Dec., 1918
T H E J O U R N A L O F I N D U S T R I A L A N D ENGTNEERI-VG C H E M I S T R Y
ON CONSTITUENTS OF OIL OF CASSIA-I1 By FRANCIS D. DODGE Received June 13, 1918
T h e examination b y t h e writer a n d A. E. Slierndall of t h e alkali-soluble portion of oil of cassia showed t h e presence of several compounds not hitherto recognized as constituents of t h e oil. More recently t h e writer has h a d occasion t o make a f u r t h e r s t u d y of this oil, a n d especially of t h e aldehyde constituents. T w o samples were examined: one, A , a redistilled oil made in this laboratory from apparently pure commercial oil; t h e other, B , a commercial U. S. P. oil. T h e results of t h e preliminary tests were as follows: S p gr. a t 2 5 O . . . . . . Aldehyde (by vol.). Rotation. Rosin test.
.......
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A 1.0528 88 per cent Slightly Negatlve
+
B 1.0514 80 per cent Slightly h-egative
+
One pound of each of t h e samples was shaken with sufficiently strong sodium bisulfite solution t o ensure complete extraction of t h e aldehydes, t h e reagent being added i n portions of about one pound, waiting after each addition until t h e crystalline compound h a d completely redissolved. About j lbs. of bisulfite were required for each l o t , a n d when t h e supernatant oil was f o u n d t o be free from aldehyde t h e aqueous solution was separated, a n d heated o n t h e water b a t h for several hours t o ensure t h e conversion of t h e bisulfite compound into t h e more stable sulfonate. On cooling, t h e solution was filtered t o remove traces of oil. This solution h a d a slight acid reaction; a portion made alkaline with sodium carbonate became slightly t u i b i d , a n d showed b y odor t h e presence of aldehyde other t h a n cinnamic, t h e l a t t e r not being liberated b y soda. T h e entire solution was accordingly made strongly alkaline with sodium carbonate, a n d extracted with ether. T h e ether solution was washed with N sodium hydroxide t o remove salicylic aldehyde, a n d t h e n with strong bisulfite t o separate other aldehydes. F r o m t h e alkaline solution t h e salicylic aldehyde was obtained b y acidifying a n d extraction with ether, a n d t h e other aldehydes similarly b y neutralizing t h e bisulfite, a n d treating with ether. T h e first ether solution, after t r e a t m e n t with bisulfite, left a small residue of t h e non-aldehyde portion of t h e oil, which had remained dissolved i n t h e original bisulfite solution. T h e results on t h e t w o samples were:
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Original.. Non-aldehyde.. Salicylic aldehyde, Other aldehydes.. Cinnamic aldehyde.
A 453 g. About 50 g. 0.985 g. 3.850 g. N o t recovered
B 453 6. About 8Og. 1.110 g. 4.860 g.
*THISJOURNAL, 7 (1915), 1055.
completely t o a crystalline acid, melting a t 91--93 O , which was found b y t h e usual tests t o be impure benzoic acid. A small portion oxidized b y permanganate gave a n acid which, after crystallization from benzene, melted a t I Z O O , a n d was evidently benzoic acid. This suggested t h e possibility of t h e presence of hydrocinnamic aldehyde, a n d Kith t h e view of limiting t h e oxidation t o t h e aldehyde group, another portion was oxidized with hydrogen peroxide as follows: 3 g. aldehyde mixture mere treated with 30 cc. official peroxide, with a few drops of ferric chloride solution, keeping the mixture slightly alkaline with sodium hydroxide, and adding peroxide until all the aldehyde was in solution. The temperature was kept a t 30 to 5 0 ° , with frequent agitation. At the end a distinct odor of anisol was noted, which proved significant. Finally the alkaline solution was filtered and concentrated to about 20 g. On acidifying, a crystalline acid mixture, melting below IOO', was precipitated. The characteristic odor of hydrocinnamic acid was not observed, and a separation of the acids by recrystallization from water was not successful. For further information as t o t h e nature of t h e aldehydes present, a portion was converted into oxime. One gram aldehyde with one g r a m hydroxylamine hydrochloride a n d 33 cc. N / 2 alcoholic potassium hydroxide was allowed t o s t a n d 3 days, heated t o 70' for 3 hrs., neutralized with HC1, diluted t o I O O cc., a n d extracted with ether. On evaporation of t h e ether solution, long white needles were depoiited, which. after pressing a n d drying, amounted t o 0 . 3 ; g., a n d melted a t g o o (corr.). I t seemed probable t h a t this oxime might be t h e oxime of hydrocinnamic aldehyde (m. p. 93-94'), or, more likely, t h e oxime of methyl salicylic aldehyde (m. p. 92'). T h e occurrence of t h e l a t t e r could in fact almost be assumed as an oxidation product of t h e methyl ortho-coumaric aldehyde already noted as a constituent of t h e oil b y Bertram.l .4 similar reaction would explain t h e occurrence of benzaldehyde. CeH6 - CH = CH - COH Cinnamic aldehyde
+
C8H6 - COH Benzaldehyde
/OCHs C6H4\ COH Methyl salicylaldehyde
CeH4
