The Morphine Alkaloids

The Morphine Alkaloids
University British Columbia

Vancouver. Canada
1.
11.
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6.
111.
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38
a.
b.
38
a.
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b.
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3
3
7
17
24
26
37
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3.
4.
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Page
2
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d.
a.
b.
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b.
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d.
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b.
C
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by
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61
74
77
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49
50
5051
52
53
59
61
65
66
66
69
69
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38
40
40
41
41
41
44
47
48
I
L..HOLMEB
. . . . . . . . . . .
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IV.
1.
b.
3.
of
4.
b.
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5.
80
82
82
84
88
89
92
93
94
98
99
107
108
109
112
.
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b.
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V.
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VI.
116
124
152
I. Introduction
Magisterium opii.
1803, by
i d
1804,
(48)
305, 3061
(49, 52, 53, 54)
alkali,
Papaver
orientale
=
THE
by
I1
I11
on
by
by
by
(331),
on
11. Elucidation of the Structure of Morphine, Codeine,

and Thebaine
1.
1880.
1831 by
by
1847
c34H3606N.2.
(51)
C34H3806N2
(329, 330)
by
of
H . L . HOLMES
(276)
(66, 279)
by
by
(13, 227, 233) ),
(188)
(227).
Methylation morphtne (227).

55.0 g.
(4.5 g.
by
42.0 g.
by
45
by
110",
15%
by
by
(23.5
20%
6.0 g.
on
by
g.
85%.
by
(76).
3-4%
by
(12)
19-20% (86)
(13, 233)
C14H70
by
120" (13).
T H E MORPHINE ALKALOIDS. I
by
(76)
by
by
69,
by
H. L. HOLMES
6
87,88,92,95).
by
81,
/
1v
by
on
Cs
Cq
32%
/
=
(131).
THE MORPHINE ALKALOIDS. I
3,4,5-trimethoxyphenanthrene
(VIII)
Ca
C4--C5 ( V I I ) .
bond
by
by
2.
AND
ISOQUINOLINE
FORMULAS
FOR MORPHINE
78,
on
a
).
(76)
a-Methylmorphimethzne (256).
1 1.
(24.0 g.
250 g.
on
3-4
by
(125 g.
10
1500
by
210-
225 g. (67-70%)
by
by
A.
H. L. HOLMES
(75)
(75)
(179),
on
Cl9HZ3O3N,
.",
'c
\(
7'"'
('H,
t Knorr was in doubt as to the location of the alcoholic hydroxyl offering

position to *.
**
as an alternative
(67, 72, 75),

50%
(78),
(75).
good
\/HZ
i-Y
,I
a
t
/I
CH3
on
des-N-methylnaphthalanemorpholine
on
10
H. L. HOLMES
on
(317)
no
on
(66)
(164).
(78),
(235)
a-
on
good
(78, 115) )
upon
(1 17)
by
(79, 80,
(CI9H2,OaN),
by
)
by
11
upon
on
).
by
by
1897
by
)
111.
by
by
of
12
L.
on
1899
upon
1900.
95,
13
by
on
by
(85, 86, 87, 88, 92,
3,4-dihydroxyphenanthrene.
3,4-diniethoxyphenanthrene
no
A
S,4-Dimethoxyphenanthrene
a-phenyl-2-amino-3,4-dimethoxycinnamic
by
10 g.
400 g. 13%
3,4-dimethoxyphenanthrene-9-carboxylic
on a
70-807,,.
bp
up
3,4-Dimethoxyphenanthrene
300
(298-303", 112
44').
14
H. L. HOLMEB
+
2-nitro-3-methoxy-4-acetoxybenzaldehyde)
by
C,)
C4.
(C16H&),
(84)
3,6-dimethoxy-4-acetoxyphenanthrene
CH3)
2-nitro-3-acetoxy-4-methoxybenzaldehyde)
Ce.
by
by
of 3.0 g. of
A . Codeinone from thebaine (129). A

6-7
by
50
30
10%
0.2 g.
of 20 g. of
B. Codeinone ,from codeine (334). A

(80 g.
25 g.
of 1 N
105 g. of
by
of a
20 g.
10 g.
of
for
on a
30
40%.
of
THE MORPHINE ALKALOIDS.
15
by
H)
Ca,
by
CH3
on
xxx
1905
no
(25),
by
by
16
H.
HOLMES
good
(
+
\ /
/ \
\
/"\
c1
Hz
),
by
on
no
upon
on
by
on
17
MORPHISE
/ \
\,
\
+
3.
von
43).
by
(55)
5.0 g.
Apomorphzne
50
3
by
1 8 g.
37.370
by
by
on
(65)
(55)
by
by
(GiHioO&).
).
18
H . L. HOLMES
I
I
/
R
by
19
by
20
H. L. HOLMES
(323)
)
by
(59, 309) ).
by
Cs,
by
2-nitro-3,4-dimethoxybenzaldehyde
3,4,8-trimethoxyphenanthrene (143).
von
by
bond
111,

A13-14
21
(140, 147).
(112),
by
by
5".
A
Hydroxycodeine
80 g.
15.0 g.
160 g.
by
4.2 g.
10.0 g.
g.
30
75
200
0.1 g.
300".
75
2.3 g.
=
f 1" ( 1
1).
(112),
(130),
on
(135).
(134).
on
a-
22
H. L . HOLMES
(210;
C
:H
N3 X H 3
'i)TH2
N,CH3
\/
CHIO \
\
=
CH3
bond
(147).
As-13
(134),
(11, 160, 241, 280, 282, 320),

(27)
a-
a-
by
(157) )
(20, 156, 202).
(284)
T H E MORPHINE ALKALOIDS.
23
C,)
(57, 145, 152,

by
157 159, 282)
(136)
1.
TABLE
PROPORTION O F ISOMERIC CODEINES FROM T H E
HYDROLYSIS OF THE CHLOROCODIDES*

Isocodeine
Pseudocodeine
Allopseudocodeine
25
55
45
10
15
20
76
70
Gohlich (57) is the only one reported to have isolated codeine from the hydrolysis of the
chlorocodides.
(160, 281, 282).
C3
by
(152, 160, 327)
2.
(112)
(158)
by
(113) )
(107). A
TABLE
RELATIONSHIP O F TH E MORPHINES
TO TH E CODEIKES
---f
-+
-+
-+
'Isocodeine has been applied at various times (282) in reference to allopseudocodeine (157).
bThe pseudo nomenc!ature of the codeine isomers could not be employed in the case of the isqmeric
morph!nes because this term had already been used to designate a dimer resulting from the oxldatlon of
with potassium ferricyanide solution.
'Pseudocodeine has, at times (150, 277). been referred to as dicodeine.
24
H . L. HOLMES
C,
by
on
no
(1)
no
CS
(2)
by
v
)
Ce
CS
4.
1905
no
on
on
80, 84,
no
THE M O R P H I N E ALKALOIDS.
25
C6.
no
no
tetrahydrophenanthrenes,
upon
on
von
by
(27)
on
26
H . L. HOLMES
a
by
on
(27).)
(32)
(3, 58), on
bond
A9-lD
5. THE CAMPHANE
AND MODERN
FORMULAS
go
on
1889
1907.
by
Cg
by
111
no
up
111.
CS
C13
CS,
C14
Cs, C7, C13

