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168 views24 pagesAmines MASTER NCERT Class 12
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© © All Rights Reserved
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CHAPTER
13
Amines
A Quick Recapitulation of the Chapter
1. Amines are the derivatives of ammonia obtained by replacing either 096, two or three H-atoms by alkyl or aryl
groups.
2. Inccommon system of nomenclature, an aliphatic aminé & hamed by prefixing alky! group to amine, Le. akylamine
In IUPAC system, amines are named as alkanamings
In amines N-atorn is sp*-hybridised while geometiy'is pyramidal Nuc tn presence af unshared pair of electrons, the:
angle C—N—E (where, EC or H) is less than 1096". i, 108°
ue to presence of ane pair on N-atom which v
4, Preparation
vey ean donate, amines act as nucleophile.
Ano, SwiOlo Fetiot
‘or HP o Lin jae
(KOHIa)
WRK
o>
(@ H* or OHTH20/4
ax Masri ar Gabriel-phthalimide synthesis Peirie
‘Hofmann ammionoWais method [anes]
nen toed leaa / |
‘Menus feaction Be KOH .RCONH, (gives amine having one
a “Amide C-atom less than amicie)
CON; 7/ Sa Hoimann bromamids:
5, Order of reactivity of halides with NH, is R—1> R—Br>R—Cl> RF.
6. In gaseous phase, ofdler Bf Basicity of amines is 3°-amine>2°-amine> 1?-amine> NH,
In aqueous phase, order of basicity of amines is (CH)p NH> (C2H.)y N > CHeNH>NH and
(CHs)2NH> CH3NH, >(CHs)3N> NH,
7. Distinction between 1°, 2° and 3° amines
Hinsberg test
Cyc | |ns
ts. cyresomnun HOH [Link]
(Soibiem sh)
oy
ate agee [PIE CoMESOAN,
aa
ia)
No reaction 364 Master The NCERT CHEMISTRY Vol-!)
8. Carbylamine test
ANH + CHCl, +3KOH M5 RNG +9KCI43H,0
This reaction does not show positive results for secondary and tertiary amines.
2. Chemical properties of amines f= alkyl or aryl group
ANH, MOH gor HO. -AINHOOR
ar, ary
i, lr, ree onsen
‘ANHCOPn oe NOCH Bendere dazor
worn ae trance
wwe fio PSOE psa
ne (tinsbeo te
NH / Ne
B. Br
Noy
& Nop
FOH + Net Heo he,
Sinperten
nH
sux
10, Nitrous acta test
‘Aromatic primary amine + Bentzenédlazonium salt
Aliphatic primary aming + Alcohols
Secondary aliphatic and aromatic amie — N-ityosamines (yellow oly compound)
Tertiary aliphatic erties > Nite salts (water soluble)
11, Diazonium Salts
CiHGNHet Nanos HHO) —GHANOr —+NaGl + 2,0.
‘nin owmesesmm te
12, Chemical properties of diazonium salts
may eee
Abs cove
BBY Ne caccen | AN
BP icu “
BE (SS owes
9) cana
Als. tt
any BEI
Anan Sti |
aos
13, Azo dye test Only primary aromatic amines give this test, Objective Questions Based on NCERT ‘Text
Topich
General Characteristics of Amines
1. Which of the following options is‘are correct for
(a) Amines are derived by replacing one or more H-atoms
of ammonia molecule by alkyLary group(s)
(6) In nature, they occur among proteins, vitamins,
alkaloids and hormones
() Synthetic amines are polymers, dye stuffs and drugs
(@) Allofthe above
2. Which of the following compounds contain secondary
amino group?
(ob Adrenaline (0) Novae
(© Benady (@Noneot hee
3, Which one ofthe following sare the dervative(s) of
(@) CN 0 (Oyns
(©) CH NUCH, @) AlLof these
4, The hybridisation and geometry of amines are sp"
and pyramidal respectively because
(@) divalent N-atom —_(b) trivalent N-afom
(©) monovalent N-atom —_(d)tetravalent N-atom
5. The figure of trimethylamine is giyen below.
~ CH
OH,
thy
7
Select the cornet option regarding above figure.
(@) Three sp -tybriised obits of nitrogen overap with
exbials of hydrogen or carbon depending upon the
composition ofthe ainines
(©) The fourth orbital of nitrogen in amines contain an
unshared pai of electrons
{won a) ana
(6) None ofthe above
6. What isthe bond angle of C =N—E (E=C or H) in
case of trimethylamine?
(a) 1095
(©) More than 109.8"
(©) 108"
(@) More than 108°
7. Ifoné H-atom of ammonia is replaced by alkyl group,
the amine thus obtained is known as,
(@) secondary amine
(©) primary amine
(©)teriary amine
(@) quatemary amine
8 Select the quatemary ammonium compound from the
given options.
(a) Trimetnylphenyl ammonium bromide
() Tribonsylamsine
(6) Dibenzylamine
(d) None ofthe above
9. IUPAC name of HN — CH, — CH, — NH, is
(2) etban-1, 3-diamine
() ethan-1, 2-diamine
(6) etbyn-l,2, diamine
(4) ethen-1, 2, diamine
NH
10, What is the common name of 2
(@) Aniline (©) Benzenamine
(6) Told (@) None ofthese
LL. What is the IUPAC name of
HCV Cy —f_CH?
H CHy cH,
() 2-4N-methylamino)
(6) 5.-methyiamino)
(6) 4(N-amethy amino)
(@) 4(N-methylamino)
-methylpentane
4-dimethybutane
-dimetbylbutane
methylpentane 366
Master The NCERT CHEMISTRY Vol-
TopicR)
Methods of Preparation of Amines
12.
13,
4,
15.
16.
17.
18,
In the given reaction,
oo
Which of the following reagents is/are used ?
(@) H,/Pé,ethanol ——b) Sn+ HCL
(©) Fe +HCl (@) Allotthese
‘The alkyl or benzyl halide on reaction with an
ethanolic solution of ammonia yield a product via
(2) nucleophilic substitution reaction
() electrophilic substitution reaction
() nucleophile addition reaction
(@) clectophilic adtion reaction
Select the correct statement(s) about ammonolysis,
(a) Itis the process of cleavage of the C—X bond by the
ammonia molecule
(6) This eatin is carried out in an open tube at 373 K
(©) Both (a) nd)
(6) None ofthe sbove
In the given rection,
NH, +2¥ —> RNH, 25 2,NH
1, anne xp
er
Select an appropriate statement(s) abgit the Feaction.
