FACT/DEFINITION TYPE QUESTIONS ‘A secondary amine is (@ a compound with two carbon atoms and an -NH) oop. (©) acompound containing two -NH, groups. (©) acompound in which hydrogens of NH, have been replaced by two alkyl groups. compound with an NH, group on carbon atom in ‘number two position. ‘The general formula of quaternary ammonium compound is (@ RNH, (b) RN (©) RX @_NHX ‘The total number of electrons around the nitrogen atom in amines are @ 8 7 © 4 @ 3 4. The IUPAC name of the compound having formula, @ o=C—CH— Ch, is OH NH, OH (a) 3-amino-hydroxy propine acid (b) 2-amino-propan-3-oic acid (©) amino hydroxy prepanoic acid (@)_ 2-amino-3-hydroxy propanoic acid 5. Thenumber ofprimary amines of formulaC,H, Nis: @ 1 ©) 3 @O4 @ 2 6. What isthe IUPAC name of the following compound ? NH) ANY (@)_2-methyl-4-hexanamine (b) S-methyl-3-hexanamine (©) 2-methyl-4-amino hexane (@)_S-methy|-3-amino hexane 10. mL 12. 13. 14. CHAPTER ‘The correct IUPAC name for CH, = CHCH,NHCH, is (@ Allyimethytamine (b) 2-amino-4-pentene (©) 4aminopent-I-ene (@)_N-methyiprop-2-en-1-amine Amines play an important role in the survival of life Naturally they are found in (@)_ proteins (b) vitamins (©) alkaloids (@ Allofthese Intermediates formed during reaction of RCONH, with Br, and KOH are (@ RCONHBrand RNCO (o) RNHCOBrand NCO (©) RNHBr and RCONHBr (d) RCONBr, Which of the following reactions will not give a primary amine? (@) CHyCONH , —H2/K0H_, ©) cHycn Hae, © cHj3Nc—HAE, @_ cHyconn, AHL, Propionamide on Hofmann degradation gives — (a) methylamine (b) ethylamine (©) propylamine (@)_ ethyl cyanide Secondary amines could be prepared by (@) reduction of nitriles (b) Honan bromamidereaction (©) reduction of amides (@ reduction ofisonitriles Gabriel’s phthalimide synthesis is used for the preparation of (@)_ Primary aromatic amines (b) Secondary amines (©). Primaryaliphatic amines (@)Testiaryamines Ethyi amine can be obtained by the (@ Action of NH, on ethyl iodide, (b) Action of NH, on ethyl aleohol. (©) Both (a) and (b) (@)_ Neither (a) nor b)15, 16. 17. 19. 20. a. 2. 23. ‘Treatment ofammonia with excess of ethy! iodide will yield (a) diethylamine (b)_ethylamine (©) triethylamine (@)_ tetraethylammonium iodide For alkylation of ammonia which of the following is not used’ (a) CH-X (b) CHy-CH-X (©) (CHy),CH-X (@) (CH,),C-X Which of the following amines can be prepared by Gabriel method? () CH,CH,NH, (iii) (CHy);CNH (a) (@and(ii) (b) Giyand (ivy (©) @,Gi)and (ii) (d) Gand (ii) Amongst the given set of reactants, the most appropriate for preparing 2° amines (a) 2°R-Br+NH; (b) 2°R-Br+ NaCN followed by H/Pt (©) I°R-NIL, + RCHO followed by Hy/Pt (d)_ 1R-Br (2 mol) + Potassium phthalimide followed by HO" sheat ‘The best reagent for converting 2 — phenylpropanamide into 2-phenylpropanamine is (a) excess H, (b) Brin aqueous NaOH (©) iodine in the presence of red phosphorus (d)_LiAIHgin ether Which of the following methods of preparation of amines will give same number of carbon atoms in the chain of amines as in the reactant? (a) Reaction of nitrite with LiAIH, (b) Reaction of amide with LiAIH, followed by treatment with water. i) (CH,),CHNH, (iv) CgHsNHy (©) Heating alkylhalide with potassium salt of phthalimide followed by hydrolysis. (d)_ Treatment of