THE ACONITE ALKALOIDS

III. THE OXIDATION OF ACONITINE AND DERIVATIVES

WITH NITRIC ACID AND CHROMIC ACID

BY WALTER A. JACOBS AND LYMAN C. CRAIG

(Prom the Laboratories of The Rockefeller Institute for Medical Research,
New York)

(Received for publication, July 6, 1940)

In earlier studies on the chemistry of aconitine and related

alkaloids a number of observations have accumulated, especially
in the case of the former, which present certain inconsist,encies.

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Although the changes produced by certain reagents do not repre-
sent extensive degradation of the alkamine portion of the molecule,
it appears that a number of reactions involving different groups
have occurred more or less simultaneously, so that mixtures of
reaction products were apt to result. This combined with the
difficulty or uncertainty in the isolation of individual subst)ances
from the mixture and the tendency to separate with solvent has
contributed to some confusion. We have previously (1) discussed
t,he case of oxonitine and suggested a revision of the formulas
proposed for it. A return to a further discussion of this formula-
tion and that of its companion oxidation product, oxoaconitine,
first described by us will be made in a subsequent paper.
In a parallel study of the behavior of aconitine and delphinine
and derivatives towards certain reagents we have had occasion to
reconsider and repeat some of the earlier observations on record
in regard to the former. Thus, the so called nitrosodicarboxylic
acid, C22H260nS2, first obtained by Brady from aconitine with
hot HNOS (2), has recently been shown by Suginome (3) to be a
product also from oxonitine and mesaconitine. The latter author,
however, described it as a nitronitrosomonocarboxylic acid,
C31H330&\;3,which he called nitronitrosoaconitinic acid, and which
retained both benzoyl and acetyl groups intact but only three
methoxyl groups and no N-alkyl group. This substance yielded
on saponification a so called nitronitrosoaconinic acid, C22H270nN3.
323
324 Aconite Alkaloids. III
Somewhat before this, Lawson (4) had reported results of a
similar study of the oxidation of both aconitine and oxonitine
with HN03. However, from each he believed that he had ob-
tained different products. From the former a crystalline acid,
C3&6013N3, was described containing three methoxyl groups and
no N-alkyl which after saponification gave an acid, C22H,,O11N,.
From oxonitine the product was described as an acid with a for-
mula, CdLO&~. Finally, with chromic acid Lawson obtained
a base, aconitoline, C30H3709N, which retained the N-alkyl group
but only three methoxyl groups and which on saponification was

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supposed to lose only the benzoyl group to give a base which was
isolated as the HCl salt; viz., CZ~H,,O~N. HCl. 3H20. With HNOS
aconitoline was reported in turn to give an acid, C&H33013N3, also
containing only three methoxyl groups but with no N-alkyl group.
In repeating the above work under the conditions employed
respectively by Suginome and by Lawson, we have become
convinced that both aconitine and oxonitine, as stated by the
former, indeed yield the same nitronitroso derivative but that the
formula is C31H36013N3 and not that given by him. This formula
was adopted by Lawson in the special case of his product from
aconitine. The analytical results published by Suginome on the
anhydrous material actually agree better with this formula than
with that of C31H33013N3 adopted by him. Therefore its saponi-
fication product should be C22H29011N3. In addition we have
found that aconitoline, contrary to Lawson, also yields the same
nitronitroso compound, GrH35013N3. This at once forces a
changed interpretation of the formula of aconitoline itself, for
which we now propose C&H41010N. This conforms with the older
results of Schulze (5) who had oxidized the alkamine aconine to a
base, C24H350sN. The base obtained by us on saponification of
aconitoline was found to be identical with that obtained according
to Schulze from aconine. As described by him, it yielded a
methiodide, C24H3508N. CHJ. Strangely enough, we have found
that aconitoline itself does not react readily with methyl iodide,
at least under the gentle conditions which so easily gave the above
quaternary salt from its saponification product.
By following also the essential procedure used by Schulze for
the oxidation of aconine to the above base in aqueous solution, we
have obtained aconitoline from aconitine, although in poorer yield
 W. A. Jacobs and L. C. Craig 325
than by Lawson’s method in acetone solution. Retention of two
free OH groups in aconitoline is indicated by the fact that its
saponification product, C24H3608N, gives a tetraacetyl derivative
according to Schulze, although the active H determinations
reported by Lawson on aconitoline indicated only one OH group.
This is a point which will have to be rechecked when opportunity
is presented.
Further, it has been found that oxoaconitine with HNOp also
yields, although apparently somewhat less readily than oxonitine,
the above nitronitroso derivative, C31H35013N3. In the case of

