NH₂(CH₃) + CHCl₃ + 3KOH = C≣N-CH₃ + 3KCl + 3H₂O.
Again the primary bases, when treated with corrosive sublimate and
carbon disulphide, evolve sulphuretted hydrogen, and mustard oil is
produced, _e.g._,
NH₂(C₂H₅) + CS₂ = CS=N-C₂H₅ + H₂S.
Ethylamine. Ethylmustard
oil.
Where a sufficient quantity of an amine is obtained, the primary,
secondary, or tertiary character of the amine may be deduced with
certainty by treating it with methyl or ethyl iodide.
A molecule of the base is digested with a molecule of methyl iodide and
distilled with potash; the distillate is in the same manner again
treated with methyl iodide and again distilled; and the process is
repeated until an ammonium base is obtained, which will take up no more
iodide. If three methyl groups were in this way introduced, the original
substance was primary, if two, secondary, if one, tertiary.
The quaternary bases, such as tetraethyl ammoniumoxhydrate, decompose,
on heating, into triethylamine and ethylene; the corresponding methyl
compound in like manner yields trimethylamine and methyl-alcohol.
On the other hand, the primary, secondary, and tertiary bases do not
decompose on heating, but volatilise without decomposition.
The chief distinctions between these various amines are conveniently put
into a tabular form as follows:--
+--------------------+-----------+-----------+-----------+-----------+
| | Primary, |Secondary, | Tertiary, |Quaternary,|
| | NH₂R. | NHR₂. | NR₃. | NR₄(OH). |
+--------------------+-----------+-----------+-----------+-----------+
|On treating with | 3 | 2 | 1 | ... |
|methyl iodide it | | | | |
|takes up the follow-| | | | |
|ing number of methyl| | | | |
|groups, | | | | |
| | | | | |
|Reaction with |Decomposes |Formation | | |
|nitrous acid, |with evolu-|of nitro- | ... | ... |
| |tion of |samine. | | |
| |nitrogen | | | |
| |gas. | | | |
| | | | | |
|Mustard oil, &c., on|Mustard oil| | | |
|treatment with CS₂ |formed. | ... | ... | ... |
|and sublimate, | | | | |
| | | | | |
|Chloroform and |Formation | ... | ... | ... |
|alcoholic potash, |of carbyl- | | | |
| |amine. | | | |
| | | | | |
|Effect of strong |Sublimes. |Sublimes. |Sublimes. |Decomposes.|
|heat, | | | | |
| | | | | |
|On addition of |Combines to|Combines to|Combines to| ... |
|acids, |form salts.|form salts.|form salts.| |
+--------------------+-----------+-----------+-----------+-----------+
§ 653. =Methylamine,= CH₃NH₂.--This is a gas at ordinary
temperatures; it is inflammable, and possesses a strong ammoniacal
odour. It has been found in herring brine, and is present in
cultures of the comma bacillus; it has also been found in poisonous
sausages, but it is not in itself toxic.
It forms crystalline salts, such as, for example, the hydrochloride,
the platinochloride (Pt = 41·4 per cent.), and the aurochloride (Au
= 53·3 per cent. when anhydrous). The best salt for estimation is
the platinochloride, insoluble in absolute alcohol and ether.
§ 654. =Dimethylamine=, (CH₃)₂NH.--Dimethylamine is also a gas; it
has been found in various putrefying substances. It forms
crystalline salts, such as the hydrochloride, the platinochloride
(Pt = 39·1 per cent.), and an aurochloride (Au = 51·35 per cent.).
It is not poisonous.
In Brieger’s process it may occur in both the mercuric chloride
precipitate and filtrate. From cadaverine it may be separated by
platinum chloride; cadaverine platinochloride is with difficulty
soluble in cold water and crystallises from hot water, while
dimethylamine remains in the mother liquor. From choline it may be
separated by recrystallising the mercuric precipitate from hot
water. From methylamine it may be separated by converting into
chloride and extracting with chloroform; dimethylamine chloride is
soluble, methylamine chloride insoluble in chloroform.
§ 655. =Trimethylamine=, (CH₃)₃N.--Trimethylamine in the free state
is an alkaline liquid with a fishy odour, boiling at 9·3°; it is not
toxic save in large doses.
It occurs in a great variety of plants, and is also found in
putrefying substances. It is a product of the decomposition of
choline, betaine, and neuridine, when these substances are distilled
with potash.
In Brieger’s process, if an aqueous solution of mercuric chloride is
used as the precipitant, trimethylamine (if present) will be almost
entirely in the filtrate, from which it can be obtained by getting
rid of the mercury by SH₂, filtering, evaporating to dryness,
extracting with alcohol, and precipitating the alcoholic solution
with platinic chloride. It forms crystalline salts with hydrochloric
acid, platinum chloride, and gold chloride; the platinum double salt
yields 37 per cent. of platinum, the gold salt 49·4 per cent. gold.
The gold salt is easily soluble, and this property permits its
separation from choline, which forms a compound with gold chloride
soluble with difficulty.
§ 656. =Ethylamine=, C₂H₅NH₂.--Ethylamine is in the free state an
ammoniacal liquid boiling at 18·7°. It is a strong base, miscible
with water in every proportion. It has been found in putrefying
yeast, in wheat flour, and in the distillation of beet sugar
residues. It is not poisonous; the hydrochloride forms deliquescent
plates melting at 76°-80°; the platinochloride contains 39·1 per
cent. of platinum, and the gold salt 51·35 per cent. of gold. In
other words, the same percentages as the corresponding salts of
dimethylamine, with which, however, it cannot be confused.
§ 657. =Diethylamine=, (C₂H₅)₂NH, is an inflammable liquid boiling
at 57·5°; it forms salts with hydrochloric acid, platinum and gold,
&c.; the gold salt contains 47·71 per cent. of gold, and its
melting-point is about 165°.
§ 658. =Triethylamine=, (C₂H₅)₃N, is an oily base but slightly
soluble in water, and boiling at 89°-89·5°. It gives no precipitate
with mercuric chloride in aqueous solution; it forms a
platinochloride containing 31·8 per cent. of platinum. It has been
found in putrid fish.
§ 659. =Propylamine.=--There are two propylamines; one, normal
propylamine, CH₃CH₂.CH₂.NH₂, boiling at 47°-48°, and
iso-propylamine, (CH₃)₂CH.NH₂, boiling at 31·5°; both are ammoniacal
fish-like smelling liquids. The hydrochloride of normal propylamine
melts at 155°-158°, and iso-propylamine chloride melts at 139·5°.
It has been found in cultures of human fæces on gelatin. None of the
above amines are sufficiently active in properties to be poisonous
in the small quantities they are likely to be produced in
decomposing foods.
§ 660. =Iso-amylamine=, (CH₃)₂CH.CH₂.CH₂.NH₂, is a colourless
alkaline liquid, possessing a peculiar odour. It boils at 97°-98°.
It forms a deliquescent hydrochloride. The platinochloride
crystallises in golden yellow plates.
Iso-amylamine occurs in the putrefaction of yeast, and is a normal
constituent of cod-liver oil. It is intensely poisonous, producing
convulsions.