{@) Inthis reaction, NIT et a a meleopile
(©) Inthis ection, RY ste acleopile
(6) R/NP.X™ is alld quaternary ammonin salt
(@) Both @ and (o)
Inammonolysis, primary amine Wabtained as a major
product by taking
(2) large exces of aly Halide
(©) large exces of arumonia
{©) Both (a) and (o)
(6) None ofthe above
‘What is the coteot order of re
(@) RCI> RBr> RE (6) RI> RBr> RCI
(©) RCI> Rl> RBr——(d) RU> RCI> RB
Which of the following eagent is required by the
following eonveisin?
ColHsCH;C—> CCH, CH,
CH;
(©) [Link],
(@) CH,[Link],
tivity of halides with
(2) CHNH, CHC
(©) NH,,CHSC
19. Which of the following reaction is used forthe
preparation of amine having one C-atom more than
the starting material?
(a) Reduction of nitriles
(6) Reduction of aides
(6) Reduction of nitro compourds
(@) Allof the above
20. For the conversion,
RCN > RCH;NH
Select the correct option(s)
(@) This aa oxidation reaction
() Reagents used inthis reaction is LiAIH, Hy /Ni,
Na(llg) /CHLO1.
(0), This reaction is used to decrease the number of C
(@) Allofthe above
21. Whielt of the following product is formed in the given
reaction?
@uam,
R-OONH, ~apit0
(@) RNH, (b) [Link];
(©) RCHCHANT, (@ RON
22, In the given reaction,
one
‘COOCH;
‘What would be the final product formed?
f
0
t
‘What would be the side produets formed with primary
amine in the ofan bromamide degradation
reaction?
(3) Na,CO, + NaBr
(b) Nabi + 11,0+ NaOH
(©) NaBr +10 +8a,00,
(@) Bry +H,0+Na,CO,
(0) BeyNs0H,
wa
23, CHAPTER 13: Amines 367
24. Which of the following statements is/are rue about Hofinann bromamide reaction?
(2) In this reaction, migration ofan alkyl or aryl group takes place from nitrogen atom of amide to the carbonyl carbon
(©) The amine so formed contains one carbon more than that present in the amide
() Wis the degradation reaction
(@) None ofthe above
25, Identify 4 and B in the following reaction,
°
ms HyP a.
Ke, 4 HM, p
on
Topic Bl
a
°
CN CHNH
@
° ° 9
cn CHNH I cN
‘CHNHy
© @
a
°
i CH:NH
N
wo
Physical and Chemical Properties of Amines
26. Choose the correct alternate from the
following.
(2) Lower aliphatic amines are soluble in Water
(0) Solubility decreases with increase in
molar mass of amine
() Higher aliphatic amines are insoluble in
water
(@) Alot the above
Which of the following statements isfire
incorrect?
() Higher amines are jsoluble in water
(0) Electronegativity of nitrogen in amine
and oxygen in aleohol is 3.5 and 3.0,
respectively
(6) Amines are solublein organic solvents
(@) Both (a) and (©)
28. Choose the correct order of the boiling point
27.
of amines,
(a) Primary > secondary > tertiary
(Uy Sevendany > esiny > prsnary
() Tertiary > primary > secondary
(@) Tertiary > secondary > primary
29. Regarding the given figure,
Which ofthe following statement is truc?
(@) Intramolecular hydrogen bonding present in primary amines
() Intermolecular hydrogen bonding present in primary amines
(6) Intramolecular hydrogen bonding present in secondary amines
(@) Intermolecular hydrogen bonding present in sevondary amines
80. The correct order of increasing boiling points for the bases,
(CH NH, (CH) NH, (CHy)3N is
(@) CH,NHy < (CH, pNH< (CH, ),N
() CH,NIL, <(CH, yN = (CH), NIE
(6) (CH, )N < (CH ), NH < CHNHy
(@) (CH,),N () > > a
(6) > I> 1 @ Ibm
40. The correct order of the basic strength of amines in
aqueous medium is
(0) GH NH, > (CH 5): NH> (GH4)sN
(©) GQHNIG> (GH, }N> (GH s)2NET
(6) (GH, ).NH> (CH, ),N> CQHSNHy
() (CH )pNH> CH NH > (CH)
41. Aniline is more stable than anilinium ion because
(@) it has more resonating structures than anilinium ion
(©) it has less resonating structures than anilinium ion
(6) ithas more m-bonding than anilinium ion
(4) None of the above
42, Which of the following group (s) increases basie
strength of substituted aniline?
() —ocH, cH,
(©) “S0sH1 (@) Both (a) and (b) 48. Which of the following statements is/are true?
() Primary and secondary amines react with acid
chlorides, anhydrides and esters by nucleophilic
Substitution reaction
(©) In the acylation reaction of amines there is
replacement of hydrogen atom of NH or NH group
by the acyl group
() The products obtained in acylation reaction of amines
(@ Allofthe above
44, N-methylbenzamide is formed when methanamine
reacts with benzoyl chloride. This reaction is
known as
() benzoylation
(b) Hinsherg test
{) Schmidt reaction
(@) Curtus reaction
45, Which of the following statements is/are true?
(@) Aromatic amines eact with nitric acid to form
diazonium sal
(6) Formation of diazonium salts occur at high
temperature
() Side products formed during the formation of
benzenediazonium chloride are NaCl and HO
molecules
(@) Allofthe above
46. Name the product(s) formed during the reaction of
primary aliphatic amines with nitrous acid a€ room,
temperature?
(a) RNS
(©) ROW
(6) Both (a)and (b)
(@) None ofthe above
47. N, N-diethyl benzene sulphonamide is not acidic
because
(@) Ht does not contain unshar palP OF eletfon on
Neato
(©) It does not contain H-stomt With the N-atom
(6) It contains OH group with N-atom
(@) None of the above
48. Which ofthe following teactions is/are electrophilic
substitution?
(@) Bromination oF aniline
(©) Nitration of aniline
(6) Sulphonation of anitine
(8) All ofthe above
49. NH, group in the aniline is activating grew and
proceed reaction at
(@) only para positon
(6) only ortho postion
(©) meta pesition
(€) Both (@) and (b)
CHAPTER 13: Amines 369
150. Which of the following product is formed in the given
reaction?
NH
4+ Bry BHO
Nth Ni
Br
© o
Be
© @
Be Br
NE
(AKCo,0 ,,_ Bry ow oe
Pyridine | CHCOOH
Axiline (Mision
Identify 1 and II given in the reaction from the
following option
1 0
nucoct Nucoctts
©
7
Nucocth, Nuicoctt
” O
te
lls lls
om om
©
be
lls ll
“O
COC; 370 Master The NCERT CHEMISTRY Vol-!)
(6) 19 81% 114 47% I> 2%
In the acidic medium, aniline is protonated to form the
anilinium ion which is meta directing
(4) [> 50% IE 20% I> 20%
In acidic medium aniline is protonated to form the
anilinium ion whieh is ortho dicecting
. Select the correct order of the reagent to carry out the
given reaction.
