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amines pdf for neet jee aspirants
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/ 23
Quotomaryy
Guwnenivmn,
Sait
13.1 Structure_of Amines
After studying this Unit, you will be
able to
‘+ describe amines as derivatives of
ammonia having a pyramidal
structure:
+ classify amines as primary.
secondary and tertiary:
name amines by common names
and IUPAC system:
© describe some of the important
methods of preparation of amines:
= explain the properties of amin:
© distinguish between primary,
secondary and tertiary amines;
+ describe the method of prepara-
tion of diazonium salts and thelr
importance in the synthesis of a
series of aromatic compounds
including azo dyes.
Rumadttyl — Antihigtomminic
— Sunfadonk
“The chief commercial use of amines is as intermediates in the
synthesis of medicines and fibres”
Amines constitute an important class of organic
compounds derived by replacing one or more hydrogen
atoms of ammonia molecule by alkyl/aryl group(s). In
nature, they occur among proteins, vitamins, alkaloids
and hormones. Synthetic examples include polymers,
dyestuffs and drugs. Two biologically active compounds,
namely adrenaline and ephedrine, both containing
secondary amino group. are used to increase blood
plessure: Novocain, a synthetic amino compounds
used as an anaesthetic in dentistry. Benadryl, a well
known antihistaminic drug also contains tertiary amino
group. Quaternary ammonium salts are used as
surfactants. Diazonium salts are intermediates in the
preparation of a variety of aromatic compounds
including dyes. In this Unit, you will learn about amines
and diazonium salts.
I. AMINES
Amines can be considered as @erivatives of amy
obtained by replaceme all the three
hydrogen atoms by alkyl and/or aryl groups.
For example:
CH,
CH-NH,, CyH-NH,, CH-NH-CH,, CNC
Like ammonia, nitrogen atom of amines is trivalent and
carries an unshared pair of electrons. Nitrogen orbitals
in amines are therefore, sp’ hybridised and the geometry
of amines is pyramidal. Each of the three sp’ hybridised
orbitals of nitrogen overlap with orbitals of hydrogen or
carbon depending upon the composition of the amines.
The fourth orbital of nitrogen in all amines contains an
unshared pair of electrons. Due to the presence of
unshared pair of electrons, the angle C-N-E, (where E is
2015-16 C or H) is less than 109.5; for instance, it is 108° in_case_of
trimethylamine as shown in Fig, 13.1.
unshared
electron
pair
on + Pyremidal
Fig. 13.1 Pyramidal shape of trimethylamine
13.2 Classification Amines are classified_as primary (1°), secondary (2%) and tertiary (3)
aryl groups in ammonia molecule. If one hydrogen atom of ammonia
is replaced by R or Ar , we get RNH, or ArNH,, a primary amine (19.
If two hydrogen atoms of ammonia or one hydrogen atom of R-NH, are
replaced by another alkyl/aryl(R) group, what would you get? You
get R-NHR’, secondary amine. The second alkyl/aryl group may be
same or different. Replacement of another hydrogen atom by alkyl/aryl
oup leads to the formation of tertiary amine, Amines are said to b
vhen all the alkyl or aryl groups are the same, an
When they are different.
RQ RY
NH, —> » RNH,—}> N-H—> N—R"
RZ RZ
Primary(1%) Secondary(2")_—_Tertiary(3")
13.3 Vomenclature 1 common system, an aliphatic amine is named by prefixing alkyl
group to amine, i.e., alkylamine as one word (e.g., methylamine). In
secondary and tertiary amines, when two or more groups are the same,
the prefix di or tri is appended before the name of alkyl group. In
IUPAC system, amines are named as alkanamines, derived by
replacement of ‘e’ of alkane by the word amine, For example, CH,NH,
is named as methanamine. In case, more than one amino group is
present at different positions in the parent chain, their positions are
specified by giving numbers to the carbon atoms bearing -NH, groups
and suitable prefix such as di, tri, ete. is attached to the amine. The
letter ‘e’ of the suffix of the hydrocarbon part is retained. For example,
H,N-CH,-CH,-NH, is named as ethane-1, 2-diamine.
jemistry B82.
2015-16 In arylamines, -NH, group is directly attached to the benzene ring.
C,H,NH, is the simplest example of arylamine. In common system, it
is known as aniline. It is also an accepted IUPAC name. While naming
arylamines according to IUPAC system, sutflix'e’ of arene is replaced by
‘amine’. Thus in IUPAC system, C,H,-NH, is named as benzenamine.
Common and IUPAC names of some alkylamines and arylamines are
given in Table 13.1
Table 13.1: Nomenclature of Some Alkylamines and Arylamines
- oe To
i
CH,—N—CH, Trimethylamine N.N-Dimethylmethanamine
OH, -N—CH,—GH,—CH,—CH, | N.N-Diethylbutylamine || N.N-Diethylbutan-1-amine
Gu,
om
a
NICH.
