P of bromine

The melting of bromine or of iodine is attended by an expansion—with bromine, J. I. Pierre 31 found a 6 per cent, expansion. M. Toepler found an expansion of 0 0511 c.c. per gram of bromine, and 0 0434 c.c. per gram of iodine. Hence, by Clausius and Clapeyron s equation the m.p. of bromine is raised 0 0203° per atm. rise of press., and iodine, 0-0314° per atm. rise of press. 

Preparation of bromine by oxidizing hydro-bromic acid by manga-nese(IV) oxide Drawing of apparatus. Reaction equations. Required calculations. Tabulated data (b.p. of bromine, density, etc.) When the reaction mixture is heated, a brown bromine vapour condensing as a heavy reddish brown liquid evolves... 

We assume that the m.p. and b.p. of bromine will be between those of chlorine and iodine. 

Isocroionic acid, -crotonic acid, cis-croionic acid. Colourless needles m.p. 14 C, b.p. 169 C. Prepared by distilling -hydroxy-glutaric acid under reduced pressure. Converted to a-crotonic acid by heating at 180 C, or by the action of bromine and sunlight on an aqueous solution. 

Colourless crystals m.p. 204 C. Prepared by photochemical isomerization ofcilraconic acid in the presence of bromine. 

Bromine. Slip slightly to one side the glass plate covering one jar of ethylene, add 2-3 ml. of bromine water (preparation, p. 525), restore the glass plate in position, and then shake the jar vigorously. The colour of the bromine rapidly disappears as 1,2-dibromoethanc is formed. Note that owing to the absorption... 

Dibromide formation. Dissolve 0 2 ml. of styrene in 0 5 ml. of CCI4 in a test-tube. Add slowly, drop by drop, a 10% solution of bromine in CCI4. Note the decolorisation of the bromine and absence of HBr fumes (therefore reaction by addition and not by substitution). Continue to add the bromine solution until a faint brown colour persists. Scratch the sides of the tube and cool it in ice-water. Filter off the crystals that separate and recrystallise the styrene dibromide from methanol m.p. 72 . 

Stilbene decolorises bromine only on heating. Proceed as above, but keep the stilbene solution hot during the addition of the CCI4 solution of bromine. Stilbene dibromide has m.p. 237 . 

Place 50 g. (57 ml.) of dry A.R. benzene and 0 5 ml. of dry p rridine (1) (dried over potassium hydroxide pellets) in a 500 ml. round-bottomed flask. Attach a reflux condenser to the flask and an inverted funnel (just dipping into some water in a beaker) to the top of the condenser (Fig. II, 13, 8, b). Partially immerse the flask in a bath of cold water, supported upon a tripod and gauze. Carefully pour 125 g, (40 ml.) of bromine (for precautions to be taken with bromine, see Section 111,35, Note 1) through a condenser and immediately insert the absorption device into the upper end of the condenser. A vigorous reaction soon occurs and hydrogen bromide is evolved which is absorbed by the water in the beaker when the reaction slackens, warm the bath to 25-30° for... 

Pour the resulting dark reddish-brown liquid into 500 ml. of water to which 17 ml. of saturated sodium bisulphite solution has been added (the latter to remove the excess of bromine). Steam distil the resulting mixture (Fig. II, 41,1) , collect the first portion of the distillate, which contains a little unchanged nitrobenzene, separately. Collect about 4 litres of distillate. Filter the yellow crystalline solid at the pump, and press well to remove the adhering liquid. The resulting crude m-bromonitrobenzene, m.p. 51-52°, weighs 110 g. If required pure, distil under reduced pressure (Fig. II, 19, 1) and collect the fraction of b.p. 117-118°/9 mm. it then melts at 56° and the recovery is about 85 per cent. 

Continue the passage of bromine vapour until the solution in A assumes a distinctly yellow colour (2-3 hours) the reaction is then complete. Filter the tribromoaniline on a Buchner funnel, wash it thoroughly with water to remove hydrobromic acid, and suck as dry as possible. Ilecr3 stallise from methylated (or rectified) spirit. The yield is 22 g. m.p. 120°. 

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. 

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