ssAmines and Urea

Introduction




Preparation








































Properties of Amine

Properties of Amine







Aliphatic amines are always more basic than aromatic amines due to absence of resonance.




Aqueous solution of amines are basic in nature, express by following reaction. When this reacts with ferric chloride it forms red
precipitate of ferric hydroxide.





























This reaction with benzoyl chloride is also known as
Benzoylation of amines or Schowtann Bowmanns Reaction.




(viii) Reaction with HNO
2
. (Nitrosation of aliphatic amines)
When sodium nitrite reacts with H
2
SO
4
or HCl it produces nitrous acid (HNO
2
) which works
as precursor of nitrosyl cation (N
+
O) this species is known as nitrosating agents.




When any secondary amines reacts with nitrous acid, amine work as nucleophile which is
attacking at nitrosyl cation to form yellow liquid nitroso solution.




Some other examples of nitroso products




When primary amines undergo process of nitrosation, nitroso compounds formed first and
can react further and finally produce various products where alcohols are formed as major
product.




Alkyl diazonium ion is the final product of this sequence but not any other species can be
isolated. When any primary amine is converted into diazonium species, it is known as
diazotisation of amines. These are not very much stable due to positively charged nitrogen
atom which is strained species. Its decompose rapidly where molecular nitrogen is a leaving
group and carbocations are formed.




As the nitrogen free products result from the formation and decomposition of diazonium salts
so these reactions are known as deamination reactions.

















The nitrosation of tertiary alkylamines is rather complicated, and these reactions are also not
very useful in general chemistry primarilly they form addition product which breakdown on
heating and form nitrasoamine.












































When primary amines reacts with excess of alkyl halide, it quaternize the starting amines to
form quaternary ammonium salt.















Above reaction is known as Hoffmanns reaction prefer less substituted alkene,
an example of kinetically control product. If we study stereochemistry a preference of trans-
periplanar (Anti)-elimination of the H and the amine. It shows, E2 mechanism with anti
stereochemistry.




By simply quaternizing the 1 amines with an excess (> 3 equivalents) of alkyl halide is also
known as Hoffmanns exhaustive alkylation. For example













In this example anti-elimination requires loss of one of the

which is trans to the nitrogen not cis

. This can be given by chair conformation where nitrogen is axial, so above product can
formed.






















Some following conversions also explain the concept of Hoffmanns quaternary ammonium
salt





(xiv) Cope elimination
When tertiary alkylamine oxides in which one of alkyl group have

atom undergo thermal cleavage to form alkenes and hydroxyl amine.














This elimination does not require the presence of baseion, actually internal base already
present inside the system as N-oxide oxygen so intramolecular base promotes a Ei
elimination by path of a five membered cyclic transition state.














Above reaction follows syn stereochemistry for elimination exactly opposite to the anti
elimination in Hoffmanns regiochemistry. For example














Second isomeric cyclohexene is not formed because it is impossible for a ring hydrogen to
becomes syn to the amine oxide group unless the cyclohexane ring is severely distorted. Cope
elimination also form less substituted alkene same as Hoffmanns orientation.

UREA




Basic Character






First organic compound to be synthasized in lab from inorganic compounds thus discarding
Vital force theory
of Berzelius which said that no organic compound can be synthesized in lab. It was
synthesized by Wholars.














On the other hand acetic acid was the first organic compound to be synthesize from elements
in their free states.





















Urea is a monoamide of carbamic acid (NH
2
COOH) and diamide of carbonic acid
H
2
CO
3


Preparation

















Manufacture of urea





Urine contains some amount of urea so when it reacts with HNO
3

, a ppt of urea nitrate is formed which on reaction with BaCO
3

gives urea. In this process coloured impurities are removed by acidic KMnO
4

.

Properties






























Breaking of urea takes place by NaOBr but Urea on Hoffmanns Hypobromite reaction forms
N
2

, CO
2

, H
2

O and NaBr while other amides furnish amines with lower homologue. Quantitative
estimation of urea done by cleavage in the presence of urease or fission by HNO
2s






Nitrosation of aromatic amines
(b) Nitrosation of aromatic amines
When aromatic amines undergo process of nitrosation by nitrosyl cation, electrophilic aromatic substitution occurs and then nitros o
derivatives are formed. For example:



Only very strong activating group, for example aniline and its derivatives can react with very weak electrophile nitrosyl with
nitrosyl cation it resemble with secondary amines where synthesis of N-alkyl nitrosoproduct takes place.



Alkyl diazomium ions are not stable due to positively charged nitrogen atom but aryl diazonium ions are much more stable due to
resonance and can be stored aqueous solution at 0C to 5C for long periods of time and loss of nitrogen form an unstable ary l
cation and is much slower than loss of nitrogen from an alkyl diazonium ion so C6H5N
+
2
immediately reacts with chloride ion to form benzene diazonium chloride.



Here NaNO2and HCl are taken in 1 : 3 so excess chloride ion quickly reacts with intermediate otherwise electrophile C6H5N
+
2
immediately reacts with nucleophilic aniline to form coupling azo product.

Aryl diazonium ions undergo a variety of reactions which makes them versatile intermediates for the preparation of many ring
substituted aromatic derivatives for example



These reactions occur only when amino group attached directly with benzene ring but when benzyl derivatives type compounds
undergo these reactions they form normal aliphatic amines type products.



When methyl amines reacts with nitrous acid they form alkoxyalkanes as major product.

(x) Separation of 1
o
, 2
o
and 3
o
Amines