Russian Journal of Coordination Chemistry, Vol. 28, No. 5, 2002, pp. 301–324. Translated from Koordinatsionnaya Khimiya, Vol.

28, No. 5, 2002, pp. 323–347.

Original Russian Text Copyright © 2002 by Seifer.

Cyanuric Acid and Cyanurates

G. B. Seifer
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 117907 Russia
Received April 17, 2001

Abstract—A review of studies concerned with an interesting group of compounds of cyanuric acid, which is
an intermediate between inorganic and organic compounds, is given. A first attempt is made to generalize and
systematize all the known compounds of this acid. The syntheses, IR studies, thermal decomposition, and the
mechanism of thermal conversion of the cyanuric acid salts are considered. This review may prove of interest
for the researchers working in different fields, chemical engineers, students, post-graduates, and teachers of
higher schools.

The organic derivatives of cyanuric acid find wide type are commonly known; therefore, we shall discuss
industrial application today, which, unfortunately, does the reactions of the second type.
not apply to its inorganic salts due to the lack of system-
In the presence of strong acids, hydrocyanic acid
atic studies on metal cyanurates. This fact, undoubt-
undergoes trimerization
edly, hampers their wide use.
The composition of cyanurates includes the S-triaz- H
ine ring formed as a result of trimerization of the C
N N
cyanato groups. Therefore, before we consider cyanuric 3H–C≡N ,
acid and its salts, we shall briefly discuss some ques- HC CH
tions in the chemistry of cyanides that are common to N
many classes of cyanogen anions. to give a ring similar to the benzene ring [2]. The
The free hydrocyanic acid HCN gives two types of obtained compound was called, in organic chemistry,
derivatives [1] since it has two tautomeric forms: symmetric 1,3,5-triazine or S-triazine. Thus, the pres-
ence of a triple bond in the cyano group predetermines
H–C≡N → H–N=C: its capability of polymerizing [3].
nitrile form isonitrile form
The synthesis conditions specify the particular form The cyano group is contained in different cyanate
that enters into a reaction. The acid itself mainly con- anions [4] that can also involve chalcogen atoms: cyan-
sists of the nitrile form (~99%) with 1% of the isonitrile ate (OCN–), isocyanate (NCO–), fulminate (CNO–),
form as an admixture. thiocyanate (SCN–), isothiocyanate (NCS–), selenocy-
Cyanides or nitriles are the most studied derivatives of anate (SeCN–), and tellurocyanate (TeCN–). The poly-
these two forms. The first name usually refers to the salts merization of HOCN gives cyanuric acid, while that of
of inorganic cations, while the latter name is applied to the HSCN yields thiocyanuric acid.
derivatives with organic radicals. As to the derivatives of The free cyanic acid HOCN has low stability. Like
the isonitrile form, the best studied of them are the organic hydrocyanic acid, it readily polymerizes in an anhy-
isonitriles, whereas the salts are only poorly studied. drous state to give a mixture of cyanuric acid and
The electronic structure of hydrocyanic acid cyamelide at room temperature [5–7]. The ratio of the
+ – components in the mixture greatly depends on the tem-
H [ :C≡N: ]
+ –
H–C≡N: H–C=N: perature. Thus, below 0°C, cyanic acid spontaneously
:

enables two types of reactions, namely, dissociation transforms into cyamelide, whereas above 150°ë, only
resulting in salt formation and addition reactions occur- cyanuric acid is formed. This can be explained by the
ring at the triple bond C≡N. The reactions of the first fact that cyanic acid has two tautomeric forms [8, 9]:

H
O
NH NH C
N N
O C O C O 0°C
H–N=C=O H–O–C≡N
150°C .
HO C C OH
N
cyamelide isocyanic acid cyanic acid cyanuric acid

1070-3284/02/2805-0301$27.00 © 2002 åÄIä “Nauka /Interperiodica”