Diamines.
§ 661. =Rate of Formation of Diamines.=--Diamines are formed in
putrefactive processes, generally where there is abundance of nitrogen.
Garcia[660] has attempted to trace the rates at which they are formed by
allowing meat extracts to decompose, precipitating by benzoyl chloride
(see p. 487) the dibenzoyl compound, and weighing; the following were
the results obtained:--
[660] _Zeit. f. physiol. Chemie_, xvii. 6. 571.
Time. Weight of benzoyl compound.
24 hours, 0·56 grm.
2 days, 0·75 „
3 days, 0·82 „
4 days, 0·73 „
5 days, 0·57 „
6 days, 0·58 „
§ 662. =Ethylidenediamine.=--Brieger found in putrid haddock, in the
filtrate from the mercury chloride precipitate:--gadinine,
neuridine, a base isomeric with ethylenediamine C₂H₈N₂ (but which
Brieger subsequently more or less satisfactorily identified with
ethylidenediamine), muscarine, and triethylamine; these bases were
separated as follows:--
The filtrate from the mercury chloride solution was freed from
mercury by SH₂, evaporated to a syrup, and then extracted with
alcohol. From the alcoholic solution platinum chloride precipitated
neuridine, this was filtered off, the filtrate freed from alcohol
and platinum, and the aqueous solution concentrated to a small
volume and precipitated with an aqueous solution of platinum
chloride; this precipitated ethylidene platinum chloride. The mother
liquor from this precipitate was concentrated on the water-bath,
and, on cooling, the platinochloride of muscarine crystallised out.
From the mother liquor (freed from the crystals), on standing in a
desiccator, the gadinine double salt crystallised out, and from the
mother liquor (freed from gadinine after removal of the platinum by
SH₂) distillation with KHO recovered trimethylamine.
From the platinochloride of ethylenediamine, the chloride can be
obtained by treating with SH₂, filtering, and evaporating; by
distilling the chloride with a caustic alkali, the free base can be
obtained by distillation.
Ethylidenediamine is isomeric with ethylenediamine, but differs from
it in the following properties:--ethylidenediamine is poisonous,
ethylenediamine is non-poisonous.
Ethylenediamine forms a platinochloride almost insoluble in hot
water, while the ethylidene salt is more easily soluble. The
properties of the gold salts are similar, ethylenediamine forming a
difficultly soluble gold salt, ethylidene a rather soluble gold
salt.
Ethylidenediamine forms a hydrochloride, C₂H₈N₂2HCl, crystallising
in long glistening needles, insoluble in absolute alcohol, rather
soluble in water. The hydrochloride gives precipitates in aqueous
solution with phospho-molybdic acid, phospho-antimonic acid, and
potassium bismuth iodide; the latter is in the form of red plates.
The platinochloride, C₂H₈N₂2HCl.PtCl (Pt = 41·5 per cent.), is in
the form of yellow plates, not very soluble in cold water.
Ethylidenediamine, when subcutaneously injected into guinea-pigs,
produces an abundant secretion from the mucous membranes of the nose,
mouth, and eyes. The pupils dilate, and the eyeballs project. There is
acute dyspnœa; death takes place after some twenty-four hours, and the
heart is stopped in diastole.
Trimethylenediamine is believed to have been isolated by Brieger from
cultivations in beef broth of the comma bacillus.
It occurs in small quantity in the mercuric chloride precipitate, and is
isolated by decomposing the precipitate with SH₂, evaporating the
filtrate from the mercury sulphide to dryness, taking up the residue
with absolute alcohol, and precipitating by an alcoholic solution of
sodium picrate. The precipitate contains the picrate of
trimethylenediamine, mixed with the picrates of cadaverine and
creatinine. Cadaverine picrate is insoluble in boiling absolute alcohol,
the other picrates soluble; so the mixed picrates are boiled with
absolute alcohol, and the insoluble cadaverine filtered off. Next, the
picrates of creatinine and trimethylenediamine are freed from alcohol,
the solution in water acidified with hydrochloric acid, the picric acid
shaken out by treatment with ether, and then the solution precipitated
with platinum chloride; the platinochloride of trimethylenediamine is
not very soluble, while creatinine easily dissolves; so that separation
is by this means fairly easy.
It also gives a difficultly soluble salt with gold chloride.
The picrate consists of felted needles, melting-point 198°.
Phospho-molybdic acid gives a precipitate crystallising in plates;
potassium bismuth iodide gives dark coloured needles.
It produces in animals violent convulsions and muscular tremors; but the
substance has hitherto been obtained in too small a quantity to be
certain as to its identification and properties.
§ 663. =Neuridine=, C₅H₁₄N₂.--Neuridine is a diamine, and is apparently
the most common basic product of putrefaction; it has been obtained from
the putrefaction of gelatin, of horseflesh, of fish, and from the yelk
of eggs. It is usually accompanied by choline, from which it can be
separated by converting the bases into hydrochlorides, choline
hydrochloride being soluble in absolute alcohol, neuridine scarcely so.
Brieger isolated neuridine from putrid flesh by precipitating the watery
extract with mercuric chloride. He decomposed the mercury precipitate
with SH₂, and, after having got rid of the sulphide of mercury by
filtration, he concentrated the liquid to a small bulk, when a substance
separated in crystals similar in form to urea; this was purified by
recrystallisation from absolute alcohol, and converted into the platinum
salt.
Another method which may be used for the separation and purification of
neuridine is to dissolve it in alcohol and precipitate with an alcoholic
solution of picric acid; the picrate may be decomposed by treatment with
dilute mineral acid, and the picric acid removed by shaking with ether.
The free base has a strong seminal odour. It is gelatinous, and has not
been crystallised. It is insoluble in ether and in absolute alcohol, and
not readily soluble in amyl alcohol. It gives white precipitates with
mercuric chloride, neutral and basic lead acetates. It does not give
Hofmann’s isonitrile reaction. When distilled with a fixed alkali, it
yields di- and trimethylamine.
The hydrochloride, C₅H₁₄N₂2HCl, crystallises in long needles, which are
insoluble in absolute alcohol, ether, benzol, chloroform, petroleum
ether, and amyl alcohol; but the hydrochloride is very soluble in water
and in dilute alcohol.
The hydrochloride gives no precipitate with mercuric chloride,
potass-mercuric iodide, potass-cadmium iodide, iodine and iodide of
potassium, tannic acid, ferricyanide of potassium, ferric chloride, and
it does not give any colour with Fröhde’s reagent.
On the other hand, phosphotungstic acid, phospho-molybdic acid, picric
acid, potass-bismuth iodide, platinum chloride, and gold chloride all
give precipitates.
Neuridine hydrochloride is capable of sublimation, and at the same time
it is decomposed, for the sublimed needles show red or blue colours.
Neuridine platinochloride, C₅H₁₄N₂2HCl.PtCl₄, yields 38·14 per cent. of
platinum; it crystallises in flat needles, soluble in water, from which
it is precipitated on the addition of alcohol.