C5
C14
C,
by
(149)
7
(210
A13-14.
27
(112)
C,
Cg
bond
A13-l'
C7
bond
A*-]'
0-
y-
bond
As-1.:
A*14
A13-lG.
bond,
von
upon
As-14
bond
p-
28
H . L. HOCMES
\
/
+
+
*Ak
1
R'
R"
* Ak represents an alkyl residue.
+ AkBr
\
'
2HzO
on
on
upon
upon
THP
=c
12x1
bond
A*-+),
29
THE
no
B, y
no
185, 195, 196,
I\
I('=<'
/
=
by
by
P,
by
bond P, y
(183),
von
no good
30
H . L. HOLMES
supposedly
6, 320) by
(242
bond.
on
+
--t
on
(287)
(57)
y-)
a-
p-
:-)
(20, 136, 152, 159, 280, 281, 282),
by
a
31
bond,
C8-Cls
bond.
AB-lO
f-
by
c
5
c
1
5
upon
c
1
3
c
1
5
bond
:
(242),
(35, 246, 251, 255).
(32, 320)
bond
A9-l0.
bond
no
(35).
von
1
: on
good
32
H . L. HOLMEB
on
111,
(62, 197).
(34).
(291)
Hz
(189) ).
bond
(209).
(293, 321)
0
on
1925
no
(34)
II
(321,326)
Cb
A7-8
on
bond
(34)
9, 10-dihydro-des-N-methyldihydrothebaine
by
by
by
33
pound.
C4
LXVI
C5
C13.
C13,
on
(321)
(128, 200, 319)
by
on
1, 2
bond,
by
34
H. L. HOLMES
has
by
on
A7-8
(289)
111.
bond
by
on
on
bond
a-
As-14
(36)
111,
no
by
on
of
by
by
"OU
35
36
H. L. HOLMEB
by
a Cq
upon
C15;
by
(238)
37
6. PROBLEMS
REMAINING
by
3,
ethyloctahydrophenanthrene,
bond
CS
(310.
ketodihydromethylmorphimethine
upon
by
3,
by
38
L. HOLMES
111. The Reactions of Morphine, Codeine,

and Related Products
1.
bond
C--K
A6-7
REDUCTION
A7-8),
bond
on
bond
A6-7J
a. Catalytic Reduction.
on
(orAB-14),
good
258,
on
39
bond
As-7)
bond.
(258),
(31, 192, 246, 251),

(31, 255),
E-
(252),
(257),
(258, 331).
and
(33).
bond
p(313).
by
(246).
p(257),
(242, 250)
(252, 258),
(255),
(246)
(259),
Dihydroallopseudocodeine (255).
200
1748
(1.34
0.2 g.
14.3 g. (SOa/O)
3.2 g. (18%)
7%) of
up
78-79".
by
(336, 337, 338).

Dihydrocodeinone (337). A
300 g.
2 1.
25 g.
on
m.p. 195';
85-9570.
40
H . L. HOLMES
(261).
b. Electrolytic Reduction.
(241,320)
CY-
(247)
(248)
(242)
(31,249)
(242)
(331)
on
(30).
c. Reduction by Chemical Means.
by
upon
111,
by
(251),
(257)
(255)
bond
AG7
6-keto-13-ethyloctahydromorphenol
6-keto-l3-ethyloctahydromorphol-3-methyl
(297)
tetrahydrochloromethylmorphimethine
desoxytetrahydro-a-methylmorphimethine (33)
(62),
(331)
on
on
(201, 203).
41
2. OXIDATION
on
(112) ).
upon
50"
5"
334)
on
a. Chromic Acid and Potassium Permanganate.

(158)
(112, 158,
by
12))
(145, 149)
(145, 149)
(5"),
LXXXIII
(112, 270)
LXXXIV
on
(130)). As
upon
(1%)
=
(291)).
b. Ozone.
(Cl8H2,O3N),
50"
42
9'
H. L. HOLMES
on
1
=
(ClsH2305N2'
(Cl,H25O5N:
\
/
0A
06'
=
=
('1
by
by
=
(207)
C6
bond
A3-4
N KOH)
a-ozo-
in
(207),
(27)).
by
bond
bkh
by
by
43
by
on
Hay?
upon
\
/
\
OPc'
(X =
of
(214).
44
H . L. HOLMES
(50),
trans
Al-?)
(214).
.
bond
(217)
c. Other Oxidizing Agents.
no
on
(253),
(253),
(253)
(253),
(253,
(39) )
85% (15, 253) )
Y-Pseudomorphine (253). A
-94")
1
(253),
(253),
(74)
274", [@ID =
1.2 g.
1.0 g.
by
(85%)
282-283"
(253).
160"
45
TH E MORPHINE ALKALOIDS. I
TABLE
THE OZONOLYSIS O F CODEINE A N D RELATED PRODUCTS

