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On the synthesis of fumaric acid
338
[J. F. I.,
Chemical Section.
peculiar blue color which a mixture of sulphuric acid and phosphorus pentoxide assumes on standing for a time. The observation was made in connection with the apl~cation of Kjehldahl's method of determining nitrogen. None of the members present had ever noticed the phenomenon. Adjourned. WM. C. DAY, Secretary.
ON THE S Y N T H E S I S OF F U M A R I C ACID. BY E. H. KEISER.
[Read at the Stated Meetin¢ of the Chemical Section, held tSebruary 2o, I89O. ] [Preliminary Communication.]
Van't Hoff ~ has proposed the following stereometric for mul~e for fumaric and maleic acids : COOH--C--H II H--C--COOH Fumaric acid.
H--C--C00H and
l]
H--C--C00H Maleic acid.
Johannes Wislicenust has shown in a series of important papers that it is possible to determine experimentally the stereometrie formulae of certain isomeric compounds. A consideration of the hypothesis pert forward by him suggested the idea that it ought to be possible to prepare both fumaric and maleic acids synthetically from acetylene. In accordance with Van't Hoff and Wislicenus' theory, the di-halogen additive compounds of acetylene can exist in two isomeric forms having the formula~ : I.
X--C--H ]] H--C--X
H--C--X a n d II.
!I H--C--X
in which X represents any halogen atom. And, further, compounds having the constitution represented by formula I are more stable than those having the structure represented by the second formula. Fumaric acid would then * LaKerunffd~r Alome im Raume, p. 2I. R~umliche Anordnunff der Atome in organischen ~IIolekulen. Chem. (Liebig), ~4-6, 53.
Ann.
April, I89O.J
C/lcmical .%ctl}m.
~:.
a p p e a r to be closely related to the halogen derivatives ,,! the first class, and maleic acid to those of the second. It occurred to m e t h a t it mihgt, perhaps, be of interes'~ in this connection to start with acetylene, and prepare, in the first place, two isomeric all-halogen additive c o m p o u n d s . and then e n d e a v o r to t r a n s f o r m t h e s e into fumaric and maleic acid. T h e i n v e s t i g a t i o n is not y e t completed, b u t one of the acids, namely, f u m a r i c acid, has been prepared in this w a y from acetylene. A c e t y l e n e was p r e p a r e d b y the action of alcoholic potash u p o n e t h y l e n e bromide, and the purified gas was passed t h r o u g h a series of wash-bottles containing crystals of iodine covered with a layer of a b s o l u t e alcohol. A f t e r a time, the iodine disappeared, a n d from the liquid two isomeric acetylene di-iodides were separated. One of t h e s e c o m p o u n d s is a solid at ordinary t e m p e r a t u r e s ; the other is a liquid. T h e solid di-iodide is m u c h more stable than t h e liquid variety. It does not d e c o m p o s e on standing, and can be s u b l i m e d w i t h o u t suffering change. On the o t h e r hand, t h e liquid di-iodide u n d e r g o e s d e c o m p o s i t i o n w h e n heated, and cannot be distilled with s t e a m w i t h o u t b e i n g decomposed. T h e s e oothpounds have been prepared b y Sabanejeff, * w h o has a n a l y z e d t h e m and f o u n d t h e m to h a v e the c o m p o s i t i o n represen(~d b y the formula C~H~Ir No a t t e m p t was m a d e b y h i m to d e t e r m i n e their constitution. In accordance with the V a n ' t Hoff hypothesis, the solid acetylene di-iodide, w h i c h is m u c h more stable than t h e liquid di-iodide w o u l d halve the constitution r e p r e s e n t e d b y the f o r m u l a - I--C--H
IX
H--C--I and would, therefore, b e l o n g . t o the s a m e general class of acetylene derivatives to w h i c h f u m a r i e acid belongs. Now, e x p e r i m e n t s h o w s t h a t this solid a c e t y l e n e di-iodide can b e t r a n s f o r m e d into f u m a r i c acid. Ann. Chem. (Liebig), 178, II8.
34O
C/wmica!
Sectzon.