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both oxonitine and oxoaconitine it has been possible by more
gentle treatment with HN03 to intercept the reaction at an inter-
mediate stage in which only a nitro group has been introduced with
simultaneous loss of a methoxyl group. Analysis of the substance
from oxonitine suggests either a formula C32H36013N2 or possibly
GH38013N2. The last, however, would not conform to a for-
mula C&H32012N for oxonitine itself. An analogous substance,
C33H38013N2, was similarly obtained from oxoaconitine which
superficially at least appeared indistinguishable in character from
the substance from oxonitine. Both of these substances with hot
HNO, were converted by nitrosation and simultaneous degrada-
tion into the above nitronitroso derivative C31H36013N3.
Finally, a substance was also described by Lawson as a nitroso
compound, C31H40012N2, resulting from the action of nitrous acid
on aconitine itself and which was briefly stated to yield with
nitric acid the above nitronitroso acid. However, no analyses of
the latter were given. The production of such a nitroso deriva-
tive has been confirmed by us as well as its very ready conversion
by HNOS to the substance C31H35013N3. But its analysis appears
to accord best with a formula C34H44013N2. Although it does not
exhibit an N-alkyl group, it still retains all four methoxyl groups.
Its production, therefore, resembles that of the nitroso derivative
C&H44010N2 from delphinine (6) which, however, did not undergo
the apparent additional oxidation of a CH2 group to CO which
obviously occurs in the production of the aconitine derivative.
The exact interpretation of interrelationships of the above oxida-
tion products is still difficult and must await the accumulation
of additional data. It is apparent, however, that the nitronitroso
derivative, C31H35013N3, represents a stage beyond all of the above
 Aconite Alkaloids. III
oxidation products and derivatives, since it is obtained from all
of them by the more or less vigorous action of HNOS. It must be
a nitroso derivative of a secondary amine.’ We have found rather
vigorous action of HCl necessary to remove the NO group as
reported by Lawson for the production of the base, C31H36012Nz.
The latter was very readily reconvert,ed into the nitroso derivative
with HN02. apparently a complicated series of steps is involved
in the conversion of aconitine into this subst,ance which is inter-
cepted at different stages and in different order in the case of each
of the intermediate substances.

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For instance, the production of aconitoline, G~H~~OWN, which
differs from aconitine by CH60 appears to result from the oxida-
tion of a secondary OH group to CO. This must be followed by
either separate loss as Hz0 of an OH group ,B to it along wit,h a
CH2 group, or all as methyl alcohol due to the labilizing effect, of
the CO group.
Triacetylaconitine in which all OH groups have been protected
does not react with chromic acid under similar conditions. Del-
phinine which does not contain two of the hydroxyl groups present
in aconitine is similarly not affected by this reagent. That> the
benzoyl and acetyl groups must occur in the general proximity
of the N atom is suggested by the fact, that aconitoline shows
little tendency if any to quaternary salt, formation, unlike its
saponification product. The unsaturated character of aconitoline
was indicated not. only by its ready oxidation with IWIn04 but
by hydrogenation, although the hydrogenation product could not
be crystallized. The latter yielded on saponification an amor-
phous substance different from the base, G&O&, given by
aconitoline itself.
The first action of HNOS on oxonitine or oxoaconitine appears
to proceed with oxidative removal of Hz and introduction of an
NO2 group. This occurs by substit,ution without loss of carbon
except that contained in the methoxyl group which is either
removed as methyl alcohol or demethylated independently of
the loss of HzO. Thus oxoaconitine C~~H.S~OEN with loss of CH60
(perhaps at this stage paralleling the formation of aconitoline
1 Suginome also adopted the view that his nitronitroso compound was
a nitrosamine since it lost the NO group on acetylation. However, the
analytical data on his acetyl derivative are not convincing.
 W. A. Jacobs and L. C. Craig 327
from aconitine) and nitration would give C33H38013N2. The pro-
duction of C31H350&s from t.his in turn is the result of a,n obviously
complicated oxidative cleavage of a cyclic amide group with
simultaneous nitrosation of a liberated secondary basic group. At
the same time degradation occurs with loss of CzH30. This
nitronitroso derivative, contrary to the statements of previous
workers, does not possess a free carboxyl group. Although it very
slowly dissolves on sta.nding in dilute aqueous alkali, it is not dis-
solved by XazC03 solution and it cannot be extracted from the
chloroform solution with the latter. It is eit,her a lactonc or a

