<SPAN name="startofbook"></SPAN>
<p class="half-title">
THESIS<br/>
<small>presented for the degree of</small><br/>
MASTER OF SCIENCE<br/>
<small>at</small><br/>
THE COLLEGE OF HAWAII<br/>
JUNE 1915<br/>
<small>by</small><br/>
ALICE A. BALL.</p>
<hr class="chap x-ebookmaker-drop" />
<p>The Thesis, herewith, on “The Chemical Constituents
of the Active Principle of the Ava Root” by Alice A. Ball,
clearly demonstrates her ability to do original work and to
present her results in logical form. Approved.</p>
<div class="inline">
<p class="center">
<ANTIMG src="images/i_002-signature.jpg" alt="" /><br/>
J. F. Illingworth<br/>
Chair of the Committee on<br/>
Advanced Degrees.</p>
</div>
<p class="hang">College of Hawaii,<br/>
May 14, 1915.</p>
<hr class="chap x-ebookmaker-drop" />
<h1> THE CHEMICAL CONSTITUENTS<br/> OF<br/> PIPER METHYSTICUM</h1>
<p class="half-title">OR<br/>
THE CHEMICAL CONSTITUENTS<br/>
OF THE ACTIVE PRINCIPLE<br/>
OF THE AVA ROOT.</p>
<hr class="chap x-ebookmaker-drop" />
<h2 class="nobreak" id="INDEX"><i>INDEX.</i></h2>
<table class="standard" summary="">
<tr>
<td class="tdl" colspan="2"></td>
<td class="tdr">Page</td>
</tr>
<tr>
<td class="tdl">1. </td>
<td class="tdl"><SPAN href="#HISTORICAL">Historical</SPAN></td>
<td class="tdr">1</td>
</tr>
<tr>
<td class="tdl">2. </td>
<td class="tdl"><SPAN href="#METHOD_OF_EXTRACTION"> Method of Extraction</SPAN></td>
<td class="tdr">7</td>
</tr>
<tr>
<td class="tdl">3.</td>
<td class="tdl"><SPAN href="#METHOD_OF_SEPARATION_OF_THE_RESINS">Method of Separation of the Resins</SPAN></td>
<td class="tdr">9</td>
</tr>
<tr>
<td class="tdl">4.</td>
<td class="tdl"><SPAN href="#THE_VARIOUS_METALLIC_SALTS">Various Metallic Salts of the Resinous Acids</SPAN></td>
<td class="tdr">12</td>
</tr>
<tr>
<td class="tdl">5.</td>
<td class="tdl"><SPAN href="#THE_TOTAL_RESINS">The Total Resins</SPAN></td>
<td class="tdr">13</td>
</tr>
<tr>
<td class="tdl">6.</td>
<td class="tdl"><SPAN href="#THE_BARIUM_ACID">The Barium Acid</SPAN></td>
<td class="tdr">15</td>
</tr>
<tr>
<td class="tdl">7.</td>
<td class="tdl"><SPAN href="#OXIDATION_PRODUCTS_OF_THE_BARIUM_ACIDS">Oxidation Products of the Barium Acids</SPAN></td>
<td class="tdr">21</td>
</tr>
<tr>
<td class="tdl">8.</td>
<td class="tdl"><SPAN href="#THE_IRON_ACIDS">The Iron Acids</SPAN></td>
<td class="tdr">28</td>
</tr>
<tr>
<td class="tdl">9.</td>
<td class="tdl"><SPAN href="#OXIDATION_OF_THE_IRON_ACIDS">Oxidation of the Iron Acids and the Free Acids</SPAN></td>
<td class="tdr">33</td>
</tr>
<tr>
<td class="tdl">10.</td>
<td class="tdl"><SPAN href="#THE_ALCOHOL_RADICALS_AND_UNSAPONIFIABLE_MATERIAL">Alcohol Radicals</SPAN></td>
<td class="tdr">34</td>
</tr>
<tr>
<td class="tdl">11.</td>
<td class="tdl"><SPAN href="#METHYSTICIN_AND_METHYSTICINIC_ACID">Methysticin and Methysticinic Acid</SPAN></td>
<td class="tdr">36</td>
</tr>
<tr>
<td class="tdl">12.</td>
<td class="tdl"><SPAN href="#PHYSIOLOGICAL_ACTION">Physiological Action</SPAN></td>
<td class="tdr">38</td>
</tr>
<tr>
<td class="tdl">13.</td>
<td class="tdl"><SPAN href="#CONCLUSION">Conclusion</SPAN></td>
<td class="tdr">43</td>
</tr>
</table>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_1">[Pg 1]</span></p>
<h2 class="nobreak" id="HISTORICAL"><i>HISTORICAL.</i></h2>
<p>“Among the customs peculiar to the inhabitants
of the South Pacific Islands, perhaps the most noted is that
of the preparation and drinking of a narcotic beverage
called <i>ava</i>, <i>kava</i>, or <i>yakona</i>. Much of its notoriety arises
from the repulsive way in which it is sometimes made. Aside
from this, it is characteristic of a certain oceanic area,
and seems to be as strikingly limited to this area as is the
stick-and-groove method of making fire. The custom, is not
confined to one ethnic stock, many notices in literature
showing that both Papuans and Polynesians practise it. In
many of the islands the Liquor is concocted by chewing the
root of the Macropiper methysticum, or long pepper, ejecting
the comminuted mass into a bowl, adding water, straining
out the pulp, and drinking the fluid. In other localities
it is made by simply grating the root and adding water.</p>
<p>“The plant from which kava is made is a shrub
of the natural order Piperaceae. It is about six feet high
with stems ranging from an inch to an inch and a half in
thickness; the leaves are cordate and from four to eight
inches long. This family is the source of the pepper of
commerce and contains several species that are of medicinal
and commercial importance.</p>
<p><span class="pagenum" id="Page_2">[Pg 2]</span></p>
<p>In making kava, the root and base of the stem is
used. The roots usually weigh from two to four pounds,
though sometimes as much as 22 pounds. Several varieties
are distinguished by the natives; for instance, in Tahiti
there is a yellow variety called <i>Marea</i>; another, which becomes
pink on exposure to the air, is called <i>avini-ute</i>.</p>
<p>“Chewed when freshly gathered, the root first
tastes sweet and aromatic, then bitter, acrid and pungent.
It provokes abundant secretion of saliva and in a few seconds
occasions a sensation of burning on the tongue. The root
contains about fifty percent of starch, a little pale-yellow
essential oil, two percent of an acrid resin, and one percent
of the neutral crystalline principle methysticin, called
kavahin. To the latter principle we must attribute the toxic
qualities of the kava preparation. The resin and the kavahin
are insoluble in water, but are soluble in saliva and the
gastric juices.</p>
<p>“In Samoa, the ava root is grated or chewed, then
soaked, the woody pulp strained off, and the fluid drunk.
The root is used either dry or green. The flavor of the
liquid is at first like that of soapsuds, but immediately
afterward a pleasant aromatic taste is imparted, faintly
bitter, as in quinine. In Samoa, ava drinking is the accompaniment
of all meetings of the men.</p>
<p><span class="pagenum" id="Page_3">[Pg 3]</span></p>
<p>“Kava is at first stimulating, but the effect of
an excess resembles that of opium, producing a drowsy drunkenness,
lasting for two hours. The inebriate is usually
peaceable, but sometimes is irritated by noises, which is
attributed by natives to the use of kava grown in moist
ground. The results of excess are skin disease, emaciation,
and general decrepitude. The peculiar whiteness of the skin
caused by kava drinking is said to be sought after in some
islands as a sign that its possessor is wealthy enough to
devote his time to its acquirement.</p>
<p>“There is some misapprehension in regard to whether
the liquid undergoes fermentation before it is consumed, but
it is positively known that there can be no fermentation, for
the liquor is drunk immediately after the addition of water
to the macerated root. Kava that is prepared by chewing
is said to be more palatable, which is perhaps due to the
conversion of the starch into a fermentable substance by the
ptyalin of the saliva.”<SPAN name="FNanchor_1" href="#Footnote_1" class="fnanchor">[1]</SPAN></p>
<div class="footnotes">
<div class="footnote">
<p><SPAN name="Footnote_1" href="#FNanchor_1" class="label">[1]</SPAN>—By Walter Hough—Reprinted from Smithsonian
Miscellaneous Collections—No. 1472—August 1904.
