THE PHARMACEUTICAL JOURNAL AND TRANSACTIONS. [December 1C, 1871. 
4S6 
"boiled, so that by evaporation the boiling-point rises to 
130° and upwards, the ultimate product contains less 
oxygen than this last body, being C cs H 82 I 2 N 4 0 6 , 4 HI. 
These three formula? might each he halved; hut inas¬ 
much as compounds containing not less than C f)8 have 
been got from these products by simple treatments, the 
higher formulae are more probable. 
All three substances are, while moist, colourless tars, 
drying at 100° to brittle waxy-looking masses, not fusing 
at 100° when perfectly dry; they are soluble in hot 
water, a decomposition being thereby produced; while 
moist they appear to absorb oxygen with avidity, rapidly 
becoming yellow or orange. They are also extremely 
hygroscopic, and from the high percentage of iodine con¬ 
tained, the ease w T ith which they decompose on heating, 
and the difficulty combustible carbon left, their analysis 
is a matter of some considerable difficulty. From all 
these circumstances combined, the numbers obtained do 
not always accord quite as closely as might be expected 
in the case of crystalline and easily purified substances. 
To obtain the compound C 68 H 86 I 2 N 4 0 12 , 4HI, 10 parts 
of codeia, 30 of 55 per cent, hydriodic acid, and 1 of 
phosphorus may be heated on the water-bath for three to 
four hours, at the end of which time the evolution of 
methyl iodide has entirely ceased: by filtering the syrupy 
hot liquid through asbestos to separate particles of amor¬ 
phous phosphorus and addition of a little water when 
cold, a colourless tar is precipitated, which soon sets to 
a hard brittle mass : this is broken up and thoroughly 
washed with water to separate the phosphorus acids 
produced simultaneously, and finally freed from moisture 
as far as possible by pressure between filter paper, and 
dried at 100°. 
The same body may also be obtained by dissolving 
the original substance in slightly warm w r ater, precipi¬ 
tating with sodium carbonate, and extraction of the mass 
thus thrown down with ether, and agitation of the first 
portions of the ether extract with hydriodic acid: the tar 
thus got is identical in all respects with the original 
substance. After drying at 100° the following numbers 
were obtained:— 
(A) Prepared by the first method:— 
0-3785 grm. gave 0-588 C0 2 and 0-173 H 2 0. 
0-359 grm. 0-2535 Agl. 
(B) Prepared by ether process:— 
0-357 grm. gave 0-5655 C0 2 and 0165 H 2 0. 
0-2635 grm. gave 0-1895 Agl. 
(C) Another specimen prepared by ether process :— 
0-316 grm. gave 0-493 C0 2 and 0-135 H 2 0. 
0-2865 grm. gave 0*2025 Agl. 
Found. 
Calc 
ulated. 
✓—-— 
A. 
B. 
c. x 
Mean. 
Cos- 
.... 816 
42-59 
42-36 
43-20 
42-54 
42-70 
D go 
.... 90 
4-70 
508 
5-14 
4-75 
4-99 
I C • 
.... 762 
39-77 
38-16 
38-87 
38-19 
38-41 
n 4 . 
.... 56 
2-92 
0 12 
.... 192 
10-02 
The iodine thus set free is, of course, reconverted into 
HI by the action of the phosphorus, a mixture of phos¬ 
phorous and phosphoi'ic acids being thereby produced. 
The reaction, 
3I 2 + P 2 + 6H 2 0=2H 3 P0 3 + 6 HI, 
requires for 50 grms. of codeia 3 - 45 grms. of phosphorus 
to be converted into phosphorous acid; whilst the equa¬ 
tion 5I 2 + P 2 + 8H 2 0 = 2H 3 PG 4 -f• SHI requires 2-07 
grms. to be converted into phosphoric acid. In one ex¬ 
periment 2-8 grms. of phosphorus, as nearly as could be 
estimated, were found to have become converted into the 
mixture of the two acids, 50 grms. of codeia having been 
employed. 
On attempting to procure the free base C 6S H 36 I 2 N 4 0 12 
from the hydriodate got as above, by precipitation with 
sodium carbonate, a snow-white mass was obtained con¬ 
taining, besides a small quantity of the desired base 
(soluble in ether), a large quantity of two other bases 
derived from this one (but sparingly soluble in ether). 
The description of the products thus got will be given in 
a subsequent section. 
By treating codeia with hydriodic acid and phosphorus 
as above described, but at a temperature of gentle ebul¬ 
lition, not rising above 115°, a product is got on filtration 
through asbestos and precipitation by water containing 
apparently 2H 2 0 less than the preceding compound. 
Dried at 100°. 
0-302 grm. gave 0-475 C0 2 and 0-135 H 2 0. 
0-248 grms. gave 0-1845 Agl. 
Calculated. 
Found. 
c fi8 . 
816 
43-40 
42-89 
H 86 . 
86 
4-58 
4-97 
I 6 . 
762 
40-53 
40-20 
n 4 . 
56 
2-98 
Ojo. 
160 
8-51 
4HI 
1880 
100-00 
Hence this substance is formed from the preceding 
one by the reaction— 
C G8 H 86 1 2 N 4 0 12 , 4III = 2H 2 0 -f- C 68 H 82 I 2 N 4 O 10 , 4HI. 
If codeia, hydriodic acid (3 to 5 parts), and phosphorus 
be heated to rapid ebullition, so that most of the aqueous 
portion distils off along with the CH 3 I formed, the 
boiling-point gradually rises to 130° or a little above, at 
which temperature the colourless liquid begins again to 
become slightly brown ; on precipitation of the filtered 
product -with water, etc., as before, the following num¬ 
bers were obtained after drying at 100°:— 
Specimen A. 0-3575 grm. gave 0-589 CO., and 0*168 H 2 0. 
0-307 Agl. 
0-583 C0 2 and 0 164 H.,0. 
0-2815 Agl. 
0-402 
Specimen B. 0-358 
0-369 
Specimen C. 0-3855 
3-363 
5) 
» 
6-635 C Oo and 0-178 H 2 0. 
0-276 Agl. 
1916 100-00 
^-'03^86^-2-^4^12) ^ HI. 
The falling short in the percentage of aodine found in 
these specimens is readily accounted for by the action of 
the water which necessarily adheres to the tarry product 
got by either of the above processes; it will be subse¬ 
quently shown that by the action of water on this body 
the elements of HI are removed from it. 
This compound is apparently formed by the reaction— 
Calculated. 
A. 
Found. 
B. 
C. 
Mean. 
c 68 . 
... 816 
44-93 
44-92 
44-41 
44-91 
44-75 
h 8G . 
... 86 
4-73 
5-22 
5-09 
5-13 
5T5 
... 762 
41-96 
41-27 
41-23 
41-09 
41-20 
n 4 
.... 56 
3-09 
0 6 
.... 96 
5-29 
1816 
100-00 
4(C 18 H 21 N0 3 ,HI) + 14HI = 
Codeia hydriodate. 
=4CH 3 I -f I 8 + C r ,sH 8G I 2 N 4 0 12 ,4HL 
New body. 
* All combustions given in this paper were made with lead 
chromate and oxygen; and the iodine determinations by 
boiling with nitric acid and silver nitrate. 
C 68 H 82 I 2 N 4 0 6 , 4HI 
Hence this substance is formed from the preceding 
one by the reaction— 
C 6S H 82 I 2 N 4 O 10 , 4HI -}- 8HI = 
= I 8 + 4H.0 C C8 H 82 I 2 N 4 0 6 , 4HI. 
(To be continued.) 
