July 29,18/1.] 
THE PHARMACEUTICAL JOURNAL AND TRANSACTIONS. 
85 
Hence the action of hydrohromic acid on bromotetra- 
codeia is 
0,, + 4 HBr = 4CH,Br + C 63 H r5 BrN 4 0,,. 
Bromotetracodeia. 
Bi-omotetramorphia. 
Carbonate of soda throws down from the solution of 
the hydrobromato a nearly white precipitate which ra¬ 
pidly oxidizes, and appears identical in all its physical 
properties and chemical reactions with bromotetracodeia. 
When crude bromotetramorphia hydrobromate is pre¬ 
cipitated by carbonate of soda, and the precipitate (after 
filtration and washing) redissolved in hydrochloric acid 
and fractionally precipitated twice or thrice by strong 
hydrochloric acid, white flakes free from bromine are 
ultimately obtained; these are the lxydrochlorate of the 
corresponding chlorinated base, which is therefore 
termed chlorotetramorphia. After drying at J00°, 
numbers were obtained which led to the formula 
C fi0 H- 5 Cl N 4 0 12 ,4II Cl. 
Converted into platinum-salt, and dried at 100°,— 
most part insoluble in ether, the insoluble portion hav¬ 
ing all the properties of bromotetramorphia; the ethe¬ 
real extract shaken with IICl or HBr yields a viscid 
liquid, which, on standing, becomes filled with crystals 
consisting apparently of a mixture of the hydrochlorates, 
or hydrobromates, of deoxycodeia and a lower homo- 
logue, the latter predominating when the digestion is 
performed in an open flask. Attempts to prevent the 
formation of the lower homologue by continuing tho 
digestion with H Br for only two or three hours did not 
succeed, as the large quantity of unaltered bromocodide 
in the ether extract obtained prevents the separation of 
the crystalline hydrochlorate or hydrobromate of deoxy- 
codcia, and hitherto no method of separating the deoxy¬ 
codeia salt from its lower homologue has been arrived 
at. 
The following numbers were obtained by the analysis 
of these crystals after re-crystallization from hot water 
to free them from adhering bromocodide salt:— 
‘Specimen A, prepared in sealed tubes, digested six 
hours at 100°:— 
0-4235 grm. gave 0-0840 Pt= 19-83 per cent. 
The formula C e3 H- 5 ClN 4 0 12 ,4-HCl,2PtCl 4 requires 
19 - 72 per cent. 
When codeia is heated on the water-bath with three 
parts of 48 per cent, hydrohromic acid for five hours, 
and the portion of tho precipitate thrown down by car¬ 
bonate of soda and insoluble in ether is dissolved in 
hydrochloric acid, and fractionally precipitated several 
times by excess of stronger acid, flakes are obtained 
which, on drying at 100°, yield numbers intermediate 
between those required for chlorotetracodeia and chloro¬ 
tetramorphia, leading to the formula,— 
C- 0 H 79 ClN 4 O 12 ,4HCl. 
Converted into platinum-salt, and dried at 100°,— 
0'4830 grm. gave 0-0935 Pt = 19-3G per cent. 
The formula C- 0 H 79 ClN 4 O 12 ,4HCl,2PtCl 4 requires 
19-40 per cent. 
Whether this is only a mixture of chlorotetracodeia 
and chlorotetramorphia hydrochlorates, or is one com¬ 
pound, is open to doubt : assuming that it is not a 
mixture, the name chloro-dicodeia-dimorphia might be 
applied to the base. It appears d priori probable that 
the following double scries of bases should be obtainable 
by successive methyl eliminations :— 
Bromotetracodeia 
Bromotetramorphia . . . 
Chlorotetracodeia . . . 
Chloro-dicodeia-dimorphia 
Chlorotetramorphia . . 
Out of these ten bases four have been prepared, and a 
substance corresponding in composition with a fifth 
(chloro-dicodeia-dimorphia) has also been obtained; but 
from the great similarity in properties between all the 
five substances and their high formulae, it is clear that 
no certainty as to the purity of the missing intermediate 
bodies could exist, and therefore it was not thought 
advisable to attempt their formation. 