“Kava Drinking as Practised by the Papuans and Polynesians.”</p>
</div>
</div>
<p>“In 1779 Captain King, R. N., who followed Captain
Cook to the Islands, describes the case of a priest as follows
‘a little old man of an emaciated figure, his eyes exceedingly<span class="pagenum" id="Page_4">[Pg 4]</span>
sore and red, and his body covered with a white leprous
scurf, the effects of an immoderate use of ava.’ He also
says, ‘The chiefs suffer dreadful effects from the immoderate
use of ava. Those who are most affected by it had their
bodies covered with a white scurf, their eyes red and inflamed,
their limbs emaciated, their whole frame trembling
and accompanied with a disability to raise the head.’”<SPAN name="FNanchor_2" href="#Footnote_2" class="fnanchor">[2]</SPAN></p>
<div class="footnotes">
<div class="footnote">
<p><SPAN name="Footnote_2" href="#FNanchor_2" class="label">[2]</SPAN> “Leprosy Prize Essays,” 2nd series by Thompson
and Cantile, 1897.</p>
</div>
</div>
<p>F. A. Griel, makes the following statement in a
foot note. “The mixture is a subnarcotic, and if drunk by
European sailors produces highly nauseous effects. If frequently
taken a dry burning heat is produced all over the
body, the eyes become red, skin peels off in flakes and then
degenerates into leprous ulcers or the whole body becomes
emaciated and wastes away.”<SPAN name="FNanchor_3" href="#Footnote_3" class="fnanchor">[3]</SPAN></p>
<div class="footnotes">
<div class="footnote">
<p><SPAN name="Footnote_3" href="#FNanchor_3" class="label">[3]</SPAN> Miquel, Systema Piperacearum.</p>
</div>
</div>
<p>Numerous attempts have been made to isolate the
active chemical constituent or constituents. As early as
1844 Morson discovered an active principal <i>Kawine</i>. This is a
greenish-yellow, strongly aromatic and acrid resin. This
was again studied by Cuzant in 1860.</p>
<p><span class="pagenum" id="Page_5">[Pg 5]</span></p>
<p>Gobley isolated from kava root a crystalline
principle (analogous to piperin), <i>methysticin</i>, or <i>kavahin</i>,
which is without odor and taste and is probably inert.<SPAN name="FNanchor_4" href="#Footnote_4" class="fnanchor">[4]</SPAN>
In 1886 Lewin separated the resin into two resins, of which
the Beta resin is greasy and of a reddish-brown color,
appearing in mass almost black. This is less active than the
alpha resin which is yellowish brown, has the characteristic
odor of the drug, is freely soluble in alcohol, and placed
upon the tongue produces a burning sensation followed by
local anaesthesia.<SPAN name="FNanchor_5" href="#Footnote_5" class="fnanchor">[5]</SPAN></p>
<div class="footnotes">
<div class="footnote">
<p><SPAN name="Footnote_4" href="#FNanchor_4" class="label">[4]</SPAN> J. P. C. Jan. 1860.</p>
</div>
<div class="footnote">
<p><SPAN name="Footnote_5" href="#FNanchor_5" class="label">[5]</SPAN> A. J. P. 1886, 450.</p>
</div>
<p>A volatile oil has been found in the root.<SPAN name="FNanchor_6" href="#Footnote_6" class="fnanchor">[6]</SPAN></p>
<div class="footnote">
<p><SPAN name="Footnote_6" href="#FNanchor_6" class="label">[6]</SPAN> J. P. C. March 1862.</p>
</div>
</div>
<p>Lavialle claimed to have obtained an alkaloid,
<i>Kavaine</i>.<SPAN name="FNanchor_7" href="#Footnote_7" class="fnanchor">[7]</SPAN></p>
<div class="footnotes">
<div class="footnote">
<p><SPAN name="Footnote_7" href="#FNanchor_7" class="label">[7]</SPAN> L’Union Pharm. Jan. 1889.</p>
</div>
</div>
<p>The following statement was found in “Watts
Chemical Dictionary”, “Kawain—a crystalline resin occurring
along with methysticin in kawa-kawa, It is not a glucoside.
On oxidation it yields benzoic acid.<SPAN name="FNanchor_8" href="#Footnote_8" class="fnanchor">[8]</SPAN></p>
<div class="footnotes">
<div class="footnote">
<p><SPAN name="Footnote_8" href="#FNanchor_8" class="label">[8]</SPAN> Gobley, J. Ph. (3) 37, 19.</p>
</div>
</div>
<p><span class="pagenum" id="Page_6">[Pg 6]</span></p>
<p>The following statement appears in the Encyclopedia
Britannica. “There appears to be little doubt that the
active principle in this beverage is a poison of an alkaloidal
nature. It seems likely that this substance is not
present as such (i.e. as a free alkaloid) in the plant, but
that it exists in the form of a glucoside, and that by the
process of chewing, this glucoside is split up by one of the
ferments in the saliva and the free alkaloid and sugar is
formed”.</p>
<p>Arthur Bossingham<SPAN name="FNanchor_9" href="#Footnote_9" class="fnanchor">[9]</SPAN> communicates the results
of a chemical examination of Kava-kava. Besides the
crystalline body, methysticin, which has already been
described by others, he was able to isolate and identify
three resins, one soluble in 5% solution of potassium carbonate,
the second insoluble in this, but soluble in 5%
solution of caustic potash, while the third was insoluble
in both of these alkaline solvents, The ash amounts to
2.495% of the air dried root, and contained besides mere
traces of Fe, Mn, mainly Calcium, Sodium and Potassium.<SPAN name="FNanchor_10" href="#Footnote_10" class="fnanchor">[10]</SPAN></p>
<div class="footnotes">
<div class="footnote">
<p><SPAN name="Footnote_9" href="#FNanchor_9" class="label">[9]</SPAN> Proc. A. Ph. A. 1898, 564.</p>
</div>
<div class="footnote">
<p><SPAN name="Footnote_10" href="#FNanchor_10" class="label">[10]</SPAN> Proc. Wisc. Pharm. Assos. 1898, 53, 55.</p>
</div>
</div>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_7">[Pg 7]</span></p>
<h2 class="nobreak" id="METHOD_OF_EXTRACTION"><i>METHOD OF EXTRACTION.</i></h2>
<p>The fresh rhizome was chopped up and then
ground up by means of a meat chopper. In the preliminary
work the material was dried in a vacuum oven at a
temperature not exceeding forty degrees Centigrade.
In the later work the material was rapidly dried in
the sun. This operation required about two days time.