Nis NH
derivatives are formed inthe reaction mixture along
‘with the reason. oe
7 ‘ ‘ ©) @ (CHLCO),O% Pyridine Gi) OF or HY
(0) 1-9 2% 1 4% > 51% fogrmeg OW fe0, 288 5
In the acidic medium, aniline is protonated to form the
snilinium ion which is ortho directing PRO (DP,0: Pyridine Ci) HNOs,H,S0,,288 K
{b) [+ 51% Il-> 2% Ill > 47% fe By, aie | oe
Intec metum ain proomaeio ome OH HNO; 1LS0,.288K GOI of
(Ooi ot CintTN0, 1480, 288K
anilinium ion which i para div
Topic a
Introduction to Diazonium Salts
54. Which ofthe following statements ineomee?
(0) The iazoniam sls hve the general fof PAP
(0) The Nj group is called as diazonium,group
(c) CgHsN2" HSOj is known as benzene diazoniuin stlphate
(6) all daemensare comes.
5. Which of the following aming al on sable diazonium sal at 273-278 K?
(CIN, (cali,
(OCHA, @EUNeK,
58. Choos he income opf6 fat thefolowing
(0) Allyl dazoiun sallar tight
(0) Ar davon stare abl low tempers fora wile
(©) Adan salar es sable than ascot als
(GG, HN. HSU famed 9 benzene dazniam yogen apt
852. The tablity Parenedzonium in is explained on the basis of resonance. Which ofthe following resonating
strcture is acomect
$1
A
“D CHAPTER 13: Amines 371.
58. Which of the following method is used in the preparation of nitrous acid?
() Reaetion of cone. HNO, and cone. H,S0,
() Reaction of sodium nitrite with hydrochloric acid
89. Which ofthe following statement is incorrect?
{(b) Reaction of cone, HCI and cone. H,SO,
{@) Reaction with hydroetorie acid and nti acid
(@) Beazenediazonium chloride is prepared by the reaction of aniline with nitrous acid at 273-278 K:
© (Op menos ome, Ox (cr + Nac 2040
() The conversion of primary aromatic amines into diazonium satis known as diazotsation
(@) Diazonium satis not generally stored, used immediately after its preparation
Topic
Physical and Chemical Properties of Diazonium Salts
60. Which of the following will be most stable?
(CBSE AIPMT 2014)
CHANEY
CG) CHSCHNSA
(a) CHANEY
(©) CHCHLNS >
61. The reaction,
SOL arc +N + CuCl
AINJCL
is named as
(2) Sandmeyer reaction ¢b) Gattermann reaction
(6) Chisen reaction (é) Carbylamine retin
62, Which ofthe following reactions statements is
incorrect?
(@) The yield in Sandmeyerreaetion is found tobe ester
than Gattemann reaction.
() ANCE +KI— Ad + KCDEN,
(o) ANICF+ HB, —s Ar NSB
‘At —14Bh +N,
(6) Mild reducing agent ees diazonium salts to arenes
63, Benzene diazonium chloride when reacts with
hhypophosphorus acid produces
(@) Benzene () Phenol
(6) Phenol isoeyanide (@ Phenyl phosphate
64, In the reaction Ais (EET 2013)
NO} NO»
Nicr
(2) HyS04/H,S0, cus
(©) MPO; and HO (@) H'/H,O
65, An organic compound (Cs HN) (4), when treated
‘With nitrous acid, gave a alcohol and N gas was
evolved, (4) on warming with CHC1; and caustic
potash gave (C) which on reduction gave
‘sopropylmethylamine. Predict the structure of (4).
(CBSE ALPMT 2012)
(@cH,cHCH,—NA,
Gh ——cH,
a,
66, Inthe reaction, (cose aur 205
Nit
a MINGICL, p CACHKES, py,
I
ay
The prot Eis
coon
Guy
oN
- oy
© l
bis 372 — Master The NCERT CHEMISTRY Vol-!)
67. Amongst the compounds given, the one that
‘would form a brilliant coloured dye on treatment with NaNO, in dil. HCI followed by addition to an alkaline solution
‘of B- naphthol is
(CBSE ALPMT 2012)
“om OC LO
Special Format Questions |
1. More Than One Correct Option
68. Choose the correct alternatives regarding the isomeric
form of amine having molecular formula C,H,
(@) Ithas only one tertiary amine
() It forms four primary amines
(6) It forms three secondary amines
(@) It shows only tree primary amines
When the dehydration of acetamide to acetonitrile
‘occuts, which of the Following observation can be
taken place?
() P.O, can be used as dehydrating agent
(6) Hybridisation of carbon in reactant to product changes
wp tosp
8
(¢) N-atom of reactant is less basic than that of product
(@) This reaction is known as nucleophile substitution
reaction
70. Consider the following reaction,
mf,
%
HC“ “cH
‘Choose the correct alternatives about the product (P).
(@) Product P contains acyclic ing with one f-bond
(©) Product Phas an open chain with only one x-bond
(©) N-atom in the product P is p"-hybridised
(€ Product P could be
Ss
uC “CH;
71. The four compounds given below undergo coupling
with diazonium salts
9° on NH, Any
1 u ul v
Choose the corréet alternatives from the following
regarding the reactivity of these compounds inthe
coupling with diazonium salt,
(2) Lrteacts fastest
(b) is more reaetive than IM and 1V
(6) IV reacts fastest
(4) Wedges n0t participate in the reaction
Il. Statement Based Questions
2.
7.
74,
1 Analiphaticamine is named by prefixing alkyl group
tw aminein the common system,
TL, Insecondary and tertiary amines, when two ormore
gious ate die sate, the pref dfs tis appealed
Deforethename of alkyl group.
Ifmore thanoneamino group ispresentat different
Positions inthe parent chain then suitable prefix
such asi, tis attached the amine. The letter‘e” of
the suffix ofthe hydrocarbon partis retained,
Select the correct statement(s) from the above
statements and choose the appropriate option.
(@) Only () Only 11
(6) Only IH (@ Allof these
Under which of the following reaction conditions,
aniline gives p-nitraderivative as the majar product?
I. Acetyl ehloride/pyridine followed by reaction with
‘cone. H,S0, +eone. NOs,
IL, Aceticanhydride/pyridine followed by
‘cone. H,S0, +cone: HNOs,
Dil, HCI followed by reaction with
‘cone. H,S0, +eone. HNOs,
UH
UL
IV, Reaction with cone, HINO, + cone. 350,
(a) Langit (&) Mand Ut
(6) Wand v (@) Land tv
Which of the following reactions belong to aromatic
electrophilic substitution?
