine. 

Dissolve 36 g. of sodium hydroxide in 160 ml. of water contained in a 500 ml. conical flask, and chill the stirred solution to 0-5° in ice-water. Now add io-8 ml. (32-4 g.) of bromine slowly to the stirred solution exercise care in manipulating liquid bromine ) during this addition the temperature rises slightly, and it should again be reduced to 0-5°. Add a solution of 12 g. of acetamide in 20 ml. of water, in small portions, to the stirred hypobromite solution so that the temperature of the mixture does not exceed 20° the sodium acet-bromoamide is thus obtained in the alkaline solution. Now remove the flask from the ice-water, and set it aside at room temperature for 30 minutes. 

Dissolve I g. of finely powdered acetanilide in 5 ml. of cold glacial acetic acid contained in a 25 ml. conical flask. Then in another small flask prepare a solution of 0 42 ml. (1 34 g.) of bromine (care ) in 6 ml. of glacial acetic acid, and add this solution slowly to the acetanilide solution, shaking the latter throughout the addition to ensure thorough mixing. Allow the final mixture to stand at room temperature for 15 minutes. Then... 

For class work it is convenient to make up a single bromine solution by dissolving 7 ml. of bromine in 100 ml. of glacial acetic acid, and using 6-5 ml. of this solution for each preparation. 

I he methyl iodide is transferred quantitatively (by means of a stream of a carrier gas such as carbon dioxide) to an absorption vessel where it either reacts with alcoholic silver nitrate solution and is finally estimated gravimetrically as Agl, or it is absorbed in an acetic acid solution containing bromine. In the latter case, iodine monobromide is first formed, further oxidation yielding iodic acid, which on subsequent treatment with acid KI solution liberates iodine which is finally estimated with thiosulphate (c/. p. 501). The advantage of this latter method is that six times the original quantity of iodine is finally liberated. 

Bromination of fatty acids in the a-position can be effected quite readily in the presence of phosphorus trichloride, red phosphorus or pyridine as catalysts or halogen carriers with acetic acid, the addition of acetic anhydride (to ensure the absence of water) improves the yield and facilitates the bromination. Examples are —... 

An alternative procedure, more suitable for the preparation of somewhat larger quantities of the bromo derivative, is the following. Dissolve 10 g, of the compovmd in 10-15 ml. of glacial acetic acid, cautiously add 3-4 ml. of hquid bromine, and allow the mixture to stand for 15-20 minutes. Pour into 50-100 ml. of water, filter off the bromo compound at the pump, and wash with a httle cold water. Recrystallise from dilute alcohol. 

A more active product is obtained by the following slight modification of the above procedure. Dissolve the succinimide in a slight molar excess of sodium hydroxide solution and add the bromine dissolved in an equal volume of carbon tetrachloride rapidly and with vigorous stirring. A finely crystalline white product is obtained. Filter with suction and dry thoroughly the crude product can be used directly. It may be recrystallised from acetic acid. 

This substance is conveniently obtained by treating p-bromoacetophenone (Section IV, 138) with the calculated quantity of bromine dissolved in glacial acetic acid ... 

Place a solution of 50 g. of p bromoacetophenone (Section IV,138) in 100 ml. of glacial acetic acid in a 500 ml. flask. Add very slowly (about 30 minutes) from a dropping funnel 40 g. (12-5 ml.) of bromine shake the mixture vigorously during the addition and keep the temperature below 20°. p-Bromophenacyl bromide commences to separate as needles after about half of the bromine has been introduced. When the addition is complete, cool the mixture in ice water, filter the crude product at the pump, and wash it with 50 per cent, alcohol imtil colourless (about 100 ml. are required). RecrystaUise from rectified (or methylated) spirit (ca. 400 ml.). The yield of pure p-bromophenac bromide (colourless needles, m.p. 109°) is 50 g. 

Bromination of quinaldine (I) (Section V,2) with bromine in glacial acetic acid in the presence of anhydrous sodium acetate aflFords dilute sulphuric acid gives quinaltiinic acid (III). 

Dibromofluorescein is prepared by treating fluorescein in 80 per cent, acetic acid solution with the theoretical quantity of bromine. 

Dibromo-o-cresolsulphonephthalein (bromocresol purple). Dissolve 6 g. of o-cresolsulphonephthalein in 50 ml. of glacial acetic acid, heat to boiling under reflux, add slowly a solution of 2 ml. of bromine in... 

This solution may also be employed in the test for bromine. If iodine has been found, add small amounts of sodium nitrite solution, warm shghtly and shake with fresh 1 ml. portions of carbon tetrachloride until the last extract is colourless boil the acid solution until no more nitrous fumes are evolved and cool. If iodine is absent, use 1 ml. of the fusion solution which has been strongly acidified with glacial acetic acid. Add a small amount of lead dioxide, place a strip of fluorescein paper across the mouth of the tube, and warm the solution. If bromine is present, it will colour the test paper rose-pink (eosin). 

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