II. Action of Hydrohromic Acid on Bromocodide . 
When bromocodide hydrobromate (prepared by two 
hours’ digestion of codeia with three times its weight of 
48 per cent. HBr, precipitation by sodium carbonate, and 
extraction with ether, etc.) is heated with four to six 
parts of the same acid to 100° for five or six hours either 
in a sealed tube or in an open flask, methyl bromide is 
copiously evolved; the tarry product, dissolved in warm 
water, and precipitated by sodium carbonate, is for the 
c 72 h 83 
C n H sl 
h 77 
C cs H 75 
C’ 7 ,H 83 
C n H sl 
C ; „H„ 
BrN 4 0 10 
BrN 4 0 12 
BrN 4 0 12 
BrN 4 O r > 
BrN 4 O r , 
cin 4 o,; 
cin 4 o 12 
Cl N O, 
CINjOj, 
cin 4 o,; 
0-3185 grm. gave 0-7850 C0 2 and 0-1970 H 2 0. 
0-2200 grm. gave 0-1025 AgCl. 
Specimen B, prepared in an open flask, digested six 
hours at 100°:— 
0-2825 grm. gave 0-6920 C0 2 and 0-1660 H 2 0. 
0-2260 grm. gave 0-1085 AgCl. 
Calculated. Found. 
s 
" -- ^ 
/- 
Deoxycodeia. 
Deoxymorphia. 
C 18 
. . . 216 67-G0 
C x7 . . . 204 66-77 
G7-22 
66-80 
II.,, 
... 22 C’S9 
II „ 0 . . 2.0 G'55 
6-87 
G"o4 
N 
. . . 14 4-39 
N ... 14 4-59 
0 2 
. . . .33 10-01 
0„ . . . 32 10-47 
Cl 
. . . 35-5 11-11 
Cl . . . 35-5 11-62 
11-53 
11-83 
-319-5 100-00 
305-5 100 00 
C 18 H 2X 4n t 0 2 IIC1 C 7 H X0 NO 2 IICl 
The hydrobromate, prepared from tho same batch a3 
specimen B above, gave the following numbers after 
drying at 100°:—- 
0-3260 grm. gave 0-7010 C 0 2 , and 0-1720 H s O. 
0-2730 grm. gave 0-1465 AgBr. 
Calculated. 
• 
Found. 
7 Deoxycodeia. 
Deoxymorphia. 
\ 
C :3 . . 
. 216 
£9-31 
Cl 7 . • 
. 204 
£8-29 
o8"64 
h 32 . . 
. 22 
G‘95 
h 20 • 
. 20 
5-71 
5-SG 
N . . 
. 14 
3-84 
N . . 
. 14 
4-00 
0 2 . . 
. 32 
8-79 
0 2 . . 
. 32 
9-14 
Br . . 
. 80 
21-89 
Br . . 
. 80 
22-86 
22-83 
364 
100-10 
350 
loo-to 
Cig h 21 
N 0 2 , HBr 
c x7 u 13 
H 0 2 , H Br 
From the above numbers, and more especially from 
the percentages of H, Cl, and Br found, it appears that 
while specimen A may have contained some little quan¬ 
tity of deoxycodeia, specimen B must have consisted 
almost wholly of the lower homologue; to this body the 
name dcoxymorphia may appropriately be given (provi¬ 
sionally), to indicate that its composition bears the same 
relation to that of morphia as deoxycodeia to codeia. 
The numbers required for apomorpliia salts are very 
close to those actually obtained above, viz., for hydro¬ 
chlorate C = 67-22, 11 = 5-93, Cl=ll-70; and for hydro¬ 
bromate C = 5S-62, H = 5T7, Br= 22-99; but the entire 
absenco of emetic properties in ail those specimens, as 
observed by Dr. Michael Foster, conclusively proves that 
this base could not have been present. 
Further research is required before it can be decided 
with certaintv which of the three oxygen atoms in codeia 
is removed in the formation of deoxycodeia; the produc¬ 
tion of deoxymorphia with simultaneous evolution of 
methyl bromide, however, indicates that the oxygen 
that links the methyl group to the rest of the codeia 
residue is still present in deoxycodeia and deoxymorplua, 
while the production of both from bromocodide renders 
the following formulae probable:— 