Product ozonized
Ozonolysis product
Ozone
Solvent
References
38,214
214
3 70
257,
(5)
211
..
211
8%
211
10%
211
8%
207,214
8%
217
207
214
207
10%
211
211
8"'/(.
211
214
211
4%
211
8%
214
8%
214
46
H . L. HOLMES
A
by
(1,l)-3,4
by
by
on
by
47
30%
on
by
on
(167),
j,
on
),
by
by
by
3.
NUCLEUS
A
by
48
H . L. HOLMES
C,)
para
C2
C1
a. Halogenation.
)
),
by
by
by
on
by
by
upon
),
on
by
Bromocodeine (201).
5.0 g.
25
162'.
6 0 7 ~(265).
by
30%
30%
is
49
+
b.
by
-4
)
by
by
).
by
by
on
).
by
on
).
Cz,
by
by
by
by
on
50
H . L. HOLMES
by
Acetylation.
by
on
by
d . Xulfonation.
by
167,
by
A
upon
(Ca4H40OI5N&)
by
)
on
51
on
221")
on
).
(2Hz
bond
+
)
).
tetramethylethylenediamine
)
by
AROUNDTHE NITROGEN
ATOM
4.
);
by
C,Hr,
52
H . L. HOLMES
a.
Fission
Type
upon
A)
by
C).
acetyltetrahydro-r-methylmorphimethine
a-
bond
Pr-
( As-l )
10
Norcodezne-Method
10.0 g.
40
on
30
1
no
4.0 g.
by
12
50
185",
1.6 g.
4.0 g.
on
no
by
1.0 g.
Method C
a
on
2
10
on
53
by
180",
8070
by
on
g.
5
by
by
263").
100 g.
80%
3 kg.
6%
b. Fission
by
55.0 g.
100 g.
TypesM and V- Neopine.
on
(59),
good
no
C4
(309)
good
(13),
(16),
(280),
54
H . L. HOLMES
TABLE
SOME METHO SALTS T H A T H A V E B E E N SUBJECTED TO
HOFMANN DEGRADATION
~~
Metho salt of
Reagent
References
Metho aalt of
Reagent References
164
152
16,148,
265
265
320
13,78
233
13,256
171
153
153
250
31
246
257
314
251
250
62
197
255
32,320
251
189
106,133,
212
19,137,
160
20
20
20
130,139,
147
160,281
171,175
316
AGO
13,93
290
119
Methiodide.
Methohydroxide.
Methomethyl sulfate.
These methmes may be isomerized to an isomeric methine.
Isomethine formation also occurs.
171,175
145
31
320
31
55
by
120")
(13).
=
upon
(93).
(83).
CH,
4)
=
E-
(-
by
=
(187).
(16),
(134).
by
by
(134),
(25) ).
56
n.
(78),
),
256). A
g.
P-Methylmorphimethzne
20.0 g.
200 g.
on
by
on
(290).
p-
a-
111
A9-lo
no
E-
CY-
by
bond,
57
(dihydro-a-methylmorphimethine
;
bond.
dihydro-p-methylmorphimethine
bond
tetrahydromethylmorphimethine by
on
on
(e-
bond
bond
bond
).
129
75,
)
).
by
AcetylmethyZrnorphol(72,75).
5
of
131".
(75)
)
),
58
H . L. HOLMES
3-methyl-6-hydroxy-13-vinyltetrahydrornorphenol,
Methylmorphenol
850
120" (140'
220 g.
250 g.
3F
15
is
64-65".
p-
y-
59
Morphenol (102). A
8 g.
2 g.
4 g.
4-5
160".
by
by
70%).
by
dihydro-a-methylmorphimethine
Tetrahydro-a-methylmorphimethine
C4
upon
on
(316),
by
by
by
dimethyldihydroapomorphinemethine
5.
bond
A6-7),
150
by
60
H.
HOLMES
(316)
).
(259)
(308) )
by 1,2-
by
(259).
CIIl
do
=
=
=
CrH,
BI
61
(CIV)
C3
by
(CIV,
CH3, R
on
by
by
by
by
6-hydroxy-l3-vinylhexahydromethylmorphenol (CV)
2
upon
(241).
6. THECODIDESAND MORPHIDES
a. Those Containing Chlorine and Bromine. A
by
a
by
by
by
157, 202),
(202),
by
by
(20, 202).
by
282).
(202,
on
62
H . L. HOLMES
TABLE
SOME HALOGENO-MORPHIDES AND -CODIDES

Reactant
Reagent
Product
References
202
265
157
20,241
202
313
156
55,157
282
11, 20, 241,
282,320
27
20,281,282
313
3 13
a-C
Tetrahydropseudochlorocodide
62
313
311
313
313
247
313
313
313
202
281
28 1
281
134
134
156,248,313
313
280
160
27,248
313
248,280
134
157
19
19,149
202
31
149);
63
51,
on
1,8-dichlorodihydrocodide
(313),
(313).
upon
on
a-
bond.
(313),
a-
52%
7.5y0
=
=
C1.
("1
64
H.
HOLMES
(55) ),
(156).
on
202, 313).
by
As-
(313, 339),
=
(313).
(-22).
by
CS-CI4
by
(313).
(313),
A
on
on
C1
Cg
on
pentachloroozycodide
bromomorphide
(267)
(313).
bromocodide
on
(20, 313),
(159)
no
(313).
iodomorphide,
(313)
T H E MORPHINE ALKALOIDS. I
65
CS
b. Iodocodide and Iodomorphide.
good
on
),
by
66
H . L. HOLMES
T h e Amino-codides a n d -morphides.
185,
by
11,
upon
As
on
bond
A6-7
bond
As-?;
on
by
bond
A7-8
d. Thiocodides and Thiomorphides.
by
(
by
67
by
(134).
2(Ci,HisOzNCl)
(CzHsOH)
+ PKSH
2(Ci,HisOzNSH)
--+
p-Chloromorphide
Hx0
2CH.31
+ (CirH,,OzNS-)2
___ +
(ClsHzoOzNS-)n
(CzHsOH)
2(C18H10021;Br) 2KSH
-+
2(C&zoOzNSH)
6rornocodide
(see
by
by
100" (20, 254),
(20, 254")
(134)
(134)
(22). A
(254).
a-
bond
by
(254).
on
+ C2H,0H)
on
(C,gH2002?SSCZH5)
(254),
(21)
(254).
68
H . L. HOLMES
).
111.
0.1 N
A5+
A5-6
bond
Thebaznone methyl enolatp (310). A

-194.5")
141-142",
2.4 g.
[a]: =
150
25').
by
9.5 g.
154-156'
dihydro-p-diethyldithiocodide
Ethylthiodihydrothebainone,
bond
AT-*
=
69
by
0
/
("XV
('XI11
aa-
6-ethylthiomethylmorphimethine,
-+
As
by
p-ethylthiomethylmorphimethine
bond
6-ethylthiomethylmorphimethine
tetrahydrovinylethylthiomorphenol
DESOXYCODEINES
7.
by
by
a. Preparation of the Desoxycodeines and Their Hydro Derivatives. A

by
(153),
=
by
34, 34 (1951) by
of
70
H . L. HOLMES
(241) on
good
(241)
by
(320)
20Oj,
(241) )
by
upon
on (1)
0.4 g.
(2)
283
by
on
(2
(241 242).
by
71
(247).
by
140"
24
(244).
by
upon
1-chloro-6-methyldesoxycodeine-C
(316).
by
on
(313) )
(314).
3 (250).
by
(242),
(153, 242),
(255),
by
(255),
(232).
(250).
72
H. L. HOLMES
et al. (320)
aa-
1 :3
(314)
on
(247)
on
95y0
on
40yo,
(5%)
on
(320).
by
73
.
(197, 242).
by
(249).
a-
upon
(243).
(320)
(153)
(242, 250).
(31).
(0-)
(62, 242).
tetrahydrodesoxycodeines
bond.
(287).
74
H . L. HOLMES
bond
a-
by
by
on
good
by
by
by
by
1900,
by
(280).
b. Location
Derivatives.
the Double Bonds in the Desoxycodeines and Their Dihydro
(a).
75
by
by
by
111
bond
by
(241),
bond
on
A6-7
A5-'j
A5-6,
by
bond
A6-'.
bond
A6-7.
bond
76
L. HOLMES
by
A7-s
A8-l4
bond
by
.
no
by
A5-6
bond
(250).
on
by
77
-C.
by
on
(244)
by
c. Reactions
the Desoxycodeines and Their Hydro Derivatives.
-El
(153).
(314).
p-
a-
bond
AS-14.
by
78
n. L.
HOLMES
(153),
on
A
(197).
Des-N-methyltetrahydrodesoxycodeine,
on
dihydro-des-N-methyltetra(244),
desoxytetrahydromethylmorphimethine
by
tetrahydrochloromethylmorphimethine
desoxytetrahydromethylmorphimethine
by
(33, 292).
by
111.
by
by
by
(265).
1-bromo-a-methylmorphimethine.
C1
C4
a
79
by
by
).
bond
on
AFT
A
bond
(265).
by
(265).
on
on
up
of
(261).
ethyldihydrodesoxycodeines
80
H . L. HOLMES
by
on
on
bond
(261).
phenyldihydrodesosycodeine
hexahydrophenyldihydrodesoxycodeine
by
ethylthiodihydrodesoxycodeine
(254).
IV. The Reactions of Thebaine and Related Products