‘NN-Dimethylaniline N,N-Dimethylbenzenamine
2015-16 13M erassity the following amines as primary, secondary or tertiary:
NH, N(CH),
w i (i) (C.HJ.CHNH, —(tv)(C,H,).NH
13.2 (i) Write structures of different isomeric amines corresponding to the molecular
formula, C,H, .N.
ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?
13.4 Dreparation Amines are prepared by the following methods:
of Amines 1. Reduction of nitro compounds
Nitro compounds are reduced to amines by passing hydrogen gas
in the presence of finely divided nickel, palladium or platinum and
also by reduction with metals in acidic medium. Nitroalkanes can
also be similarly reduced to the corresponding alkanamines.
NO. iypa mED
o Ethanol”
NO sneticl ae
a or Fe+HCL
—
re =
ton with CGR and roca acD ee
formed gets Jn to release bydrochlouic acid during the
reaction. Thus, only a small amount of hydrochloric acidis required
to initiate the reaction.
Ammonolysis of alkyl halides
You have read (Unit 10, Class XIl) that the carbon - halogen bond
in alkyl or benzyl halides can be easily cleaved by a nucleophile.
Cleayoge of C-2 action
bond ammonia
‘This process of cleavage of the C-X bond by ammonia molecule is
known as ammonolysis. The reaction is carried out in a sealed
(eS on (ube at 373 K. The primary gmnine thus obtained behaves as a
Aenmenolysis \d can further react with alkyl halide to form secondary
‘and tertiary amines, and finally quaternary ammonium salt.
Na eos
H, + ROX —> RNHX
Nucleophite Substituted
ammonium salt
Chemistry side
2015-16 RX,
RNH, 2S RH BS RN BS =
‘The Gee amineycan be obtained from the ammonium salt by treatment
with a strong base:
R-NH,X + NaOH —> R-NH,+ H,0 + Nax
jas the disadvantage CREED orinay.
secon amines and also a quaternary ammonium salt.
However, GEN aM Is obtained as a HABE ETE by taking
large excess of ammonia.
“The order of reactivity of halides with amines is(RIS_RBr SRCD)
le 3
Write chemical equations for the following reactions: Exar
of Reaction of ethanolic NH, with C,H,Cl.
‘Ammonolysis of benzyl chloride and reaction of amine so formed
with (vo moles of CH,CL
H Solution
HCY y CHeCh
© cna 4s oun, SS oH-cH, CHeN=CH, SES ,H,),N C1
I
Cus
Chloroethane Ethanamine—-N-Ethylethanamine _N,N-Diethylethanamine Quaternary
ammonium Salt
@) qH-cH-cl “S c.H-cH.ni, 89 ¢,4-cH-N-CH,
i
cH,
Benzylehloride Benzylamine N.N-Dimethylphenylmethanamine
3. Reduction of nitriles
Nitriles on reduction with(ithium aluminium hydride (LiAIH Jjor
catalytic hydrogenation produce primary amines. This reaction is
# 4 used for(Gecent Of anTTRe-GETTESD Lc for preparation of amines
a 4 containing one carbon atom more than the starting amine.
Hh/Ni
R-c=N RON agian
4. Reduction of amides
‘The amides on reduction with lithtum aluminium hydride yield
R-CH;NH,
amines.
a
Yow Ati
R-C~ NH, A> RCH, NH,
¢
wh
RC,
2015-16 a® c cles x :
FO”
5. Gabriel phthalimide synthesis obigrotic.
Gabriel synthesis is used for the preparation
)wou 4 Phthalimide on treatment with ethanolic potassium hydroxide forms
2) R—=< potassium salt of phthalimide which on heating with alkyl halide
is produces the corresponding primary
3) NaoriCo4) annot be prepared by this method
e=
the anion formed by phthalimide.
° °
HI cA te tI
Cw ec Ou AS — Cr
n-u Gx) ni Bek N-R
= = =
—c sc GF — c —
fi F fi
fe} oO oo
Phthalimide t i
-Alkylphthalimide
°
vor
I
cc © N20 Haq) OQ
i
°
6. Hoffmann bromamide degradation reaction
Hoffmann developed a method for preparation oGGrimary aminyby
treating an amide with bromine in an aqueous or ethanolic solution,
of sodium hydroxide. Tn this n
the amide
carbon |
\e amine so formed.
than that present in the amide.
NH, 4#{Br, + 4NaOH R-NH, + Na,CO, + 2NaBr + 2H,O
Mple 13.2 Write chemical equations for the following conversions:
(i) CH,-CH,-Cl into CH,-CH,-CH,-NH,
(i) C,H,-CH,-Cl into C,H,-CH,-CH,-NH,
Solution
( CH-CH,-cr BBancllNACN, CH cH-c=n auton, CH _CH,-CH-NH,
Chioroethane Propanenitrile Propan-1-amine
(i) = GH-CH,-cl Ethanoltle ACN Gy cH-c=n F/M, ¢.HcH,-CH,-NH,
Chlorophenylmethane Phenylethanenitrile 2-Phenylethanamine
(Benzyl chloride) (Benzyl cyanide)
Chemistry 9386)
2015-16 Write structures and IUPAC names of 3.3,
(@ the amide which gives propanamine by Hoffmann bromamide
reaction.
