10.2 PERHIN AND DUPPA ON BIBROMOSUCCINIC ACID X.-On Bibromosuccinic Acid and the Artijkial Production of Tartaric Acid. BY TV. H. PERKIN,F.C.S. AND B. F. DUPPA,ESQ. INApril of last year we published a paper on the action of penta-chloride of phosphorus on malic acid,* in which we stated that there seemed reasons for believing that there existed a close relation between succinic malic and tartaric acids similar to that which exists between acetic glycollic and glyoxylic acids; and for the purpose of verifying that supposition we proposed endeavouring to obtain mono -and bibromo-succinic acids thinking that by hyclrat- ing them by means of hydrate of silver or by decomposing their silver-salts in the presrnce of water we might obtain malic and tartaric acids.Since that time we have obtained both of these bromo-acids but up to the present haveonly studied the bibromo- succinic acid. Bibromosuccinic Acid. We endeavoured to produce this snbstance by the direct action of bromine on succinic acid but did not obtain any satisfactory results. The process by which we have succeeded in obtaining this acid is as follows Equal volumes of bromine and chloridc of succinpl are heated in a strong sealed tube to a temperatureof 120 or 130%. for three or four holm. The tube after having cooled mixst be very care- fully opened so that the hydrobromic acid which has formed may slowly issue fwth ; if the tube be opeqed too rapidly its contents will be projected and lost. The product thus obtained is an oily liquid consisting of impure chloride of bibromosuccinyl.This is * Phil. Mag. April 1859. PERKIN AND DUPPA ON BIBBOMOSUCCINIC ACID 103 decomposed by being well agitated for an hour or two with two or three times its volume of water afier which the liquid will contain considerable quantities of the new acid in the form of a crystalline precipitate; this is purified by being well washed on a filter to separate hydrochloric acid and also another extremely soluble acid which has been formed. It is then dissolved in a moderately strong solution of carbonate of sodium and filtered for the purpose of removing a small quantity of an oily substance. The resulting sodium salt is then decomposed by nitric acid which causes the new product to separate as a crystalline precipitate which when thoroughly washed ona filter with cold water and then dried con- stitutes pure bibrornosuccinic acid.Carbon hydrogen and bromine determinations of specimens dried in vacuo over sulphuric acid gave the following numbers :-I. *4150of substance gave *2643of carbonic acid and *0600of water. 11. *2950of substance ga1.e -4035 of bromide of silver. Percentage composition :-I. n. Carbon . 17’36 -Hydrogen . 1.60 -Bromine. 58.2 I which agree with the formula as may he seen from the following table :-Theory. Experiment. -Carbon 8 equiv. . . 48 17.39 17-36 Hydrogen 4 , . .4 1.44 1-60 Bromine 2 , . 160 57-97 58.20 Oxygen 8 , . -64 23.20 -276 100*00 Bibromosuccinic acid is difficultly soluble in cold but tolerably so in hot water from which it crystdises on cooling in opaque 104 PERKIN AND DUPPA ON BIBROMOSUCCINIC ACID prisms; it is very soluble in alcohol and extremely so in ether.We have found the latter solvent very useful in separating small quantities of this acid from its aqueous solutions. Crystals of bibromacetic acid decrepitate when gently heated but when subjected to a high temperature decompose with formation of hydrobromic acid. It has a strong acid taste and reddens litmus rapidly. We have but cursorilg examined the salts of this acid. Bibromosuccinate of sodium is very soluble and appears to contain water of crystallisation. Acid bibromosuccinate of potassium is a white crystalline salt sparingly soluble.Bibromosuccinate of silver is obtained by adding a solution of nitrate of silver to either of the above salts. It is a white salt nearly insoluble in water The following determinations were made of a specimen dried over sulphuric acid in vacuo :-I ,5316 of substance gave 01879of carbonic acid and *0288of water. 11. 04163of substance gave -2418of chloride of silver and 03195of bromide. These results agree with the theoretical numbers as may be seen by the following table :- - Theory. Experiment. Carbon 8 eyuiv. . 48 9-79 9.63 Hydrogen 2 , b 2 *40 060 Bromine 2 , 160 4&08 43.71 Silver Oxygen 2 8 , Jj . b . 216 64- 32.65 33.08 - 32.64- 490 100~00 On boiling a quantity of bibromosuccinate of silver with water it graduall? decomposes with evolution of carbonic acid and forma- tion of bromide ot silver; the ebullition must be continued until no more cnrkonic gas is evolved.The resulting mixture is then thrown on a filter; the less soluble portion which consists chiefly of bromide of silver is well washed with water; and to the filtrate PERIC'IN AND DUPPA ON BIBROMOSCCCINLC ACID 105 which contains a small quantity of silver in solution a few drops of hydrochloric acid are added. The liquid is then separated from the chloride of silver by means of a filter and evaporated on a water bath until of a syrupy consistence. After remaining at rest for four and twenty hours under a bell-jar over sulphuric acid it is found to contain a considerable quantity of large crystals which are then separated from the residual syrupy acid by washing rapidly with cold alcohol; the product thus obtained is tartaric acid.A portion of this acid was dissolved in water and divided into two equal quantities. One of these was neutralized with carbonate of potassium and then the other added to it which caused the well-known precipitate of the acid tartrate of potassium to form whereof we made the following carbon hydrogen and potassium determinations :-I. 0202p. of substance gave *18875grm. of carbonic acid and *0540of water. 11. -205grm. of substance gave *19200grm. of carbonic acid and 10500 of water. 111. 01545grm. of substance gave 00590of chloride of potassium. Percentage composition :-I.11 In. b Carbon . 25.49 25.5 -Hydrogeii . 2.9 2.7 -Potassium -7 20a These numbers agree very closely with the theoretical as may be seen by the subjoined table :-Theory Experiment. Carbon 8 equiv. . 48 25.60 25-49 4 5 2*65 2.80 Hydrogen 5 , Potassium 1 , . . 39.2 20.00 zo*o 96 51.75 -Oxygen 12 , -188.2 100*00 HADOW ON THE This intepesting formation of tartaric acid may be thus explained ('SHZBr )' 0 + H!2°2 = (C8H'204K{ 0 + 2AgBr; 2ig) Bibroniosuccinate of Silver. Tartaric Acid. evidently showing that it is derived from four molecules of water. We have alluded to a syrupy acid which is formed at the same time astartaric acid and from which it had to be separated by means of cold alcohol. This we have not investigated as its nature shows that it would be very difficult to obtain pure and consequeritly would require considerable quaD tities which coupled with the expense and labour of obtaining only a few grammes of bibrumosuccinic acid has induced us to lay this part of the investigation aside for the present.It seems however probable that it is pyruvic acid which it will be remembered is formed from tartaric acid by the loss of carbonic acid and water; arid mag it not be possible that part of the tartitric acid at the moment of formation splits up into carbonic acid water arid pyruvic acid ? We are now investigating monobromosuccinic acid from which we expect to obtain some interesting results.