[ J. F. I.,
N i n e g r a m s of the acetylene all-iodide crystals (m. p. 73 °) were dissolved in alcohol, and five g r a m s (two molecules) of p o t a s s i u m cyanide added, and the solution was b o i l e d for thirty-six h o u r s in a flask w i t h an i n v e r t e d condenser. C a u s t i c p o t a s h was t h e r e u p o n added, and the b o i l i n g cont i n u e d for two h o u r s longer. On cooling the c o n t e n t s of t h e flask a considerable q u a n t i t y of needle-shaped crystals separated from the liquid. T h e y were r e m o v e d f r o m the solution, and on e x a m i n a t i o n proved to be the p o t a s s i u m salt of f u m a r i c acid, w h i c h crystallizes in t h e form of needles, insoluble in cold alcohol. More of the salt was o b t a i n e d from the mother-liquor. T h e aqueous s o l u t i o n of the p o t a s s i u m salt was t r e a t e d w i t h silver n i t r a t e and a w h i t e precipitate c o n s i s t i n g of the silver salt was obtained. T h e silver salt was purified by dissolving it in nitric acid a n d r e p r e c i p i t a t i n g it by carefully n e u t r a l i z i n g the solution w i t h a m m o n i a . T h e silw'x salt of f u m a r i c acid is characterized by its g r e a t i n s o l u b i l i t y in water, a n d b y ~the fact t h a t when it is h e a t e d it deflagrates like g u n p o w d e r . Both of these properties were e x h i b i t e d by the silver salt of t h e acid m a d e by synthesis. A q u a n t i t a t i v e d e t e r m i n a t i o n of the p e r c e n t a g e of silver g a v e the following r e s u l t : •2o39 gram of the salt, dried at Ioo° gave "I786 gram of Ag C1 = 65"97 per cent. Ag. Calculaled f o r AK'-' C4 tt"~ 04.
Ag. . . . . . . . . . . . . .
65"43
Found.
65"97
T h e free acid itself was recognized by its i n s o l u b i l i t y in w a t e r ; it was p r e c i p i t a t e d from m o d e r a t e l y e o n e e n t r a t e d solutions of its salt by the a d d i t i o n of s t r o n g acids. I t will be a n a l y z e d as soon as l a r g e r q u a n t i t i e s of it h a v e been o b t a i n e d in pure condition. In 1882, Sabanejeff + s t u d i e d the action of p o t a s s i u m c y a n i d e u p o n acetylene di-bromide a n d o b t a i n e d an acid h a v i n g the f o r m u l a C4H6Ov It is probable t h a t f u m a r i c or maleic acid was first f o r m e d in his experiments, w h i c h a f t e r wards, b y the prolonged action of boiling caustic alkali, was + Ann. Chem. (Liebig), 216, 275.
April, 189o.]
Scientific Notes and 6~omments.
34 I
c o n v e r t e d i n t o t h e a c i d C4H60~. It has been shown by Linnemann and Loydl* that when fumaric acid is heated w i t h ' c a u s t i c a l k a l i s , i t is g r a d u a l l y c h a n g e d i n t o a n i n a c t i w ~ maleic acid, thus: C4H404 -~ H 2 0 ~ C4H605 Fumaric acid. Inactive maleic acid. A more detailed study of the reactions, which gives rise to the formation of the two acetylene di-iodides, as well as t h e a t t e m p t t o p r e p a r e m a l e i c a c i d f r o m a c e t y l e n e , is r e s e r v e d for future work. BRYN MAWR, PA., February, I89o. NOTES
AND C O M M E N T S . CHEMISTRY.
I889. By ProL George Lunge-Barium t~eraxide and hydroffen ~eroxide are acquiring a constantly increasing importance ; woollen bleaching makes large use of them; the bleaching of feathers, of ivory, and of wild silk can hardly be done without them, and as they become cheaper, the range of their applications will certainly widen. These products were shown in Paris by a large number of exhibitors. One of the principa,1 firms decomposes the barium peroxide with aqueous carbonic acid under pressure, and carries out the filtration from barium carbonate also under pressure. Another manufacturer uses hydrofluoric acid, for which, as a decomposing agent, he claims the best results. He commences with barium nitrate, which, in order to avoid the later swelling up, he fuses and then spreads out in shallow trays where it is changed into barium oxide and then into peroxide. He loses the nitric acid in this case, although that could be easily recovered. The change of oxide into peroxide takes place in a current of air, purified from moisture and carbon dioxid¢l by passage through caustic potash~;and drawn through by chimney draft. The change is completed in five to six hours. The barium peroxide is powdered, hydrated and decomposed by the hydrofluoric acid in a vessel cooled externally to a temperature of I5 ° C. The barium fluoride is used again for the manufacture of the hydrofluoric acid, The hydrogen peroxide is chiefly used in the bleaching of feathers, which requires twenty-four hours in a very slightly ammoniacal bath, repeated if necessary ; for Tussah silks, which are not attacked at all, although barium peroxide robs them "f their lustre ; ana for woollens which do not turn yellowish again. S.P.S. 13enaenesfrom Coke-Oven Gases.--The fact that coal tar has until recently been obtained only as a side product in the gas manufacture, has led to great NOTES FROM THE PARIS EXPOSITION OF
* Ann. Chem. (Liebig), 1 9 2 , 8o.