The aurochloride has the formula C₅H₁₄N₂2HCl2AuCl₃; it is rather
insoluble in cold water, and crystallises in bunches of yellow needles.
On ignition, it should yield 41·19 per cent. of gold.
The picrate, C₅H₁₄N₂,2C₆H₂(NO₂)₃OH, is almost insoluble in cold water,
and crystallises in needles. It is not fusible, but decomposes at about
230°.
Neuridine is not poisonous.
§ 664. =Cadaverine= (Pentamethylenediamine, C₅H₁₄N₂ =
NH₂CH₂--CH₂--CH₂--CH₂CH₂NH₂) is formed in putrid animal matters, and in
cultures of the genus _Vibrio_. It has been found in the urine and fæces
in cases of cystinuria, and Roos[661] has separated it by the
benzoyl-chloride method from the fæces of a patient suffering from
tertian ague. It may be formed synthetically by dissolving
trimethylcyanide in absolute alcohol, and then reducing by sodium
(Mendius’ reaction).
[661] _Zeit. f. physiol. Chemie_, xvi., 1892.
Cadaverine is a thick, clear, syrupy liquid, with a peculiar coniine- as
well as a semen-like odour. It absorbs eagerly CO₂ from the air, and
ultimately is converted into a solid crystalline mass. It volatilises
with the steam when boiled with water, and may be distilled in the
presence even of the caustic alkalies and the alkaline earths without
decomposition. It does not give oil of mustard when treated with CS₂ and
mercuric chloride, nor does it give with chloroform and alcoholic
potash, carbylamine (isonitrile). If dehydrated by KHO, it boils at from
115°-120° (_Brieger_).[662]
[662] Brieger has also given to the pure base a boiling-point of 175°.
When cadaverine is treated with methyl iodide, two atoms of hydrogen may
be replaced with methyl, forming the base C₅H₁₂(CH₃)₂N₂; the
platinochloride of this last base crystallises in long red needles.
Cadaverine forms well-defined crystalline salts as well as compounds
with metals.
Cadaverine hydrochloride, C₅H₁₄N₂2HCl, crystallises in needles which are
deliquescent, or it may be obtained from an alcoholic solution in
plates. The crystals are insoluble in absolute alcohol, but readily
soluble in 96 per cent. alcohol. Putrescine hydrochloride, on the other
hand, is with difficulty soluble in alcohol of that strength; hence the
two hydrochlorides can be separated by taking advantage of their
difference in solubility in 96 per cent. alcohol; but the better
method for separation is the benzoyl-chloride process (p. 487). On
dry distillation, cadaverine hydrochloride decomposes into
NH₃,HCl and piperidine C₅H₁₁N. The compound with mercury
chloride--C₅H₁₄N₂2HCl,4HgCl₂ (Hg = 63·54 per cent.); melting-point,
214°-216°--is insoluble in alcohol and in cold water; this property is
also useful to separate it from putrescine, the mercury compound of
which is soluble in cold water. The platinochloride, C₅H₁₄N₂2HCl,PtCl₄
(Pt = 38·08 per cent.), crystallises in dirty red needles; but, by
repeated crystallisation, it may be obtained in clear chrome yellow,
short, octahedral prisms; it is soluble with difficulty in hot water,
insoluble in cold water. The salt decomposes at 235°-236°.
The aurochloride--C₅H₁₄N₂2HCl2AuCl (Au = 50·41 per cent.), melting-point
188°--crystallises partly in cubes and partly in needles, and is easily
soluble in water.
Other salts are the picrate, C₅H₁₄N₂2C₆H₂(NO₂)₃OH, melting-point 221°
with decomposition; with difficulty soluble in cold, but dissolving in
hot water, and insoluble in absolute alcohol. There are also a neutral
oxalate, C₅H₁₄N₂,H₂C₂O₄ + 2H₂O, melting-point 160°; and an acid oxalate,
C₅H₁₄N₂2H₂C₂O₄ + H₂O, melting-point 143° with decomposition; both these
oxalates are insoluble in absolute alcohol.
Cadaverine dibenzoyl--C₅H₁₀(NHCOC₆H₅)₂, melting-point
129°-130°--crystallises in needles and plates, soluble in alcohol and
slightly soluble in ether, insoluble in water.
It is not acted on by hot dilute acids or alkalis, and when dissolved in
concentrated hydrochloric acid and alcohol it is, only after prolonged
boiling, decomposed into benzoic acid and the free base. The benzoic
acid after getting rid of the alcohol by evaporation, can be removed by
shaking up with ether; then the hydrochloride can be decomposed by an
alkali and the free base obtained, or the platinum salt of cadaverine
may be formed by precipitation with platinum chloride. Should cadaverine
and putrescine be in the same liquid, the dibenzoyl compounds may be
separated as follows:--the crystalline precipitate is collected on a
filter, washed with water until the filtrate runs clear, and then
dissolved in warm alcohol; this solution is poured into twenty times its
volume of ether and allowed to stand; after a short time crystals form
of the putrescine compound, which are far less soluble in alcohol than
those of cadaverine dibenzoyl; these crystals are filtered off and
repeatedly crystallised from alcohol until the melting-point is about
175°-176°. The filtrate contains the cadaverine compound; this latter is
recovered by evaporating off the ether-alcohol.
§ 665. =Putrescine--Tetramethylenediamine=,
C₄H₁₂N₂=NH₂CH₂CH₂CH₂CH₂NH₂.
The free base is a clear liquid, with a semen-like odour, boiling-point
135°. It is a common base in putrefying animal substances, and also
occurs in the urine in cases of cystinuria. It can be obtained
synthetically by reducing ethylene cyanide by the action of sodium in
absolute alcohol.
The best method of separating putrescine is the benzoyl chloride method
already given.
Putrescine forms crystalline salts, of which the following are the most
important:--
Putrescine hydrochloride, C₄H₁₂N₂2HCl, forms long colourless needles,
insoluble in absolute alcohol, easily soluble in water.
The platinochloride, C₄H₁₂N₂2HCl.PtCl₄ (Pt = 39·2 per cent.), is with
difficulty soluble in cold water. When pure, the salt is in the form of
six-sided plates.
The aurochloride, C₄H₁₂N₂2HCl.2AuCl₃ + 2H₂O (Au = 51·3 per cent.), is
insoluble in cold water, in contradistinction to cadaverine
aurochloride, which easily dissolves.
The picrate, C₄H₁₂N₂2C₆H₂(NO₂)₃OH, is a salt of difficult solubility. It
crystallises in yellow plates. It browns at 230°, and melts with
evolution of gas at 250°.
Dibenzoylputrescine, C₄H₈(NHCOC₆H₅)₂, forms silky plates or long
needles, melting-point 175°-176°. By boiling it for twelve hours with
alcohol and strong hydrochloric acid the compound may be broken up into
hydrochloride of putrescine and free benzoic acid. As stated before, it
is less soluble in alcohol than the corresponding compound of
cadaverine.
Putrescine is not poisonous. On the other hand, by repeated treatment
with methyl iodide, it takes up four methyl radicals, and the
tetramethyl compound, C₄H₈(CH₃)₄N₂, produces symptoms similar to those
of muscarine poisoning.
