923 
THE PHARMACEUTICAL JOURNAL AND TRANSACTIONS. 
[May 18, 1872 
CONTRIBUTIONS TO THE HISTORY OP THE 
OPIUM ALKALOIDS. 
BY C. It. A. WRIGHT, D.SC. 
(Continued from page 885.) 
The portion of the first Na 2 C0 3 precipitate insoluble 
in ether is dissolved in HC1, and fractionally precipi¬ 
tated by Na 2 C0 3 , to remove colouring-matters as much 
as possible; the last precipitate, after thorough wash¬ 
ing and drying, forms a light buff-coloured amorphous 
powder that does not soften at 100° when perfectly dry, 
but clots to a resinous mass if heated in the water-bath 
while still moist; it is soluble in alcohol, is precipitated 
from this solution on addition of ether, and yields salts 
that have no vestige of crystalline characters. 
Both the crystalline and the non-crystalline hydro¬ 
chlorates yield on analysis numbers identical with those 
required for codeia hydrochlorate; for the reasons de¬ 
veloped in the subsequent sections, they are regarded as 
respectively di- and tetra-codeia. 
The filtrate from the original Na 2 C0 3 precipitate 
contains much unaltered codeia; by extracting with 
ether and agitation of the extract with excess of phos¬ 
phoric acid solution, a mixture of phosphates is obtained, 
from which a further quantity of each polymeride is 
obtainable by simply boiling down the liquid till the 
boiling-point reaches 200° 
The hydrochlorate of tetracodeia obtained as above 
described forms a brownish brittle tar not fusible at 
100° when dry; dried at 100° it yields the following 
numbers :— 
Specimen A. 0'325 grm. gave 0-773 CCb and 0-186 H 2 0. 
„ B. 0-3145 „ 0-732 ~ „ 0-185 „ 
0T215 „ 0-0495 AgCl. 
Calculated. 
Found. 
f 
C 14l . 
1728 
64-38 
64-87 
03-48 
U 1:6 . 
176 
6-56 
6-36 
6-54 
l t 8 . 
112 
4-17 
— 
0,4. 
384 
14-30 
— 
284 
10-59 
10-08 
C 144 H ]G8 N 8 0 24 ,8HC1 
2684 
100-00 
The free base gave the following numbers : — 
0-8095 grm. gave 0-818 C0 2 and 0T90 H 2 0. 
Calculated. Found. 
C 144 . 1728 72-24 72-08 
H lfi o. 168 7-02 6-82 
Ng . 112 4-68 
0 24 . 384 16-06 
Ci4 4 Hi 68 N 8 0 24 2392 100-00 
In appearance and most physical properties tetracodeia 
and its salts bear a great resemblance to c-hloro- and 
bromo-tetracodeia; and they further agree in that all 
yield a blood-red colour on warming with silver nitrate 
and nitric acid, or with nitric acid alone; it differs from 
‘Chloro-tetraeodeia in that the aqueous solution of the 
hydro-chlorate does not precipitate on the addition of 
strong HC1, the salt being apparently as soluble in di¬ 
luted HC1 as in water ; also the free base does not oxi¬ 
dize so readily. In all respects tetracodeia agrees with 
the description given by Anderson of his “Amorphous 
Codeia”* obtained by the action of sulphuric acid on 
codeia; on comparison with the product obtained by 
Anderson’s process, no essential differences could be 
detected between the two substances, except that the 
phosphoric acid product was somewhat darker in tint, 
owing no doubt to the presence of colouring-matters 
from the higher temperature employed in its production. 
The hydrochlorate of dicodeia obtained as above 
described crystallizes with 3H 2 0 for every C 18 con¬ 
tained, this water of crystallization being wholly lost 
at 100° and partially by standing over sulphuric acid. 
* Anderson, Ed. Phil. Trans., vol. xx. (i), p. 57. 
Dried at 100°,these crystals gave the numbers :— 
0 306 grm. gave 0 719 CO, and 0-182 H.,0. 