Papaver somniferum
(Cl9H2,U3S)
young
Papaver orientale,
by
by
81
24
by
by
),
(73)
no
).
)
.
0
=
=
/
As-
to
As-14
A5-6
A7-8)
(7%
)
(a
82
H . L. HOLMES
1.
a. Catalytic Reduction.
on
upon
189, 191,
179,
).
bond
(47%)
(18%)
A*-14
bond
by
by
(308)).
T H E M O R P H I N E ALKALOIDS.
83
on
by
ZOS),
on
(C,
by
bond
on
by
A7-8
bond.
by
on
des-N-methyldihydrothebaine.
84
H. L. HOLMES
'
6-methoxy-13-vinyltetrahydromorphenol
(189, 297).
by
(297)
(297).
des-N-methyldihydrothebaine
(34)
bond
A9-lo
(297)
(297)
on
(34)
(2Hz
(34).
b. Chemical Methods.
+
by
=
Thebaznone (42).
10.0 g.
120
15
15
12
(41,42).
by
58.0 g.
37.2oj,
(50")
no
9.5 g.
30
2.0 g.
(7.0
0.8 g.
30
145')
4.9 g.
130-140)
3.4 g.
151-152".
A
144-147'.
(A
1.2 g. (44y0)
2.6 g.
(19%)
85
a,
by
(2H2
on
by
a,
).
on
no
+
1-Bromodihydrocodeinone
32.0 g.
30.0 g.
by
300
300
7N
205-207".
86
H . L. HOLMES
(37, 122, 288)

(123),
1931 (41) )
100"
(37, 122, 288).
by
Metathebainone (37, 288).

6.0 g.
18.6 g.
72 g.
20
10%
800
by
is
5301,
30
115-
118')
(122).
(124) ).
upon
(37).
(37)
(42) ).
no
=
(249),
(122, 288) )
by
(122) ) ,
CI4(37)
on
(36, 37, 249).
upon
TH E MORPHINE ALKALOIDS.
87
(124) ).
bond
CI4
Ab13,
by
(249).
3
(249) ).
by
Cc
bond
1x1
C14
(37).
88
H . L. HOLMES
by
(249).
183,
+
bond,
5.2%),
bond,
CI4.
by
2. OXIDATION
by
on
89
a. Hydrogen Peroxide.
of 20
Hydroxycodeinone
20
g.
10
3.0
bond
dihydro-7-hydroxycodeinone
.)
(2H2
bond
by
).
by
319,
90
H . L. HOLMES
+
on
upon
on
111.
bond,
319)
=
=
BY,
C8
on
on
120".
91
x=
by
bond
A?-8
by
by
by
by
).
),
by
by
92
H. L. HOLMES
(31
-C
(311).
;
(311).
(31 1).
(31
C6,
by
to
by
1
1
on
311)
(311),
to
P-tetrahydrodesoxycodeine.
b. Ozone.
on
5%
bond
(38, 151).
by
(151)
by
(38).
by
(38, 21 1)
T H E MORPHINE .4LKALOIDS.
93
200"
bond,
by
by
by
(38) ).
by
(3.8%
c. Other
Oxidizing Agents.
bond
94
H. L. HOLMES
by
,
=
by
a-
3.
ORGANOMETALLIC
bond
As-).
A
(262)
(308)
upon
by
95
).
Dihydrocodeinone enol acetate (308). A4
1.5 g.
75
105
15.0 g.
on
(16.4
152-153")
on
153-153.5'.
%1
0,
1,2-
C1
by
by
5-
by
96
H . L . HOLMES
Ci
on
on
is
no
bromodimethyldihydrocodeinone
(308).
by
dimethyldihydrothebainone
by
C,
97
by
on
(13
(125, 309) ),
(41-490/0)
(2426%)
(309)
(loyo; 100"
24
(309)
aa-
(125)
1,21,4-
(125) ).
do
(309).
98
H. L. HOLMES
up
CI3,
(309).)
(38),
(183),
do
ATOM
4.
do,
by
)
84,
)
:
99
).
3,4,6-triacetoxyphenanthrene
upon
on
of
7)-phenyl-6-keto-5,6,7,8-
bond
phenyltetrahydrothebaimine
a. Hofmann Method.
dihydrohydroxycodeine-B,
)
(309)
1\1
=
100
H. L .
..
30
309
(-)
38
36
on
..
319
36
189,297
125
+
..
190
37
124
125
NaOCzH6
..
125
..
125
38
..
36
319
..
36
TABLE
Methiode of
Reagent
101
6 (Continued)
Basic
Nitrogen-free product
C,& o08
References
34
34
310
..
..
38
..
311
..
36,319
..
319
..
36
..
37
..
34,189
89
..
..
125
..
190
..
189
..
292
..
310
..
39
..
319
38
..
30
102
H . L . HOLMES
TABLE
6 (Continued)
~~
Methiodide of
Reagent
~~
Basic product
Nitrogen-free product
References
37
37,122
..
309
309
309
309
309
..
+
+
(
309
309
..
309
..
309
..
309
..
309
..
309
..
125
125
125
AgOH
73, 84,
116
38
103
(124).
by
a
by
on
a-
N-C16
a-
2c=c
(309).
bond,
(309).
a-
by
(309).
by
Cb
104
H . L. HOLMES
a-
n
a-
(des-N-methyldihydrothebaine)
by
on
by
(37).
des-N-methylphenyldihydrothebaine
105
C4
C4
(125) ).
by
=
a-
by
a-methyl-9-dimethylamino-6-methoxythebendiene
(f )-
racemic-vinyldihydro-X-niethylthebaol
hy
hy
dihydro-des-N-methyldihydrothebainone,
d hy
*
by
(34)
(34).
(CrOa)
106
H . L. HOLMES
dihydro-des-N-methyldihydrohydroxythebainone
dihydro-des-N-methyldihydrothebaine
by
(34),
-+
C15-C16
(2 N
(34).
Dihydro-des-N-methyldihydrothebainone
upon
by
Dihydro-des-N-methyldihydrohydroxycodeinone,
107
des-N-methyldihydrohydroxycodeinone
by
(36).
b. Cyanogen Bromide Method.