§ 666. =Metaphenylenediamine=,
NH₂¹
/
C₆H₄ ,
\
NH₂³
is a crystalline substance, melting-point 63°, boiling-point 276°-277°.
The crystals are easily soluble in alcohol or ether, with difficulty in
water. The least trace of nitrous acid strikes a yellow colour from the
formation of triamidobenzol.
§ 667. =Paraphenylenediamine=,
NH₂¹
/
C₆H₄ ,
\
NH₂⁴
is in the form of tabular crystals, melting-point 140°, boiling-point
267°. If this substance is oxidised with ferric chloride or manganese
binoxide and sulphuric acid, chinone is produced; if treated with SH₂
and ferric chloride, a violet sulphur-holding colouring matter, allied
to methylene blue, is formed; these reactions are tests for the presence
of the para-compound.
Both these diamines are poisonous. Metaphenylenediamine produces, in the
dog, the symptoms of an aggravated influenza with continual sneezing and
hoarse cough, which, if the dose is large enough, ends in coma and
death. Paraphenylenediamine produces exophthalmia, the tissues of the
eye undergoing complete alteration.[663]
[663] _Comptes Rend._, cvii. 533-535.
Both compounds, in doses of 100 mgrms. per kilo., cause more or less
salivation, with diarrhœa. The para-compound is more poisonous than the
meta-compound. So far as the author is aware, neither of these diamines
have been separated with certainty from the urine of sick persons, nor
from products of decomposition.
§ 668. =Hexamethylenediamine=, C₆H₁₆N₂.--Hexamethylenediamine has been
found by A. Garcia[664] in a putrefying mixture of horse-flesh and
pancreas.
[664] _Zeit. f. physiol. Chemie_, xvii. 543-555.
§ 669. =Diethylenediamine=, C₄H₁₀N₂, is a crystalline substance,
melting-point 104°, boiling-point 145°-146°. After melting, it
solidifies on cooling, forming a hard crystalline mass. It is extremely
soluble in water, and is deposited from alcohol in large transparent
crystals. A technical product called “spermin piperazidin” or
“piperazine” has been found by A. W. v. Hoffmann[665] to be identical
with diethylenediamine. The hydrochloride crystallises in colourless
needles, insoluble in alcohol, readily soluble in water. The
platinochloride, C₄H₁₀N₂H₂PtCl₆, is in small yellow needles, and is
fairly easily soluble in hot water, but dissolves but slightly in hot
alcohol. The mercuro-chloride, C₄H₁₀N₂H₂HgCl₄, crystallises in
concentrically grouped needles, and is readily soluble in hot water, but
is reprecipitated on adding alcohol. The picrate, C₄H₁₀N₂,C₆H₂(NO₂)₃OH,
crystallises from water in yellow needles, almost insoluble in
alcohol.[666]
[665] _Ber._, xxiii. 3297-3303.
[666] Sieber, J., _Ber._, xxiii. 326-327.
§ 670. =Mydaleine= is a poisonous base discovered by Brieger in putrid
animal matters. It is probably a diamine, but has not been obtained in
sufficient quantity for accurate chemical study. The platinochloride is
extremely soluble in water, and only comes down from an absolute alcohol
solution. It has been obtained in a crystalline form, giving on analysis
38·74 per cent. of platinum, C. 10·83 per cent., H. 3·23 per cent.
Mydaleine is very poisonous. Small quantities injected into guinea-pigs
cause dilatation of the pupil, an abundant secretion from the nose and
eyes, and a rise of temperature. Fifty mgrms. cause death. The
_post-mortem_ appearances are not distinctive; the heart is arrested in
diastole; the intestines and bladder are contracted. In cats it causes
profuse diarrhœa and vomiting.
§ 671. =Guanidine.=--Guanidine may be considered to have a relation to
urea; for, if the oxygen of urea is replaced by the imide group NH,
guanidine originates thus:--
NH₂
/
Urea = O=C
\
NH₂
NH₂
/
Guanidine = NHC
\
NH₂
Hence guanidine from its structural formula is a carbodiamidimide.
Guanidine may be formed by the action of oxidising agents, such as
potassic chlorate and hydrochloric acid, on guanine; or by heating amide
cyanide with ammonium chloride, and so forming guanidine chloride. It is
also produced from the oxidation of albumin. When boiled with
baryta-water it decomposes into urea and ammonia. It combines with acids
to form salts; the gold salt, CH₅N₃HCl,AuCl₃, is in the form of long
yellow needles, with difficulty soluble in water. Guanidine nitrate,
CH₅N₃HNO₃, is also almost insoluble in cold water and similar to urea
nitrate. By dissolving equivalent parts of phenol and guanidine in hot
alcohol, triphenylguanidine is formed; on adding picric acid to a
solution of triphenylguanidine, phenylguanidine picrate,
CH₂Ph₃N₃C₆H₂(NO₂)₃OH, is formed, and falls as a precipitate of slender
needles, melting-point 208°; this picrate is very slightly soluble, 1
part dissolving in 12,220 parts of water at 15°. Guanidine is
poisonous.[667]
[667] O. Prelinger, _Monatsb._, xiii. 97-100.
A method of separating guanidine from urine has been worked out by
Gergers and Baumann.[668] The principle of the method is based upon the
fact that guanidine is precipitated by mercurous oxide. The urine is
precipitated by hydrate of baryta, the precipitate filtered off, the
alkaline filtrate neutralised by hydrochloric acid, and the neutral
filtrate evaporated to a syrup on the water-bath; the syrup is exhausted
by absolute alcohol, and the alcoholic solution filtered; this filtrate
is freed from alcohol by distillation, the alcohol-free residue
dissolved in a little water, shaken up with freshly precipitated mercury
oxide, and allowed to stand for two days in a warm place; the
precipitate formed is collected, acidulated with HCl and treated with
SH₂; the mercury sulphide thus obtained is separated by filtration, the
filtrate evaporated, and the residue dissolved in absolute alcohol. This
solution is precipitated by platinum chloride, filtered, separated from
any platinum ammonium salt, and evaporated to a small volume. After long
standing the guanidine salt crystallises out. The best method to
identify it appears to be, to ascertain the absence of ammonia and of
urea, and then to gently warm the supposed guanidine with an alkali,
which breaks guanidine up into ammonia and urea, according to the
following equation:--
NH=C(NH₂)₂ + H₂O = NH₃ + CO(NH₂)₂.
[668] Pflüger’s _Archiv_, xii. 205.
The physiological effects of guanidine are as follows:--
A centigrm. of guanidine salt injected into the lymph sac in the back of
frogs produces, after a few minutes, muscular convulsions: first, there
are fibrillar twitchings of the muscles of the back; next, these spread
generally so that the whole surface of the frog seems to be in a
wave-like motion. Irritation of the limbs produces tetanus. There is, at
the same time, increased secretion from the skin. The breathing is
irregular. In large doses there is paralysis and death. The heart is
found arrested in diastole. The fatal dose for a frog is 50 mgrms.; but
1 mgrm. will produce symptoms of illness. In dogs there is paralysis,
convulsions, vomiting, and difficult breathing.