I. Bromination of acetanilide
I, Coupling reaction of aryl diazonium salts
UL, Diazorisation ofaniline
TV, Acylationofaniline Choose the correct option,
(@) Vand
(©) Mland IV
(&) Mand 1
(@ Land iv
75.1. Diazoniumsaltsare very good intermediates forthe
introduction of F, Cl, Br, LCN, OH, NO; groups ito
thearomatiering,
I, Aryl fluorides nd iodides canbe prepared by direct.
halogenation.
IL, Cyano group cannot be ntroducedby nucleophilic
substitution of chlorine inchlorobenzene.
IV. Thereplacementof diazo group y other groups
{cholpful in proparing those eubetitutod
‘aromatic compounds which cannot be prepared
by direct substitution in benzene or substituted
benzene,
Select the incorrect statements,
(@) Vand 1 (6) Wand tt
(©) Mland IV (@) Land V
76. Consider the following reagents:
RNC TL CHC,
ML Coc, IV. NaNO; + HCI
Which of the following species are involved in the
carbylamine test for primary amines?
(@) Vand it (©) Land
() Tand1v (@) Wand Ut
IIL Assertion-Reason Type Questions
= Directions Q. Nos. (77-89) In the following.
questions, an Assertion (A) is followed by a
corresponding Reason (R). Use the following keys to
choose the appropriate answer.
(2) Both A and R are correct R js the Gomesteyplanation
of
(©) Both A and R are corrects Ris no the correct
explanation of A
(6) A iscomect; Ris incorrect
(@) Ris correct, A is incorrect
77. Assertion (A) The angle of C-N—C in the
trimethylamine is 108°.
Reason (R) There:is unshared pair of electron in
the trimethylamine which makes the angle less
than 109.5°,
78. Assertion (A) Fe + HCI is preferred as a
reagent in the oxidation of nitroalkanes to
alkanamines,
Reason (It) Iron scrap and HCI is preferred in the
reduction reaction of nitrobenzene.
CHAPTER 13: Amines 373
79. Assertion (A) Aromatic primary amines cannot be
prepared by Gabriel phthalimide synthesis.
Reason (R) Ary! halides do not undergo
electrophilic substitution with anion formed by
phthalimide,
80. Assertion (A) Substituted ammonium ion formed
from the amine is stable
Reason (R) There is dispersal ofthe positive
charge on ammonium ion by the + /effect of the
alkyl group.
Assertion (A) Onder of basicity ofumines in gaseous
phase is NH, > primary amine > secondary amine >
tertiary amine.
Reason (R) In gascous phase the basie nature of
aliphatic amine increases with the increase in number
‘of alkyl groups.
82, Assertion (A) In acylation reaction of amines
‘equilibrium shifts to the right hand side in the
presence of pyridine
Reason (R) In the presence of strong base, HCI
{s removed and reaction shifts toward the right hand
side
81
88. Assertion (A) Aliphatic amines are weaker bases,
than ammonia and aromatic amines are stronger bases
than ammonia.
Reason (R) */-effect of alkyl groups on aliphatic
amines increase the electron density on nitrogen
‘tom, Aromatic amines are weaker due to electron
withdrawing nature of the aryl group.
84. Assertion (A) Aniline does not undergo alkylation
and acetylation
Reason (R) Nitrogen of aniline acquires positive
charge in the presence of AICI;.
Assertion (A) MeNH, is the weaker base than
McOH.
Reason (R) N is ess electronegative than O, lone
of electrons on N is more easily available for the
MeNH,
(A) Benzenediazonium salts are soluble in
85,
donation
Reason (R) They are covalent in nature, so they are
soluble in water.
87. Assertion (A) Tertiary butylamine can be prepared
by the action of NHson rert-butylbromide
Reason (R) Tertiary butylbromide being
3° alkylhalide prefers to undergo elimination on the
treatment with a base. 374 — Master The NCERT CHEMISTRY Vol-!)
88. Assertion (A) Consider the given reaction,
(CHNH, —> HyCNHCH,CH,OH
[p-amioo aot}
Reason () f-aminoalcohol is less reactive than the
starting amines.
89. Assertion (A) p-fuoroanilinium ion is more acide than
anilinium ion.
Reason (R) Electron density in the N—H bond of
_p-fluoroanilinium ion decreases and release of a proton
from p-Mluoroanilinium ion is much easier than from
anilinium ion,
IV. Matching Type Questions
90, Match the amines given in Column with heir
clasificaton inthe Column [land choose the corrct
cpton from the codes given below
Colm Colm
i.
‘ 1. Primary amine
Ncin
b. Ce 2 Secondary amine
© Gynt 3 Tory aia
Cortes
A BOC
@1 23
@1 32
@2 13
2 301
91. Match the following structutes of amine given in
Colum t Column t
inne) (common ane)
cs
D. 4. NNimetyaiie
Bea FUaaaho ohae
oy,
PT
7. Mexaethlenedianine
Codes
A Bc DE
of RE 5 2
Dom io7 41
oa 4 71
> 4/7 31
92: Match the following Column I (reactant) with their
products given in Column If and choose the correct
‘option from the codes given below,
Column 1 (Column
A. HLGNHL * Hh, CCOCL 1. Acetaniide
B HjC—NH—Cili H,CCOCI 2, NN-iethylethanamide
Codes
A BOC A BoC
@i 3 2 m3 1 2
@l 2 3 @3 201
V. Passage Based Questions
= Directions (Q. Nos. 98-95) Answer the following
questions from the reaction given below.
Column I with their common name given in Column IL 9 9
and choose the comrct option from the codes given
below va rs Bat
‘Column Column I ae
‘Amn (common ae)
X 6 é
ws 1
° °
A on 1. Thimaianine Pk
2. NAN-dimety methanamine
3. Allylamine
B. HN—CH,—cH=cH,
© HN (CH— NH,
CO ONa’ | Neowin (TN
ONG A 98. What is I and Il inthe above reaction?
1 0
(9) Phthalimide; Ethanolie KOH
(b) Phuhalamide; —Ethanolie KOT
() Phuhalimide; HCL
(@) Phihalamide; HCL
‘The reaction shown above is known as
(@) Hofinann bromamide degradation reaction
(©) Gabriel phthalimide synthesis
(©) Ammonolysis
(6) None of the above
‘The above reaction
(@) primary amines
(©) secondary amines
used for the preparation of
(€) quaternary ammonium sats
= Directions (Q. Nos. 98-99) In the given reaction,
CHy
CUCONO_, CO HNOS
“Pyne v 180
ng NHOOCH,
1
Answer the following questions from the above reaction.
98. Predict the reagent (1) and the product (II) of the reaction,
Hy
ms sonr a>
is
CHAPTER 13: Amines 375
= Directions (Q, Nos. 96.97) Answer the following
‘questions based on the below paragraph.