(i) the amine produced by the Hoffmann degradation of benzamide.
( Propanamine contains three carbons. Hence, theamide molecule must
contain four carbon atoms. Structure and IUPAC name of the starting
amide with four carbon atoms are given below:
(CH,-CH-CH,-C-NH, Butanamide
°
(i) Benzamide is an aromatic amide containing seven carbon atoms.
Hence, the amine formed trom benzamide is aromatic primary amine
containing six carbon atoms. N wy
NH, —
Aniline or benzenamine
——_—_—eee
low will you convert
() Benzene into aniline (ti) Benzene intoN, N-dimethylaniline
(4) C(CH,),-Cl into hexan-1,6-diamine?
13.5 Dhysical ‘The lower aliphatic amines are gases with fishy odour. Primary amines
with three or more carbon atoms are liquid and still higher ones are
Properties. Siid. Aniline and other arylamines are usually colourless but get
coloured on storage due to atmospheric oxidation,
Lower aliphatic amines are soluble in water because they can form
hydrogen bonds with water molecules. However, solubility decreases
with increase in molar mass of amines due to increase in size of the
hydrophobic alkyl part. Higher amines are essentially insoluble in water.
Considering the electronegativity of nitrogen of amine and oxygen of
alcohol as 3.0 and 3.5 respectively, you can predict the pattern of
solubility of amines and alcohols in water. Out of butan-1-ol and
SStoility butan-1-amine, which will be more soluble in water and why? Amines
are soluble in organic solvents like alcohol, ether and benzene. You
0 may remember that than amines and form
Qutan-t-of. > Botan. |-omingtronger intermolecular hydrogen bonds than arnines
Primary and secondary amines are engaged in intermolecular
association due to hydrogen bonding between nitrogen of one_and
hydrogen of another molecule. This intermolecular association is(morp
in primary aminetha?) in secondary amines as there are two hydrogen
slams available for hyerogen bond formation mit, Tertiary amines do
hot have intermolecular association due to the absence of hydrogen
atom available for hydrogen bond formation. Therefore, the order of
= ;
VP >a rs
2H 4 ow
yu
<
W— bonding 2015-16 [~ Primary > Secondary > Tertiary
Intermolecular hydrogen bonding in primary amines is shown in
Fig, 13.2.
—i t —
RUN-H—— NoHo NR
aH
i
ie R
a—
Won, < amine < alcohol Fig. 13.2 Intermolecular hydrogen bonding in primary amines
Aikone < anmint = leoot
Boiling points of amines, alcohols and alkanes of almost the same
molar mass are shown in Table 13.2.
Comparison of Boiling Points of Amines, Alcohols and
Alkanes of Similar Molecular Masses
Erm
Pores
1 n-C\H,NH, 350.8
ES (C,H)).NH 329.3
3. CHNCH), 310.5
4 CH,CHCH), 300.8
5 n-C,HOH, 390.3
13.6 Chemical _ Difference in electronegativity between nitrogen and hydrogen atoms and
the presence of unshared pair of electrons over the nitrogen atom makes
amines reactive. The number of hydrogen atoms attached to nitrogen
atom also decides the course of reaction of amines; that is why primary
Reactions
N N
(NH), secondary (°>N—H) and tertiary amines (> N—Jaitfer in many
reactions. Moreovec(@iRiaea veh ave a MSOPRIEDS 2 to the presence
ofunshared electron pair. Some ole eactions Oramires are described
below:
1. Basic character of amines
‘Amines, Ging basTgin nature Gace with BER) form salts.
¢ oe
7 RON +HX SRN, X (ald
. ae
iim, NH,CL
as O + HCL =
Aniline Anilintum chloride
Chemistry 9388)
2015-16 ‘Amine salts on treatment with a base Lke@eor) regenerate the
nt amin
de atts, X + OH —> RiH,+ HO +X
like This
the pon_basic organic compounds insoluble in_water.
‘The reaction of amines with mineral acids to form ammonium salts
shows that these 2 e. Amines have@n_unshared pair
clectronsSon nitrogen atom due to which th
Basic character of amines can be better understood in terms ol K
and pK, values as explained below:
a
R— NH, +H,0 == R—NH,+0H
R-nii fon]
© [R-NH, ][H,0]
R-Nx, on]
or KIH,O] =
[R-NH,]
R-Nx, on]
or = Renin]
PK, = -log_K,
Larger the value of K, or smaller the value of pK,, stronger is the
base. The pK, values of few amines are given in 7 Table 13.3.
value of ammonia is 4.75.