§ 672. =Methylguanidine=,
NH.CH₃
/
NH=C .
\
NH₂
--Methylguanidine has been isolated by Brieger from putrefying
horse-flesh; it has also been found in impure cultures in beef broth of
Finkler and Prior’s _Vibrio proteus_. Bocklisch isolated it, working
with Brieger’s process, from the mercuric chloride precipitate, after
removal of the mercury and concentration of the filtrate, by adding a
solution of sodium picrate. The precipitate contained the picrates of
cadaverine, creatinine, and methylguanidine; cadaverine picrate,
insoluble in boiling absolute alcohol, was separated by filtering from a
solution of the picrates of the bases in boiling absolute alcohol; the
alcohol was evaporated from the filtrate and the residue taken up with
water. From this aqueous solution the picric acid was removed and then
the solution precipitated with gold chloride; methylguanidine was
precipitated, while creatinine remained in solution.
Methylguanidine aurochloride, C₂H₇N₃HCl.AuCl₃ (Au = 47·7 per cent.),
forms rhombic crystals easily soluble in alcohol and ether;
melting-point 198°. The hydrochloride, C₂H₇N₃HCl, crystallises in
needles insoluble in alcohol. The picrate, C₂H₇N₃C₆H₂(NO₂)₃OH, comes
down at first as a resinous mass, but, after boiling in water, is found
to be in the form of needles soluble in hot absolute alcohol;
melting-point 192°. The symptoms produced by methylguanidine are rapid
respiration, dilatation of the pupils, paralysis, and death, preceded by
convulsions. The heart is found arrested in diastole.
§ 673. =Saprine=, C₅H₁₄N₂.--Saprine is isomeric with cadaverine and
neuridine; it was found by Brieger in human livers and spleens after
three weeks’ putrefaction. Saprine occurs, in Brieger’s process, in the
mercury precipitate. Its reactions are very similar to those of
cadaverine; the main difference being that cadaverine hydrochloride
gives a crystalline aurochloride, saprine does not; the platinum salt is
also more soluble in water than the cadaverine salt. It is not
poisonous.
§ 674. =The Choline Group.=--The choline group consists of choline,
neurine, betaine, and muscarine.
All these bodies can be prepared from choline; their relationship to
choline can be readily gathered from the following structural formulæ:--
CH₂OH
|
CH₂
|
N(CH₃)₃.OH
Choline.
CH₂
║
CH
|
N(CH₃)₃.OH
Neurine.
CO₂H
|
CH₂
|
N(CH₃)₃.OH
Betaine.
CH₂OH
|
CHOH
|
N(CH₃)₃.OH
Muscarine.
Choline is a syrup with an alkaline reaction. On boiling with water, it
decomposes into glycol and trimethylamine. It gives, when oxidised,
muscarine. It forms salts. The hydrochloride is soluble in water and
absolute alcohol; neurine hydrochloride and betaine hydrochloride are
but little soluble in absolute alcohol, therefore this property can be
utilised for their separation from choline. The platinochloride is
insoluble in absolute alcohol; it melts at 225° with effervescence, and
contains 31·6 per cent. of platinum. The mercurochloride is soluble with
difficulty even in hot water. The aurochloride (Au = 44·5 per cent.) is
crystalline, and with difficulty soluble in cold water; but is soluble
in hot water and in alcohol; melting-point 264° with decomposition.
Choline is only poisonous in large doses.
§ 675. =Neurine= (Trimethyl-vinyl-ammonium hydrate),
C₂H₃N(CH₃)₃OH.--Neurine is one of the products of decomposition of
choline. It is poisonous, and has been separated by Brieger and others
from decomposing animal matters. In Brieger’s process, neurine, if
present, will be for the most part in the mercuric chloride precipitate,
and some portion will also be in the filtrate. The mercury precipitate
is decomposed by SH₂, the mercury sulphide filtered off, and the
filtrate, concentrated, treated with absolute alcohol and then
precipitated by platinum chloride. It is usually accompanied by choline;
the platinochloride of choline is readily soluble in water, neurine
platinochloride is soluble with difficulty; this property is taken
advantage of, and the platinochloride crystallised from water until
pure. Neurine has a strong alkaline reaction.
Neurine chloride, C₅H₁₂N.Cl, crystallises in fine needles. The
platinochloride, (C₅H₁₂NCl)₂PtCl₄ (Pt = 33·6 per cent.), crystallises in
octahedra. The salt is soluble with difficulty in hot water.
The aurochloride, C₅H₁₂NClAuCl₃ (Au = 46·37 per cent.), forms flat
prisms, which, according to Brieger, are soluble with difficulty in hot
water.
Neurine is intensely poisonous, the symptoms being similar to those
produced by muscarine.
Atropine is an antidote to neurine, relieving in suitable doses the
effects, and even rendering animals temporarily immune against the toxic
action of neurine.
When a fatal dose of neurine is injected into a frog there is in a short
time paralysis of the extremities. The respiration stops first, and
afterwards the heart, the latter in diastole.
The symptoms in rabbits are profuse nasal secretion and salivation with
paralysis, as in frogs. Applied to the eye, neurine causes contraction
of the pupil; to a less degree the same effect is produced by the
ingestion of neurine.
=Trimethyloxyammonium= hydrochloride causes similar symptoms to neurine,
but the action is less powerful.--V. Cervello, _Arch. Ital. Biol._, vii.
232-233.
§ 676. =Betaine.=--Betaine may be separated from a solution in alcohol
as large deliquescent crystals; the reaction of the crystals is neutral.
Distilled with potash, trimethylamine and other bases are formed.
Betaine chloride, C₅H₁₂NO₂Cl, forms plates permanent in the air and
insoluble in absolute alcohol. A solution of the chloride in water
gives, with potassium mercuric iodide, a light yellow or whitish yellow
precipitate, soluble in excess; but, on rubbing the sides of the tube
with a glass rod, the oily precipitate crystallises as yellow needles;
probably this is characteristic.
The aurochloride (Au = 43·1 percent.) forms fine cholesterine plates,
soluble in water; melting-point 209°. Betaine is not poisonous.
§ 677. =Peptotoxine.=--Brieger submitted to the action of fresh gastric
juice moist fibrin for twenty-four hours at blood heat. The liquid was
evaporated to a syrup and boiled with ethylic alcohol, the ethylic
alcohol was evaporated, the residue digested with amylic alcohol, and
the amyl alcohol in its turn evaporated to dryness; the residue was a
brown amorphous mass that was poisonous. It was farther purified by
treating the extract with neutral lead acetate and then filtered; the
filtrate was freed from lead by SH₂ and treated with ether, the ethereal
extract being then separated and evaporated to dryness; this last
residue was taken up with amyl alcohol, the alcohol evaporated to
dryness, and the residue finally taken up with water and filtered. The
filtrate is poisonous. The poisonous substance, to which Brieger gave
the provisional name of peptotoxine, is a very stable substance,
resisting the action of a boiling temperature, and even the action of
strong alkalies. It gives precipitates with alkaloidal group reagents,
and strikes a blue colour with ferric chloride and ferricyanide of
potassium. The most characteristic test seems to be its action with
Millon’s reagent (a solution of mercury nitrate in nitric acid
containing nitrous acid); this gives a white precipitate which, on
boiling, becomes intensely red.