“An aromatic compound Aon treatment with aqueous
ammonia and heating forms compound B which on
heating with Br, and KOH forms a compound C of
molecular formula CgH,N:
96. Whatis 4, B, Cin the above paragraph?
(0) 4 BenzoieacidsB > Berzamide;C > Benzenamine
(6) 4 Benzamide: 8 Beroieacid:C > Benzenamine
(6) A Benzamide; B > Benzznamine; C—> Benzoie acid
(@) A Benzoicaeid; B > Benzenamine;C > Benzamide
97. Name the redetion(s) involved during the formation of
C' irom 'B.
(2) Gabel phibalimide synthesis
(b) Hofmann bromamside reaction
(6) Sandmeyerneaetion
(All ofthe above
“Hy CH CH;
a
NN, IS
or ene ea
NaI
NO:
NH
ci
M300, >
No»
NuCOCHs
Hy a
(©) D> sauct > 0300, ws
No: SOsH
‘NHCoCH,
99. Select an appropiate reagent III and IV for the above reaction.
(a) (II) H,0/F* (LV) HPO, #0
(©) (I) H,0/HT (IV) > 1,0,
(O)(I)> H,0 (IV) H,PO,
(A) H,0 AV) HPO, 7,0 376 — Master The NCERT CHEMISTRY Vol-!)
NCERT & NCERT Exemplar Questions
NCERT
100. Arrange the following, in ineeeasing order of solubility
in water, CgHNH,, (CH); NH,CjHNH,
(a) CaHGNIy < (C3H NH CgH,CH,NHR
Which of the following alkyl halides is best suited
for this reaction through $1 mechanism?
(@) ChhBr () CollsBr
(OCQUGCH:Be (GUBr
108, Which of the following reagents would not be a
{good choice for reducing an aryl nteo compound 0
un amine?
(a) Hyfexcesy PL (©) LIAM, in ether
(6) Fe and HCI (@) Sn and HCL
120. In order to prepare 1° amine from an alky! halide
with simultaneous addition of one CH, group in
the carbon chain, the reagent used as source of
nitrogen is
(a) sodium amide, NaNHy
(b) sodium azide, NaN
(6) potassium eyanide, KCN
(@) potassium phthalimide C,l,(CO):
LL. The source of nitrogen in Gabriel synthesis of
(a) sodium azide, NaN
(b sodium nite, NaNO
(©) potassium cyanide, KCN
(@) povassium phthalimide C,H(CO).-K™
112, Amongst the given set of reactants, the most
appropriate for preparing 2° amine is
(@)2'R—Br+NHy
(0)2'R— Br + NaCN followed by Ih/Pt
(01 RNA = RCHO followed by Hy/Pt
(1 R—BrC2 mob + potassium phialimide Followed
by HO" Heat 118. Which of the following isthe best reagent for
converting 2-phenyl propanamide into
2-phenyl propanamine?
() Excess H,
(©) Bry in ag. NaOH
(©) lodine inthe presence of red phosphorus
(@) LAI in ether
114, Which of the following isthe best reagent for
converting 2-phenyl propanamide to I-phenyl
cthanamine?
() Excoss H,/Pt
(0) NaBH, /mothanol
145. Hofmann bromami
(©) NaOH/Br,
(8) LAI, /othor
c degradation reaction is shown,
by
(a) ANH, (6) ATCONH,
(0) ANOS, (@) ACHNIL,
116. The coreet increasing order of basie strength for the
following compounds is
Ni NH Nis
1 0 um
@u OIF > NH, > H,0
(©) OH > NH > H,0> NH
(6) NIL, > 10> NIG > OFF
(€)H,0> NH, > OH > NHS
128. Which of the following should be most volatile?
1. CH,CH,CH,NH, IL (CH3)5N
OS ny wecHcr
on ww
31 om Answers
ajo] aa sfo] «lel sel eo] ze so] s[@| ola) te] 2a) ala] mal 1s]
46. (0), 170)) 18) 18./@)/ am ()) a 0) aelte)| 28 | 2a] | 28) 28), 2.) Blo] 22.10) 30.0)
3. 2/0) BO) MO) 36.) 610) TO) mW Ow MO Ao BW alo wa ao
46 (0) 47. (o)| 48 ()|49./(0)| 50. oh] 51. cy] 82 (0) (| 54) (| 55) (86) 57!) 58) ()| 50. 0) 60.)
4), 62] ea)c| 64 (| 65 | 66 (0| or (| 8 (au) | 6 av), m ite) 71. ah rae Ta ad] 74 75/0)
Tf), T7|()| 78 ld) 78|()| 00, | et. ()| 62) (@)| 88) 1) | 84] | #5 (| 86/(E)) e706) 68.0)| eB a) 90,0)
1), 921 (| 98 (| 94 )| 98, | 96. (| 97. )| 98] fe) | 98] a) 100) | 40k | YOQia)/ 108 | 106.) 108, ()
406,407) 408 | 4000) |140 e)|14, (0) #12) 40) [Ate] wT) An () UA (6) 118|(0)| 118.) 120100
(22) 128) | 124 (0) 125. (9) [126.0] eT | 1, CA
Hints & Explanations
2. (a) Adrenaline contains secondary amino group, 1
‘whereas Novecaine and Benadeyl conn teary amino
group.
4. (6) Dueto presence of trivalent N-sto in amines,
hybridisation and geometry become span pyramidal
respectively
T. (6) one H-tom of NH, is replaced by alkyl oF aryl
sroup the primary (1) amine obtained.
9. (6) H,N—CH,CH,NH, is named as
cthan-1,2-amine
10, (a) nary amines, when NH group is diet
stiached tothe benzene ing, it snow es niin,
‘common system and benzenamine in TUPAC system
11, (@) TUPAC name is [Link]
16.
pentane "
12, (@) Nitro compounds are reduced 19 coFesponing
mines by passing hydrogen gas in he presence of
finely divided nickel, palladiu or platinum and also by 1
reduction with meta aeiic med
NO Nth
Hany
Ei
Noe Gov actie
Geena,” 19,
19, (@) The alkyl or benz hslde on reaction with an 20,
cthanole solution of ammonia undergoes nucleophilic
Substitution reaction in which halogen atom is replaced
bby am amine (NH, aroup.
14, (o) The process of cleavage of C—1 bond by ammonia
‘molecule is known as amnsonolyss of ay halide. The
‘reaction i earied out in sealed tube at 373 K.