amide with bromine in aquesous solution of sodium hydroxide. The reduction of nitro compounds is most preferred in the presence of (a) Pd/H,in ethanol (b)_Sn+FICL (©) finely divided Ni (d)_ironserap and HCL. An alkyl or benzyl halide on reaction with an ethanolic solution ofammonia undergoes (a) electrophilic substitution reaction (b) nucleophilic substitution reaction (©) free radical mechanism. (d)_ nucleophilic addition reaction In the ammonolysis of alkyl halides the halogen atom is, replaced by an amino(—NI,) group which of the followii represent the correct order of reactivity of halides with amines. (@)_RBr> RI>RCI (©) RI>RB> RCL (by RI>RC>RBr (@) RCI>RBr>RI 24. 28. 26. 21. 28. 29. 30. 3h. 32, 33. 34. Which of the following will give primary aminc only? (ammonia + propylchloride Gi) potassium pthalimide ~ ethylchloride i) potassium pthalimide + chlorobenzene (a) (iand(ii) (b) (i)and (iii) (©) (ijund Gi) (@) (@,GiandQii) Amines have (a) Garlic odour (b) Fishy odour (©) Jasmine odour (d) Bitter almonds odour cis less soluble in water than ethyl amine duc to resonance stablization of benzene ring resonance stabilization of anilium ion more hydrophobic nature of CH; group than CyHg group more hydrophobic nature of CsH, group than C,H, group Which of the following should be most volatile? () CH,CHACH,NH, (1) (CH),N @) CCH (VY) CH,CH,CH, cH 13CH,CH, @ 0 o) Vv ol @ m Amines behave as (a) lewis acids (6) lewis bases (© aprotic acids (d)_amphotericcompounds ‘The basic character of amines is due to (a) presence of nitrogen atom (b)_ lone pair of electrons on nitrogen atom (©) tetrahedral structure (@)_ high electronegativity of nitrogen Aliphatic aminesare....basic than NH, butaromaticamines are....basie than NH (a) more, less (6) less, more (©)_ both (a) and (b) (@)_None of these Substitution of one alkyl group by replacing hydrogen of primaryamines (a) increases the base strength (b) decreases the base strength (©) remainsthe same (@)_None of the above Which of the following is not characteristic of amines? (a) Theysmellfikeammonia (b) Theyare inflammable in air (©). They show the property of hycrogen bonding (@)_ Theyare amphoteric in nature ‘The correct order of basicity in amines © CGHNH, (i) CHyNH, ii) (CH).NH (ivy (CH),N @ H<(y)A>c (b) A>B>C (©) C>A>B @ C>B>A Which ofthe following statement is correct ? (2) Ammonia ismore basic than methylamine (b) Methylamine is more basic than ammonia. (©) Dimethylamineis less basic than methylamine, (@)_ Dimethylamineis tess basic than trimethylamine, Which of the following compounds is most basic? @ ox) () } Which of the following compounds is the weakest Brinsted base? @ NH NH, @) oO 0) OH OH © OQ @ The correct decreasing order of basic strength of the following species is H,O, NH,, OH-, NH~ (a) NH,-> OH-> NH, >H,0 (0) OH > NH > H,0 > NH; (©) NH,> 1,0 > NH-> OH @ H,0>NH,>OH> Ni Which of the following factorsaftect the basic strength of amine? () Inductive effect (i) Steric hinderance (i) Solvation effect (iv) Solubility in organic solvents. @) (@and(v) (©) (,Gianddii) (©) Giyand ii) (@) Gidand (iy) 42. 44, 45. 46. 47. 