Table 13.3: pK, Values of Amines in Aqueous Phase
Reeser’
W Methanamine Cry-NHD 3.38 °
Qw-methyimethanamine Cay — Nery sar [ Datos
QN.w-Dimethylmethanamine Cys — cy 422
Qethanamine cH a-Ne, — Oy on 3.29
@©N-Ethylethanamine Cav -NH- GMs s>2 3.00 Prazgrre
Q©Nw-iethylethanamine “Gy —w— ets G3 3.25
(Penzenamine Ney tng 9.38
Phenylmethanamine €3y— “2 4.70
N-Methylantline nee 9.30
ANDmetvaniine Gey mone) 7@DO| sen
oa
oes => Ammonia, > Meewatic
mins
2015-16 oe
You may find some discrepancies while trying to interpret the K,,
values of amines on the basis of +I or -I effect of the substituents
present in amines. Besides inductive effect, there are other effects like
solvation effect, steric hinderance, etc., which affect the basic strength
of amines, Just ponder over. You may get the answer in the following
paragraphs
Structure-basicity relationship of amines
Basicity of amines is related to their structure. Basic ¢ ofan
amine depends upon the ease of formation of ne sation secs ting te
a proton Irom the acid’) Thmore stable the cation)is relative to the
Sone MGS ERaCT the ambit
(g@Alkanamines versus ammonia
Let us consider the reaction of an alkanamine and ammonia with
a proton to compare their basicity.
H
Mkawonin Ron: VO = RWoH
Pas
o
° i
ae 1K = + aha
Zh
Due to theGletron releasing nature it (R) pushes
towards ni thus makes the tushazed dlecron (QI)
elect
fee, availableyfor sharing with the proton of ihe
the substituted ammonium ion fc
group.
Thus, the basic nature of aliphatic amines shoul
ts stabilised
al
increase wil
+ = increase in the number of alkyl groups. This trend is followed in
| Br2 ov >NMg) =_theaeeris phase) Tre order of basicity of amines in the gaseous
fe expected order: tertiary amine > second:
phase Tollows
> primary amine > NH,. The trend is not regular in_th
state as evident by their pK, values given in Table 13.3. In the
aqueous phase, the substituted ammonium cations get(stabill
not only by electron releasing effect of the rou] ut also
OH,
a R. HOH, R
RAH on, SKC wore OH,
ti R’ “H-OH, K
On,
o 2 s
ei by sfaian “CH =MNE tense at
Chemistry 9890)
2015-16 Greater is the stability of the substituted ammonium cation, stronger
should be the corresponding amine as a base. Thus, the order of basicity
of aliphatic amines should be: primary > secondary > tertiary, which
is opposite to the inductive effect based order. Secondly, when the
alkyl group is small, like ~CH, group, there is no steric hindrance to
H-bonding. In case the alkyl group fs bigger than CH, group, there will
be steric hinderance to H-bonding, Therefore, the change of nature of
the alkyl group, e.g., from -CH, to -C,H, results in change of the order
of basic strength. Thus, there is a subtle interplay of oD
ee # the allyl group WAC
L ery t jecicles sie st ee ‘OF alkyl amines in the aqueous Stat aqueone state. The
order of basie strengiiin Case of methyl substitured amines and ethyl
. . substituted amines in aqueous solution is as follows:
2° > BS > SNMg (C,H),NH > (C,H),N > C,HNH, > NH,
a gS NM,
(b)
(CH,),NH > CH,NH, > (CH,),N > NH,
Arylamines versus ammonia
t PK, value of aniline is quite high.) Why is it so? It is because in
Trak aniline or other arylamines, the "NH, group is attached directly to
the benzene ring. It results in the unshared electron pair on nitrogen
atom.jo be in conjugation with the benzene ring and thus making
ides alse fr pronatn> If you write different resonating
structures of aniline, you will find thatCaniline)is_a resonance
hybrid of the following five structures.
‘ ‘
‘NH, NH,
WP)
0 Cc
On the other handJanilinium ionobtained by accepting a proton
can have only(two resonating Structures (kekule).
ag
NH, NH,
structures) is! ence, the proton
acceptability or the basic nature of aniline or other aromatic amines
would be less than that of ammonia) Tn case of substituted aniline, it
ts observed that electron releasing groupe like -OCH,, ~CH, increase
basic strength whereas electron withdraw electron withdrawing groups like -NO,, -SO,H,
-COOH, -X decrease it, "
13Qdy Amines
2015-16 le 13.4 Arrange the following in decreasing order of their basic strengt
C,H,NH,, CNEL, (C,H),NH. NH,
Solution The decreasing order of basic strength of the above amines and ammonia
follows the following order:
(C,H),NH > C,H,NH, >NH, > CH,NH,
2. Alkylation
Amines undergo alkylation on reaction with alkyl halides (refer Unit
10, Class XI).