It is poisonous, killing rabbits in doses of 0·5 grm. per kilogrm., with
symptoms of paralysis and coma. The nature of this substance requires
further elucidation.
§ 678. =Pyridine Alkaloid from the Cuttle Fish.=--O. de Coninck[669] has
obtained, by Gautier’s process, an alkaloid from the cuttle fish, of the
formula C₈H₁₁N, in the form of a yellow, mobile, strongly odorous
liquid, very soluble in alcohol, ether, and acetone, boiling-point 202°.
It quickly absorbs moisture from the air. It forms two mercuric
chlorides, one of which has the formula (C₈H₁₁N,HCl)₂HgCl₂; this
compound crystallises in small white needles, slightly soluble in water
and dilute alcohol, but insoluble in absolute alcohol, and decomposing
when exposed to moist air. The other salt is a sesqui-salt, forming long
yellowish needles, insoluble in ordinary solvents, and decomposing when
exposed to moist air. The alkaloid also forms deliquescent very soluble
salts with hydrochloric and hydrobromic acids. A platinum salt is also
formed, (C₈H₁₁N)₂H₂PtCl₆; it is of a deep yellow colour, almost
insoluble in cold, but soluble in hot water; it is decomposed by boiling
water, with the formation of a very insoluble compound in the shape of a
brown powder, (C₈H₁₁N)₂PtCl₄. Coninck’s alkaloid, on oxidation with
potassic permanganate, yields a gummy acid; this acid, on purifying it
by conversion into a potassium salt and then into a cupric salt, was
found to be nicotinic acid; so that the alkaloid is undoubtedly a
pyridine compound; indeed, the acid, distilled with lime, yields
pyridine.
[669] _Comptes Rend._, cvi. 858, 861; cviii. 58-59, 809-810; cvi.
1604-1605.
§ 679. =Poisons connected with Tetanus.=--Brieger, in 1887, isolated a
base of unknown composition, to which he gave the name of
“spasmotoxine.” It was produced in cultures of the tetanus bacillus in
beef broth.
Two more definite substances have also been discovered, viz., tetanine
and tetanotoxine.
=Tetanine=, C₁₃H₃₀N₂O₄, is best isolated by the method of Kitasato and
Weyl.[670] Their method of treating broth cultures of the tetanus
bacillus is as follows:--
[670] _Zeit. f. Hygiene_, viii. 404.
The broth is digested with 0·25 per cent. HCl for some hours at 460°,
then rendered feebly alkaline, and distilled in a vacuum. The residue in
the retort is then worked up for tetanine by Brieger’s method; the
distillate contains tetanotoxine, ammonia, indol, hydrogen sulphide,
phenol, and butyric acid. On treating the contents of the retort by
Brieger’s mercury chloride method, the filtrate contains most of the
poison. The mercury is removed by SH₂, the filtered solution evaporated
and exhausted by absolute alcohol, in which the tetanine dissolves. Any
ammonium chloride is thus separated, ammonium chloride being insoluble
in absolute alcohol. The alcoholic solution, filtered from any insoluble
substance, is next treated with an alcoholic solution of platinum
chloride, which precipitates creatinine (and any ammonium salts), but
does not precipitate tetanine. The platinum salt of tetanine may,
however, be precipitated by the addition of ether to the alcoholic
solution. The platinum salt, as obtained by precipitation from ether, is
very deliquescent; it has, therefore, to be rapidly filtered off and
dried in a vacuum. It can then be recrystallised from hot 96 per cent.
alcohol, forming clear yellow plates; these plates, if dried in a
vacuum, become with difficulty soluble in water.
Tetanine may be obtained as a free base by treating the hydrochloride
with freshly precipitated moist silver oxide. It forms a strongly
alkaline yellow syrup, and is easily decomposed in acid solution, but is
permanent in alkaline solutions.
The platinochloride, as before observed, is precipitable by ether from
alcoholic solution; it contains 28·3 per cent. of platinum, and
decomposes at 197°.
The base produces tetanus.
§ 680. =Tetanotoxine= may be distilled, and be found in the distillate
with other matters. It forms an easily soluble gold salt, melting-point
130°. The platinochloride is soluble with difficulty, and decomposes at
240°. The hydrochloride is soluble in alcohol and in water,
melting-point about 205°.
Tetanotoxine produces tremor, then paralysis, and lastly, violent
convulsions.
§ 681. =Mydatoxine=, C₆H₁₃NO₂.--A base obtained by Brieger from
horse-flesh in a putrefactive condition and other substances. It is
found in the mercury chloride precipitate. The free base is an alkaline
syrup, isomeric with the base separated by Brieger from tetanus
cultures. The hydrochloride is a deliquescent syrup, not forming any
compound with gold chloride, but uniting with phospho-molybdic acid in
forming a compound crystallising in cubes. It forms a double salt with
gold chloride, sparingly soluble in water. The platinochloride (Pt = 29
per cent.) is very soluble in water, but not soluble in alcohol;
melting-point 193° with decomposition.
The base in large doses is poisonous, causing lachrymation, diarrhœa,
and convulsions.
§ 682. =Mytilotoxine=, C₆H₁₅NO₂.--This is believed to be the poison of
mussels. Brieger isolated it as follows:--
The mussels were boiled with water acidified by hydrochloric acid; the
liquid was filtered, and the filtrate evaporated to a syrup, and the
syrup was repeatedly extracted with alcohol. It was found advisable to
exhaust thoroughly with alcohol, otherwise much poison remained behind.
The alcoholic solution was treated with an alcoholic solution of lead
acetate. The filtrate was evaporated and the residue extracted with
alcohol. The lead was removed by SH₂, the alcohol distilled off, water
added to the remaining syrup, and the solution decolorised by boiling
with animal charcoal. The solution was neutralised by sodium carbonate,
acidulated with nitric acid, and precipitated with phosphomolybdic acid.
The precipitate was then decomposed by warming with a neutral solution
of lead acetate, and the filtrate (after the removal of the lead by the
action of SH₂) was acidulated with HCl and evaporated to dryness. The
residue was then extracted with absolute alcohol, filtered from any
insoluble chloride, _e.g._, betaine chloride, and precipitated by
mercury chloride in alcohol.
The free base has a most peculiar odour, which disappears on exposure to
air; at the same time, the poisonous properties also diminish. The base
is destroyed by boiling with sodium carbonate; on the other hand, the
hydrochloride may be evaporated to dryness or be boiled without
decomposing.
The hydrochloride crystallises in tetrahedra; the aurochloride
crystallises in cubes (Au=41·66 per cent.). Its melting-point is 182°.