(Fig, I, acs a8.a nucleophile which forms primary amine
shat reat with alkyl hide wo form secondary and tertiary amines and
finally quatertary ammonium sat
ha
FRx aN
Nu,
Nebel OF Subaaes
‘RNH, + RX —> RNH 2S RN AX Rte
o @ 6) Ounerary
‘sete smo
(®) Primary amine is obtained asa major prodct by taking large
excess af ammonia, Beeause RX 6 not avilable for the formation of|
2 or amines
(0) The onder of reactivity of halides with amines is RE > RBie> RCL
Oo
@ Ro
cl
CHCl b—N—CH
CHINE >
id
CH, NH
(CH),
souscy
HNC “CHC,
(8) Nisiles on elution with lithium aluminiun hydride (LAI) or
«tale hydrogenation produce primary amines
This reaction i used for preparation of amines containing one carbon
stom more han te starting amine
HN:
Re
Natliay COR
R—CHNH, BL. (6) The amides om ection with
cuan,
IH, yield amine
22 (eo) ~
COOCHs Hofmann —
af
3. () In the Hofinann bromamide degradation, amine is formed
‘with side products Na,COs, NaBr and H,0.
RCONH; +B, + 4NOH —+ RNH, + NaC + 2NabBe
#210
24, (c) In this degradation reaction, migration of a alkyl or aryl
group fakes place fiom earbonyl earbon ofthe amide to the
tom, The amine so formed contains one carbon ess than
‘that present inthe amide
9 o
cl cx
© ES,
4
jo
25.
°
(CHNH
e
26. ( secondary > tertiary
BO. (c) (CH,),N<(CH,),NH-< CH, NH, because the order of
boiling points > 2°> ¥,
4
CHAPTER 13: Amines 379
7
[Osan
(Reon
neta
[eto
Opie
NAA meta oie
oo
pes
O~
NAAeiedhyniin
(a) Amines being basic in nature forms salt on treatment with
cis.
{Amina clear clube in wor but incoluble in org
solvents lke ether. Amines have an unshared par of electrons
‘on nitrogen atom due to which they behave as Lewis base,
‘Basie character of amines canbe explained by their K, and
x, values,
() R—NH, +H, ”? ANH, + OFF
[281 0H")
(NH, 1H,0]
oe Ko} =LENHMOH) _, g, (ARH, 10H)
[aN] [RN]
Welnow that pK, =~ logy
(d) Larger the value of Kor sale the vale of pK,
stronger is the base. Hence, N-methyl methananin is the
strongest base among the give,
(6) Basic nature of amine depends upon case of formation of
cation by accepting a proton from acid, Thus, more stable be
the cation, mare basic isthe corresponding amine
(4) In the aqueous phase the substituted ammonium cation get
stabilised not only by electron releasing effect of alkyl group
(CA) but als by solvation with water molecule
The greater the sizeof the ion, lesser wl be the solvation and
‘he less stabilise i the fon, Hen, the onder of sability of|
font are a follows
ferers 380 Master The NCERT CHEMISTRY Vol-II
40. (c) There isa subi icenplay ofthe inductive effet, solvation
effect and steric hindrance ofthe ally group which decides
the basic strength of alkylamines inthe aqueous medium. The
‘order of base stength incase of ethyl substituted amines in
aqueous solution i as follows
(CoHls):NH > (GH) > C,HNH > NH,
41, (@) Aniline is resonance hybrid of five resonating structures
and anilinium ion is obtained by acepting a proton and have
‘only two resonating structures. Greate the number of
resonating structures, greater ste stably
42, (d) Incase of substituted aniline, electron releasing soups
like OCH, CH increase hase stength whereas, eletron
‘withdrawing groups like —NO,, —SO,H,— COOH, —¥°
‘decrease the basi strength.
43. (d) Aliphatie and aromatic primary and secondary amines
react with aed chlorides, anhydrides and esters by
nucleophile substitution reaeton, which is known as
acylation. In this typeof reaction, der ste replacement of
Inydrogen atom of NH, oF NH group by acyl group. The product
‘obtain in seyatonreaeton of amine is known as amide
44, (@) Amines react with benzoyl chloride wo give N-methyl
‘benzamide. This reaction is known as henzolaton
CHANH, +GH,COCL > CH,NHCOCH, + HCI
Metinamine Rerwoy! meter
‘iy metyiberamie
445. (c) Only primary aromatic aincs react with tous acid a
low temperatures (273 ~278 K) 10 form diazonium salts,
Nicr
soa Oo mC +210)
Berzanidaznium,
‘lore
48. (c) Primary aliphatic amines react with cous avid frm
Aliphatic diazonium salts which being nstabe, fon alcohol
and liberate nitrogen gas quantitatively
NaNO AHCI
RANE, + HNO layer]
2 rotten, T HHL
41. ()N. edeynan pal conan any
{Pan tac! 0 att nt id hence,
(nota naa
49. (0 Onto anipurfostso teh, gop teomes cents
SPagrccnn ey Tas Nis arp corto an
paraesceng dager oss ep.
50. (0 Aniline wer il one water ot om tempera to
‘ewe peepnt 3, 6uienoanine
sa xt
Bs Be
remo.
Be
2 rbomoeniine
51, (@) NEL, group of aromatic amine ean be protected by
acetylation with aceti anhydride and then followed by
hydrolysis ofthe substituted amide tothe substituted amie.
NE NHICOCHS 1NHICOCH
(C0010,
‘Sn (Ora
scone
om oe
©
Br
'52,_(c) Inthe strongly acidic medium, aniline is protonated vo form
the anilinium on whieh i meta-irectng. That is why besides
the ortho and para-dervatives, significant amount of
‘mota-derivative is also formed
t
Pee
158. (H) Niaion on NH, group can be controlled by protecting NH,
group hy acetylation reaction with acetic anhydride and p-nitro
derivative canbe obtained as major prot,
NH NHCOCH,
ICHCOVO ane 1804288 K
~aridne ”
oe
NHIcOcH
om fen
No,
patos psitoanilne
5A. (c) [Link] HO; is known ss benzene diazonium hydrogen
sulphate.
{55. (2) Primary aromatic amines form arene diazonium salts which
fr stable fora shor time in solution at low temperatures
(C1278).
56. (c) Primary aliphatic amines form highly unstable alkyl
dliazoniun sats, Primary aromatic amines form arenedizonium
salts which are stable for short time in solution at low
temperatures (273 ~278 K) [BT._(c) The stahiliy of arenetazonium ion is explained onthe basis
‘of esonaice as below.
ak i: i
() Nitrous acid is produced in the reaction mixture by the
reaction of sodium nitrite with hydrochloric ae
NaNOs+2HCL—> HNO:
Nios
58,
59, (6) Benzene diszonium chloride is prepared by the reaction of|
aniline with nitrous acid at 273 278K which f known as
iazoisation,
‘Due ots nstabiliy, the diszonium salts not generally stored and
is used immediately after its preparation.