3. Acylation
Aliphatic and aromatic@rimanan’ react with
acid chlorides, anhydrides and esters
This reaction is known as acylation. Yo
fs reaction as the(replacement of hydrogenyatom of -NH, or >N-H
group by the acyl group. The products obtained by acylation reaction
are known as amides. is carried out in the presence of
ia a GH
H Ye-cl ss CHENG 2Gh > CHEECH, + HCL
So 16 HO
N-Ethylethanamide
I
GH + cH-e=cl ase, cH. N —c— cH, +H—c1
\ i
CH; ° CH; 0
N-Ethylethanamine N.N-Diethylethanamide
CH,— C—O—C—CH, ——> C,H,—N —C— CH, + CH,COOH
id ri
Benzenamine Ethanofe anhydride N-Phenylethanamide
or Acetanilide
(C,H,COCD. This reaction
is Known a:
CH,NH, + C,H,COCl > CH,NHCOC,H, +HCl
Methanamine Benzoyl chloride _N - Methylbenzamide
What do you think is the product of the reaction of amines with
carboxylic acids ? They form salts with amines at room temperature.
Chemistry 9392)
2015-16 2°2 3° amin
dent show this Heaction
4. Carbylamine reaction Cisecyanide test)
Aliphatic and aromatic primary amines on heating with chloroform
and ethanolic potassium hydroxide form is yanides or carbylamines
which a ‘Secondary and tertiary amines
do not show this reaction. This reaction is known as carbylamine
reaction or isocyanide test and is used as.
R-NH, + (HCL SKOH) Hy RNC + 3KCI + SHO
5. Reaction with nitrous acid
ree classes of amines react differently with nitrous acid which is
Tine ae or rae et eo in stu from a mineral acid and sodium nitrite.
Wry halos C° bowce — () (EEMATEANDTRTC amIMesreact with nitrous acid to form@aipatie
iazonium salts which being unstable, liberate_nitrogen gas
e fuarumgarmnd posses quantitaliyely and alcohols. Quantitative evolution of nitrogen is
tum On Seqas Used in estimation of amino acids and proteins.
ae
R-NH, + HNO, N@NO+HC, fR_N,cy #29 RoW +N, + HCL
(> GESRATETARTS react with nivous acd a ow temperature
(273-278 K) to form diazonium salts, a very important class of
compounds used for synthesis of a variety of aromatic compounds
discussed in Section 13,7.
NaNO, + 2HCL + = No canbacation,
C\H, — NH, SOT TIED CoH, Nh + NaCl + 24,0
Aniline Benzenediazonium
chloride
‘Secondary and tertiary amines react with nitrous acid in_a
different manner)
6. Reaction with arylsulphonyl. chloride
which is also known as
reacts with primary and secondary amines to mov 2* Amius
form sulphonamides. es
(a) The reaction of benzenesulphonyl chloride with primary amine
iba N-ethythfiaénesulphonyl amide.
g
i
ree
to_nitrogen_in_sulphonamide is strongly
ble in alkali
n
benzenesulphonamide is ene
t
OF Cl + HON-C,H,—> ea NAc, + Hel
I
CH, é & H,
N,N-Diethylbenzenesulphonamide
139%) Amines
2015-16 Chemistry 98Q4e
Since N,_N-diethylbenzene sulphonamide @oes_not_contai
fiydrogen atomattached to nitrogen atom. nd_hencé
(c) Tertiary amines do not_react with benzenest Uphonyl chloride)
‘This property of amines reacting with benzenesulphonyl chloride
in_a_different_manner_ is used for the distinction of Pans
| Standing an errr amngsind also for the separation of a
Tixture of amines. However, these days benzenesulphonyl
7. Electrophilic substitution
You have read earlier ‘hat GERD = a resonance hybrid of (Ge)
Where do you find the maximum electron density in
these structures? Ortio- and para-positions to the -NH, group
become centres of high electron density. Thus -NH, group is ortho
and para directing and a
(a) Bromination: Aniline reacts with(bromlne_water)at room
temperature to give a white precipitate of 2,4,6-tribromoaniline.
NH, NH,
Br
B
O +3pr, Bal, 4 SHBr
Aniline Br ,
24 6-rnibromoanuine CW Ht ppt)
‘The main problem encountered during electrophilic substitution
reactions Garomatio amines fs that of their very high reactivity.
Substitution tends to occur at ortho- and para-positions. If we
have to prepare(monosubstituted_anilinelerivative, how can
the activatins =NH, group be ‘This can be
done by with acetic
anhydride) then carrying out fesired substitution followed
by hydrolysis of the substituted amide to the substituted amine.
9 °
NH, HoN-C— cH, HoN-eo CH,
(cH.co1.9 Bry Ot or Hy
“Pyridine” —- ‘CoO!
Aniline _-N-Phenylethanamide nae 4-Bromoaniline
(acetanilide) Cstearic tction)
Th n_nitrogen of acetanilide interacts
with oxygen atom due to resonance as shown below:
is al
N+ c—CH, <7 >N= c—CH,
2015-16 Hence, the lone pair of electrons on nitrogen is less available for wk
donation to benzene ring by resonance. TI
effect of -NHCOCH, group is less rou
(b) Nitration: Direct nitration of aniline yields tarry oxidation
oducts in addition to the nitro derivatives. Moreover, in the
aniline is_protonated_to foun the
That is why besides the
Significant amount of meta derivative
‘ortho and para derivatives
is also formed.
