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SEXIER : CYANURIC CHLORIDE AXD CYANURIC ACID. 3 11

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XXX.-Contributions to the History of Cyanuric Chloride and

G y ~ n u r i cAcid.

M.D.
By ALFREDSENIER,
RECEX'T experiments on cyanuric acid and melamine have shown
beyond much doubt that these substances are normal, and not is0 in
their constitution. Nevertheless, it seemed interesting to extend the
data upon which this view rests by the preparation and study of other
syanuric derivatives. With this object, I have investigated the action
of cyanuric chloride on the salts of various organic acids.
Podium Acetate.-If this salt be heated with cyanuric chloride in a
closed tube for eight hours at loo", a reaction takes place, and on
opening the tube the characteristic odour of acetyl chloride is per-
ceived. By treating the conteuts of the tube with cold ether, the
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312 SENIER: COKTRIBUTIONS TO THE HISTORY O F

acetyl chloride is readily dissolved, whilst any unchanged cyanuric

chloride, being but sparingly soluble, remains for the greater part
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with the residue. By repeated washing with hot ether, the whole of
the cyanuric chloride can be removed and a yellow residue is left,
mostly sodium cyanurate. This when dissolved in water gives, on
the addition of hydrochloric acid, a crystalline precipitate, which
readily responds to the cnprammonium test for cyanuric acid.
The reaction, therefore, is quite different from what was expect,ed.
It was hoped that a, triacetyl cyanurate would be formed thus :-
+
C3N3C13 3C2H30*ONa= CaN3(O*C2H30), 3NaC1, -+
instead of which the following took place :-
c3N$& + 3C2H30*ONa= C,N,(ONa), +3C2H30C1.
By converting the acetyl chloride into acetic acid, and finally into
silver acetate, the proportion formed was ascertained to be 22.5 per
cent. of the theoretical yield.
Between silver acetate, in place of sodium acetate, and cyanuric
chloride, no reaction was observed, and in the same manner cyanuric
acid itself conld not be induced to act on acetic anhydride.
Sodium Formate.-This salt behaves in a, manner similar to the
acetate. On opening the tube a gas is evolved, which on examination
was found to be carbon monoxide, whilst the rcsidue contains cyanuric
acid in abundance. Apparently formyl chloride is produced in the
first instance, immediately, however, breaking down into carbon
monoxide and hydrochloric acid. The reaction is therefore -
+
C3N3C13 3CHO*ONa = C3N3(ONa)3 3CO + +8HC1.
Sodium Benzoate.-In the benzoyl series, the same general reaction
takes place, but whereas in the previous instances it was only partial,
here 88 per cent. of the theoretical yield of benzoyl chloride is
obtained. The reaction is expressed by the following equation :-
+
C3N3C13 3C7H,0*ONa = C3N3(ONa), 3C7H50C1. +
Action of Cyanuric Chloride on Benzamide.-In the hope of obtaining
a,benzoyl substituted melamine, cyanuric chloride and benzamide were
heated in a closed tube for eight to ten hours at 100". It was thought
possiblo that instead of the desired action melamine and benzoy i
chloride might be formed. But on opening the tube, there was a
distinct odonr of bitter almonds, and treatment with cold ether
yielded abundance of an oily liquid having the character of benzo-
nitrile, and easily converted into benzamide by treatment with con-
centrated sulphurie acid. The residue in the tube was almost pure
cyanuric acid. The following action, therefore, had taken place :-
+
C3N3C& 3CsHs*CONH, = CsN3(OH)3 + 3C6H5.CN +
3HC1,
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CYASTJRIC CHLORlDE AND CYAKURIC ACID. 31 3

Notably, the cyanuric chloride, acting like phosphorus penta-
chloride, takes away water from the amide, leaving the nitrile, while it
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is itself resolved by the liberated water into cyanuric acid and

hydrogen chloride.
Action of Benzoyl Chloride on Xilver Cyanurate.-While I wzts
engaged in these experiments, J. Ponomctrew's "Zur Frage iiber die
Constitution der Cyanursaiire " appeared (Ber., 18,3261), in which
the author describes triacetyl cy anurate, one of the substances which
I was seeking. It is obtained by the action of the acid chloride cn
silver cyanurate. By this elegant method, i t seemed easy to prepare
the other acid derivatives, and, in fact, it has already given me tlie
corresponding t r ibenzoy1 cyanurate.
Benzoyl chloride has no action on silver cyanurate in the cold, but
by heating a mixt'ure of the two in theoretical prcportions, in closed
tubes, for eight to ten hours at loo", an action takes place, and on
opening the tube much of the odour of the benzogl chloride is found
to have disappeared. The contents are extracted with boiling
chloroform, which on evaporation gives a crystalline precipitate repre-
seuting 25 to 30 per cent. of the theoretical yield. This recrystal-
lised from chloroform, gives colourless needles of tribenzoyl cyanurate,
G3N3( OC,H,O), = CZ4H15N306, which requires-
Experiment.
Theory. ,-7
- A
f--h- 7 I. 11.
C, ........ 288 65.31 65.32
H15 ........ 15 3.40 3-86 -
N3 .........
42 9.52 - 10.23
Os ......... 96 21-77 -
--
441 100.00
The new compound shows no distinct melting point, being decom-
posed on heating. It is but sparingly soluble in chloroform, and
insoluble in ether. By heating with water, it is converted into
cyanuric and benzoic acids, this being effected very readily if the sub-
stance is enclosed in a tube with water and heated for a short time at
100". This behaviour with water, which Po-nomarew observed to
occur in an analogous manner in the case of the acetyl-derivative,
chamcterises this class of compound as mixed anhydrides.
In conclusion, I may mention that two experiments were instituted
to obtain two cyanuric nuclei joined to each other. Cyanuric chloride
was brought together, in closed tubes, with melamine, and also with
silver cyanurate, but no reaction took place at temperatures from 100"
to 250".
Un iuersity Lnborntoy,
Berlin, February, 2886.