4B. 49. Si. 52. Which statement is not true among the following? (@) Amines are bases (b)-Theyturn red litmus blue (©) Trimethyl amine is less basic than dimethyl amine (©) _ Amines yield alcohols on aqueous hydrolysis Aniline is used (a) incrimping of wool (b)_ in dyeing industry (©) inmakingofglue —(@) in fast drying vanish Which of the following statements about primary amines is “False”? (a) Alkyl amines are stronger bases than aryl amines (b) Alkyl amines react with nitrous acid to produce alcohols (©) Arylamines react with nitrous acid to produce phenols (d)_Alkylamines are stronger bases than ammonia ‘Mark the correct statement (a) Methylamine is slightly acidic (b) Methylamine istess basic than ammonia (©) Methylamine is.a stronger base than ammonia (@)_ Methylamine forms salts with alkalies. For carbylamine reaction, we need hot aleoholic KOH and (@)_anyprimary amine and chloroform (b) chloroform and silver powder (© aprimary amine and an alkyl halide (© amonoalkylamine and trichloromethane. ‘The compound obtained by heating a mixture ofa primary amine and chloroform with ethanolic potassium hydroxide (KOHDis (a) analkyleyanide —(b)_ nitro compound (© analkylisocyanide (@) an amide R=NH) +CHj;COCI— A (excess) ‘The product (A) will be ~ (a) RNHCOCH, (6) RN(COCH,), (© RN(COCH,),Cr— (@) R-CONH, Carbylamine reaction is used for the detection of (2) aliphatic 2° amines () aliphatic 1° amines (©) aromatic 1° amines (@)_ Both (b) and (c) In the reaction, RNH, "2 5 ROH +H,0+C1; Cis (@) NH; (b) Ny © 0, @ CO, ‘An organic amino compound reacts with aqueous nitrous acid at low temperature to produce an oily nitrosoamine. The compound is (a) CHyNH, (0) CH,CH,NH (©) CHjCHjNHCH,CH, (@) (CH,CH,)3N Ethylamine reacts with HNO, giving (a) C,H,OH ()CyHNO, (© NH, @ GH61. Primary amines can be distinguished from secondary and tertiary amines by reacting with (2) Chloroform and alcoholic KOH (b) Methyl iodide 66. (©) Chloroformalone @ Zine dust Which of the following is not correct ? (a) Ethyl amine and aniline both have—NH, group (b) Ethyl amine and aniline dissolve in HCL (©) Ethyl amine and aniline both react with CHCl; and 67, KOH to form unpleasant smelling compound (@)_ Ethyl amine and aniline both react with HNO, in cold to give hydroxy compounds Hinsberg reagent is (@) [Link],H (b) CgHNO (©) CgH;S0,C1 (@) CgHGN,CL 68. Reaction of aniline with benzaldehyde is (@) substitution (b) addition (©) condensation (d) polymerization ‘The amine that does not react with acetyl chloride is (@) CH,NH, (b) (CH,),NH (©) (CH) (d)__ None of these Which of the following compounds cannot be identified gy, by carbylamine test? (@) CH,CH,NH, ) CHC, (©) CoHlsNH (d) CgHs-NH-CcHs (CH,)3CHNH) is reacted with excess acetic anhydride, the compound formed is (@) (CH,),CHNCOCH, — (b)_ (CH,),CN(COCH,), (©) (CH);CHOH (d)_(CHy)CN(COOCHS), In order to distinguish between C)Hs-NH, and CHis-NH, which of the following reagent is useful (a) Hinsberg’s reagent (b) HNO, (©) CHCI,+KOH (qd) NaOH All three amines 1°,2°, 3° react with L 10 2 RX 3 HO 4. (CH,CO),0 @ 1.2 (b) 4only © 1,24 (a) 1,23 NHL group in aniline is (a) onlyo-directing (b) only p-directing 70. (©) onlymedirecting (qd). o-andp-directing Strong activating effect of NH, group is reduced by using (@ CH,Cocl (b) CHC (©) CH,ONa (@) CH,-CHO 71. When bromination of aniline is earried out by protecting -NH,, The product is (a) o-bromeaniline (b) 2,4, 