NH, NH, NH,
HNO. H.SO,, 288K. QO . OL . or
No,
1H,
(619%) a7 (2%)
However, by protecting the -NH, group by acetylation reaction
with aceti d
and th
NH, NHCOCH; NHCOCH,
{cH.cong HINO, H,S0., 288K, OHor Hy
‘Sine
wetanilide pNitoacetaniide —p-Nitroaniine
‘TD Aniline reacts with concentrated sulphuric acid
to form aniinium hydrogensulphate which _on_heating with
sulphuric acid at 453-473K produces{p-aminobenzene sulphonic)
acid, commonly known asfsulphanilic acid] as the major product.
NH, NHHSO, NH, NH,
3K 0 QO
So,H s6,
Anilinium
hydiogensuiphate -Sulphanilic acid_—_Zwitter ion
acetylation the
Lewis acid, which is used as a catalyst. Due to this, nitrogen of
aniline acquires positive charge and hence acts as a strong
deactivating group for further reaction.
1395) Amin
2015-16 _I
Note: Kich spacily na liza he to @-@ -@ -<0<®
Aqptour manna hai ® <0-@-@
@ (i) (C,HJ.N + HCL + @prtgdg WHC (Anicrhoa
13.6 Write reactions of the final alkylation product of aniline with excess of methyl Y”"Suww)
Jose iodide in the presence of sodium carbonate solution
18.7 Write chemical reaction of aniline with benzoyl chloride and write the name of
the product obtained.
13.8 Write structures of different isomers corresponding to the molecular formula,
C,HN. Write IUPAC names of the isomers which will liberate nitrogen gas on
treatment with nitrous acid
our any
te 9 [eS] er acon sauzs
2
‘The diazonium salts have the general formule(RNs X) where R stands
for anfaryl group)and(x ion may be CI Br, HSO,. BF, } etc. They are
named by suffixing diazonium to the name of the parent hydrocarbon
from which they are formed, followed by the name of anion such as
chloride, hydrogensulphate, ete. The Leon sp ad
(@oup\ For example, c,H,N.C1 is named~as (@enzenediazoniumy
chloride and C,H,N,'HSO, is known as (benzenediazonium
hydrogensulphat
(refer to
salts which ar
273-278 1). THE Stability of arenediazonium ion is explained on the
basis of resonance.
13.7 Method of Benzenedtazonium chloride is prepared by the reaction of aniline with
D, tion Bilrous acid at 273-278K. Nitrous acid is produced in the reaction
reparation’ nixture by the reaction of sodium nitrite with hydrochloric acid. The
of Diazoniun conversion of is known.
Salts as Due {o its instability, the diazontum salt isCod
7d ts Pane? wher ts preperation.
C,H,NH, + NaNO, + 2HCl 22 5,1, N,
+NaCl +2H,0
Chemistry 896)
2015-16 13.8 Dhysical _ Benzenediazonium non as aa) is It is readily
° ; repeat nage Glas cline 8) when
13.Q Chemical ‘The reactions of diazonium salts can be broadly divided into two
categories, namely (A) reactions involving displacement of nitrogen and
Reactions (B) reactions involving retention of diazo group.
A. Reactions involving displacement of nitrogen
Diazonium group being a@@ery good leaving group» is substituted
ae ee as Cl, Br I CN and ON which displace
nitrogen from the aromatic ring. The nitrogen formed escapes from
the reaction mixture as a gas.
1. Replacement by halide or cyanide ton: 7
‘ily be introduced in the benzene ring in the
reaction is calle(Sandmeyer FETC)
CuCl/HCL, acl + N,
ArN.x —{SMBH/HBES arr +N
cucn”/KCN
Se
‘ATCN +N,
Alternatively, Caf og Brome can also be introduced in the
benzene ring by treating the Mlazonfum salt solution with corresponding
hal a acid in_the presence of €opper powder) This is referred as
+ Cu/HCl, ArCl +N, + CuX
av
Xow arr +N, + CuX
‘The yield in Sandmeyer reaction is found to b¢Celtg) than
Gattermann reaction.
2. Replacement by iodide ton Cegine 1s not casi) introduced into
the benzene ring directly, but, when the diazonium salt solution
is treated with potassium iodide, iodobenzene is formed.
ArNCl+ KI—> Arl + KCl + N,
3. Replacement by fluoride ion: When arenediazonium chloride is
treated witl arene is
precipliated Which on heaung decomposes to yield aryl fluoride.
ANC + HBF, —> Ar—N,BR, 4+ Ar-F + BF,+ N,
4. Replacement _by H: Certain like
0 educe
fiazonium salts t and themselves get
phosphorous acid and ethanal, respectively.