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=CH. NO2 deriva,tive which dissolves in alkali as a. salt, of the
aci- form.
Further work is now in progress which it is hoped will help to
establish the exact, interrelationship of these substances as well
as the exact nature of the groups involved in their transformations.
Henry and Sharp (7) in their study of pseudoaconitine have
described the production of several oxidation products which are
doubtless analogous to those obtained from aconitine. With
chromic acid a weakly basic substance was obtained to which the
formula C34H45011N was ascribed and which while retaining the
so called N-alkyl group contained one less methoxyl group. Since
pseudoaconitinc has veratric acid in place of benzoic acid and
contains one less OH group t,han aconitine, the formula of this
substance if exactly analagous to aconitoline should be CJ146011N.
With nitric acid two oxidation pr0duct.s were obtained. One
of these to which the formula C33H400&4 was ascribed, if analo-
gous to the nitronitroso compound from aconitine, C31H36013N3,
should instead have the formula, C&&80&4, since it would not
only contain one OH group less than the aconitine derivative but
nitroveratric acid in place of benzoic acid. If such conclusions
are correct, consistent, changes would have to be made also in the
formulas of the hydrolytic and ot,her products described by Henr)
and Sharp.

EXPERIMENTAL

Aconitine and Nitric Acid-O.75 gm. of aconitine was oxidized

in 5 cc. of HNO, (1.42) according to Brady (2) by heating on the
steam bath for 1 hour. The precipitate formed on dilution was
crystallized by solution in chloroform followed by addition of
328 Aconite Alkaloids. III
alcohol and concentration in order to remove the chloroform.
The melting point depended upon the conditions of crystallization.
When the substance separated from the hot alcoholic solution, it
formed small faintly yellow four sided prisms which colored above
240”, became dark, and melted at 278“ with decomposition. When
the separation occurred more slowly from the cool solvent, minute
wedge-shaped crystals formed which gradually softened to a resin
at 185-200” and then crystallized again and melted at 277-279”.
For analysis it was dried in uacuo at 120”.

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‘&Hadh~N~. Calculated. C 56.60, H 5.37, N 6.39, OCHI 14.16
Found. “ 56.39, “ 5.38, “ 6.49, “ 14.16

The procedure described by Lawson (4) was repeated in which

1.1 gm. of aconitine were heated for 2 hours at 100’ in 10 parts of
HNOS (1.2). After dilution the collected precipitate was crystal-
lized first from acetone and then as above. The product was
indistinguishable in properties from the above substance.
Found. C 56.40, H 5.11

The substances as obtained directly from aconitine gave the

impression of being more homogeneous than those obtained from
oxonitine or oxoaconitine as given below.
Oxonitine and HN08-0.1 gm. of oxonitine was dissolved in 1 cc.
of HN03 (1.42) at 25” and kept at this temperature for 1 hour.
Liberation of nitric oxide fumes indicated an obvious reaction.
On dilution, an amorphous precipitate formed which was collected
with water. After solution of the dried material in acetone and
concentration a trace of unchanged oxonitine separated. The
filtrate on careful dilution gave needles which melted with decom-
position at 288-289“ after preliminary darkening and sintering.
On occasion, however, depending upon conditions, it gradually
softened to a paste at 175-195”, resolidified, and decomposed at
280-282". The substance gave no Liebermann nitroso reaction.
[a]‘,” = $14” (c = 0.57 in ethyl acetate)
C33H38013N2. Calculated. C 59.08, H 5.71, N 4.18, OCHs 13.88
CJMhN~. ” 58.51, ‘I 5.53, “ 4.26, “ 14.18
Found. (a) “ 58.66, “ 5.69
1‘
@I “ 58.43, “ 5.39, N 4.12, OCH, 14.22

When the reaction was allowed to proceed at this temperature

for 17 hours, some contamination with the nitroso derivative given
 W. A. Jacobs and L. C. Craig 329
below was apparent, since the substance gave an appreciable
though weak Liebermann test.
Found. C 58.28, H 5.51, N 4.64

