Slides 09 Chemistry Advanced Le Gresley

Amines
With Adam Le Gresley
Mohammed sofyan Alqadsi, fas.cn11@gmail.com

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Nomenclature 1
General formula: R-NH2
Nomenclature: name the longest chain alkyl group attached to the N followed by
the suffix amine. A number prefix should indicate the position of the amine on the
chain by the lowest possible number.
A substitution at nitrogen is preceded by the prefix N-
Examples
NH2
(CH3)2NCH2CH3
CH3CHCH2CH2CH3
2-pentylamine N,N-dimethylethylamine

Nomenclature 2
The substitution on nitrogen can be referred to as primary, secondary or tertiary, depending

on the number of carbons attached.
H H R H R H R R''
N N N N
H H R' R'
amonia 10 20 30

Physical and chemical properties
d+ d-
ENC = 2.550
ENN = 3.066
¨ 2
R-NH
D (Dipolar moment)
Amines form intermolecular hydrogen bonds. They can also form H bonds with H2O and as a
result amines with a linear chain shorter than 3 ( C-3) are soluble in water.
Odours: fish-like except CH3-NH2 and CH3CH2-NH2 which smell similar to NH3

Stereochemistry of nitrogen
N: sp3 hybridized
.. bond angles: 108 o

N
Pyramidal structure (common to ammonia and amines). The nitrogen is at the apex of a
pyramid and the other groups are at each apex of a triangular base.
The N is sp3 hybridized (like Csp3) but one of the sp3 position is occupied by a lone pair (2e-)

Preparation of amines
Nucleophilic substitution on alkyl halides by ammonia
RX RX RX
NH3 RNH2 R2NH R3NH
10 20 30
The highest yields are given by those substrate which favour SN2
Order of reactivity of RX = 10 > 20 > 30
Disadvantages: The reaction can give a mixture of different amines as the alkylated amine
obtained as a product is a stronger nucleophile than the starting one and can give a second
a nucleophilic substitution on the alkyl chloride.
Nevertheless, by operating in large excess of NH3 it is possible to stop the reaction at the 10
amines.

Reactivity of amines
The chemical behaviour of amines is due to the tendency of N to share its lone pair
of electrons.
We will analyse
i) basicity of amines
ii) reactivity of amines as nucleophilic agents (e.g. in SN reactions)

Basicity of amines
H2O +
R-NH2 + HCl R-NH3 Cl-
ammonium chloride
Insoluble in water if C>3 soluble in water (salt)
The R-NH3+ ion is called ammonium ion and is produced when an amine is in
presence of an acid

Alkylation of amines
RNH2 + R'X R N H + HX
R'
H
+
R N H + X-
R'
The reaction can be used to produce amines having different alkyl groups
on the nitrogen

Acylation of amines
O O
RNH2 + + HCl
R' Cl R' NHR
This is the synthesis of amide via nucleophilic substitution on a carboxylic

acid derivative

Amino acids - Structure
O
¨
H2N- + C
OH
amino group acid group

Amino acids - Structure
O
¨
H2N- C
OH
R H
H2 N a COOH
S
chiral center a - amino acids L

Zwitterion
+
NH2 NH3
H C COOH H C COO - Dipolar ions at
biological pH (7.38)
R R
a-amino acid dipolar structure
pI = isoelectric point = Ph at which the aminoacid is in the zwitterion form
NH3+ NH3+ NH2

H C COOH H C COO- H C COO-
R R R
predominant at pH = 1 predominant at pH = 7 predominant at pH = 11

Importance of amino acids
Amino acids are basic building block of peptides and proteins.
Proteins play crucial roles in practically every biological process.
R H
H2 N COOH
Haemoglobin protein Natural aminoacids (20)