2015-16 ACNCl + H,P0,+ H,0 —> ArH + N,+ H,PO,+ HCl
ArNCl + CH,CHOH —> ArH + N, + CH,CHO + HCl
5. Replacement by hydroxyl group: If the temperature of the
diazonium salt solution is allowed to rise upto 283 K, the salt
gets hydrolysed to phenol.
ArN.Cl + HO —> ArOH + N, + HCI
6. Replacement by -NO, group: When diazonium fluoroborate is
heated with aqueous Godium nitrite solution in the presence of
copper) the diazonium group is replaced by -NO, group.
=
CS Syn
Nc NBF,
aving
+ HBP, —> OQ
Fluoroboric
jese compounds
acid
B. Reactions involving!
are oft fenizene diazonium chloride
reacts with phenol in which the phenol molecule at its parg position is
coupled with the diazonium salt’to form p-hydroxyazobenvene. This
type of reaction is known as coupling reaction. Similarly the reaction of
diazonium salt with aniline yields p-aminoazobenzene. This is an example
of reaction.
Orn Og On) aver
Cpe : wenn, Cyne Op means
p-Aminoazobenzene
‘The azo products obtained have a
13.10 Importance From the above reactions, it is clear that the diazonium salts are very
of Diazonium S204 intermediates for the introduction of -F, Cl, -Br, -1, -CN, -OH,
-NO, groups into the aromatic ring,
Salts in nnot be prepared by direct halogenationy
Synthesis Prrochacer pectcopTle SabSOOMTOTT A luced by nucleophilic substitution of
of Aromatic chlofimeMchforobenzene but cyanobenzene Cah De casily obtajned
diazontumy sal
Compo
Compounds ‘Thus, the replacement of diazo group by other groups is helpful in
Chemistry 9398)
2015-16 preparing those substituted _aromatic compounds which cannot be
prepared by direct substitution in benzene or substituted benzene.
How will you convert 4-nitrotoluene to 2-bromobenzoie acid ? Sxample_13.5
CH, CH, v,
Br
Buy Sn/HCI © NaNo,/ticl,
SES (Taam
cats w
COOH
Cent
13.9 Convert
() 3-Methylaniline into 3-nitrotoluene.
(i) Aniline into 1,3,5 - tribromobenzene.
Summar
Amines can be considered as derivatives of ammonia obtained by replacement of
hydrogen atoms with alkyl or aryl groups. Replacement of one hydrogen atom of
ammonia gives rise to structure of the type R-NH,, known as primary amine.
Secondary amines are characterised by the structure R,NH or R-NHR' and tertiary
amines by R,N, RNR'R" or RNR. Secondary and tertiary amines are known as
simple amines if the alkyl or aryl groups are the same and mixed amines if the
groups are different. Like ammonia, all the three types of amines have one unshared
electron pair on nitrogen atom due to which they behave as Lewis bases.
Amines are usually formed from nitro compounds. halides. amides, imides, ete.
They exhibit hydrogen bonding which influence their physical properties. In
alkylamines, a combination of electron releasing, steric and H-bonding factors
influence the stability of the substituted ammonium cations in protic polar solvents
and thus affect the basic nature of amines. Alkyl amines are found to be stronger
bases than ammonia, In aromatic amines, electron releasing and withdrawing groups,
respectively increase and decrease their basic character. Aniline is a weaker base
1390) Amines
2015-16 than ammonia, Reactions of amines are governed by availability of the unshared pair
of electrons on nitrogen. Influence of the number of hydrogen atoms at nitrogen atom
on the type of reactions and nature of products is responsible for identification and
distinction between primary, secondary and tertiary amines. p-Toluenesulphonyl chloride
is used for the identification of primary, secondary and tertiary amines. Presence of
amino group in aromatic ring enhances reactivity of the aromatic amines. Reactivity of
aromatic amines can be controlled by acylation process, t.e., by treating with acetyl
chloride or acetic anhydride. Tertiary amines like trimethylamine are used as insect
attractants.
Aryldiazonium salts, usually obtained from arylamines, undergo replacement of
the diazonium group with a variety of nucleophiles to provide advantageous methods
for producing aryl halides, eyanides, phenols and arenes by reductive removal of the
diazo group. Coupling reaction of aryldiazonium salts with phenols or arylamines give
rise to the formation of azo dyes.
Exercises
13.1 Write IUPAC names of the following compounds and classify them into primary,
secondary and tertiary amines.
(i) (CH,),CHNH, (i) CHCH),NH, (ii), CHyNHICH(CH,),
(iv) (CH,),CNH, () C.H,NHCH, (vi) (CH,CH,),NCH,
(i) mBrC,H.NH,
18.2 Give one chemical test to distinguish between the following pairs of compounds.
() Methylamine and dimethylamine (i) Secondary and tertiary amines
(i) Ethylamine and aniline (iv) Aniline and benzylamine
(©) Aniline and_N-methylanitine.
18.3 Account for the following:
() pK, of aniline 1s more than that of methylamine.
(i) Ethylamine is soluble in water whereas aniline is not.