0-3135 „ 0 742 „ 
0-229 „ 0 098 AgCl. 
0-194 „ 
Calculated. 
Found. 
C72 
64-38 
64-08 64-54 
H-ss 
. 88 
6"56 
6-61 6-88 
n 4 
. 56 
4-17 
— 
0 12 
. 192 
14-30 
— 
Cl 4 
10-59 
10-60 
C- 
2 H S4 N 4 0 12 ,4HC1 1342 
3 ^ w ^ »» Ai. xiuui mu ouiuwuu vji liiu uiu- 
chlorate white amorphous flakes that do not oxidize 
spontaneously in the air. Dried at 100°, 0-2965 grm. 
gave 0-7765 C0 2 and 0-189 H 2 0. 
h 84 
0 12 
Calculated. 
Found. 
864 
72-24 
71-43 
88 
7-02 
7-08 
56 
4-68 
192 
16-06 
C 72 H 84 N 4 0 12 1196 100-00 
If the solution of the hydrochlorate be concentrated 
the addition of Na 2 C0 3 solution throws down tarry 
globules consisting of a mixture of the base and its 
hydrochlorate, the salt being sparingly soluble in the 
NaCl solution formed by the decomposition. 
Dicodeia and its salts do not yield a blood-red colour 
with N0 3 H, only a slight orange tint; FeCl 6 , also S0 4 H 2 
-j- KoCr (J 0 7 , give no colour reactions. 
In general properties, and in the fact that water of 
crystallization possessed by the hydrochlorate is lost at 
100°, dicodeia bears a great resemblance to the “ isomer 
of codeia” oqtained by Drs. Matthiessen and Armstrong 
by the action of diluted sulphuric acid on codeia. On 
comparison with the product obtained by Armstrong’s 
process, no difference whatever was discernible provided 
the hydrochlorate obtained by the action of sulphuric 
acid, etc., were several times re-crystallised; the crude 
hydrochlorate contains, besides the dicodeia salt, the 
hydrochlorate of another polymeride, which differs from 
dicodeia hydrochlorate in that it is non-crystalline, 
drying up to a gummy, extremely hygroscopic and 
deliquescent substance ; it yields a blood-red 
colour with N0 3 H, and with S0 4 H 2 +K 2 Cr 2 0 7 
a very evanescent purplish-red ; Fe 2 Cl 6 gives no coloura¬ 
tion at first, but on standing a reddish-purple tinge 
appears, gradually becoming more intense. Na 2 CO ;i 
throws down an amorphous white precipitate, which is 
soluble in ether, and but little changed by exposure to 
air. From these properties, which seem to be analogous 
in some respects to dicodeia, in others to tetracodeia, 
the base is considered to be intermediate between these 
two polymerides, i.e., to be tricodeia . The crude hydrochlo¬ 
rate of dicodeia obtained by Armstrong’s process on re¬ 
crystallization furnished mother-liquors which, on stand¬ 
ing over S0 4 H 2 for several weeks, gradually deposited 
crystals, and finally became a crystalline mass wetted 
with a viscid non-crystalline liquid; by gentle pressure 
in filter-paper the liquid portion was separated from the 
crystals, which were found to be only dicodeia hydroch¬ 
lorate ; and finally, the treacly hydrochlorate of trico¬ 
deia was extracted from the papers by water. On repe¬ 
tition of the treatment over S0 4 H 2 , no crystals were 
obtained; at .100° a brittle, gummy, hygroscopic sub¬ 
stance was obtained, of which. 
0.309 grm. gave 0.730 C0 2 and 0-191 H 2 0. 
0-208 „ 0-0895 Agl. 
Calculated. Found. 
C 108 . 1296 64-38 64-43 
Hw,. 132 6-56 6-87 
n’ . 84 4-17 - 
0 18 288 14-30 — 
Cl 6 . 213 10-59 10-64 
C 108 II 12C N c Oi R ,6HC1 2013 100-00 