[J. F. I.,
Chemical Section.
peculiar blue color which a mixture of sulphuric acid and phosphorus pentoxide assumes on standing for a time. The observation was made in connection with the apl~cation of Kjehldahl's method of determining nitrogen. None of the members present had ever noticed the phenomenon. Adjourned. WM. C. DAY, Secretary.
ON THE S Y N T H E S I S OF F U M A R I C ACID. BY E. H. KEISER.
[Read at the Stated Meetin¢ of the Chemical Section, held tSebruary 2o, I89O. ] [Preliminary Communication.]
Van't Hoff ~ has proposed the following stereometric for mul~e for fumaric and maleic acids : COOH--C--H II H--C--COOH Fumaric acid.
H--C--C00H and
l]
H--C--C00H Maleic acid.
Johannes Wislicenust has shown in a series of important papers that it is possible to determine experimentally the stereometrie formulae of certain isomeric compounds. A consideration of the hypothesis pert forward by him suggested the idea that it ought to be possible to prepare both fumaric and maleic acids synthetically from acetylene. In accordance with Van't Hoff and Wislicenus' theory, the di-halogen additive compounds of acetylene can exist in two isomeric forms having the formula~ : I.
X--C--H ]] H--C--X
H--C--X a n d II.
!I H--C--X
in which X represents any halogen atom. And, further, compounds having the constitution represented by formula I are more stable than those having the structure represented by the second formula. Fumaric acid would then * LaKerunffd~r Alome im Raume, p. 2I. R~umliche Anordnunff der Atome in organischen ~IIolekulen. Chem. (Liebig), ~4-6, 53.
Ann.
April, I89O.J
C/lcmical .%ctl}m.
~:.
a p p e a r to be closely related to the halogen derivatives ,,! the first class, and maleic acid to those of the second. It occurred to m e t h a t it mihgt, perhaps, be of interes'~ in this connection to start with acetylene, and prepare, in the first place, two isomeric all-halogen additive c o m p o u n d s . and then e n d e a v o r to t r a n s f o r m t h e s e into fumaric and maleic acid. T h e i n v e s t i g a t i o n is not y e t completed, b u t one of the acids, namely, f u m a r i c acid, has been prepared in this w a y from acetylene. A c e t y l e n e was p r e p a r e d b y the action of alcoholic potash u p o n e t h y l e n e bromide, and the purified gas was passed t h r o u g h a series of wash-bottles containing crystals of iodine covered with a layer of a b s o l u t e alcohol. A f t e r a time, the iodine disappeared, a n d from the liquid two isomeric acetylene di-iodides were separated. One of t h e s e c o m p o u n d s is a solid at ordinary t e m p e r a t u r e s ; the other is a liquid. T h e solid di-iodide is m u c h more stable than t h e liquid variety. It does not d e c o m p o s e on standing, and can be s u b l i m e d w i t h o u t suffering change. On the o t h e r hand, t h e liquid di-iodide u n d e r g o e s d e c o m p o s i t i o n w h e n heated, and cannot be distilled with s t e a m w i t h o u t b e i n g decomposed. T h e s e oothpounds have been prepared b y Sabanejeff, * w h o has a n a l y z e d t h e m and f o u n d t h e m to h a v e the c o m p o s i t i o n represen(~d b y the formula C~H~Ir No a t t e m p t was m a d e b y h i m to d e t e r m i n e their constitution. In accordance with the V a n ' t Hoff hypothesis, the solid acetylene di-iodide, w h i c h is m u c h more stable than t h e liquid di-iodide w o u l d halve the constitution r e p r e s e n t e d b y the f o r m u l a - I--C--H
IX
H--C--I and would, therefore, b e l o n g . t o the s a m e general class of acetylene derivatives to w h i c h f u m a r i e acid belongs. Now, e x p e r i m e n t s h o w s t h a t this solid a c e t y l e n e di-iodide can b e t r a n s f o r m e d into f u m a r i c acid. Ann. Chem. (Liebig), 178, II8.
34O
C/wmica!
Sectzon.