upon
=
=
(319)
(25% H2SOI)
=
upon
205),
A
by
by
by
108
H. L. HOLMES
bond,
(205) ).
I
I
i
I
4H2
5 . REARRASGEMLSTS
up
on
M O R P H I N E ALKALOIDS.
109
a. Thebenine
Thebenine (84, 113).
100
upon
by
by
235"
13).)
by
1470
).
by
).
113,
be
).
very
110
H.
HOLMES
CS
by
(84),
by
no
+
)
no
by
+
hoxyp
by
(24),
111
).
to
on
Cb
C5.
84,
84,
on
by
by
2-methoxy-5-ethylphenylacetate)
to,
to
112
H . L . HOLMES
(294).)
(294)
(23)
(315) ),
on
(Ma),
bond
(204)
dimethyldihydrothebeninemethine
by
of
C6
bond
(89).
b. Morphothebaine
good
by
Morphothebaine
70, 121). A
on
10.0 g. of
50
3
by
by
on
687,
121.)
(70),
(89, 113).
(70) ),
(89).
(73)
113
).
(89) :
1N
).
(58,
(23)
([a]: = -
).
by
(89).
(23)
by
).
3,4,8-trimethoxyphenanthrene. A
).
on
114
H . L. HOLMES
by
by
)
[a]: =
on
bond
111
by
CI4
CHART
CODEINE AND THEBAINE AND THEIR PRODUCTS OF TRANSFORMATION AND DEGRADATION

c
-
tI
r
Axcthyr-
2M
'I
1
1
Allo-
(? )
+ 1
c---
116
H . L. HOLMES
(37)
on
on
V. Synthetic Hydrophenanthrenes Related

to The Morphine Alkaloids
by
on
11
(2)
no
(C13
ethyl-5,6,7,8,9,10,13,1-l-octahydrophenanthrene
I1
117
tetrahydromethylmorphimethine
by
).
Desoxytetrahydro-a-methylmorphimethine
dihydrodesoxytetrahydro-a-niethylmorphimethine
by
+ K2C03)
+
C4
(03)
(2)
CI3
T y p e 1.
on
118
H. L. HOLMES
by
1,2,3,4-tetrahydronaphthalene
by
on
by
T y p e 2.
3,4-dimethoxy-l3-ethyloctahydrophenan-
(4-5
l-keto-5-chloro-7,8-dimethoxy-l,2,3,4-tetrahydronaphthalene
l-ethy1-2-keto-5-chloro-7,8-dimethoxy1,2,3,4-tetrahydronaphthalene
on
by
3,4-dimethoxy-7-keto-13-ethyl-5,6,7,9,10,13-hexahydrophenanby
by
3,4-dimethoxy-13-ethyloctahydro-
119
266,
),
5-bromo-7,8-dimethoxy-3,4-dihydro-l-naphby
=
~-brom0-3,4-dimethoxy-6-ketooctahydrophenanthrene-l3-~arboxylate,
=
CI3by
bond
111.
no
C9 by
=
C1,
. .
by
by
7,8-dimethoxy-3,4-dihydro-S-naphthoate
5-bromo-7,8-dimethoxy-3,4-dihydro-2-
L. F. Fieser and R. C. Clapp, private communication.
120
H . L. HOLMES
(230, 272)
on
by
(223) ).
by
(225).
(225).
by
(225).
121
+
bond,
by
on
299,
no
by
good.
122
H . L. HOLMES
(268).
syn-
RI
cc
R1 =
=
=
=
of
I11
123
on
of
on
hlorphinane
124
H. L. HOLMES
VI. Table of Physical Constants

1930.
The Chemistry
the O p i u m Alkaloids (331).

6
7.
TABLE
T H E MORPHINE ALKALOIDS AKD THEIR PRODUCTS O F

TRANSFORMATION AND DEGRADATION
Compound
M.p.
b.p.
"C.
Crystal form
References
A
..
..
..
. .
..
..
..
..
240
*202
..
. .
222
222
267
267
267
218
..
218
..
170
312
312
312
255
255
255
312,222
312
. .
*300-305
308
-9.3"
177
308
..
. .
308
308
308
308
308
(V)
308
125
7
M.p;or b.p.
Compound
308
308
(V)
HzO)
308
308
308
15
308
308
249
166
249
313,263
263, 313
..
..
128
. .
..
313
313
308
307
..
307
307
307
249 (V.
(V. gas)
70
307
307
-88.1'
21
17
307
(V.
307
307
(H20)
307
307
(V. gas)
..
307
307
126
H . L. HOLMES
TABLE
7 (Continued)
~~
M.p. or b.p.
"C.
Compound
[a],
..
~~
Crystal form
..
(V)
Referenoea
308
..
308
308
308
(V.
308
307
307
307
307
(V.
..
243
243
243
..
243
308
..
308
308
-
308
308
..
..
..
265
222
222
265
314
..
313
(?)
265
2
..
308
127
TABLE
7 (Continued)
M.p.
b.p.
OC
Crystal
20
308
(V)
308
67
308
..
316
..
-
145
316
316
262
262
(V.
265
265
..
..
24 1
241
..
..
..
..
..
241
241
24 1
241
313
..
..
..
91
-
226
..
..
..
..
..
313
311
..
..
311
145
163.5
..
313,247
313
313
313
313
..
..
311
247
247
313
128
H. L. HOLMES
TABLE
7 (Continued)
M.p. or b.p.
'C.
Compound
171-172
[=ID
Crystal form
-226"
Referencea
316
..
316
260-262
23&239
-73.6'
-81.4"
-372.4"
..
..
..
..
316
316
247,248
247
313
313
314
..
0"
..
159.5-161
..
131.5-132.5'
-51.0"
26 1
250-251
-26.3"
261
193-193.5
- 14.2'
261
235-236
+14.8"
261
247
259
P-Tetrahydrodesoxycodeine)
* 191.5-1 92
144.5-145.5
..
+7.4"
..
175-176
250
, .
250
250
..
46
..
46
244
- 13.8"
160-1 61
295
152-154
f66.2"
159- 161
- 118.8"
135"
247,241
(0.001
(is
122- 126
..
255-260
265-270
219-22 1
..
..
+95.7"
220.5-221
+104.4"
241
..
241
241
247
..
247
..
129
TABLE
7 (Continued)
M.p. or b.p.
'C.
[a],
241,247
..
165
196
114
..
..
..
..
..
..
..
247
241
241
241
261
247
314
314
314
0"
314
314
314
..
..
247,248
247
248,247
247
247
..
151
..
247
247
314
..
(V.
265
..
..
..
..
..
308
313
..
.
265
308
..
313
313
..
..
..
(V)
313
267
267
267
267
130
H . L. HOLMEE
TABLE
7 (Continued)
b.p.
267
267
255,258
..
255,258
255
255
255
..
255
255
267
267
249
*255
..
170
..
..
..
313
218
310
310
310
310
244
..
..
244
250,254
250
242,250
175
242
242
242
242,250
..
11
..
242,250
242,250
242,250
242,247,
314
247,314
242,247,
313
131
7
Compound
M.p.
"C
. b.p.
[QID
..
256
139
242
..
..
..
..
242
242
311
..
72
..
249
..
249
248,247,
253
248
..
248
248,253
248
248
248
254
..
..
..
..
..
-
254
..
..
..
..
254
254
254
46
46
46
311
..
365
-
311
-
311
311
311
311
311
168
103
-70"
311
132
H.
HOLMES
7 (Continued)
b.p.
ID
'C.
311
311
67
203
311
.
311
218
311
..
218
218
207.5
-6
311
309
65
143
180
-
..
. .
..
..
104
(V)
..
309
..
..
311
..
..
311
258,313
246
258
258
258
258
258
307
307
307
277 (V.
..
..
..
- 87"
307
307
307
307
258
258
258
258
133
TABLE
Compound
7 (Continued)
M.p. b.p.
"C.
Crystal form
[a10
..
..
References
307
307
307
252
252
252
..
252
252
* 13
252
307
307
307
0'.
gas)
307
307
307
307
307
307
307
259
*198
120
..
..
249
249
309
..
309
246
..
+16.4"
..
167
..
+
+
246
(HzO)
246
257
257
257
134
HOLMES
H.
TABLE
M.P.
7 (Conlinued)
b.p.
[QlD
form
Reference8
251
..
150
251
99
257
255
*175
255
307
17
307
307
307
307
307
167
260
307
307
307
307
307
307
307
307
307
307
307
307
307
307
49
307
w. gas)
307
307