(iil) Methylamine in water reacts with ferric chloride to precipitate hydrated
ferric oxide.
(iv) Although amino group is o- and p- directing in aromatic electrophilic
substitution reactions, aniline on nitration gives a substantial amount of
m-nitroaniline
(©) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic
amines,
(vit) Gabriel phthalimide synthests 1s preferred for synthesising primary amines,
18.4 Arrange the following:
(i) In decreasing order of the pK, values:
CyH,NH,, CoH,NHCH,, (C)H,)NH and C,H,NH,
(i) In increasing order of basic strength:
C\H,NH,. CjH,N(CH),, (CgH,),NH and CHNH,
(iil) In increasing order of basic strength:
roaniline and p-toluidine
Chemistry 9400)
2015-16 13.5
13.6
13.7
13.8
13.9
(0) CoHsNHy, GjHsNHCH,, CH,CHNHp.
Gv) In decreasing order of basie strength in gas phase:
C,HNH,, (C,H,),NH, (CyH,),N and NH,
() In increasing order of boiling. point:
C,H,OH, (CH,,NH. C,H,NH,
(v) In increasing order of solubility in water:
CcHgNH,, (CH,).NH, C,H,NH,,
How will you convert:
() Ethanote acid into methanamine
(ii) Hexanenitrile into 1-aminopentane
(it) Methanol to ethanoic acid
(v) Ethanamine into methanamine
(©) Bthanoie acid into propanoie acid
(vi) Methanamine into ethanamine
(vil) Nitromethane into dimethylamine
(vill) Propanoie acid into ethanoic acid?
Describe a method for the identification of primary, secondary and tertiary amines.
Also write chemical equations of the reactions involved.
Write short notes on the following:
() Carbylamine reaction (ii) Diazotisation
(it) Hofmann’s bromamide reaction (iv), Coupling reaction
() Ammonolysis (wi) Acetylation
(vi) Gabriel phthalimide synthesis.
Accomplish the following conversions:
W) Nitrobenzene to benzole acid
(i) Benzene to mbromophenol
(iil) Benzoic acid to aniline
(iv) Aniline to 2.4,6-tribromofluorobenzene
(©) Benzyl chloride to 2-phenylethanamine
(si) Chorobenzene to p-chloroaniline
(vil) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(tx) Aniline to benzyl alcohol
Give the structures of A, B and C in the following reactions:
(1) OFCHat 8 A age? BOM ©
(8) CgHN,CI—E 4 q—HOM 5 pyc
(i) CHCH,Br—22 5 aH 4p IB 5
(iv) CoHigNO, UCL, MNO, 5 HOV
(v) CH,COOH “5 A —_S28"_, p__ANO INA
ey tc xo, tion
(vi) CgHgNO, P2421 A P25 BSAC
1AQly Amines
2015-16 13.10 An aromatic compound ‘A’ on treatment with aqueous ammonia and heating
forms compound ‘B’ which on heating with Br, and KOH forms a compound ‘C°
of molecular formula C,H,N. Write the structures and IUPAC names of compounds
A, B and C.
13.11 Complete the following reactions:
() CyHgNH, + CHG, + ale.KOH >
(i) CgHgN,Cl+H,PO, + H,0 >
(it) CgHNH, + H,S0, (cone) >
(iv) CgHgN,Cl+ C,H,OH
(©) CyHgNH, +Br,(aq) >
(i) CoHgNH, + (CH,CO),0 >
(wit) CgHgN,Cl—
GRO, /05
13.12 Why cannot aromatic primary amines be prepared by Gabriel phthalimide
synthesis?
13.18 Write the reactions of (i) aromatic and (ti) aliphatic primary amines with nitrous
acid,
13.14 Give plausible explanation for cach of the following:
(i) Why are amines less acidic than alcohols of comparable molecular masses?
(ii) Why do primary amines have higher boiling point than tertiary amines?
iii) Why are aliphatic amines stronger bases than aromatic amines?
Answers to Some Intext Questions
13.4 (i) CyHjNH,< NH, < C,H,CH,NH,
(i) CgHgN,Cl+H,PO, + H,0 >
(it) CgHNH, + H,S0, (cone) >
(iv) CgHgN,Cl+ C,H,OH
(©) CyHgNH, +Br,(aq) >
(i) CoHgNH, + (CH,CO),0 >
(wit) CgHgN,Cl—
GRO, /05
13.12 Why cannot aromatic primary amines be prepared by Gabriel phthalimide
synthesis?
13.18 Write the reactions of (i) aromatic and (ti) aliphatic primary amines with nitrous
acid,
13.14 Give plausible explanation for cach of the following:
(i) Why are amines less acidic than alcohols of comparable molecular masses?
(ii) Why do primary amines have higher boiling point than tertiary amines?
iii) Why are aliphatic amines stronger bases than aromatic amines?
Answers to Some Intext Questions
13.4 (i) CyHjNH,< NH, < C,H,CH,NH,