After being thoroughly dried, the material was finely
powdered, and then extracted with ether. The following
continuous extraction apparatus was used. Due to the
extreme rapidity with which the ether evaporated, it
was necessary to surround the coils with ice so as to
keep the condensers cold.</p>
<p><span class="pagenum" id="Page_8">[Pg 8]</span></p>
<div class="figcenter illowp60" id="i_012" style="max-width: 50em;">
<ANTIMG class="w100" src="images/i_012.jpg" alt="Diagram of apparatus" /></div>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_9">[Pg 9]</span></p>
<h2 class="nobreak" id="METHOD_OF_SEPARATION_OF_THE_RESINS"><i>METHOD OF SEPARATION OF THE RESINS.</i></h2>
<p>After the removal of the crystalline methysticin
from the extract, the following method of separation of
the resinous products was used.</p>
<p>The free acids were removed by shaking the total
resins successively with solutions of one percent ammonium
carbonate, one percent sodium carbonate and one percent
sodium hydroxide. The acids thus removed were recovered
by treating the alkaline solution with dilute hydrochloric
acid and shaking out with ether. The three acids were not
markedly different in their physical properties. They
possessed the characteristic odor of the crude drug, were
viscous, brown in color and did not solidify at minus ten
degrees Centigrade. These free acids constitute about five
percent of the total resins.</p>
<p>The remainder of the extract was treated with
alcoholic potassium hydroxide and saponified by heating the
solution to about eighty degrees for fifteen minutes. After
the alcohol was removed by distillation a small quantity
of water was added. This resulting solution was then extracted
with ether to remove the alcohol radical or radicals and
the unsaponifiable material from the saponified product.
The ether extract was saved to be used in the work on the<span class="pagenum" id="Page_10">[Pg 10]</span>
alcohol radicals. The aqueous portion was evaporated to a
semi-solid mass. Carbon dioxide was passed over this mass
for about fifteen minutes to change any excess of potassium
hydroxide to potassium carbonate. Alcohol (95%) was then
added to precipitate the carbonate. The carbonate was then
filtered off and water added to the filtrate.</p>
<p>To the clear filtrate a solution of barium
chloride was added. Immediately a dense thick cream yellow
precipitate formed. Barium chloride was added in excess.
The barium salt was filtered off by means of a suction pump
and the precipitate washed with water. The filtrate was
treated with a few drops more of barium chloride so as to
be sure that an excess had been added, which was proven if
no further precipitate formed. To this clear filtrate an
excess of a solution of ferric chloride was added.
Immediately a thick heavy precipitate of the iron salt came
down, which was filtered off by means of a suction pump and
the precipitate washed with water.</p>
<p>The barium precipitate was treated with dilute
hydrochloric acid and heated to boiling to decompose the
barium resinate, and to liberate the free resin acid. The
liberated acid was a brown resin of a thin consistency and
had a characteristic odor. This acid was removed by<span class="pagenum" id="Page_11">[Pg 11]</span>
shaking out with ether. The ethereal solution was dried
with anhydrous sodium sulphate, filtered, and the ether
removed by distillation. The last traces of ether were
removed by heating the resin acids in a vacuum oven at sixty
five degrees Centigrade. This resinous acid is the acid
spoken hereafter in this paper as the BARIUM ACID.</p>
<p>The iron precipitate was treated with dilute sulphuric
acid (ferric chloride is soluble in ether and
ferric sulphate is not) and heated to boiling to decompose
the iron resinate. The acid when liberated had a strong
characteristic aromatic odor. It was extracted with ether
in the same manner as the barium acid. This resinous acid
is the acid spoken of in this paper as the IRON ACID.</p>
<p>The resinous extract left after the removal of the
crystalline methysticin is spoken of as the TOTAL RESINS.</p>
<p>The resin acids removed by the preliminary shaking
out with the various aqueous alkalies are spoken of as the
TOTAL FREE ACIDS.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_12">[Pg 12]</span></p>
<h2 class="nobreak" id="THE_VARIOUS_METALLIC_SALTS"><i>THE VARIOUS METALLIC SALTS OF THE RESINOUS ACIDS.</i></h2>
<p>After obtaining the potassium salts of the acids
and having freed the same from the excess of the potassium
hydroxide and potassium carbonate, the possibilities of the
formation of different metallic salts were tried.</p>
<p>The soluble salts of the following metals yielded
precipitates:—</p>
<ul>
<li>Manganese</li>
<li>Barium</li>
<li>Cobalt</li>
<li>Silver</li>
<li>Mercury</li>
<li>Iron</li>
<li>Zinc</li>
<li>Copper</li>
<li>Calcium</li>
<li>Lead</li>
</ul>
<p>The following metallic salts gave a complete
precipitation:—</p>
<ul>
<li>Silver</li>
<li>Iron (ferric)</li>
<li>Manganese</li>
</ul>
<p>Since the barium and iron (ferric) salts gave the
best means of separation, they were used to separate the
resins.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_13">[Pg 13]</span></p>
<h2 class="nobreak" id="THE_TOTAL_RESINS"><i>THE TOTAL RESINS.</i></h2>
<p>The total resins were brown in color, thick syrupy
consistency and possessed the characteristic odor of the drug.</p>
<p>A molecular weight determination was made in the
same manner as with the Barium acids, and the following
data obtained.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of pipette before</td>
<td class="tdl">18.7660</td>
</tr>
<tr>
<td class="tdl">Wt. of pipette after</td>
<td class="tdl">14.7160</td>
</tr>
<tr>
<td class="tdl">Wt. of resin used</td>
<td class="tdl">4.0500</td>
</tr>
<tr>
<td class="tdl">Temperature before</td>
<td class="tdl">3.52</td>
</tr>
<tr>
<td class="tdl">Temperature after</td>
<td class="tdl">3.71</td>
</tr>
<tr>
<td class="tdl">Change in temperature</td>
<td class="tdl">.18</td>
</tr>
<tr>
<td class="tdl">Volume</td>
<td class="tdl">37 cc.</td>
</tr>
<tr>
<td class="tdl">Constant for solvent</td>
<td class="tdl">3280</td>
</tr>
<tr>
<td class="tdl">Approximate molecular weight</td>
<td class="tdl">2000</td>
</tr>
</table>
<p>Combustions were made and the following data
obtained.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of boat</td>
<td class="tdl">3.4722</td>
<td class="tdl">3.4720</td>
</tr>
<tr>
<td class="tdl">Wt. of boat and resin</td>
<td class="tdl">3.6355</td>
<td class="tdl">3.6220</td>
</tr>
<tr>
<td class="tdl">Wt. of resin</td>
<td class="tdl">.1633</td>
<td class="tdl">.1500<span class="pagenum" id="Page_14">[Pg 14]</span></td>
</tr>
<tr>
<td class="tdl">Sulphuric acid tube</td>
<td class="tdl">79.1051</td>
<td class="tdl">79.3865</td>
</tr>
<tr>
<td class="tdl">Tube plus water</td>
<td class="tdl">79.2073</td>
<td class="tdl">79.4770</td>
</tr>
<tr>
<td class="tdl">Water</td>
<td class="tdl">.1022</td>
<td class="tdl">.0905</td>
</tr>
<tr>
<td class="tdl">Hydrogen equivalent</td>
<td class="tdl">.01136</td>
<td class="tdl">.01006</td>
</tr>
<tr>
<td class="tdl">KOH bulb</td>
<td class="tdl">49.4316</td>
<td class="tdl">50.8720</td>
</tr>
<tr>
<td class="tdl">Bulb plus carbon dioxide</td>
<td class="tdl">49.8350</td>
<td class="tdl">51.2430</td>
</tr>
<tr>
<td class="tdl">Carbon dioxide</td>
<td class="tdl">.4034</td>
<td class="tdl">.3710</td>
</tr>
<tr>
<td class="tdl">Carbon equivalent</td>
<td class="tdl">.12102</td>
<td class="tdl">.1010</td>
</tr>
<tr>
<td class="tdl">Percent Carbon</td>
<td class="tdl">67.31%</td>
<td class="tdl">67.3</td>
</tr>
<tr>
<td class="tdl">Percent Hydrogen</td>
<td class="tdl">6.9 %</td>
<td class="tdl">6.7</td>
</tr>
<tr>
<td class="tdl">Percent Oxygen</td>
<td class="tdl">26.8 %</td>
<td class="tdl">27.0</td>
</tr>
</table>
<p>The total resins when placed on the end of the
tongue produced a marked stinging sensation followed by a
local anaesthesia. After the first stinging was produced