[ J. F. I.,
N i n e g r a m s of the acetylene all-iodide crystals (m. p. 73 °) were dissolved in alcohol, and five g r a m s (two molecules) of p o t a s s i u m cyanide added, and the solution was b o i l e d for thirty-six h o u r s in a flask w i t h an i n v e r t e d condenser. C a u s t i c p o t a s h was t h e r e u p o n added, and the b o i l i n g cont i n u e d for two h o u r s longer. On cooling the c o n t e n t s of t h e flask a considerable q u a n t i t y of needle-shaped crystals separated from the liquid. T h e y were r e m o v e d f r o m the solution, and on e x a m i n a t i o n proved to be the p o t a s s i u m salt of f u m a r i c acid, w h i c h crystallizes in t h e form of needles, insoluble in cold alcohol. More of the salt was o b t a i n e d from the mother-liquor. T h e aqueous s o l u t i o n of the p o t a s s i u m salt was t r e a t e d w i t h silver n i t r a t e and a w h i t e precipitate c o n s i s t i n g of the silver salt was obtained. T h e silver salt was purified by dissolving it in nitric acid a n d r e p r e c i p i t a t i n g it by carefully n e u t r a l i z i n g the solution w i t h a m m o n i a . T h e silw'x salt of f u m a r i c acid is characterized by its g r e a t i n s o l u b i l i t y in water, a n d b y ~the fact t h a t when it is h e a t e d it deflagrates like g u n p o w d e r . Both of these properties were e x h i b i t e d by the silver salt of t h e acid m a d e by synthesis. A q u a n t i t a t i v e d e t e r m i n a t i o n of the p e r c e n t a g e of silver g a v e the following r e s u l t : •2o39 gram of the salt, dried at Ioo° gave "I786 gram of Ag C1 = 65"97 per cent. Ag. Calculaled f o r AK'-' C4 tt"~ 04.
Ag. . . . . . . . . . . . . .
65"43
Found.
65"97
T h e free acid itself was recognized by its i n s o l u b i l i t y in w a t e r ; it was p r e c i p i t a t e d from m o d e r a t e l y e o n e e n t r a t e d solutions of its salt by the a d d i t i o n of s t r o n g acids. I t will be a n a l y z e d as soon as l a r g e r q u a n t i t i e s of it h a v e been o b t a i n e d in pure condition. In 1882, Sabanejeff + s t u d i e d the action of p o t a s s i u m c y a n i d e u p o n acetylene di-bromide a n d o b t a i n e d an acid h a v i n g the f o r m u l a C4H6Ov It is probable t h a t f u m a r i c or maleic acid was first f o r m e d in his experiments, w h i c h a f t e r wards, b y the prolonged action of boiling caustic alkali, was + Ann. Chem. (Liebig), 216, 275.
April, 189o.]
Scientific Notes and 6~omments.
34 I
c o n v e r t e d i n t o t h e a c i d C4H60~. It has been shown by Linnemann and Loydl* that when fumaric acid is heated w i t h ' c a u s t i c a l k a l i s , i t is g r a d u a l l y c h a n g e d i n t o a n i n a c t i w ~ maleic acid, thus: C4H404 -~ H 2 0 ~ C4H605 Fumaric acid. Inactive maleic acid. A more detailed study of the reactions, which gives rise to the formation of the two acetylene di-iodides, as well as t h e a t t e m p t t o p r e p a r e m a l e i c a c i d f r o m a c e t y l e n e , is r e s e r v e d for future work. BRYN MAWR, PA., February, I89o. NOTES
AND C O M M E N T S . CHEMISTRY.
I889. By ProL George Lunge-Barium t~eraxide and hydroffen ~eroxide are acquiring a constantly increasing importance ; woollen bleaching makes large use of them; the bleaching of feathers, of ivory, and of wild silk can hardly be done without them, and as they become cheaper, the range of their applications will certainly widen. These products were shown in Paris by a large number of exhibitors. One of the principa,1 firms decomposes the barium peroxide with aqueous carbonic acid under pressure, and carries out the filtration from barium carbonate also under pressure. Another manufacturer uses hydrofluoric acid, for which, as a decomposing agent, he claims the best results. He commences with barium nitrate, which, in order to avoid the later swelling up, he fuses and then spreads out in shallow trays where it is changed into barium oxide and then into peroxide. He loses the nitric acid in this case, although that could be easily recovered. The change of oxide into peroxide takes place in a current of air, purified from moisture and carbon dioxid¢l by passage through caustic potash~;and drawn through by chimney draft. The change is completed in five to six hours. The barium peroxide is powdered, hydrated and decomposed by the hydrofluoric acid in a vessel cooled externally to a temperature of I5 ° C. The barium fluoride is used again for the manufacture of the hydrofluoric acid, The hydrogen peroxide is chiefly used in the bleaching of feathers, which requires twenty-four hours in a very slightly ammoniacal bath, repeated if necessary ; for Tussah silks, which are not attacked at all, although barium peroxide robs them "f their lustre ; ana for woollens which do not turn yellowish again. S.P.S. 13enaenesfrom Coke-Oven Gases.--The fact that coal tar has until recently been obtained only as a side product in the gas manufacture, has led to great NOTES FROM THE PARIS EXPOSITION OF
* Ann. Chem. (Liebig), 1 9 2 , 8o.