TABLE
135
7 (Continued)
b.p.
'C.
269
307
307
307
Pas)
(V.
307
(V.
308
308
308
308
(V.
-
308
308
267
267
*155
246,313
*287
246
246
246
257
257
{
{
*113
251
16
251
..
257
257
257
257
259
259
259
136
H . L. HOLMES
TABLE
7 (Continued)
M.p. or b.p.
Compound
"C.
Crystal form
73
259
..
16
References
63
273
..
259
262
310
..
46
qu non
143
254
> 220
310
310
310
310
310
310
310
..
..
..
..
..
..
310
(H20)
310
..
310
310
310
..
310
(V)
310
..
2 0 )
..
9,
, ,
261
..
..
310
310
310
310
^.
308
..
308
T H E M O R P H I N E ALKALOIDS.
TABLE
7 (Continued)
M.P. or b.p.
"C
Compound
[alD
Crystal form
120 (1')
References
308
308
308
..
.,
2
137
316
316
19
316
-
308
308
308
261
261
261
261
308
308
308
1.5
308
308
gas)
308
261
0.001
261
234
261
77-79
-340.7" (C2HsOH)
254
254
254
138
HOLMES
H.
M.p.
b.p.
Referencea
~~
..
..
254
254
254
254
254
..
46
330
..
46
222
..
..
257
276
308
..
46
46
46
46
46
273
253
..
..
251
..
> 350
..
..
..
..
46
46
46
46
246,251
246
246
257
*138
..
..
..
255
255
261
261
250
261
311
..
311
311
311
TH E MORPHINE ALKALOIDS.
TABLE
7 (Continued)
M.P. or b.p.
'C.
Compound
139
[-ID
Crystal
References
311
311
311
-80"
185
(V)
311
..
..
..
..
313
313
..
160
..
..
..
161
71
..
..
..
..
..
24 1
241, 313
241
241
313
313
313
313
258
246
310
310
310
308
308
308
04
308
308
308
(V.
262
308
non
308
(V.
140
H . L. HOLMES
TABLE
7 (Continued)
M.p. or b.p.
"C.
Compound
[a],
Crystal form
References
262
262
308
308
262
262
58
308
172
308
..
..
243
264
..
253
307
307
307
307
307
307
307
307
307
..
182
..
..
..
..
278
..
184
..
258
307
307
307
307
252
252
307
307
307
307
307
141
ALKIILOIDS.
TABLE
Or
7 (Continued)
b.p.
'C.
References
[
.
.
I
D
307
307
307
307
2
15
308
308
..
..
..
..
308
308
308
308
308
non
308
308
308
308
-
308
308
308
308
308
308
308
308
308
..
308
308
308
142
H. L. HOLMES
TABLE
Compound
7 (Continued)
M.p.
b.p.
"C.
[do
Crystal
References
11
249
..
249
249
249
..
220
225
140
. .
..
249
249
150
..
249
21
18
..
..
249
..
249
249
315
..
118.5
315
..
309
309
309
..
0"
309
316
316
316
262
262
262
262
316
316
..
(LO)
116
25
316
TABLE
7 (Continued)
M.p.
b.p.
"C.
C0 p0 u nd
143
lalD
Crystal form
References
316
316
262
262
262
261
158
26 1
261
239
..
, ,
261
316
316
316
316
262
262
262
18
316
316
316
262
262
308
308
308
+103.1
308
308
+
..
309
309
309
144
H . L. HOLMES
TABLE
7 (Continued)
~~
M.p. or b.p.
"C.
Compound
Crystal form
..
..
178
..
..
References
309
309
309
..
309
309
259
..
..
309
..
..
..
.,
-80"
..
64.5
309
309
309
309
198
..
..
309
..
309
309
309
106110
..
233
309
11
..
309
309
309
309
..
..
( +)
92
(
..
..
4 1.5
.
309
309
..
309
309
309
309
309
0"
..
..
dide
..
..
+14"
..
309
309
309
..
309
THE M O R P H I N E ALKALOIDS.
TABLE
7 (Continued)
M.p. or b.p.
[-ID
'C.
Compound
145
Crystal form
References
309
..
309
309
..
309
207
309
309
-
309
..
309
262
262
262
262
179.5
244 (V.
262
244 (V.
..
..
..
-
..
*I
..
..
..
..
262
256
246
246
246
255
255
255
255
261
261
261
261
316
240.5
+8.0"
316
146
7 (Continued)
b.p.
b.1,
316
..
316
254
..
254
256
..
..
..
145
282
307
307
307
307
307
(V.
-
(HzO)
242
..
172
249
..
307
253
253
..
222
222
222
..
253
..
..
253
..
253
253
> 200
313
316
316
..
316
316
147
7 (Continued)
M.p. or b.p.
'C.
Compound
308
261
261
26 1
261
308
308
201
308
308
308
308
gas)
308
261
267
267
267
267
267
+
..
..
267
267
267
267
267
267
267
259
259
259
Hz0)
148
H. L. HOLMES
TABLE
M.p.
"C.
7 (Continued)
b.p.
Crystal
References
253
253
253
253
253
276
272
.
253
253
253
253
253
..
..
..
..
..
..
253
253
..
253
..
..
..
..
. .
..
,
253
253
253
253
253
253
..
.
1
..
253
253
253
.
.
*145.5
255,258
255
255
255
267
..
25
..
267
247, 244
244,250
241,247,
250
244
TABLE
M.p.
149
7 (Continued)
b.p.
IQlD
..
263
..
2
18
..
244,242
244,242
244
244
244
244
311
249
..
249
247,248,
258
247
247
247,258
,253
318
57
267
..
..
267
267
254
258
..
..
* .
..
*187
258
252
252
..
252
246
246
246
246
246
150
n. L.
TABLE
Compound
HOLMES
7 (Continued)
M.p.oor b.p.
C.
'196-197
Crystal form
+192"
* 123-124
*156.5-157
98.5
*251-252
110
Referencea
246
..
246
+199"
257
+54"
257
+42"
257
-26"
255
175-175.5
..
..
..
..
255
255
*249
+47.6"
255
125
+36.7"
267
270-280
+45.1"
267
(V.
..
179-180
..
251
246,251,
259
246
246
246
*115-120
-9.9"
*263
+1.9"
-0.9"
..
..
165-166
-1.7"
..
135-136
125-130
*251-252
*250-255
* 170-1 71
..
..
-5"
257
+6" (HzO)
+25.5" (H,O)
$8.0"
257
257
259
-5.9'
-6.2"
259
259
259
* 137-138.5
*154-155
*165-166
*21&2 19
246
..
259
151
7 (Continued)
b.p.
[a],
253
..
253
254
253
..
253
..
..
220
..
..
..
..
..
270
..
46,220
..
220
..
46,220
270
280
212
259
238
261
259
..
..
..
..
..
..
..
..
ch 1
46
46
46
152
248
d
..
..
..
..
46
46
46
46
46
46
310,245,
254
254,245,
310
254
245,254
310
310
310
310
310
(V.
310
310
220.5
310
152
L. HOLMES
TABLE
Compound
7 (Continued)
M.p. or b.p.
"C.
Crystal form
[PI,
..
References
310
310
90
310
310
265
313
..
195
313
313
..
313
..
309
309
REFERENCES
1.
2.
3.
4.
5.
6. 0.
7.
8.
9.
10. 0.
11.
v.
12.
v.
13. 0.
14.
15.
16.
17.
18.
19.
20.
v.
v.
Angew. Chem. 20, 1672