the sensation was rather pleasant. The local anaesthesia
persisted a long time, giving a sensation much the same as
that produced by cocaine. The barium and iron acids also
produced this local anaesthesia, but the initial stinging
sensation was much more pronounced, which was probably due to
the acid nature of the substance.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_15">[Pg 15]</span></p>
<h2 class="nobreak" id="THE_BARIUM_ACID"><i>THE BARIUM ACID.</i></h2>
<p>The resinous material used and spoken of as the
“Barium Acid” is the material prepared and so named as given
under the “Method of Separation”.</p>
<p>PHYSICAL PROPERTIES:—Dark reddish brown in
color, syrupy in consistency and has a characteristic odor;
heavier than water; soluble in benzol, ether, alcohol and
acetone, but insoluble in petroleum ether and water.</p>
<p>This resin constitutes about sixty percent of the
total ester resins; i.e. the resins left after the free
acids have been removed with aqueous potassium hydroxide.</p>
<p>An analysis of the barium salt obtained by precipitation
from the potassium soap was made and the following
data obtained:—</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of substance used</td>
<td class="tdl">1.1715</td>
<td class="tdl">.5860</td>
</tr>
<tr>
<td class="tdl">Wt. of barium sulphate</td>
<td class="tdl">.4430</td>
<td class="tdl">.2205</td>
</tr>
<tr>
<td class="tdl">Barium equivalent</td>
<td class="tdl">.2606</td>
<td class="tdl">.1298</td>
</tr>
<tr>
<td class="tdl">Percent barium</td>
<td class="tdl">22.2%</td>
<td class="tdl">22.1%</td>
</tr>
</table>
<p>The following method was used in making the
above analysis. The weighed material was ignited in a
platinum crucible by gently heating until the combustible
gases formed were given off. The crucible was then more<span class="pagenum" id="Page_16">[Pg 16]</span>
strongly heated to completely burn off the carbonaceous
material left. The residue was extracted with nitric acid
and the barium precipitated as the sulphate with dilute
sulphuric acid, and the weight of the barium sulphate
determined.</p>
<p>Expressed as the ACID NUMBER, or the number of
milligrams of potassium hydroxide required to neutralize
the free acids in one gram of the substance, the following
data was obtained:—</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Barium equivalent</td>
<td class="tdl">.2606</td>
<td class="tdl">.1298</td>
</tr>
<tr>
<td class="tdl">Barium expressed as KOH equiv.</td>
<td class="tdl">.2131</td>
<td class="tdl">.1062</td>
</tr>
<tr>
<td class="tdl">Wt. of material used</td>
<td class="tdl">1.1715</td>
<td class="tdl">.5860</td>
</tr>
<tr>
<td class="tdl">Milligrams of KOH per gram</td>
<td class="tdl">181.9</td>
<td class="tdl">181.3</td>
</tr>
<tr>
<td class="tdl">ACID NUMBER</td>
<td class="tdl">181.9</td>
<td class="tdl">181.3</td>
</tr>
</table>
<p>The following gives the ACID NUMBER obtained by
direct titration of the barium acid; in “A”, barium
hydroxide was used and in “B”, sodium hydroxide was used.</p>
<p>A small quantity of the material was dissolved
in a sufficient quantity of neutralized alcohol to give a
liquid of a light yellow color, Phenolphthalein was used as
the indicator, and the alkali was added until a red color
was produced.</p>
<p><span class="pagenum" id="Page_17">[Pg 17]</span></p>
<table class="standard" summary="">
<tr>
<td class="tdl"></td>
<td class="tdl">“A”</td>
<td class="tdl">“B”</td>
</tr>
<tr>
<td class="tdl">Wt. of substance</td>
<td class="tdl">.6160</td>
<td class="tdl">.2345</td>
</tr>
<tr>
<td class="tdl">Cc. of alkalie</td>
<td class="tdl">4.54</td>
<td class="tdl">1.75</td>
</tr>
<tr>
<td class="tdl">KOH equiv. per gram</td>
<td class="tdl">41.40</td>
<td class="tdl">41.90</td>
</tr>
<tr>
<td class="tdl">Acid number</td>
<td class="tdl">41.40</td>
<td class="tdl">41.90</td>
</tr>
</table>
<p>On evaporating a portion of the alcohol from the
material left after titrating with the sodium hydroxide,
and adding water to obtain an aqueous solution of the sodium
salt, an emulsion was formed, and on standing globules
of the free resinous acid separated. From the data thus
obtained, it can readily be seen that the acid or acids
which constitute the BARIUM ACID must have a number of
carboxyl groups and form a different series of salts by
precipitation than by direct titration. The salt or salts
formed by direct titration, although neutral to phenolthalein
may be acid in structure. This is further shown
by the fact that the potassium salts produced by direct
titration are readily hydrolyzed. The acid number obtained
by the precipitation of the barium salt may be called the
COMBINING VALUE, and the acid number obtained by titration
the TITRATION VALUE.</p>
<p>A number of molecular weight determinations were<span class="pagenum" id="Page_18">[Pg 18]</span>
made on the free barium acid. McCoy’s Boiling Point Apparatus
was used and Merk’s benzol (free from thiophene) was used
as the solvent. A weighing pipette with a bulb was used
to introduce the material, the bulb being weighed before
the material was introduced into the apparatus, and afterwards,
the difference being the weight of the material used.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of pipette (before)</td>
<td class="tdl">16.3670</td>
<td class="tdl">14.8895</td>
</tr>
<tr>
<td class="tdl">Wt. of pipette (after)</td>
<td class="tdl">14.8895</td>
<td class="tdl">12.4610</td>
</tr>
<tr>
<td class="tdl">Wt. of material used</td>
<td class="tdl">1.5225</td>
<td class="tdl">2.4285</td>
</tr>
<tr>
<td class="tdl">Original temperature</td>
<td class="tdl">3.53</td>
<td class="tdl">3.53</td>
</tr>
<tr>
<td class="tdl">Final temperature</td>
<td class="tdl">3.60</td>
<td class="tdl">3.62-3</td>
</tr>
<tr>
<td class="tdl">Change in temperature</td>
<td class="tdl">.07</td>
<td class="tdl">.09</td>
</tr>
<tr>
<td class="tdl">Volume of solution</td>
<td class="tdl">37 cc</td>
<td class="tdl">43.5 cc</td>
</tr>
<tr>
<td class="tdl">Constant for solvent</td>
<td class="tdl">3280</td>
<td class="tdl">3280</td>
</tr>
<tr>
<td class="tdl">Approx. Molecular Wt.</td>
<td class="tdl">2000</td>
<td class="tdl">2100 or 1800</td>
</tr>
</table>
<p>Combustions were made using the barium acids. By
qualitative tests it was found that the acids contained only
carbon, hydrogen and oxygen. The following gives the results
of the combustions.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of boat</td>
<td class="tdl">2.8402</td>
<td class="tdl">2.8402</td>
</tr>
<tr>
<td class="tdl">Wt. of boat and resin</td>
<td class="tdl">3.0500</td>
<td class="tdl">3.0250</td>
</tr>
<tr>
<td class="tdl">Wt. of resin</td>
<td class="tdl">.2098</td>
<td class="tdl">.1848<span class="pagenum" id="Page_19">[Pg 19]</span></td>
</tr>
<tr>
<td class="tdl">Wt. of H2SO4 tube</td>
<td class="tdl">78.0250</td>
<td class="tdl">78.1415</td>
</tr>
<tr>
<td class="tdl">Wt. of tube plus water</td>
<td class="tdl">78.1520</td>
<td class="tdl">78.2550</td>
</tr>
<tr>
<td class="tdl">Wt. of water</td>
<td class="tdl">.1270</td>
<td class="tdl">.1135</td>
</tr>
<tr>
<td class="tdl">Hydrogen equiv.</td>
<td class="tdl">.0143</td>
<td class="tdl">.0126</td>
</tr>
<tr>
<td class="tdl">Wt. of KOH bulb</td>
<td class="tdl">48.8140</td>
<td class="tdl">51.7095</td>
</tr>
<tr>
<td class="tdl">Wt. of bulb plus CO2</td>
<td class="tdl">49.3800</td>
<td class="tdl">52.2085</td>
</tr>
<tr>
<td class="tdl">Wt. of CO2</td>
<td class="tdl">.5660</td>
<td class="tdl">.4990</td>
</tr>
<tr>
<td class="tdl">Carbon equiv.</td>
<td class="tdl">.1543</td>
<td class="tdl">.1361</td>
</tr>
<tr>
<td class="tdl">Percent Hydrogen</td>
<td class="tdl">78.5%</td>
<td class="tdl">73.6%</td>
</tr>
<tr>
<td class="tdl">Percent Carbon</td>
<td class="tdl">6.8%</td>
<td class="tdl">6.8%</td>
</tr>
<tr>
<td class="tdl">Percent Oxygen</td>
<td class="tdl">19.7%</td>
<td class="tdl">19.6%</td>
</tr>
</table>
<p>An attempt was made to make the potassium salts
of the barium acids by saponification with alcoholic potash.