302 SEIFER

At low temperatures, the polymerization of cyanic The entropy changes and the heat effect of the HCN
acid occurs due to the cleavage of the double bond polymerization are calculated in [22], while the mag-
C=O. As the temperature is increased, this process netic anisotropy and the charge delocalization in S-tri-
occurs through the rupture of the triple bond C≡N. In azine are considered in [23]. The IR spectrum of the
the latter case, a S-triazine ring is formed that is incor- polymerized HCN is given in [3] (ν, cm–1): 3450, 3370,
porated in the composition of many cyanuric com- 3314, 3260, 3219, 3184 ν(NH2); 2222, 2172 ν(C≡N);
pounds of the C3N3X3 type (where X = OH, H, Hal, R, 1648, 1611 δ(NH2); 1624 ν(C=N); 1249 δ(NH2).
OR, SR, SH, NH2, N3, CN, NH–NH2). Thus, cyanuric Cyanurcyanide or hexacyanogen C3N3(CN)3 forms
acid C3N3(OH)3 (or H3C3N3O3) appears to be the ances- during the thermal decomposition of the substances
tor of this class of compounds that can be treated as its (such as AgCN or Hg(CN)2) that proceeds with the evo-
derivatives. For example, cyanuramide C3N3(NH2)3 lution of large quantities of free cyanogen. In this case,
(also called melamine in industry) is the triamide of cyan- the major portion of cyanogen rapidly polymerizes into
uric acid, while cyanuric chloride C3N3Cl3 is its acid brown and thermally stable paracyanogen (CN)x, while
chloride. The complete hydrolysis of these compounds the remaining portion removed as (CN)2 polymerizes
always gives cyanuric acid. At the same time, the deriva- on cooling into colorless monoclinic crystals of cyanur-
tives of cyanuric acid are mainly produced not from cyan- cyanide that melt at 119°ë [24, 25]. The boiling point
uric acid but via the polymerization of the nitrile groups of C3N3(CN)3 was found to be 262°C at 771 mmHg.
due to the cleavage of their triple bond C≡N. This substance is isolated from benzene solution in the
The cyanuric acid derivatives containing the S-triaz- form of a solvate with two benzene molecules.
ine ring (C3N3) are considered to be promising com- Cyanuric chloride or cyanuric acid trichloride
pounds for the synthesis of complexes. In terms of their C3N3Cl3 [26–31] forms white monoclinic crystals with
capability of forming complex compounds, the cyanate a pungent odor. Its vapors are very toxic and harmful to
anions can be arranged in the following order [10–15] the eyes and olfactory organs. Their maximum permis-
(atoms bonded to the central atom of the complex are sible concentration (MPC) in air is 0.1 mg/m3 [32]. The
underlined): SeCN– < SCN– < OCN– < H2O < NCO– < boiling point of the compound is 190°ë at 720 mmHg;
NCS– < NCSe– < CH3CN < NC– < NH3 < RNC < CNO– < its density is 1.32 g/cm3. The authors of [30, 33]
CN–. The ligand in the cyanuric acid complex is bonded reported different melting points of C3N3Cl3. Today, the
to the central atom through the nitrogen atom of the S- C3N3Cl3 crystals are believed to melt in the interval of
triazine ring. Therefore, one can suppose that, accord- 146–146.5°C [34].
ing to their field strength, the cyanuric acid derivatives Cyanuric chloride dissolves poorly in water. How-
and its anions will be arranged in this series to the right ever, when its aqueous solution is allowed to stand or is
of H2O but to the left of NH3; i.e., they are supposed to heated, it undergoes hydrolysis to form cyanuric acid:
be moderate-field ligands.
The introduction of cyanuric cycles into complex C 3 N 3 Cl 3 + 3H 2 O = C 3 N 3 ( OH ) 3 + 3HCl.
compounds seems to be a promising direction of inves- Thus, cyanuric chloride can be regarded as the oxy-
tigations, since the complexation can noticeably change chloride of this acid. On the contrary, cyanuric chloride
the ligand properties. Unfortunately, this question dissolves readily in organic solvents (acetone, chloro-
remains open. Only one paper [16] is available today form, benzene). It crystallizes from benzene as the
that is devoted to the complexing properties of herbi- crystal solvate C3N3Cl3 · 2C6H6.
cides of the S-triazine series.
This compound is one of the most important deriva-
There are several methods of preparation of the cya- tives of S-triazine and is widely used in nucleophilic
nuric compounds C3N3X3, but the most frequently used substitution reactions to produce a great variety of sub-
technique is the polymerization of the XCN nitriles. stances containing cyanuric rings. The chlorine atoms
Depending on the nature of the X atom at the cyano in cyanuric chloride are very mobile and are replaced in
group, the polymerization reaction can occur either succession, which makes it possible to synthesize
spontaneously or with heating or even with a catalyst. mono-, di-, or trisubstituted derivatives. However, the
Cyanurhydride or the S-triazine C3N3H3 forms as a replacement of the chlorine atoms by other atoms or
result of the hydrocyanic acid polymerization catalyzed groups is gradually hampered such that the third chlo-
by hydrogen halides (HCl, HBr, HI). The polymeriza- rine atom is replaced with difficulty. Cyanuric chloride
tion of HCN in the presence of HCl occurs in solutions reacts with different nucleophiles: alcohols, phenols,
even in the cold [17] to give sesquihalides with the naphthols [35, 36], ammonia, and organic amines [37].
empirical formula 2HCN · 3HHal [18]. The products of the partial replacement of organic
It was established in [19–21] that sesquihalides con- amines were used to obtain amidohydrides [37].
tain a S-triazine ring that forms upon the removal of Cyanuric chloride that has lost one chlorine atom
HHal as follows: can enter into the composition of polymers. Thus, the
2 [ C 3 N 3 H 6 Cl 3 ] ⋅ 3HCl organotin compound {Me2SnH(C3N3Cl2}3 has the
structure of a polymer, which was confirmed by X-ray
–3HCl
2 [ C 3 N 3 H 3 ] ⋅ 3HCl –3HCl
2C 3 N 3 H 3 . diffraction analysis in [38].

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 5 2002