0.23 gm. of oxonitine was heated in 3 cc. of HNOI (1.42) at

100’ for 1.5 hours. The amorphous material obtained on dilution
was recrystallized first from dilute acetone (yield 70 mg.) and then
from methyl alcohol by boiling down the solution in chloroform
with the latter solvent. It formed small faintly yellowish
pyramidal prisms or wedges which softened gradually from 175-

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205” and then resolidified and melted with decomposition at 272-
274” after preliminary darkening. The melting point depended
greatly upon the rate of heating as well as upon the solvents used
for recrystallization.
[a]:: = -31’ (c = 0.92 in ethyl acetate)

This rotation was taken with the substance that had been dried
in the desiccator but recalculated on the anhydrous basis.
For analysis it was dried in vacua at 120”.
CJL@ISNS. Calculated. C 56.60, H 5.37, N 6.39, OCH3 14.16
Found. (a) “ 56.64, “ 5.69, “ 6.16, “ 14.05
‘I “ 56.72, “ 5.50
(b)
‘I “ 56.56, “ 5.54
(cl

The substance gave a strong Liebermann test. It is not an

acid, since it does not dissolve in dilute Na2C03. It does not
immediately dissolve in dilute NaOH solution but only slowly on
standing owing to an obvious chemical change. It was also not
removed from chloroform solution by extraction with Na2C03
solution.
This nitronitroso derivative was also obtained by substituting
the above nitro compound, C&HSSO~~NS, in the reaction with
HNOS at 80” for 1 hour. It behaved in the same way in the melt-
ing point apparatus and showed identical properties.
Found. C 56.92, H 5.58, N 5.81

Oxoaconitine and HNOB-A solution of 0.1 gm. of oxoaconitine

in 1 cc. of HNO, at 25” remained practically colorless after 1 hour.
After dilution and collection of the colorless precipitate it was
dried and recrystallized from dilute acetone. It formed small,
330 Aconite Alkaloids. III

stout, colorless prisms which melted gradually to a resin at 180-

190”. In contrast to the substance from oxonitine, however, it
showed no tendency to resolidify and melt again at a higher tem-
perature. Repeated efforts to obtain a substance with such a
behavior even by seeding with the oxonitine derivative were not
successful. It also appeared t,o be more stable towards nitric
acid than the lat,ter, since, when this reagent, was allowed to act
on oxoaconitine for 45 hours at 25’, a substance with the same
properties was readily obtained which still gave a practicalI>
negative Liebermann test.

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For analysis both samples were dried in vacua at, 120”.
C33H&k3X2. Calculated. C 59.08, H 5.71, S 4.18, OCHa 13.88
Found. (a) “ 58.82, “ 5.49, “ 4.19, “ 14.10
“ “ 58.86, “ 5.52
@)
[a]: = $11.5” (c = 1.13 in ethyl acetate)

The experience with HN03 under more severe conditions was

as follows: 0.25 gm. of oxoaconitine was heated in 2.5 cc. of HNO,
(1.42) at 100” for 2 hours. The development of nitric oxide fumes
was only gradual and not nearly as marked as in the case of oxoni-
tine. The substance obtained from dilute acetone by seeding
with material from oxonitinc soft,ened to a resin at 180-195’, and
then partly resolidified and decomposed at 265-267” after pre-
liminary darkening. It appeared indistinguishable from the
oxonitine derivative.
[a]: = -31” (c = 0.9 in ckhyl acetate)

This rotation was taken with substance dried in the desiccator

but was recalculated on the anhydrous basis.
For analysis the substance was dried in vucuo at 120”.
CS,H~SOI~X~. Calculated. C 56.60, H 5.37, K 6.39
Found. (a) “ 56.88, “ 5.57, “ 6.07
I‘
(b) “ 57.05, “ 5.30

The Substance C31H3~0dV3 and HCZ-0.1 gm. of the nitronitroso

derivative (from oxonitine) was suspended in 2 cc. of absolute
alcohol and saturated with HCl with chilling at 0”. The sub-
stance finally dissolved as the HCl approached the saturation
point. The clear solution was allowed to stand at 25” in a sealed
tube for 18 hours and was then concentrated in vacua. After
 MT. A. Jacobs and L. C. Craig 331

treatment with an excess of Na2C03 solution the base was ex-

tracted with chloroform. The residue from the latter crystallized
from alcohol as microneedles or prisms which melted with decom-
position at 252-253” after softening above 245’. Lawson reported
a melting point of 207” for this base which without analysis was
called an amino acid. It proved to be a secondary base since it
gave at once the nitroso derivative on treatment with acid
and NaNO*.
For analysis the substance was dried in vucuo at 120”.