A small quantity of the acid was treated with an excess of
ten percent alcoholic potash and heated to eighty degrees
Centigrade to complete the saponification. Instead of the
formation of the potassium salts, a thick dark brown solid,
gummy mass separated. On cooling it solidified to a brittle
solid which had all the physical properties of a true resin.
This solid is soluble in ether, chloroform and benzol,<span class="pagenum" id="Page_20">[Pg 20]</span>
slightly soluble in alcohol and insoluble in petroleum
ether and water. It burns without the formation of an ash.
Evidently, this brittle material is a condensation product
of the original barium acid.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_21">[Pg 21]</span></p>
<h2 class="nobreak" id="OXIDATION_PRODUCTS_OF_THE_BARIUM_ACIDS"><i>OXIDATION PRODUCTS OF THE BARIUM ACIDS.</i></h2>
<p>A small amount of the Barium acids was sealed
with concentrated nitric acid in a hard glass tube and
heated in a bomb furnace for an hour and a half at 115 to
120 degrees Centigrade. On cooling a yellow solid separated.
Qualitative tests showed that this oxidation product contained
no nitrogen, combined with sodium hydroxide readily,
is soluble in hot water, slightly soluble in cold water,
easily soluble in ether, alcohol and benzol and slightly
soluble in carbon tetrachloride. It decolorizes alkaline
permanganate but does not decolorize bromine water.</p>
<p>That there are a number of intermediate products
formed and that nitration also takes place during the
formation of these intermediate products is shown by the
following. A small quantity of the acids were placed in
a test tube and covered with concentrated nitric acid. This
was suspended in an H2SO4 bath and a thermometer inserted
so as to observe the temperature. On being gently warmed
the nitric acid and the resin began to react with a rapid
evolution of carbon dioxide and oxides of nitrogen. As soon
as the reaction had modified and before the temperature rose
above one hundred degrees Centigrade, a small amount was removed
and added to water. Some of the solid acid was formed<span class="pagenum" id="Page_22">[Pg 22]</span>
and also a number of globules of oil and there was a strong
persistent odor of nitrobenzene. The original test tube was
heated to about one hundred and twenty degrees centigrade
and a small portion again removed. There was more of the
solid material formed and the odor was similar to vanillin
or coumarin or cinnamic aldehyde. The test tube was again
tested when the temperature had reached one hundred and
thirty five degrees Centigrade. There was no aromatic odor
and a large amount of the solid formed. When viewed under
the microscope the substance had the appearance of curled
threads.</p>
<p>When the barium acids were treated with the standard
nitrating mixture, a solid was obtained which showed
the presence of nitrogen when the standard test was applied.</p>
<p>After the preliminary tests were made, the following
method of preparation was used. Two or three grams of
the barium acids were introduced into a hard glass tube of
about thirty centimeters in length and fifteen or twenty
cubic centimeters of concentrated nitric acid added.
The reaction which is very vigorous at first was regulated
by keeping the tube under running water. After this vigorous
action was over the tube was placed in a sulphuric acid
bath, and the temperature gradually increased until it had<span class="pagenum" id="Page_23">[Pg 23]</span>
reached one hundred and twenty five degrees Centigrade, at
which temperature it was kept for about five hours. It was
necessary to add a small quantities of nitric acid from
time to time to make up the loss by evaporation. When the
oxidation was completed the product was poured into water
and then heated to boiling. The resulting solution was
filtered and the filtrate allowed to cool. On standing a
quantity of a pale yellow substance separated. The following
data gives the percent yield of this oxidation product.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of container</td>
<td class="tdl">6.7220</td>
</tr>
<tr>
<td class="tdl">Wt. of container and substance</td>
<td class="tdl">7.5920</td>
</tr>
<tr>
<td class="tdl">Wt. of substance</td>
<td class="tdl">.8700</td>
</tr>
<tr>
<td class="tdl">Wt. of oxidation product</td>
<td class="tdl">.1240</td>
</tr>
<tr>
<td class="tdl">Percent yield</td>
<td class="tdl">14%</td>
</tr>
</table>
<p>The oxidation product was dried by placing it in
a vacuum over sulphuric acid for several days. The neutralization
equivalent of this crude oxidation product was 157.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of substance used</td>
<td class="tdl">.0502</td>
</tr>
<tr>
<td class="tdl">Number Cc. of NaOH N/10</td>
<td class="tdl">3.2 cc.</td>
</tr>
<tr>
<td class="tdl">Neutralization equivalent</td>
<td class="tdl">157</td>
</tr>
</table>
<p>The oxidation product was heated on a watch crystal
and the sublimate allowed to collect on a funnel. The
first sublimate gave a melting point of 109 degrees Centigrade.</p>
<p><span class="pagenum" id="Page_24">[Pg 24]</span></p>
<p>Combustions were made on this sublimate with the
following results.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">(1)</td>
<td class="tdl">C</td>
<td class="tdl">66%</td>
</tr>
<tr>
<td class="tdl"></td>
<td class="tdl">H</td>
<td class="tdl">4.7%</td>
</tr>
<tr>
<td class="tdl">(2)</td>
<td class="tdl">C</td>
<td class="tdl">65.7%</td>
</tr>
<tr>
<td class="tdl"></td>
<td class="tdl">H</td>
<td class="tdl">4.8%</td>
</tr>
<tr>
<td class="tdl">(3)</td>
<td class="tdl">C</td>
<td class="tdl">65.15%</td>
</tr>
<tr>
<td class="tdl"></td>
<td class="tdl">H</td>
<td class="tdl">4.8%</td>
</tr>
<tr>
<td class="tdl">(4)</td>
<td class="tdl">C</td>
<td class="tdl">65.8%</td>
</tr>
<tr>
<td class="tdl"></td>
<td class="tdl">H</td>
<td class="tdl">4.85%</td>
</tr>
</table>
<p>The neutralization equivalent was obtained by
titrating an alcoholic solution of the sublimate with standard
sodium hydroxide. The following results were obtained
on two different lots of the sublimed oxidation product.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of substance</td>
<td class="tdl">.09</td>
<td class="tdl">.1006</td>
</tr>
<tr>
<td class="tdl">Cc. of alkali N/10</td>
<td class="tdl">7 cc</td>
<td class="tdl">7.9cc</td>
</tr>
<tr>
<td class="tdl">Neutralization equiv.</td>
<td class="tdl">128.6</td>
<td class="tdl">127.3</td>
</tr>
</table>
<p>Using a third sample the neutralization equivalent
was obtained from the analysis of the silver salt. The
silver salt was formed by adding silver nitrate solution to a
carefully neutralized solution of the sublimate. The insoluble
silver salt was filtered off, washed with water to re<span class="pagenum" id="Page_25">[Pg 25]</span>move
the excess of silver nitrate, and dried in a vacuum over
sulphuric acid for several days. A weighed quantity of the
silver salt was ignited in a platinum crucible and the residue
of metallic silver was weighed. The following data were
obtained using material from the same sample for each
analysis.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of dish</td>
<td class="tdl">12.8825</td>
<td class="tdl">12.8826</td>
</tr>
<tr>
<td class="tdl">Wt. of dish and substance</td>
<td class="tdl">13.0060</td>
<td class="tdl">13.1310</td>
</tr>
<tr>
<td class="tdl">Wt. of substance</td>
<td class="tdl">.1235</td>
<td class="tdl">.2484</td>
</tr>
<tr>
<td class="tdl">Wt. of dish and silver</td>
<td class="tdl">12.9400</td>
<td class="tdl">12.9980</td>
</tr>
<tr>
<td class="tdl">Wt. of silver</td>
<td class="tdl">.0575</td>
<td class="tdl">.1154</td>
</tr>
<tr>
<td class="tdl">Neutralization equiv.</td>
<td class="tdl">125</td>
<td class="tdl">125.3</td>
</tr>
</table>
<p>Using the same sample, a neutralization equivalent
was obtained by titration with standard NaOH.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of substance</td>
<td class="tdl">.0912</td>
</tr>
<tr>
<td class="tdl">N/10 NaOH</td>
<td class="tdl">7.25cc</td>
</tr>
<tr>
<td class="tdl">Neutralization equiv.</td>
<td class="tdl">125.8</td>
</tr>
</table>
<p>The above data shows that the sublimate is a mixture.
