104 
the pharmaceutical journal and transactions. 
[August 5,1871. 
THE ACTION OF HYDROBROMIC ACID ON 
CODEIA AND ITS DERIVATIVES. 
1Y C. R. A. "WEIGHT, D.SC. 
{Concluded from page 86 .) 
The portion insoluI)l 6 in ether of the hatch fiom 
^hich hydrochlorate B was obtained was treated with 
HC 1 , and fractionally precipitated by strong acid several 
times successively. This mode of treatment was adopted 
rather than that with HBr, as a much larger yield is 
obtained thus, the hydrochloratcs of chlorotetracodeia 
and chlorotetramorphia being much less soluble in dilute 
HC 1 than the corresponding brominated bodies are in 
dilute H Br. Finally, nearly white flakes were obtained, 
presenting all the characters of chlorotetramorphia hy- 
drochlorate, and yielding tne following numbers aftci 
drying at 100 °:— 
0-2480 grm. gave 0*5610 C0 2 and 0T410 ILO. 
0-1390 grm. gave 0-0755 AgCl. 
Calculated. Found. 
/---N /-^-"s 
CVo. 
816-0 
61-79 
61-70 
^68 * * 
.. 
79-0 
5-98 
6-32 
J-L 9 . 
€1. 
177-5 
13-44 
• • 
56-0 
4-24 
4 • • 
o 12 . 
192-0 
14-55 
C 68 H, 5 C1N 4 O j2 ,4HC1 
1320-5 
1000.00 
Hence the portion insoluble in ether must have been 
bromotetramorphia. 
The simultaneous formation of bromotetramorphia and 
deoxymorphia from bromocodide is explainable in two 
ways, either— 
(I.) 5 C ls H g 0 BrN O, + 4ILO 
Bromocodide. 
= C 72 H s3 BrN 4 Q u , + C I 8 H 2 1 NQ 2 + 4 H Br. 
Bromotetracodeia. Deoxycodeia. 
(II.) C 72 H 83 Br N 4 Op + 4II Br 
^ _ _/ 
Bromotetracodeia. 
= C 6 s H ? 5 BrN 4 0 1; , + 4CH 3 Br. 
B romotetramorphia. 
(in.) C 18 H 2 i KQ 2 + HBr = C 11 H 19 X0 2 + CH 3 Br; or 
Deoxycodeia. Deoxymorphia. 
(IV.) C 18 H 20 BrNO p + HBr = C 17 H l 8 BrN0 2 + CH 3 Br. 
Bromocodide. Bromomorphide. 
(V.) j>C 1 ;H ls BrNO, + 4H,,0 
\/ -- ^ 
Bromomorphide. 
= C 63 H 75 Br N_j Ojo + C 17 H 19 N O, + 4 HBr. 
v ---—^ v _ v 
Bromotetramorphia. Deoxymorphia. 
Of these two views, the first involves only known sub¬ 
stances and reactions similar to those already known in 
the codeia series of derivatives, and is, moreover, pro¬ 
bable from the circumstances that the numbers obtained 
in some instances indicate the presence of deoxycodeia 
as well as deoxymorphia; whilst the second view in¬ 
volves the not improbable existence of bromomorphide 
CtfHisBiN O 2 , on the other hand, it will be shown in 
the next section that equation (III.) represents a reac¬ 
tion v Inch does not readily take place with deoxycodeia 
■when not in the nascent condition at any rate. 
Whichever Hew be adopted, the ultimate formation of 
bromotetramorphia requires the action of water on a 
brominated body, substituting hydroxyl for bromine by 
a reaction perfectly parallel to that whereby codeia is 
regenerated from c-hlorocodide by the action of water,* 
viz.:— 
C 1S IU 0 C1NO, + II 2 0 = HC1 + C 13 H 21 N O a . 
3. Action of Hydrobromic Acid on Deoxycodeia. 
In the hope that this action would give rise to methyl 
bromide and deoxymorphia, deoxycodeia hydrobromate 
was heated to 100 ° for two hours with about five parts of 
48 per cent HBr; no change whatever took place, no 
methyl bromide being found on opening the tube in 
which the digestion -was carried on after complete cool- 
in^. After an hour’s additional exposure to a tempera¬ 
ture of 120°-130°, the contents of the tube were found to 
have become black and tarry, -while a small quantity of 
methyl bromide floated on the top. Precipitated by 
sodium carbonate, a very dirty substance was obtained, 
which was almost insoluble in ether; the ethereal ex¬ 
tract, shaken with HBr, gave a small quantity of a tarry 
hydrobromate, of which 0-1330 grm. gave 0-0790 AgBr, 
or Br = 25-20 per cent., deoxymorphia hydrobromate 
requiring only 22-86 per cent. 
Nothing fit for analysis could be obtained from the 
portion insoluble in ether, and the minute yield of pure 
deoxycodeia from codeia precluded a repetition of the 
experiment. 
4 . On the Physiological Action of the Foregoing Codeia 
Derivatives. 
BY MICHAEL EOSTER, M.A., M.D. 
The hydrochlorate of chlorotetracodeia and the hydro¬ 
bromate of bromotetramorphia, in doses of a decigramme 
by subcutaneous injection or by the mouth, produced in 
adult cats in a very few minutes a condition of great 
excitement, almost amounting to delirium, accompanied 
by a copious flow of saliva and great dilatation of the 
pupils. Micturation and defalcation occurred in some 
instances, and vomiting was observed on two occasions 
with the morphia-salt, but was very slight. The excite¬ 
ment -was very peculiar, being apparently due partly to 
increased sensitiveness to noises, and partly to an im¬ 
pulse to rush about. 
The same doses of the morphia-salt given to a young 
kitten produced the same flow of saliva, dilatation of 
pupils, and excitement (without vomiting); but the stage 
of excitement, which in adult cats passed gradually off 
in a few hours, was followed by a condition marked by a 
want of co-ordination of muscular movements, and pre¬ 
senting the most grotesque resemblance to certain stages 
of alcoholic intoxication. This stage was followed in 
turn by sleepiness and stupor, in which the kitten was 
left at night; in the morning it was found dead. 
Two observations have shown these salts paralyse (in 
dogs and cats) the inhibitory fibres of the pneumogas- 
tric; they also seem to lower the internal tension, but 
want of material has prevented from ascertaining how 
this is brought about. 
On rabbits neither salt, even in doses of a decigramme, 
seems to have any effect, except perhaps a slight excite¬ 
ment. There is no dilatation of the pupils, no flow of 
saliva, and, if one observation can be trusted, no paralysis 
of the inhibitory fibres of the pneumogastric. 
No marked difference was observable between the two 
salts, except that the morphia salts seemed rather more 
potent than the corresponding- codeia bodies. 
The salts of deoxycodeia and deoxymorphia given by 
mouth or by subcutaneous injection, in doses of a deci¬ 
gramme, produced in adult cats, almost immediately 
after exhibition, a series of convulsions much more 
epileptic in character than tetanic. In one case there 
was a distinct rotatory movement. 
In a few minutes these convulsions passed away, 
leaving the animal exhausted and frightened. Then 
followed a state of excitement with dilated pupils and 
flow of saliva, very similar to the effects of the tetra- 
codeia and tetramorphia salts, but less marked. 
* Matthiessen and Wright, Proc.Boy. Soc ., vol. xviii. p. 88 . 
