Cyanic acid
Cyanic acid
Cyanic acid,
HNCO. Urea, on dry distillation, gives cyanuric acid:
3CO(NH2)2 ⟶ H3N3C3O3 +
3NH3
Cyanuric acid
is a colorless, crystalline solid, not very soluble in water, and is strongly
acid, reacting as a mono-, di- and tribasic acid. It has a cyclic structure (a triazine
derivative) and X-ray analysis indicates that the acid is best represented as a
resonance hybrid.
When cyanuric
acid is heated, it does not melt but decomposes into cyanic acid vapour which,
when condensed below 0oC, gives a colorless condensate:
H3N3C3O3 ⟶ 3HNCO
Cyanic acid
is a colorless, volatile, strongly acid liquid which above 0oC, readily
polymerises to cyanuric acid and cyamelide, (HNCO)n. Aqueus
solutions of cyanic acid rapidly hydrolyse to give carbon dioxide and ammonia:
HNCO + H2O ⟶ CO2 + NH3
There are
two possible structures for cyanic acid, H-O-C=N and H-N=C=O. There is
very little evidence for the existence of the former (cyanic acid), e.g.,
infra-red absorption spectra indicate the litter (isocyanic acid).
When a
solution of potassium isocyanate (usually called potassium cyanate) and
ammonium sulphate is evaporated to dryness, urea and potassium sulphate are
obtained, the urea being formed by the molecular rearrangement of the
intermediate product ammonium isocyanate:
NH4NCO ⟶ CO(NH2)2
Cyanic acid
reacts with alcohols toform urethans; excess fo cyanic acid converts urethans into
allophanates, which are esters of the unknown acid, allophonic acid, NH2CONHCO2H.
ROH +
HNCO ⟶ NH2CO2R (HNCO) ⟶ NH2CONHCO2R
N-substituted
urethans are formed bythe reaction between alkyl or aryl isocyanates and an
alcohol. Phenyl isocyanate is also used to characterize primary and secondary
amines, with which it forms substituted ureas.
Phenyl isocyanate
is usually prepared by the action of carbonyl chloride on aniline:
C6H5NH2 + COCl2 ⟶ HCl + C2H5NHCOCl
(Heat) ⟶ HCl + C6H5NCO
This is a
general method for preparing isocyanates; another general method is the Curtius
reaction.
Di-isocyanates,
e.g., hexamethylene di-isocyanate, OCN(CH2)6NCO
are used to prepare polyurethane plastics by reaction with di- and
polyhydroxyalcohols, e.g., tetramethylene glycol:
HO(CH2)4OH +
OCN(CH2)6NCO
+ HO(CH2)4OH + …. ⟶
HO(CH2)4OCONH(CH2)6NHCOO(CH2)4O-….
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