No empirical formula can be calculated from the
combustions, and different samples give different neutralization
equivalents although the duplicate determinations on
the same sample showed good agreement thus demonstrating<span class="pagenum" id="Page_26">[Pg 26]</span>
the reliability of the methods.</p>
<p>By fractional sublimation it was possible to obtain
fractions with different melting points. The first
sublimate melted sharply at 109 degrees. From the last
fraction it was possible to separate some crystals that melt
at 200 degrees Centigrade. These might possibly be p-acetyl-benzoic
acid, as its properties of solubility, crystalline
form, its melting point and power of sublimation agree with
those of p-acetyl-benzoic acid.</p>
<p>Those crystals that appeared identical with benzoic
acid were placed in a melting point tube, and some
known benzoic acid (from toluol) was placed in another tube.
These two tubes were placed in the same sulphuric acid
container and their melting points taken at the same time.
They melted at the same temperature.</p>
<p>The sublimate had a very pleasant aromatic odor
resembling benzoin. It gave no coloration with ferric
chloride, thus eliminating a large group of aromatic compounds.
Some of the crystals were found to be identical with benzoic
acid when examined under the microscope. The characteristic
odor of methyl benzoate was produced when a small quantity of
the crystals were heated with methyl alcohol and concentrated
sulphuric acid. On treating some of the carefully<span class="pagenum" id="Page_27">[Pg 27]</span>
neutralized product with ferric chloride solution, a flesh
colored precipitate was formed. It agreed closely in its
analysis with the precipitate formed with known benzoic acid.</p>
<p>The filtrate left after the removal of the iron
precipitate was acidified and extracted with ether, and the
ether removed by evaporation. The resulting substance
decolorized alkaline permanganate solution, but did not decolorize
bromine water. When the leaflet needles that melt
at 200 degrees were mechanically removed from the original
sublimate, the substance left after precipitating with
ferric chloride melted at 109 degrees. When these crystals
were not removed, the melting point of this material was
not definite, but was over a range of five degrees, from 110
to 115 degrees Centigrade.</p>
<p>The oxidation product contains at least three
distinct substances, benzoic acid, a substance melting at
200 degrees and—which is probably p-acetyl benzoic acid
and a third substance melting at 110 degrees.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_28">[Pg 28]</span></p>
<h2 class="nobreak" id="THE_IRON_ACIDS"><i>THE IRON ACIDS.</i></h2>
<p>The resinous material used and spoken of as the
IRON ACIDS is the material prepared and so named under the
“Method of Separation”.</p>
<p>PHYSICAL PROPERTIES:—Transparent and reddish
brown in color, oily in consistency and has a characteristic
tea like odor, heavier than water, freely soluble in benzol,
ether, alcohol and acetone, but insoluble in petroleum ether
and water.</p>
<p>This resin constitutes about eighteen percent of
the total ester resins.</p>
<p>By qualitative tests it was shown that the acids
contained only carbon, hydrogen and oxygen. Combustions
made on the iron acids gave the following results.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of boat</td>
<td class="tdl">2.6950</td>
<td class="tdl">2.6950</td>
</tr>
<tr>
<td class="tdl">Wt. of boat and substance</td>
<td class="tdl">2.8470</td>
<td class="tdl">2.8495</td>
</tr>
<tr>
<td class="tdl">Wt. of substance</td>
<td class="tdl">.1520</td>
<td class="tdl">.1545</td>
</tr>
<tr>
<td class="tdl">KOH bulb</td>
<td class="tdl">50.9620</td>
<td class="tdl">51.0805</td>
</tr>
<tr>
<td class="tdl">Bulb and CO2</td>
<td class="tdl">51.3370</td>
<td class="tdl">51.4610</td>
</tr>
<tr>
<td class="tdl">Wt. of CO2</td>
<td class="tdl">.3750</td>
<td class="tdl">.3805</td>
</tr>
<tr>
<td class="tdl">Carbon equivalent</td>
<td class="tdl">.1023</td>
<td class="tdl">.10376<span class="pagenum" id="Page_29">[Pg 29]</span></td>
</tr>
<tr>
<td class="tdl">Sulphuric acid tube</td>
<td class="tdl">76.2448</td>
<td class="tdl">76.3450</td>
</tr>
<tr>
<td class="tdl">Tube and water</td>
<td class="tdl">76.3400</td>
<td class="tdl">76.4453</td>
</tr>
<tr>
<td class="tdl">Wt. of water</td>
<td class="tdl">.0952</td>
<td class="tdl">.1003</td>
</tr>
<tr>
<td class="tdl">Hydrogen equiv.</td>
<td class="tdl">.0106</td>
<td class="tdl">.01114</td>
</tr>
<tr>
<td class="tdl">Percent Carbon</td>
<td class="tdl">67.3%</td>
<td class="tdl">67.2%</td>
</tr>
<tr>
<td class="tdl">Percent hydrogen</td>
<td class="tdl">7.0%</td>
<td class="tdl">7.2%</td>
</tr>
<tr>
<td class="tdl">Percent Oxygen</td>
<td class="tdl">25.7%</td>
<td class="tdl">25.6%</td>
</tr>
</table>
<p>An analysis of the iron salt obtained by precipitation
from the potassium soap gave the following data.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of substance used</td>
<td class="tdl">.2955</td>
<td class="tdl">.3387</td>
</tr>
<tr>
<td class="tdl">Wt. of FeSO4</td>
<td class="tdl">.0445</td>
<td class="tdl">.0509</td>
</tr>
<tr>
<td class="tdl">Ferric equiv.</td>
<td class="tdl">.03208</td>
<td class="tdl">.03676</td>
</tr>
<tr>
<td class="tdl">Percent Iron</td>
<td class="tdl">10.85%</td>
<td class="tdl">10.85%</td>
</tr>
</table>
<p>The following method was used in making the above
analysis. The weighed material was ignited in a platinum
crucible by gently heating until the combustible gases
formed were given off. The crucible was then strongly heated
until the carbonaceous material was completely burned off.