Naturally occurring amino acids
Name Abbrev Formula Name Abbrev Formula

H H
Gly, G H C CO2H
Phe, F CH 2 C CO2H
Glycine Phenylalanine
(6.0) (5.5)
NH 2 NH 2
H H
Ala, A H3C C CO2H Tyr, Y HO CH 2 C CO2H
Alanine Tyrosine
(6.0) (5.7) NH 2
NH 2
H H
Val, V H3CHC C CO2H
Trp, W CH 2 C CO2H
Valine Tryptophan
(6.0) (5.9) N
H3C NH 2 NH 2
H
H H
Leu, L CH3CHCH 2 C CO2H Asp, D HOOC CH 2 C CO 2H
Leucine Aspartic acid
(6.0) H 3C NH 2 (3.0) NH 2
H H
Ile, I CH 3CH 2CH C CO 2H Glu, E HOOC CH 2CH 2 C CO 2H
Isoleucine Glutamic acid
(6.0) H3C NH 2 (3.2) NH 2
H O H
Ser, S HO CH2 C CO2H
Asn, N H2N C CH 2 C CO 2H
Serine Asparagine
(5.7) (5.4) NH 2
NH 2
H3C H O H
Thr, T Gln, Q H2N C CH 2CH 2 C CO 2H
Threonine HO CH C CO 2H Glutamine
(5.6) (5.7) NH 2
NH 2
H H
Cys, C HS CH 2 C CO 2H Lys, K H2N CH2 C CO2H
Cysteine
Mohammed sofyan Alqadsi, fas.cn11@gmail.com Lysine 4
(5.0)
© www.lecturio.de | Dieses Dokument ist urheberrechtlich geschuetzt. (9.7)
H H
Leu, L CH3CHCH 2 C CO2H Asp, D HOOC CH 2 C CO 2H
Leucine Aspartic acid
(6.0) H 3C NH 2 (3.0) NH 2
Naturally occurring amino acids H H
Ile, I CH 3CH 2CH C CO 2H Glu, E HOOC CH 2CH 2 C CO 2H
Isoleucine Glutamic acid
(6.0) H3C NH 2 (3.2) NH 2
H O H
Ser, S HO CH2 C CO2H
Asn, N H2N C CH 2 C CO 2H
Serine Asparagine
(5.7) (5.4) NH 2
NH 2
H3C H O H
Thr, T Gln, Q H2N C CH 2CH 2 C CO 2H
Threonine HO CH C CO 2H Glutamine
(5.6) (5.7) NH 2
NH 2
H H
Cys, C HS CH 2 C CO 2H Lys, K H2N CH2 C CO2H
Cysteine Lysine 4
(5.0) NH 2 (9.7) NH 2
H H 2N H
H
Met, M CH3S CH2CH2 C CO2H Arg, R N CH2 C CO2H
Methionine Arginine 3
(5.7) NH 2 (10.8) HN NH 2
H
H
H2C C CO 2H N
Pro, P NH
His, H CH2 C CO2H
Proline H 2C Histidine
(6.3) C (7.6) N NH 2
H2 H

Essential AA
These amino acids are required in the diet.
Lys, His, Ile, Leu, Met, Phe, Thr, Trp, Val, Arg
Supplied by meat and dairy products; if those are not consumed, they can be supplied
by a combination of cereal grains (wheat, corn, rice, etc.) and legumes (beans,peanuts, etc.).

Amino acids, Peptides and Proteins
Many aminoacids joined by peptide bonds form a polypeptide chain.

An aminoacid unit in a polypeptide is called a residue.
The peptide bond peptide (amide ) bond

O R O R
H2 N + OH
OH H2 N H2 N OH
N
R' O H
R' O
N terminal aa C terminal aa
A polypeptide chain has direction because its building blocks have different ends; the a-amino
and the a-carboxylic group. By convention the amino end (N terminal) is taken as the beginning
of a polypeptide chain.

Aspartame: a dipeptide
NH2
H
H2 N N COOMe
O
Ph
NH2 H2 N COOMe
H2 N OH
O Ph
aspartic acid phenylalanine methyl ester

Protein and polypetides
Longer chain peptides (Polypeptides) are called proteins

(the boundary of these definitions is a bit blurred!)
Proteins can be formed of

thousands of aminoacids residues.
human insulin (a protein)

Dieses Dokument gehört: Mohammed sofyan Alqadsi
Hinweis: Dieses Dokument ist urheberrechtlich geschützt. Die Vervielfältigung,

Verbreitung, Wieder- bzw. Weitergabe und sonstige Nutzung ist ohne die schriftliche
Genehmigung der Lecturio GmbH nicht gestattet.


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Amines

With Adam Le Gresley

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

General formula: R-NH2

A substitution at nitrogen is preceded by the prefix N-

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

The substitution on nitrogen can be referred to as primary, secondary or tertiary, depending

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

.. bond angles: 108 o

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

ii) reactivity of amines as nucleophilic agents (e.g. in SN reactions)

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

This is the synthesis of amide via nucleophilic substitution on a carboxylic

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

chiral center a - amino acids L

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

a-amino acid dipolar structure

pI = isoelectric point = Ph at which the aminoacid is in the zwitterion form

NH3+ NH3+ NH2

predominant at pH = 1 predominant at pH = 7 predominant at pH = 11

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Amino acids are basic building block of peptides and proteins.

Proteins play crucial roles in practically every biological process.

Haemoglobin protein Natural aminoacids (20)

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Name Abbrev Formula Name Abbrev Formula

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

These amino acids are required in the diet.

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Many aminoacids joined by peptide bonds form a polypeptide chain.

The peptide bond peptide (amide ) bond

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Longer chain peptides (Polypeptides) are called proteins

Proteins can be formed of

human insulin (a protein)

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

Hinweis: Dieses Dokument ist urheberrechtlich geschützt. Die Vervielfältigung,

Mohammed sofyan Alqadsi, fas.cn11@gmail.com

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