Bromination, preparation

D-lysergic acid propargylamide (0.016 mole) was dissolved in a mixture dichloro-methane/dioxane (85/15), 400 ml. Under vigorous stirring into this solution the polymer supported bromine (prepared acc. to ref. 29) containing 0.024... 

Date October 15, 1985 Name of experiment Topic Bromine. Preparation and running of experiment Observations. Conclusions... 

Bromination of ethylene oxide vu reported as early as 1862 by Wurtz18 7 to give a red solid of unknown constitution. Maas and Boomer1081 obtained the same red solid on warming to room temperature oxonium complexes of ethylene oxide and bromine prepared at —80°. Freezing-point results indicated for these complexes the empirical formulas CsH40 Bt and CxH 0-2Br. No explosion occurs on warming to room temperature, however. 

Bromobenzene,Cf,HfSr. B.p. 155°C. Prepared from benzene by direct bromination in the presence of a carrier (Ij, Fe, AICI3) or by... 

CH2Br COOH. White crystalline solid, m.p. 50"C, b.p. 208 C. Soluble in water and alcohol. Prepared by the action of dry bromine on dry ethanoic acid in presence of small amounts of red phosphorus. Produces sores upon the skin used in chemical syntheses. See Reformatski reaction. 

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. 

In the laboratory, bromine is prepared by oxidation of bromide ion the oxidation is carried out by mixing solid potassium bromide with manganese(IV) oxide and distilling with concentrated sulphuric acid ... 

Hydrogen bromide cannot be prepared readily by the action of sulphuric acid on a bromide, because the latter is too easily oxidised by the sulphuric acid to form bromine. It is therefore obtained by... 

Hydrogen bromide may also be prepared by dropping bromine into benzene containing aluminium powder, which acts as a catalyst to the reaction ... 

Dibromine monoxide, BtjO, is prepared, similar to the corresponding dichlorine compound, by the action of a solution of bromine in carbon tetrachloride on yellow mercury(II) oxide ... 

Chlorine, bromine and iodine form halic(V) acids but only iodic(V) acid, HIO3, can be isolated. Solutions of the chloric) V) and bromic) V) acids can be prepared by the addition of dilute sulphuric acid to barium chlorate(V) and bromate(V) respectively, and then filtering (cf. the preparation of hydrogen peroxide). These two acids can also be prepared by decomposing the corresponding halic(I) acids, but in this case the halide ion is also present in the solution. 

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... 

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. 

A -Bromosuccinimide (prepared by the action of bromine on succinimide at o in the presence of sodium hydroxide) is a valuable specific reagent for brominating olefines in the a-methylene position to the double bond without simultaneously adding bromine to this bond. For example, if A -bromosuccini-mide is represented by (C4H40t)NBr —... 

A solution prepared by dissolving 2 g. of biomine in 100 g. of carbon tetra. chloride is satisfactory. Carbon tetrachloride is employed because it is an excellent solvent for bromine as well as for hydrocarbons it possesses the additional advan. tage of low solubility for hydrogen bromide, the evolution of which renders possible the distinction between decolourisation of bromine due to substitution or due to addition. 

The hydrobromic acid sulphuric acid solution may be prepared by the reduction of bromine with sulphurous acid (Section 11,49, 1) distillation of the reaction product is unnecessary ... 

This acid mixture may be prepared (compare Section 11,49, 1) by placing 120 g. (37-5 ml.) of bromine and 130 g. of crushed ice in a 500 ml. flask, cooling the latter in ice, and passing sulphur dioxide (from a siphon of the liquefied gas) into the bromine layer at such a rate that the gas is completely absorb. The flask is shaken occasionally, and the flow of gas is stopped inunediately the red colour due to free bromine has disappeared the mixture will then have a yellow colour. The resulting acid mixture is equivalent to 260 g. of 48 per cent, hydrobromio acid to which 75 g. of concentrated sulphuric acid have been added it need not be dis. tilled for the preparation of n-butyl bromide. 

Owing to the comparatively negligible difference in the cost of bromine and the equivalent quantity of constat boiling point hydrobromio acid, there is little to be gained—apart from the instructional value—in preparing the hydrobromio acid from bromine in the preparation of alkyl bromides. 

Owing to the corrosive action of bromine upon corks j-jg 7, l. and rubber stoppers, ground glass joints are recommended in this preparation. The apparatus, depicted in Fig. Ill, 37, 1, is particularly convenient for the preparation of bromides from alcohols. A double surface condenser is fitted into D and a round-bottomed flask is fitted on to the ground glass joint at C R is a three-way stopcock f which permits the removal of the contents of A without disconnecting the apparatus. For preparations of moderate size, A has a capacity of 60 or 100 ml. and a 250 or 500 ml. flask is attached at C. 

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