The residue was weighed and the percentage of iron determined.</p>
<p>Expressed as the ACID NUMBER, or the number of
milligrams of KOH required to neutralize the free acids in<span class="pagenum" id="Page_30">[Pg 30]</span>
one gram of the substance, the following data was obtained.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Ferric equivalent</td>
<td class="tdl">.03208</td>
<td class="tdl">.03676</td>
</tr>
<tr>
<td class="tdl">Fe expressed as KOH equiv.</td>
<td class="tdl">.0965</td>
<td class="tdl">.1107</td>
</tr>
<tr>
<td class="tdl">Wt. of material used</td>
<td class="tdl">.2955</td>
<td class="tdl">.3387</td>
</tr>
<tr>
<td class="tdl">Mg. of KOH per gram</td>
<td class="tdl">326.6</td>
<td class="tdl">326.7</td>
</tr>
<tr>
<td class="tdl">Acid number</td>
<td class="tdl">326.6</td>
<td class="tdl">326.7</td>
</tr>
</table>
<p>The following gives the ACID NUMBER obtained by
direct titration of the Iron acid. The method is the same
as that used in getting the titration value of the Barium
acid.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of substance</td>
<td class="tdl">.2450</td>
<td class="tdl">.2472</td>
</tr>
<tr>
<td class="tdl">Cc of alkalie</td>
<td class="tdl">2.2</td>
<td class="tdl">2.3</td>
</tr>
<tr>
<td class="tdl">KOH equiv.</td>
<td class="tdl">.01232</td>
<td class="tdl">.01288</td>
</tr>
<tr>
<td class="tdl">KOH equiv. per gram</td>
<td class="tdl">53.87</td>
<td class="tdl">52.</td>
</tr>
</table>
<p><span class="pagenum" id="Page_31">[Pg 31]</span></p>
<p>An attempt was made to saponify some of the iron
acid, but it was impossible. The alcohol was partially
distilled off, and the acid freed by making the mass acid
with sulphuric acid, and shaking out with ether. The ether
was distilled off, but the remaining acid had different
physical properties from the acid with which the experiment
was started. It was lighter in color, and solidified at
zero degrees. At room temperature it was almost solid.
On ignition it left no ash. This probably is a polymerization
product of the original acid.</p>
<p>Since many organic acids whose salts cannot be
prepared by the ordinary methods can be prepared by passing
dry ammonia gas through a solution of the acid in anhydrous
ether, this method was tried with the iron acid. The iron
acid was dissolved in anhydrous ether, and the dry
ammonia gas was bubbled through this ether solution. At
first no change was noted, but after several minutes there
was a flocculent thready precipitate formed which was light
brown in color. The experiment was repeated. At first the
precipitate was a very light brown, but after forming it
quickly darkened. After standing a few hours the flocculent
precipitate changed to a sticky brown mass. This same change
was produced immediately if the precipitate was exposed to
the air. The resulting mass had no odor of ammonia.</p>
<p><span class="pagenum" id="Page_32">[Pg 32]</span></p>
<p>The flocculent precipitate formed at first was probably
the ammonium salt of the iron acid, which like most
ammonium salts, it was precipitated due to its insolubility
in ether. Due to the ease of hydrolysis this salt immediately
decomposed to the acid and ammonia when traces of moisture
were present.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_33">[Pg 33]</span></p>
<h2 class="nobreak" id="OXIDATION_OF_THE_IRON_ACIDS"><i>OXIDATION OF THE IRON ACIDS AND THE FREE ACIDS.</i></h2>
<p>When the iron acids were oxidized in the same manner
as the barium acids the amount of the oxidation product
formed was about one fourth of that produced with an equal
amount of the barium acids. The time necessary to completely
oxidize the iron acids was much less then required for
the barium acids. On sublimation the iron acid gave a
product melting at 110 degrees Centigrade and is probably
identical with the one formed from the barium acids. The
iron acid also yielded a sublimate melting at 208 degrees C.</p>
<p>The free acids when oxidized in a like manner
gave as one of the products a low melting crystalline
compound that contained nitrogen.</p>
<p>The iron acid although related to the barium
acid as shown by the formation of a common oxidation product
is different in structure as shown by the difference in the
amount of the oxidation product formed and the time to
complete the oxidation.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_34">[Pg 34]</span></p>
<h2 class="nobreak" id="THE_ALCOHOL_RADICALS_AND_UNSAPONIFIABLE_MATERIAL"><i>THE ALCOHOL RADICALS AND UNSAPONIFIABLE MATERIAL.</i></h2>
<p>The material that was shaken out with ether after
the saponification consists of the unsaponifiable material
and the alcohol radicals of the acids produced by saponification.</p>
<p>On allowing the ether to evaporate from this
material, feathery needles separated. These were removed
by means of a suction pump and recrystallized from hot
acetone. The melting point of this product was 122-125
degrees Centigrade. The precipitate was dissolved in benzol
and allowed to slowly crystallize. It formed long prismatic
needles with melting point of 130 degrees Centigrade.
When heated with concentrated sulphuric acid, a brown green
fluorescent solution was produced.</p>
<p>The remaining material was steam distilled, and
the distillate extracted with ether to remove the oil. The
ether was dried with anhydrous sodium carbonate, the solution
filtered and the ether removed by distillation. The oil that
remained was light yellow, specific gravity less than that of
water, and possessed a very characteristic odor resembling
that of musk. The material left after the steam distillation
was cooled and shaken out with ether. The ethereal solution<span class="pagenum" id="Page_35">[Pg 35]</span>
was dried with anhydrous sodium sulphate and the ether removed
by distillation. The resulting mass was a dark brown
resin without any characteristic odor, solidifying at zero
degrees.</p>
<p>The crystalline product with a melting point of
130 degrees and the essential oil are evidently the alcohols
formed through saponification of the resin esters. The
crystalline product could be readily separated from the
resinous material because of its slight solubility in acetone.
Since this product was not precipitated when the unsaponified
resin esters were treated with acetone and because it did
not make its appearance until after the process of saponification,
it is quite probable it is a product of saponification.
The essential oil can be detected in extremely small
amounts due to its penetrating characteristic odor. Before
the process of saponification it could not be detected, but
as soon as saponification took place the odor was very marked.
From this it is quite evident that this oil is a product
of saponification.</p>
<p>The dark brown resinous mass that remained may be
either an alcoholic resin formed through the hydrolysis of
the ester resins or it may be a resin belonging to the class
known as resenes<SPAN name="FNanchor_11" href="#Footnote_11" class="fnanchor">[11]</SPAN> which resist saponification.</p>
<div class="footnote">
<p><SPAN name="Footnote_11" href="#FNanchor_11" class="label">[11]</SPAN> Com. Organic Analysis. Allen Vol. II, 146.</p>
</div>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_36">[Pg 36]</span></p>
<h2 class="nobreak" id="METHYSTICIN_AND_METHYSTICINIC_ACID"><i>METHYSTICIN AND METHYSTICINIC ACID.</i></h2>
<p>The crystalline product obtained from the ether
extract was recrystallized several times from absolute
alcohol to remove all traces of any resinous material. It had
a melting point of 122-123. It therefore was not pure
methysticin, which has a melting point of 138-139 degrees.
On examining this product under the microscope it was found
to contain two distinct forms of crystals, long needles and
prismatic plates. Some free methysticinic acid, melting
point 180 was examined under the microscope and found to
consist entirely of prismatic plates. Therefore the original
crystalline body contains some methysticinic acid.</p>
<p>Some of the original precipitate was crystallized
once from absolute alcohol and thoroughly dried. This was
used for the following data to determine the percent of
free methysticinic acid in the crystalline product.