Angew. Chem., 24, 1122
Angew. Chem., 26, 625
Ann., 16, 27
Ann., 21, 201
Ann., 77, 341
Ann., 163, 47
W.
Ann., 168, 131
Ann., 169, 387
Ann., 174, 177
Ann., 176, 189
Ann., 210, 105
Ann.. 210, 396
Ann., 222, 203
Ann., 267, 1
Ann., 294, 206
Ann., 297, 204
Ann., 301, 1
Ann., 317, 267
Ann., 368, 305
A.
Ann., 373, 1
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
Ann., 373, 15
R.
R.
Ann., 373, 45
Ann., 373, 51
Aitn., 373, 75
Ann., 373, 80
Ann., 382, 50
Ann., 382, 306
v.
C.
C.
C.
pvl. A.
M. A.
W.
A.
W,
W.
61.
62. C.
63.
64. A.
65.
66.
67. A.
v.
68.
69.
v.
Ann., 391, 40
Ann., 394, 223
31.
Ann., 430, 1
by.
Ann., 432, 233
Ann., 433, 267
Ann., 438, 34
11.
Ann., 444, 69
Ann., 461, 55
Ann.. 462, 211
Ann., 468, 148
Ann., 467, 17
Ann., 481, 81
Ann., 483, 157
Ann., 483, 169
Ann., 489, 224
Ann., 492, 213
Ann., 497, 47
Ann., 497, 289
Ann. 611, 202
Ann.., 636, 216
Ann. chim., 46, 257
Ann. chim., 92, 225
Ann. chim. et phys.,
6, 275
47, 147
19, 359
(Gilberts) Ann. Physik, 66, 56
A.
Ann. Suppl., 7, 170, 177
Brch. Pharm., 229, 161
Arch. Pharm., 231, 235
Arch. Pharm. 263, 266
Arch. Pharm. 268,295
Ber., 4, 121
Ber., 13, 86, 91, 92, 93, 98
Ber., 14, 2406
Ber., 16, 1484
Ber., 16, 2179
153
154
H . L. HOLMES
70.
C.
71. M.
72. 0.
73.
C.
74.
75. L.
76.
77. L.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
91a.
92.
93.
94.
95.
96.
v.
v.
v.
v.
v.
v.
v.
v.
v.
v.
v.
57.
97a.
v.
98. J. v.
99. J. v.
100.
v.
101.
v.
v.
102.
103.
v.
104.
105.
106.
107.
108.
v.
109.
110.
v.
111.
v.
112.
113. L.
114.
115.
116. L.
117. L.
Ber., 17, 527 (1884).

Ber., 18, 1612 (1885).
v.
Ber., 19, 792 (1886).
Ber., 19, 1596 (1886).
Ber., 19, 1760 (1886).
Ber., 22, 181 (1889).
Ber., 22, 1113 (1889).
Ber., 22, 2081 (1889).
Ber., 27, 1144 (1894).
Ber., 27, 2961 (1894).
Ber., 28, 941 (1895).
Ber., 29, 65 (1896).
Ber., 29, 496 (1896).
Ber., 30, 354 (1897).
Ber., 30, 1357 (1897).
Ber., 30, 2439 (1897).
Ber., 31, 51 (1898).
Ber., 31, 2924 (1898).
Ber., 31, 3198 (1898).
Ber., 32, 168 (1899).
Ber., 32, 736 (1899).
Ber., 32, 742 (1899).
Ber., 32, 1047 (1899).
Ber., 32, 1521 (1899).
Ber., 32, 2379 (1899).
Ber., 33, 176 (1900).
Ber., 33, 352 (1900).
Ber., 33, 1438 (1900).
Ber., 33, 1810 (1900).
Ber., 33, 1824 (1900).
Ber., 33, 2728 (1900).
Ber., 33, 2734 (1900).
Ber., 34, 767 (1901).
Ber., 34, 1162 (1901).
Ber., 34, 2722 (1901).
Ber., 36, 1279 (1902).
Ber., 36, 3009 (1902).
Ber., 36, 3010 (1902).
Ber., 36, 4377 (1902).
C.
W.
Ber., 36, 4400 (1902).
Ber., 36, 4410 (1902).
Ber., 36, 4412 (1902).
Ber., 36, 1196 (1903).
Ber., 36, 1590 (1903).
Ber., 36, 3067 (1903).
Ber., 36, 3074 (1903).
C.
Ber., 37, 2780 (1904).
Ber., 37, 3494 (1904).
Ber., 37, 3499 (1904).
Ber., 37, 3507 (1904).
THE MORPHINE
118.
v.
119.
v.
120.
121.
122.
123.
124.
125. IM.
126.
127.
128.
129.
130.
v.
131.
132.
133.
134.
135. 1,.
136.
137.
138.
139.
140.
141.
142.
143.
144.
145.
146.
147.
148.
v.
149.
150.
151.
152.
153.
154.
v.
155.
v.
156.
157.
158.
159.
160.
161.
162.
163.
Ber., 38, 1851

Ber., 38, 1857
Ber., 38, 3143
Ber., 38, 3153
Ber., 38, 3160
Ber., 38, 3171
Ber., 38, 3172
Ber., 38, 3234
Ber., 39, 16
Ber., 39, 19
Ber., 39, 844
Ber., 39, 1409
Ber., 39, 1414
Ber., 39, 1718
0.
Ber., 39, 3106
Ber., 39, 3124