§ 683. =Tyrotoxicon= (Diazobenzol, C₆H₅N₂(OH)).--It appears, from the
researches of Vaughan and others, that diazobenzol is liable to be
formed in milk and milk products, especially in summer time. It is
confidently asserted by many that the summer diarrhœa of infants is due
to this toxine; however that may be, it is well established that
diazobenzol is a violent poison, causing sickness, diarrhœa, and, in
large doses, an acute malady scarcely distinguishable from cholera, and
which may end fatally. There will always be difficulty in detecting it,
because of its instability. The following is the best process of
extraction from milk. The milk will probably be acid from decomposition;
if so, the whey must be separated by dilution and filtration; without
dilution it may be found impracticable to get a clear filtrate. In order
to keep the bulk down, 25 c.c. of the milk may be diluted up to 100
c.c., and, having obtained a clear filtrate from this 25 c.c. thus
diluted, the filtrate is used to dilute another 25 c.c. of milk and so
on. The acid filtrate is neutralised by sodium carbonate, agitated with
an equal volume of ether, allowed to stand in a stoppered vessel for
twenty-four hours, and the ether then separated and allowed to evaporate
spontaneously. The residue is acidified with nitric acid and then
treated with a saturated solution of potash, which forms a stable
compound with diazobenzol, and the whole concentrated on the water-bath.
On cooling, the tyrotoxicon compound forms six-sided plates. Before the
whole of this process is undertaken, it is well to make a preliminary
test of the milk as follows:--A little of the ether is allowed to
evaporate spontaneously. Place on a porcelain slab two or three drops of
a mixture of equal parts of sulphuric and carbolic acids, and add a few
drops of the aqueous solution; if tyrotoxicon be present, a yellow to
orange-red colour is produced. A similar colour is also produced by
nitrates or nitrites, which are not likely to be present under the
circumstances, milk having mere traces only of nitrates or nitrites; it
may also be due to butyric acid, which, in a decomposed milk, may
frequently be in solution. Therefore, if a colour occurs, this is not
absolutely conclusive; if, however, no colour is produced, then it is
certain that no diazobenzol has been separated. That is all that can be
said, for the process itself is faulty, and only separates a fractional
part of the whole.
§ 684. =Toxines of Hog Cholera.=--Toxines have been isolated by F. G.
Novy[671] from a cultivation of Salmon’s bacillus in pork broth. The
fluid possessed a strong alkaline reaction. For the isolation, Brieger’s
method was used. The mercury chloride precipitate was amorphous and was
converted into a chlorine-free platinum compound, to which was assigned
the composition of C₈H₁₄N₄PtO₈. After separation of this compound, the
mother liquor still contained a platinum salt crystallising in needles,
and from this was obtained the chlorhydrate of a new base, to which was
given the name of _susotoxine_; it had the composition of
C₁₀H₂₆N₂2HCl,PtCl₄. Susotoxine gives general alkaloidal reactions, and
is very poisonous.
[671] _Med. News_, September 1890.
§ 685. =Other Ptomaines.=--Besides the ptomaines which have been already
described, there are a number of others; the following may be mentioned:
isoamylamine,[672] (CH₃)₂CH.CH₂.CH₂NH₂; butylamine, CH₃CH₂CH₂CH₂NH₂;
dihydrolutidine,[673] C₇H₁₁N; hydrocollidine,[674] C₈H₁₃N; C₁₀H₁₅N (a
base isolated by Guareschi and Mosso[675] from ox-fibrin in a state of
putrefaction by Gautier’s method; it forms a crystalline hydrochloride
and an insoluble platinochloride; its action is like that of curare but
weaker); aselline,[676] C₂₅H₃₂N₄, isolated from cod-liver oil;
typhotoxine,[677] C₇H₁₇NO₂, isolated from cultures of Eberth’s bacillus.
So far as the published researches go, it would appear that other
crystalline substances have been isolated from the urine, from the
tissues, and from the secretions of patients suffering from various
diseases; the quantity obtained in each case has, however, been, under
the most favourable circumstances, less than a gramme; often only a few
milligrms. To specifically declare that a few milligrms. of a substance
is a new body, requires immense experience and great skill; and, even
where those qualifications are present, this is too often impossible.
This being so, the long list of named ptomaines, such as erysipeline,
varioline, and others, must have their existence more fully confirmed by
more than one observer before they can be accepted as separate entities.
[672] Hesse, _Chem. Jahresb._, 1857, 403.
[673] Gautier, A., and Morgues, _Compt. Rend._, 1888.
[674] Gautier et Etard, _Bull. Soc. Chim._, xxxvii., 1882.
[675] Guareschi et Mosso, _Les ptomaines_, 1883.
[676] Gautier, A., et Morgues, _Compt. Rend._, 1888.
[677] Brieger, 1885, _Ptomaines_, iii.
DIVISION III.--FOOD POISONING.
§ 686. A large number of cases of poisoning by food occur yearly; some
are detailed in the daily press; the great majority are neither recorded
in any journal, scientific or otherwise; nor, on account of their slight
and passing character, is medical aid sought. The greatest portion of
these cases are probably due to ptomaines existing in the food before
being consumed; others may be due to the action of unhealthy
fermentation in the intestinal canal itself; in a third class of cases,
it is probable that a true zymotic infection is conveyed and develops in
the sufferer; the latter class of cases, as, for instance, the
Middlesborough epidemic of pleuro-pneumonia, is outside the scope of
this treatise.
Confining the attention to cases of food poisoning in which the symptoms
have been closely analysed and described, the reader is referred to
thirteen cases of food poisoning, investigated by the medical officers
of the Local Government Board between the years 1878 and 1891, as
follows:--
1878. =A Case of Poisoning at Whitchurch from eating Roast Pork.=--Only
the leg of pork was poisonous, other parts eaten without injury. Two
persons died after about thirty hours’ illness. The pork itself, on a
particular Sunday, was innocuous; it became poisonous between the Sunday
and the Monday; the toxicity appeared to gradually increase, for those
who ate it for dinner on the Monday were not taken ill for periods of
from seven to nineteen hours, while two persons who ate of it in the
evening were attacked four hours after eating.
1880. =The Welbeck Epidemic=, due to eating cold boiled ham. Over fifty
persons affected. Symptoms commenced in from twelve to forty-eight
hours.
1881. =A Series of Poisoning from eating Baked Pork,
Nottingham.=--Probably the gravy was the cause and not the pork itself.
Many persons seriously ill. One died.
1881. =Tinned American Sausage.=--A man in Chester died from eating
tinned American sausage. Poison found to be unequally distributed in the
sausage.
1882. =Poisoning at Oldham by Tinned Pigs’ Tongues.=--Two families
affected. Symptoms commenced in about four hours. All recovered. After a
few days’ keeping it would appear that the poison had been decomposed.
1882. =A Family Poisoned by Roast Beef at Bishop Stortford.=--Only a
particular piece of the ribs seemed to be poisonous, the rest of the
carcase being innocuous. Symptoms did not commence until several hours
after ingestion.
1882. =Ten different Families at Whitchurch Poisoned by eating
Brawn.=--First symptoms after about four hours.
