INDUSTRIAL AND ENGINEERING CHEMISTRY
June 1951
Extraction
I
of ground m a t e r i a l
Concentration 01 combined l i l l r a l e and w a s h i n g s under v a c u u m
Counter-current,liquidliquid eatroction with a Iu min u m su I f are sol u I ion
5
z Woter s o l u t i o n containing
Ethylene dichloride
7
Addition 01 coneentroted a m m o n i a to p r e c i p i t a t e olumlnum hydroxide
8
JAluminum hydroxide
F i l l rote ( w a t e r solut!on)made a l k a l i n e with ommonio a n d extracted w i l h ethylene dichloride
‘O
4 Reduce and f r a c t i o n o l e under v o c u u m
*
1.
II
the alkaloid is found as a salt in the aluminum sulfate solution. This solution is treated with sufficient ammonia to bring the pH to 8. The precipitated aluminum hydroxide is filtered off through filter paper, using suction, and the filtrate is then made more alkaline with ammonia to free the alkaloid. The precipitating a 1uminum hydroxide rem o v e s additional contaminants but does not itself absorb the anabasine. Any loss of alkaloid in the aluminum hydroxide is that held u p i n a n y liquid still in the solid on the filter. The free alkaloid is extracted from the water solution with e t h y l e n e dichloride, again by a countercurrent, 1i q u i d-liquid ext r a c t i o n . Room temperature is suff i c i e n t Countercurrent extraction a t this stage is not essential because stable emulsions do not form readily a t this part of the procedure.
.
The new ethylene dichloride extract is then reduced in v o l u m e under Figure 2. Diagram of Extraction vacuum. The free Process ammonia, ethylene dichloride, and water present distill over first,. The free alkaloid distills over later as the temperature is raised and can be collected in a single fraction or in several cub. Chemical analyses were obtained on a batch distilled as follows: The first drop collected in the receiver was a t a temperature of 100”C. and a pressure of 4 mm., with 10 mI. collected in the receiver a t 119 ” C. and 4-mm. pressure, and a total of 47 ml. collected in the receiver a t a final temperature of 120” C. and 4-mm. pressure when the distillation was stopped. The chemical and physical findings included the following: refractive index of 1.5400 at 21.2” C., compared to literature readings of n z = 1.5443 (6)and n z = 1.536-1.538 (If). Carbon, hydrogen, and nitrogen determinations (per cent by weight) gave the duplicate values of 72.35 and 72.10 for carbon, 8.51 and 8.57 for hydrogen, and 16.80 and 16.84 for nitrogen. These results show an empirical formula of (C6H7N)nwhich corresponds to the isomers nicotine and anabasine, A dipicrate made from alcohol and recrystallized twice from water had a melting point of 213214”C. corrected. This dipicrate gave no depression in a mixed melting point determination with a dipicrate made from anabasine obtained from another source. Other salts of the alkaloid and of the N-methyl alkaloid were made; their melting points checked closely the literature values ( 4 ) for anabasine dipicrolonate, anabasine 2,4,6-trinitro-mcresolate, N-methylanabasine 2,4,&trinitro-m-cresolate, and N-methylanabasine dipicrolonate.
1403
TABLE I. DISTRIBUTION OF ASABASINBIN TREE
.
Part of Tree Leaves Small branches and twigs Large branches Roots
12-20
Approximate $7 of Total AnabssLe Found in Tree 29
20-30
45
% by Weight of Tree
8 50-55
7 1s
The authors, thereforc, feel that the alkaloid present is anabasine. While nicotine may be present in hybrids of N. rustica and N . glauca (the authors have found none present with the anabasine in wild samples of tree tobacco), nicotine can be removed by azeotropic distillation from the mixture (6). A diagram of the process is shown in Figure 2. RESULTS AND DISCUSSION
Wild trees less than two years old were used in this study. Leaves from the Quemado samples contained 0.25% anabasine by air-dried weight, while the roots had 0.20%. The large branches from the Quemado samples averaged 0.07% of anabasine; large branches from Del Rio averaged 0.05%, while small branches and twigs had 0.38%. Leaves which had dropped off trees in Whittier, Calif., gave 0.26% anabasine. Table I shows the distribution of anabasine in the principal parts of the Nicotiana glauca plant. N . glauca grows on well-drained sandy waste land along or near irrigation canals or streams and usually occurs as colonies of trees. It is a fast-growing plant; one tree 4 inches in diameter and 25 feet tall was only 18 months old. Cultivation and selection might lead to strains containing greater amounts of anabasine. It has been reported that hybrids of N. rustica and N . glauca have an anabasine content almost double (1.99, 1.45%) that of the parental species N . glauca, which when grown under the same environmental conditions contained O.&i%, and that decapitation of the hybrids can increase the anabasine content about three times ( I d ) . ACKNOWLEDGMENT
The authors wish to thank J. C. Ard and Mary E. Stutzman for their aid in the carbon, hydrogen, and nitrogen analyses. LITERATURE CITED
(1) Feinstein, L.,and Hannan, P. J. (people of United States of America), U. S. Patent 2,525,784(Oct. 17,1950). (2) Ibid., 2,525,785(Oct. 17,1950): (3) Garman, P.,Conn. Agr. Expt. Sta., Bull. 349,433-4(1933). (4) Manske, R. H.F., and Holmes, H. L., “The Alkaloids,” New York, Academic Press, 1950. (5) Nelson, 0.A,, J. Am. Chem. SOC.,56, 1989 (1934). 34,251 (1942). (6) Smith, C.R.,IND.ENG.CHEM., (7) Smith, C.R.,J . Am. Chem. Soc., 53,313-17 (1931). (8)Ibid., 54,397-9 (1932). (9)Ibid., 57,959-60 (1935). (10) Smith, C. R., U. S. Dept. Agr. Yearbook, 1928,pp. 388-9. (11) Zerbey, M. E.,Orinick, M. T., and Willard, M. L., Mikrochemie 21, 171 (1937). (12) Zukov,N.I., Compt. rend acad. sci. U.R.S.S., (N.S.) 22 (3),11618 (1939). RmCEIVED
AugusO 9,1950.
Preparation and Properties of Urea-Form-Correction I n the article on “Preparation and Properties of Urea-form” [Clark, K. G., Yee, J. Y., Love, K. S., and Boyd, T. A., IND. ENG.CHEM.,43, 871 (1951)j an error occurred on page 873, Erst column, second paragraph below Figure 2, ninth line, where “0.75 inch” should read “0.25 inch.” K. G. CLARK