GHNH,+NaN0, © 2H ZZ=ZBK, cy ayer
“+ NaCl +214,0
“Temperature must vary from 08°C
(&) Diazonium salt containing aryl group directly linked tothe
[N-atom is mos stable due to resonance stabilisation between the
benzene nucleus and N-atom,
Nn
=n N=!
6-8-8
oe
(#)Chiorin or bromine cae introduced inthe benzene ring by
treating the ditzonium st solution with eoeresponding halogen
acid in the presence of copper powder, Ths i erred as
(Gattermann reaction,
(6) The yield in Sandieyer Feacion is found tobe better than
‘Garermann ration,
Todine isnot easy intodced into the benzene ring dretly but
‘when the diazoniu salt solution streted with potassium
iodide, iodobenzene is formed.
ANC +KI—+ Ad+KCL+N,
61.
‘When arene diaroninm chloride treated with Sune sci,
arene diazonium fuoroborate is precipitated which on heating
decompose o yield aryl uoride
ANCE + HBF, —s Ar—NjBR
Sars +
oz.
CHAPTER 13: Amines 381
Certain mild reducing agents like hypopbosphorus acid
(phosphoric acid) or ethanol reduce diazanium salts to arenes
and themselves gt oxidised to phosphorus aid and ethan
respectively
ARNJCI + H,PO, + HO —> AMI#Ny + HPO, +H
64. (€) When dizonium satis aied with HPO. followed by
hhydeolyss, diazonium group is replaced by —H resulting
to the formation of hydrocarbon, Thus, 4, must be
,P0, 11,0.
(0) On treating with nitrous Wi, primary amine gives
an leobol and N, gas. So, 4 shouldbe primary amine.
cory hgh) FO ownon
+N; + HO
HC
ne7
cHNH,
(recy
HC,
a
7
as
OREO
ans ae
alevenken
Hy
nti
HC
cnc +
me ean
© ge
_Nasonticl_,
iazition
(6)As we know, benzenediazonium sal forms biliant
coloured dye with naphthol, the compound under
consideration must be pioluiin (38 itisaprimary
Primary aromatic amine, on treatment with NaNO in
Ail, HCL forms the coresponding diazonium chloride salt
: Lf2. =o oo"
_— 382 Master The NCERT CHEMISTRY Vol-II
68. Co
on
Primary amines Sscondary amines Tertiary amines
CHECHEN, CHLCH,[Link], cH —¥— Cc
' u
&
tt
eT — BG HN,
Mi ba,
w v
il, GH CHN, CCH NH CH, CH,
& vt
v1
on,
con,
bu,
va
“Thorfoe, amine of molecular formula, C4HyyN exhibits
four primary, three secondary and only one erry isomer,
69. (he) Dehydration of acetamide to seetonitile can be
‘carried out using P.O, a8 a dehydrating agent
Hye—E— Ee
oO
2, amide Acetoisile
sp aybescd ess basic ——_p-hybided me base
Tis reaction is known as Dehytation reaction.
7. (b,c) Inthe teaction,
u
Cyr ows Oey
RNa Ry
nc Yen
wc cr
The product? has an open chai ttre wi one
bond The Neato is 9?-bpbidsed as wll.
TA. (a, ) Duct the highest scvaingtendescy of tis the
fastest reacting poses coupling of dazniu sal
Similars, deo same reason sore easive tan
TV On the other hand dt east stating tendency
of, its east octive
1A, (a) Aniline gives oniaodeivasive asthe major praduetby
1 acetyl chloride pre by reaetion with
‘one, H,S0, and eine. HNO,
1. acetic anhydride pyridine followed by cone H,S0,
+ cone. HNO,
7S. (b) Diazniun sls are very goo terest forthe
induction of ~F Cl, Br, 1, CN, OH, NO. groups into
‘he aromatic ing. Aryl ores nd odes cannot be
induced by meleopibe subsiution of ehorine in
chlorobenzene but eyanobenzene can be esl obtained
from dizonin sl
7.
Replacement of diazo groups shelf in preparing those
substituted aromatic compounds which cannot be prepared by diret
Substitution in benzene of substituted benzene.
(@) Aliphatic and aromati primary amines on heating with
chloroform and ethanolic KOH form isoeyanides or carbylamines
‘which is known as carbylamine test and is used to test only primary
RNH, + CHCI, + 3K BESS "RNE 4 3KCI + 31,0.
(4) Theangle C—-N—C i les than 109°, 108" due tothe
presence of unshared pat of elton
(@) Reduction of nto compounds With Fe scrap and HCl is.
referred cause Fel med pes hydensed to slease HCI
‘uring the reaction,
“Thus, oaly a small amount of HCI is roquited to nsiate the reaction.
(6) Aromatie primary amines cannot be prepared by the Gabriel
phthalimide synthesis because aryl halides do not undergo
‘neleophilic substitution reaction with the anion formed by
phthalimide
(a) The substituted ammonium ion formed from the amine gets
stabilisod duc to dispersal of positive charge by the +/-ffectof alkyl
‘toup.
(4) Ord of basicity of amines in gaseous phase follows the order
‘Tertiary amine > secondary amine > primary amine > NH
Thebasic nature of aliphatic amines increases with increase inthe
Ma of allyl arom ie gnome lie)
(@) In acylation reaction of amines equilibrium shifts tothe right
Side in the presence of pyridine because it isa stonger base than
amine whieh removes HCL 30 formed in the reaction,
(4) Aliphatic amines are stronger base than ammonia du to
‘effect of alk! groups leading to hig electron density on the
nitrogen atom, Thee PK, values lie inthe range of 3 to 4.22. Which
4s lower than pXvalue of NH, i. 4.75. On the other hand,
aromatic amines are weaker base than ammonia due tothe eletton
‘withdrawing nature ofthe aryl group.
(@) Aniline doesnotundergo Friedel Craftsreaction alkylation and
scctlation) ductosaltformationvvith AICI (the Lewisacid) whichis
‘wedas catalyst Ductothisnitrogenofanilinesequitespositivecharge
aandhenee,aetasestrong deactivating group forfurtherreaston.
(4) MeN isthe stronger base than MeOH because N is less
sfectroneyitive than O, lone par of electrons on N is more easly
available fr the donation in MeNH,
(6) Benzene diazonium salts are soluble in water because they are
cH, cu,
(@) HCC Br HC—C—NH,
1 “Hie wsaion
cn, ca,
{ert-buty bromide prefer to undergo elimination rater than
substitution on testment witha base. The products isobutylene
rather than fr-butylaine.
() [Link], ——> HLeNHCH,CH,OH
{pani alot
{amino alcohol is less reactive than the starting amines 90,
m1.
92.