1884. =Tinned Salmon at Wolverhampton.=--Five persons, two being
children, ate of tinned salmon at Wolverhampton. All suffered more or
less. The mother’s symptoms began after twelve hours, and she died in
five days; the son died in three days, the symptoms commencing in ten
hours. The _post-mortem_ signs were similar to those from phosphorus
poisoning, viz., fatty degeneration. Mice fed on the material also
suffered, and their organs showed a similar degeneration.
1886. =The Carlisle A Case.=--At a wedding breakfast in Carlisle
twenty-four persons were poisoned by food which had been kept in an
ill-ventilated cellar. The articles suspected were an American ham, an
open game pie, and certain jellies. The bride died. Symptoms commenced
in from six to forty-three hours.
1886. =Poisoning by Veal Pie at Iron Bridge.=--Twelve out of fifteen ate
of the pie; all were taken ill in from six to twelve hours.
1887. =Poisoning at Retford of Eighty Persons from eating Pork Pie or
Brawn.=--Symptoms commenced at various intervals, from eight to
thirty-six hours.
1889. =The Carlisle B Case.=--Poisoning by pork pies or boiled salt
pork. Number of persons attacked, about twenty-five.
1891. =Poisoning by a Meat Pie at Portsmouth.=--Thirteen persons
suffered from serious illness. Portions of the pies were poisonous to
mice.
The symptoms in all these cases were not precisely alike; but they were
so far identical as to show as great a similarity as in cases when a
number of persons are poisoned by the same chemical substance. Arsenic,
for instance, produces several types of poisoning; so does phosphorus.
Severe gastro-enteric disturbance, with more or less affection of the
nervous system, were the main characteristics. These symptoms commenced,
as before stated, at various intervals after ingestion of the food; but
they came on with extreme suddenness. Rigors, prostration, giddiness,
offensive diarrhœa, followed by muscular twitchings, dilatation of the
pupil, drowsiness, deepening in bad cases to coma, were commonly
observed. The _post-mortem_ appearances were those of enteritis, with
inflammatory changes in the kidney and liver. Convalescence was slow;
sometimes there was desquamation of the skin.
In many of these cases Dr. Klein found bacteria which, under certain
conditions, were capable of becoming pathogenic; but in no case does
there seem to have been at the same time an exhaustive chemical inquiry;
so that, although there was evidence of a poison passing through the
kidney, the nature of the poison still remains obscure.
The deaths in England and Wales from unwholesome food during ten years
were as follows:--
DEATHS IN ENGLAND AND WALES FROM UNWHOLESOME FOOD DURING THE TEN YEARS
1883-1892.
+----------+-----+---+-----+---+-----+---+-----+---+-----+----+----+
| |1883.| |1885.| |1887.| |1889.| |1891.| |To- |
| | |1884.| |1886.| |1888.| |1890.| |1892.|tal.|
+-----------+---+-----+---+-----+---+-----+---+-----+---+-----+----+
|Diseased | 1 | ... |...| ... |...| ... |...| ... |...| ... | 1 |
|meat, | | | | | | | | | | | |
|Poisonous | 2 | 3 | 2 | 1 | 1 | 4 | 3 | 2 | 9 | 6 | 33 |
|fish, | | | | | | | | | | | |
|Unwholesome|...| 1 |...| ... |...| ... |...| ... |...| ... | 1 |
|brawn, | | | | | | | | | | | |
|Tinned |...| 2 |...| ... |...| ... |...| ... |...| ... | 2 |
|salmon, | | | | | | | | | | | |
|Putrid |...| 1 | 1 | 1 |...| ... | 1 | ... |...| ... | 4 |
|meat, | | | | | | | | | | | |
|Diseased |...| 1 |...| ... |...| ... |...| ... |...| ... | 1 |
|food, | | | | | | | | | | | |
|Mussels, |...| 1 |...| ... |...| ... | 1 | ... |...| ... | 2 |
|Tinned |...| ... |...| ... | 2 | ... |...| ... |...| ... | 2 |
|foods, | | | | | | | | | | | |
|Whelks, |...| ... |...| ... | 1 | ... |...| ... |...| ... | 1 |
|Winkles, |...| ... |...| ... |...| ... |...| 1 |...| ... | 1 |
|Ptomaines, |...| ... |...| ... |...| ... |...| ... | 1 | ... | 1 |
| +---+-----+---+-----+---+-----+---+-----+---+-----+----+
| | 3 | 9 | 3 | 2 | 4 | 4 | 5 | 3 |10 | 6 | 49 |
+-----------+---+-----+---+-----+---+-----+---+-----+---+-----+----+
§ 687. =German Sausage Poisoning.=--A series of cases may be picked out
from the accounts of sausage poisoning in Germany, all of which
evidently depend upon a poison producing the same symptoms, and the
essentially distinctive mark of which is extreme dryness of the skin and
mucous membranes, dilatation of the pupil, and paralysis of the upper
eyelids (ptosis). In an uncertain time after eating sausages or some
form of meat, from one to twenty-four hours, there is a general feeling
of uneasiness, a sense of weight about the stomach, nausea, and soon
afterwards vomiting, and very often diarrhœa. The diarrhœa is not
severe, never assumes a choleraic form, and is unaccompanied by cramps
in the muscles. After a considerable interval there is marked dryness of
the mucous membrane (a symptom which never fails), the tongue, pharynx,
and the mouth generally seem actually destitute of secretion; there is
also an absence of perspiration, the nasal mucous membrane participates
in this unnatural want of secretion, the very tears are dried up. In a
case related by Kraatzer,[678] the patient, losing a son, was much
troubled, but wept no tear. This dryness leads to changes in the mucous
membrane, it shrivels, and partly desquamates, aphthous swellings may
occur, and a diffuse redness and diphtheritic-like patches have been
noticed. There is obstinate constipation, probably from a dryness of the
mucous lining of the intestines. The breath has an unpleasant odour,
there is often a croupy cough, the urinary secretion alone is not
decreased but rather augmented. Swallowing may be so difficult as to
rise to the grade of aphagia, and the tongue cannot be manipulated
properly, so that the speech may be almost unintelligible. At the same
time, marked symptoms of the motor nerves of the face are present, the
patient’s sight is disturbed, he sees colours or sparks before his eyes;
in a few cases there has been transitory blindness, in others diplopia.
The pupil in nearly all the cases has been dilated, also in exceptional
instances it has been contracted. The _levator palpebrae superioris_ is
paralysed, and the resulting ptosis completes the picture. Consciousness
remains intact almost to death, there is excessive weakness of the
muscles, perhaps from a general paresis. If the patient lives long
enough, he gets wretchedly thin, and dies from marasmus. In more rapidly
fatal cases, death follows from respiratory paralysis, with or without
convulsions.
[678] Quoted by Husemann, _Vergiftung durch Wurstgift_ (Maschka’s
_Handbook_).
=The post-mortem appearances= which have been observed are--the mucous
membranes of the mouth, gullet, and throat are white, hard, and
parchment-like; that of the stomach is more or less injected with
numerous hæmorrhages: the kidneys are somewhat congested, with some
effusion of blood in the tubuli; the spleen is large and very full of
blood, and the lungs are often œdematous, pneumonic, or bronchitic.