A weighed amount of the crystalline product was dissolved
in carefully neutralized alcohol, and titrated with tenth
normal NaOH, using phenolthalein as the indicator.</p>
<table class="standard" summary="">
<tr>
<td class="tdl">Wt. of substance used</td>
<td class="tdl">.2590</td>
</tr>
<tr>
<td class="tdl">NaOH N/10</td>
<td class="tdl">.5 cc</td>
</tr>
<tr>
<td class="tdl">% methysticinic acid.</td>
</tr>
</table>
<p><span class="pagenum" id="Page_37">[Pg 37]</span></p>
<p>The potassium salts of the various resin acids
formed by the saponification of the ester resins should
yield a resinous mass syrupy or oily in consistency when
acidified, if it consists entirely of the two groups of acids
spoken of as the iron acids and the barium acids. Also the
weight of the barium acids plus the weight of the iron
acids should nearly equal the weight of the ester resins, if
these are the only two acids, because the alcohol radicals
constitute not more than two percent of the ester resins.
But when the total potassium salts were acidified the product
formed contained a crystalline substance in addition to the
resinous acids. This crystalline substance was separated
from the resinous acids by means of their difference in
solubility in ether. On recrystallization from absolute
alcohol, it had a melting point of 179 degrees Centigrade.
It is therefore methysticinic acid. This acid constitutes
about twenty percent of the total acids from the ester
resins because the barium and iron acids constitute only
about seventy five percent.</p>
<p>This methysticinic acid cannot be entirely formed
by hydrolysis of methysticin which was incompletely removed
from the resinous material. The methysticinic acid existed
either combined with some other alcohol than methyl alcohol
or was combined with one of the resin alcohol radicals.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_38">[Pg 38]</span></p>
<h2 class="nobreak" id="PHYSIOLOGICAL_ACTION"><i>PHYSIOLOGICAL ACTION.</i></h2>
<p>Due to the impossibility of preparing the alkali
salts of the barium and iron acids so as to be positive
that the resulting preparations completely represented the
barium and iron acids, and due to the insolubility of the
acids and the total resins in solvents from which they
would not again be precipitated when introduced into the
circulation, it was found necessary to make an emulsion.
The emulsifying agent used was acacia (gum arabic). It
was possible by careful preparation to make a permanent
emulsion that was miscible with water in all proportions
to form a homogeneous mixture. The animals used were rabbits
of about six pounds weight. The injections were made by
Dr. Geo. McCoy, director of the Leprosy Investigation
Station at Kalihi. All the physiological experiments were
made at the bacteriological laboratory at the Leprosy
Investigation Station.</p>
<p>One cubic centimeter of the emulsion of the total
resinous extract (strength 1 in 5) was injected into the ear
of a rabbit; the animal died immediately. Another rabbit
was injected in the same manner with one half cubic centimeter<span class="pagenum" id="Page_39">[Pg 39]</span>
of the same preparation. The animal immediately stretched
out and became rigid, or appeared to be paralyzed, but after
several minutes these symptoms lessened and after about five
minutes the rabbit appeared normal as far as activity was
concerned. As soon as the rabbit had recovered a second
injection of one quarter of a cubic centimeter of the same
preparation was injected in the same manner into the same
animal. The same symptoms were produced and with equal
intensity, but ten minutes passed before the animal again
became conscious. For several minutes after recovery the
animal appeared somewhat drowsy and stupid but it soon
regained its former activity.</p>
<p>One half cubic centimeter of the iron acid emulsion
(strength 1 in 7) was injected into the ear of a rabbit.
Immediate paralysis and apparent anaesthesia set in lasting
very pronouncedly for eight minutes. The rabbit’s head
was drawn backwards and its legs stiffened giving symptoms
similar to strychnine poisoning but they did not persist.
When a second injection of one quarter cubic centimeter
was given to the same animal, the same symptoms were produced,
the animal remaining under the influence of the injection
for about fifteen minutes.</p>
<p><span class="pagenum" id="Page_40">[Pg 40]</span></p>
<p>The iron acid injection was repeated on another
rabbit with the same pronounced symptoms of strychnine
poisoning but the effect lasted only about ten minutes.</p>
<p>One half cubic centimeter of the barium acid
emulsion (strength 1 in 7) was injected into the ear
vein of a rabbit. The animal uttered several loud cries
and after moving several feet it became spastic and went
into a sort of a stupor, beginning to come out of it after
ten minutes. As soon as the animal recovered, a second
injection of one quarter cubic centimeter was made. The
animal again uttered loud cries and then it went into a
stupor, but it was not spastic. This lasted approximately
ten minutes. The animal did not completely recover until
about twenty minutes.</p>
<p>Thinking that the action might be largely mechanical
and that the symptoms produced were from the emulsion
itself and not from the effect of the material that was
emulsified, an emulsion of olive oil was used in a like manner.
This olive oil emulsion was made in approximately the
same consistency as the resinous emulsions, and one cubic
centimeter was injected into the ear vein of a rabbit.
No visible effects followed this injection during the one
hour’s time the rabbit was under observation.</p>
<p><span class="pagenum" id="Page_41">[Pg 41]</span></p>
<p>One cubic centimeter intraperitoneal injections
of the total resinous extract emulsion and the same amount
of the iron acid emulsion were made into rabbits. During
the three hours the animals were under observation no symptoms
were produced. This may have been due to the extreme
slowness of absorption as compared with the rate of elimination
from the circulation.</p>
<p>Dr. J. F. Illingworth states as the result of his
observations while in the Fiji Islands that the kava beverage
even when taken in large amounts, does not apparently affect
the brain to an extent as to cause the drinker to appear
as if under the influence of alcohol, but he appears as if
the muscles from the hips downward are paralyzed. These
symptoms last for about half an hour, at the end of which
time the person is perfectly able to walk home.</p>
<p>In general the active constituent of any drug
produces a more pronounced but more fugitive effect than
the crude drug itself, and one might therefore expect more
violent reactions from the isolated active constituents of
the Ava then from the crude infusion. Judging from the
negative results obtained from the injection of the olive
oil emulsion, it is probable that the physiological effects<span class="pagenum" id="Page_42">[Pg 42]</span>
described above following the intravenous injections of the
various preparations were not mechanical but must be
ascribed to the action of the constituents of the Ava.</p>
<hr class="chap x-ebookmaker-drop" />
<p><span class="pagenum" id="Page_43">[Pg 43]</span></p>
<h2 class="nobreak" id="CONCLUSION"><i>CONCLUSION.</i></h2>
<p>The crystalline product consists, largely of
methysticin, the methyl ester of methysticinic acid. In
addition to this there is about five percent of the free
methysticinic acid present.</p>
<p>The resinous product consists of about five percent
of free resinous acids, which acids can be separated into
three different acids or groups of acids according to their
solubility in the different alkalies. The remaining resinous
product is composed of ester resins. On hydrolysis these
esters yield three distinct acids, two resinous acids and
methysticinic acid. The two resinous acids are distinctly
different, both in physical properties and in chemical
properties. They can be sharply separated by means of the
difference in solubility of their barium and iron salts.
These acids may be separate individual substances, or a group
of related substances. The barium and iron acids although
different chemically, have some groups in common as shown
by the formation of a common oxidation product. There are
at least three alcohol radicals formed through hydrolysis,
a resinous alcohol radical, a crystalline substance with a
melting point of 130 degrees, and a volatile oil.</p>
<p><span class="pagenum" id="Page_44">[Pg 44]</span></p>
<p>The physiological action of the Ava is due to the
ester resins. The two resinous acids formed through the
hydrolysis of these esters seem to be the two active
constituents of the resin ester.</p>
<p>From the above outlined work it appears that the
ava root does not contain any alkaloidal substance, as none
of the constituents were found to contain nitrogen.</p>
<p>That the aqueous infusion used by the ava
drinkers contains the same constituents as are extracted
by the ether is shown by the following. An infusion of the
ava was made by allowing some of the powdered drug to
remain in contact with water for about twelve hours. The
infusion was then filtered and the filtrate extracted
with ether. A resinous mass remained which from all
appearances was identical with the resins obtained from the
ether extract. It also gave the same action when placed
on the tongue as was produced by the resins from the ether
extract.</p>
<SPAN name="endofbook"></SPAN>
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