93.
because it stabilised by intramolecular hydrogen bonding which
lowers nucleophilcity of OH group,
@ Fe Mtn
, ‘
Due to ~/-efect of Fatom, it withdraws electrons from NH group,
{Asa res, eleetton density the N—H bond of p-luoroanifiniaa.
jon decreases and ence release ofa proto from pfhuoroanilinium
jon is mach more ease than from anilinium ion. Thus,
p-uoroanlinium ion is more aii than anilinium ion
(WAS1,B53,052
)A46,B93,C57,D94E>1
@A3,B52,051
out Hott
Ad
cai H tego Be, “yg —E
a }
a 6 H
Ethane
HO
: Nstitinmide
cats + che a Bs
cara °
Nedyltenanie
Gays a p09
Beazzuthine
°
aoe aye
cats ¥ Sg cane scoot
Ho
AlPtemlttonanc o
(2) Phthalic on treatment with ethanoie potassium hydroxide
forms potassium slt of phalimide which on beating with,
alky halide followed by allaline hydrolysis produces the
corresponding primary amines
: :
°
° °
sue! Naot
-antt, e :
ons Prmay
é
cay NE H
im
CHAPTER 13: Amines 383
94, (b) Reaction i known as Gabriel phthalimide synthesis.
95. (a) This reaction suse forthe preparation of I° amines,
96, (a) COOH cONH
an Xtt , Beko
ws? lina
romani
enamine
97, (b) Hofmaan bromsiide reaction takes place during
convetsion of B10.
98, (6) Soh
cH,
Ww
NO:
NHICOCE,
98. (0) I> H,O/H' 14 H,80, 110
100. (6) Higher dhe tendency to form H-bond, more isthe
solubility. Extent of H-bonding is more in amine than
in and 2*amines,
Therefore, the increasing order of solubility ofthe given
amines in water ean be arrange as,
GENE, < (CaH,),NH < GNU
Noe
101, (@)CH,cOoH—MScH,CONH, MOH,
‘ate at He” Acti
HN, 8220 cH,018
Mesniarie Mata
102. (a) In Gabriel phhalimide reaction, pousium salt of
[ihalimide is formed, Iereets readily with alk halide
to form the corresponding alkyl derivative
ce
NS feat
Cl
ae
wate
OIC ee
Nall pind
Poussin
ptimide
But aryl halide docs not react with potassium phthalimide
‘because C—1 bond in haloarene (alkyl halide) is difficult
to be cleaved due to purtal double bond character 384 — Master The NCERT CHEMISTRY Vol-II
So, aromatic primary amines cannot be prepared by Gabriel Here lone pair of nitrogen are less available for donation to
phthalimide sythess the acid
OL 108, (0) Sylreacton proceeds tough famation of
Cx Bk & cqtiy—x ESS noreanon —_etbovaton. Hence, more sable be te carbocation, more
co
Js thereatvity towards Sy I mechanism
Histo
Pox ptatinide __ Alt hatdes —_atretiane
Cie °
108. (c) Amines are less acidic than alcohols of comparable molecular 7 4 ee
Imases because NTT bond istess polar than OH bond. Hence, ) GHB. GAP
nines release Hon wilh ore difclly ax compared skool. (@)GHYCH,Br ‘Gh, cH," more sabe)
104. (d) IUPAC name of Ct, = CHCHNHCH, is @
Nemetiyorop-2-¢n-lamine
105. (6) The structure of given amines are as follows: ‘Hence, te reaction will proceed through S yc1
inccani, when CC Hye the state esas
HB ene
i on ionisation it gives a resonance stabilised earbocation
NH eee (GHCH)
© CHCA | CHC, 498,/ (Arp nitro compound cannot be converted into amine
cucu, ‘using LAI, in ether.
it
tei a a
Euan) ‘aren us Sr
mew oH
* See Nos Nis
© Oo
ETM @ NH
106. «) 110, (6 nor pare aine om an alk ade
o_O RG ‘Sms ation aon Cis eu he
pou Factors repanieoF “ance eget ed Suc nop
ee basic character are ‘is KCN.
GN ee
0b Ne— enn,
fe) (oN
®
Hist snd resonance
Since, + Leffet and slvon increases basic character while
—/ofce and resousplRgeatemaye characte. AL. 4 Souree of nitrogen in Gabriel phthalimide synthesis is
1107. (a) Aniline is weakest Bronsted base among the given four pei phe
‘compounds. ey fo resonance present in ease of aniline.
or “ere oa OD its somos (ST
frit wos -cooH
oe ANH
0% ‘COOH amine
Resonating structure of aniline tae m2.
us.
14,
5.
6.
(6) Chemical transformation eam be shown as
NH, +RCHO—> [R-N=C—R]
4H
won|
"
RNC
H
nu
\Whileoter given set of reactants give primary amine oly
(2 The bes wagent for converting 2-phenylpropanamnide
2-phenylpropunamine is LiAIH in eter. Reaction is given
below.
2 stemipnromne 2 pnb
(8) The best reagent for converting 2-phenylpropanamide
ito I-phenylthanamine is NAOH/Br, and chemical
transformation can be done as
©
cry
2 ppm ateniieamine
This occurs duct intramolecular migration oll
group, It is an example of Hofinann bromamide reaction.
() Hofinann bromamide degradation i$ shown by
°
Ar— CNH in which Smid is converted into amine via
“undergoing intramolectar migration of phenyl group.
(@) The correet increasing order of basi strength isa follows
cus
ut
Greater the electron density towards ing, greater willbe
itsbasi strength. Electron withdrawing group decreases basic
strength while electron donating group increases basic
strength
CHAPTER 13: Amines 385
1117, (c) Methylamine reaets with HINO, (nitrous ae) to form
neal
cn, — cH, A
oe ie
ciiou
118, (4) Chemical reaction takes place dating reaction of
snethlamine with nro aid lows
CH) NH, > CHy—Nes er
etytiage Ube
[ano
cH,on+ N,
119.(c) Nitration of bet sing 8 mixture of cone. H,SO, and
‘one. HNO, prosesds as
Ho NZ? yfys0, —> nyc Ro, +21,0-50
0
O.6"
(c) Aromatic nto compound on esetion with Fe and HCL
ives aromatic primary amine as shown below
one
120,
This reaction is known as electrophilic substitution
121, (0) Greater be the strength o base, greater ts reactivity
towards di. HCI. Since, (CH,)aNH has highest base stength
So thas highest eativiy.
wr Np og
7 N
ne oe
(a) Acid anhydride on reaction with primary amine produces
amide as
DL RY a8 386 Master The NCERT CHEMISTRY Vol-II
124. (2) Nitmbenzene will noe undergo ao coupling reaction with js not more hase because the lone pair of electrons onthe
‘benzene diazonius chloride, while other thee undergo Naatom is donated towards aromatie sextet formation.