Ber., 39, 3130
Ber., 39, 3252
Ber., 39, 4409
Ber., 39, 4412
Ber., 40, 376
Ber., 40, 1980
Ber., 40, 1984
0.
Ber., 40, 1995

0.
Ber., 40, 1998
Ber., 40,2001
W.
Ber., 40, 2004
Ber., 40, 2032
Ber., 40, 2040
Ber., 40, 2042
0.
Ber., 40, 2827
Ber., 40, 3341
Ber., 40, 3355
Ber., 40, 3652
Ber., 40, 3844
Ber., 40, 3860
Ber., 40, 3933
0.
Ber., 40, 4146
Ber., 40, 4281
Ber., 40, 4883
Ber., 40, 4889
Ber., 41, 969
Ber., 41, 975
Ber., 41, 3050
J.
Ber., 41, 3696
Ber., 42, 3503
42, 3511
Ber., 42, 3521
164.
164a.
165.
166.
v.
Ber., 43, 1353

Ber.. 43, 2128
155
156
H . L. HOLMES
167. 11.
168.
169.
170. 11.
171.
172.
173.
174.
175.
176.
177.
178.
179.
180.
181.
182.
183.
183.
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
207.
208.
209.
210.
211.
212.
213.
214.
215.
1,.
0.
v.
11.
v.
11.
0.
v.
v.
v.
31,
A.
v.
v.
F;.
1.
v.
v.
Ber., 43, 3310

E.
Ber., 44, 105
Ber., 44, 1829
Ber.. 44, 2339
Ber., 44, 2633
Ber., 44,. 2754
1. 13.
Ber., 44, 2862
iV.
Ber., 46,
Ber., 46, 1354
Ber., 46, 1567
Ber.. 46, 1570
(1.
Ber., 46, 2212
Ber., 47, 2043
Ber., 47, 2312
Ber.. 48, 497
Ber., 49, 750
UP,., 49, 977
Bw..49, 1287
Ber., 49, 1721
Bey., 49, 2655
E.
Ber., 60,43
Ber., 62, 1999
B u . , 63,1839
Btr., 63, 2250
S.
Ber.. 64, 1519
Rer., 64, 1560
Ber.. 64, 2647
Ber.. 64, 2976
Ber., 66, 1329
Rer., 66, 3536
iV.
Ber., 66, 538
Ber., 67,
Bw.,67, 1309
Be?., 67, 1422
Ber., 67, 1427
Her., 68, 1110
Her., 68, 1113
Ber.. 68, 1117
Ber.. 68, 1120
Ber., 68, 1125
11.
Ber., 68, 2009
Rer.. 69,390
11.
Rer., 69, 1081
Ber.: 69, 2490
11.
Ber., 60, 2551
Ber., 62, 209
B P ~ 62,
. , 321
0.
Ber.. 62,325
Ber., 63,539
Ber., 63, 646
THE M O R P H I N E ATJKALOIDS. I
216.
217.
218.
219.
220.
221.
222.
223.
224.
225.
226.
227.
228.
229.
230.
231.
232.
233.
234.
235.
236.
237.
238.
239.
230.
241.
242.
243.
241.
245.
246.
247.
248.
249.
250.
251.
252.
253.
254.
255.
256.
257.
258.
259.
260.
261.
262.
263.
264.
265.
K.
Her., 63, 852

Ber.. 64, 2815
Ber., 66, 1214
Ber.. 67, 197

Ber.. 71, 648
Ber., 72, 426
0.
Ber., 72,684
Ber., 72, 785
Ber., 72, 1311
Ber., 76, 1072, 1076
11.
Bull. soc. ch.iin.,
17, 109
\I-.
H u l l . soc. chiin., [1]39, 305
Bull. sor. chim. biol., 6, 231
IT.
Can. J . Research, 22B, 56
1,.
Can. J . Research. 26B, 396
11.
Chem. Zty., 30, 1207
U.
Chem. Zty.. 36, 648
Conipt. re?td., 93, 591
Conipt. rend., 113, 747
1.
Conipt. rerctl., 126, 1799
128, 181
Compt. Tend., 166, 1161
31.
Compt. rend., 176, 169
Helv. Chim. Acta, 13, 1035
11.
Hrlo. Chim. Acta, 26, 2251
11.
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The Morphine Alkaloids

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The Morphine Alkaloids

University British Columbia

11. Elucidation of the Structure of Morphine, Codeine,

Methylation morphtne (227).

THE MORPHINE ALKALOIDS. I

t Knorr was in doubt as to the location of the alcoholic hydroxyl offering

(67, 72, 75),

THE MORPHINE ALKALOIDS. I

THE MORPHINE ALKALOIDS. I

THE MORPHINE ALKALOIDS. I

(85, 86, 87, 88, 92,

A . Codeinone from thebaine (129). A

B. Codeinone ,from codeine (334). A

THE MORPHINE ALKALOIDS.

THE MORPHINE ALKALOIDS. I

THE MORPHINE ALKALOIDS.

(11, 160, 241, 280, 282, 320),

(57, 145, 152,

157 159, 282)

PROPORTION O F ISOMERIC CODEINES FROM T H E

HYDROLYSIS OF THE CHLOROCODIDES*

(160, 281, 282).

Cs, C7, C13

THE MORPHINE ALKALOIDS. I

* Ak represents an alkyl residue.

185, 195, 196,

THE MORPHINE ALKALOIDS.

THE MORPHINE ALKALOIDS.

(128, 200, 319)

THE MORPHINE ALKALOIDS.

THE MORPHINE ALKALOIDS.

111. The Reactions of Morphine, Codeine,

THE MORPHINE ALKALOIDS.

(31, 192, 246, 251),

(336, 337, 338).

THE MORPHINE ALKALOIDS. I

a. Chromic Acid and Potassium Permanganate.

THE MORPHINE ALKALOIDS.

c. Other Oxidizing Agents.

THE OZONOLYSIS O F CODEINE A N D RELATED PRODUCTS

THE MORPHINE ALKALOIDS. I

THE MORPHINE ALKALOIDS. I

THE MORPHINE ALKALOIDS.

THE MORPHINE ALKALOIDS.

TypesM and V- Neopine.

SOME METHO SALTS T H A T H A V E B E E N SUBJECTED TO

THE MORPHINE ALKALOIDS.

THE MORPHINE ALKALOIDS. I

THE MORPHINE ALKALOIDS.

SOME HALOGENO-MORPHIDES AND -CODIDES

b. Iodocodide and Iodomorphide.

d. Thiocodides and Thiomorphides.

THE MORPHINE ALKALOIDS.

Thebaznone methyl enolatp (310). A

a. Preparation of the Desoxycodeines and Their Hydro Derivatives. A

THE MORPHINE ALKALOIDS.

THE MORPHINE ALKALOIDS. I

the Double Bonds in the Desoxycodeines and Their Dihydro

THE MORPHINE ALKALOIDS. I

the Desoxycodeines and Their Hydro Derivatives.

THE MORPHINE ALKALOIDS.

IV. The Reactions of Thebaine and Related Products

THE MORPHINE ALKALOIDS.

(37, 122, 288)