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C31H36012NJ2. Calculated. C 59.21, H 5.77, N 4.46
Found. “ 59.40, “ 6.10, “ 4.57

When the nitronitroso derivative was heated in 20 parts of 4

per cent absolute methyl alcoholic HCl at 100’ for 18 hours, it was
recovered almost entirely unchanged.
Found. C 56.56, H 5.57

Aconitine and Nitrous Acid (4)-0.6 gm. of aconitine dissolved

in 20 cc. of 25 per cent acetic acid was treated with 10 cc. of 30
per cent NaNOz solution. After 14 hours on the water bath and
cooling, the crystalline deposit was collected with water. The
yield was 0.1 gm. When recrystallized by addition of ether to
the concentrated chloroform solution, the analytical results showed
tenacious retention of small amounts of solvent. It was accord-
ingly recrystallized from acetic acid as described by Lawson and
melted with decomposition at 281”. The Liebermann nitroso test
was not marked and the substance showed no appreciable N-alkyl
group.
C34H44013X~. Calculated. C 59.27, H 6.44, OCH3 18.03
Found. “ 59.04, “ 6.54, “ 18.68
‘I “ 59.18, “ 6.67, “ 18.22

50 mg. of this nitroso derivative were dissolved in 0.5 cc. of

HNOS (1.42). After 4 hours at 25” the clear solution was diluted.
The collected precipitate was recrystallized from dilute acetone.
The yield was 41 mg. It gradually soft.ened to a melt over the
range 175-197”.
CSIH~SOI~N~. Calculated. C 56.60, H 5.37, N 6.39, OCH3 14.16
Found. ‘I 56.50, “ 5.44, “ 6.18, ‘I 14.13
332 Aconite Alkaloids. III
Aconitoline-This was prepared essentially as described by
Lawson (4) by the oxidation of aconitine in acetone solution with
CrOs. 2 gm. yielded 0.86 gm. which melted at 221-222’ after
slight preliminary sintering.
CS~HUODIN. Calculated. C 64.78, H 6.76
Found. “ 64.42, “ 6.89
‘I ‘I 64.93, “ 6.46
I< ‘I 64.63, “ 6.66

The analytical results reported by Lawson were in close agreement

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with the above formula.
2.5 mg. were refluxed for 2 hours in a mixture of 0.15 cc. of
0.1 N NaOH and 0.15 cc. of alcohol and titrated back with 0.1 N
HCl against phenolphthalein. Found, 0.0875 cc. Calculated for
2 equivalents, 0.0818.
9.2 mg. were refluxed for 2 hours in 0.095 cc. of N NaOH and
0.1 cc. of alcohol and titrated back with N HCI. The color change
was gradual but the first fading out of indicator occurred at a
point corresponding to a consumption of 0.0414 cc. of NaOH.
Calculated for 3 equivalents, 0.0453. Further cautious addition
of HCl was followed by successive gradual reappearance of indi-
cator color until the consumption of NaOH was reduced to
0.0354 cc. Calculated for 2 equivalents, 0.0302.
The following procedure based essentially upon that employed
by Schulae (5) for aconine was less advantageously used.
1.1 gm. of aconitine were dissolved in a mixture of 8 cc. of 10
per cent H.#.04 and 42 cc. of HzO. To this 0.5 gm. of CrOa was
added which caused a precipitate of the chromate. On heating
on the water bath the latter gradually dissolved as oxidation very
slowly occurred. Although the reagent appeared to be used up
after several hours, heating was continued for 4.5 hours in all.
The cooled acid solution was first extracted with ether and then
after being rendered alkaline with Na2C03, was repeatedly ex-
tracted with chloroform. The washed and dried extract on con-
centration and removal of the residual chloroform with alcohol
yielded 0.22 gm. of crystalline base. After recrystallization it
melted at 221-222’ and proved to be identical with the substance
obtained by the above procedure.
Found, C 64.49, H 6.61
 W. A. Jacobs and L. C. Craig 333

When aconitoline was heated with methyl iodide at 100” for

several hours, no evidence of a reaction was obtained and the
base was recovered unchanged.
0.1 gm. of aconitoline was oxidized according to Lawson in
1 cc. of HN03 (1.2) at 100”. After 1.5 hours the diluted mixture
yielded an amorphous solid which was recrystallized from dilute
acetone. It separated as yellowish microcrystals which gradually
softened from 175-195”, again crystallized, and then decomposed
at 272-273” after preliminary softening and darkening.

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[a]‘,” = -28” (c = 0.98 in ethyl acetate)

Recalculated on the anhydrous basis,

C~&SOIBNB. Calculated. C 56.60, H 5.37
Found. “ 56.41, “ 5.40

The Base C24H350&N-0.22 gm. of aconitoline was dissolved in

2 cc. of absolute alcohol and treated essentially according to the
procedure of Lawson with 1.5 cc. of N sodium ethylate. A reaction
quickly occurred with crystallization of a sodium derivative, the
nature of which was not determined. After dilution with water
and acidification with HzSO+ benzoic acid, etc., were removed by
extraction with chloroform. It was then made alkaline with
Na&03 and repeatedly extracted with chloroform (best in an
extractor) to remove the base. This was finally obtained from
alcohol-ether as the HCl salt which when desiccator-dried slowly
softened above 214” and finally melted with slow effervescence
at 219-220”.
For analysis it was dried in vacua at 120”.
C2~Ha~08N~HC1. Calculated. C 57.40, H 7.23, OCH3 18.55, Cl 7.07
Found. “ 56.95, “ 7.34, “ 18.31, “ 6.78
‘I “ 57.24, ” 7.03

This showed no depression of melting point when mixed with

the HCl salt prepared by oxidation of aconine according to
Schulze (5).
The base liberated from the salt readily reacted when heated
with methyl iodide at 100”. It formed fine needles,m.p. 222-225’,
from methyl alcohol and ether.
GHasOsNI. Calculated. C 49.40, H 6.31, OCHa 15.33, (N)CHa 4.95
Found. “ 49.57, “ 6.27, “ 16.29, “ 4.48
334 Aconite Alkaloids. III

SUMMARY

A study of the oxidation of aconitine and a number of its deriva-

tives with nitric acid and chromic acid has shown that a compli-
cated series of steps is involved which may be intercepted at
different stages or in different, orders. The product of vigorous
action of HN03 on aconitine, oxonitine, oxoaconitine, aconitoline,
etc., is a neutral N-nitrosonitro derivative containing only three
methoxyl groups with the formula C31H35013N3 which represents
a stage beyond all of the others. On acid hydrolysis this yields
the corresponding secondary base C31H36012N2. Gentler action

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of HNOs on oxonitine and oxoaconitine gives intermediate nitro
derivatives with loss of one methoxyl group, respectively
C32H36013N2 (or possibly C&H38013N2) and C~~H~~OI~NZ.
The formula of Lawson’s aconitoline, obtained from aconitine
with chromic acid, has been revised to C33H4~0~0N and apparently
results from oxidation of a secondary OH group to CO with simul-
taneous loss of methyl alcohol. On saponification it yields the
tertiary base, C24H3608N, obtained by Schulze from aconine which
in turn readily gives a methiodide, in contrast to aconitoline
itself.
The production and interpretation of other substances from
aconitine and related substances arc discussed.

BIBLIOGRAPHY

1. Jacobs, W. A., and Craig, L. C., J. Biol. Chem., 128, 439 (1939).
2. Brady, 0. L., J. Chem. Sot., 103, 1821 (1913).
3. Suginome, H., Ann. Chem., 633, 172 (1937).
4. Lawson, A., J. Chem. Sot., 80 (1936).
5. Schulae, H., Arch. Pharm., 244, 165 (1906); 246, 281 (1908).
6. Jacobs, W. A., and Craig, L. C., J. Biol. Chem., 136, 303 (1940).
7. Henry, T. A., and Sharp, T. M., J. Chem. Sot., 1105 (1928).
THE ACONITE ALKALOIDS: III. THE
OXIDATION OF ACONITINE AND
DERIVATIVES WITH NITRIC ACID
AND CHROMIC ACID
Walter A. Jacobs and Lyman C. Craig
J. Biol. Chem. 1940, 136:323-334.

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