6tribromoaniline (©) p-bromeaniline (@)_ mixture of o-and p-bromoaniline Hinsberg’s method to separate amines is based on the use of (a) benzene sulphonyl chloride (b)_ benzene sulphonic acid (©) ethyloxalate (@)_ acetyl chloride ‘The reaction, CgH;NHy+ CICOCH; —> CcH;NHCOC, (a) Friedel-erattsreaction (b) Claisen condensation (©) Benzoylation or Schotien Baumann reaction (@)_ None of these Which of the following statements is not correct regarding aniline? (a) Itis less basic than ethylamine (b)_Itean be steam-distilled (©) It reacts with sodium to give hydrogen (@)_ Itis soluble in water Benzylamine may be alkylated as shown in the following equation: CgHsCH,NH, +R -X—+CH,CH,NHR Which of the following alkylhalides is best suited for this reaction through SI mechanism? (a) CH,Br (0) CgHsBr (©) CglCHBr @) CyMeBr ‘The product of the following reaction is NHCOCH; OQ +BryCH,COOH __, NHCOCH, NHCOCH, Br 0 wo Br NHCOCH, NHCOCH, Br Br (aii) (wy) Br Br () @and Git) (©) (@andGi) (©) Gii)and (iv) (@)_ (),Gii)and (it) Aniline and other arylamines are usually colourless but get coloured on storage due to (a) hydrolysis (b) dehydration (©) reduction (d)_atmospheric oxidation ‘The acylation reaction of amines is carried out in presence of pyridine because (@_ pytidine is stronger base than amine. (i) _pytidine is weaker base than amine (i) pyridine removes HCI formed and shifts the equilibrium to the right hand side. pyridine removes HCI formed and shifts the equilibrium to the left hand side (iv) (0) Gijand Gv) @ @and(ivy72. 73. 74. 7B. 76. N- ethyl benzene sulphonyl amide is strongly acidic and soluble in alkali due to presence of @)_ strong electron donating sulphonyl group, (b)_ strong electron withdrawing sulphonyl group. (©) weak electron donating sulphony! group. (@)_ weak electron withdrawing sulphonyl group, Arrange the following in increasing order of their basic strength? p-nitroaniline(1);m-nitrooniline (2), 2,6-trimethylanilino(3), [Link](4), @) 13,24 (by 2,3,4,1 82. ©) 31,24 (@) 1,243 NH) NaNODINC! , (py CUBE, (@y oc br The compound Q is — (a) bromobenzene (b) chlorobenzene (©) benzyl bromide (d)_ benzyl chloride Diazonium salt is obtained when aniline reacts with (@) cold NaOH (b) NaNO, and HCI(0-5°C) (©) SnCl,at 10°C (d) N,Oat(0-S°C) 83. Azo dye is prepared by the coupling of phenol and @) iazonium chloride (b) o-nitroaniine (©) benzoicacid (d)_ chlorobenzene In the reaction sequence NH, AON, gp LAI oc NaNO, HCL oC the product ‘C’is: (@) benzonitrile (©) benzoicacid a Chlorobenzene (0) benzaldehyde (d)_ benzylamine Above reaction is known as: (a) Strecker'sreaction _(b)_ Sandmeyer's reaction (©) Wohl-Ziegler reaction (d) Stephen's reaction Which of the following reagents will convert p-methylbenzenediazonium chloride into.p-cresol? (@) Cupowder () HO (© HPO, () C(HOH ‘When phenol and benzene diazonium chloride are coupled, the main product is (a) aniline (©) azobenzene (b)_p-hydroxyazobenzene (d)_ chlorobenzene In the chemical reactions, N the compounds ‘A’ and ‘B” respectively are (a) nitrobenzene and fluorobenzene (b)_ phenol and benzene (©) benzene diazonium chlorideand fluorobenzene (@)_ nitrobenzene and chlorobenzene In the chemical reactions : NaNO, Tic 278K HBF, A——t>B NH, NaNO, CuCN nck 7A a? B. the compounds A and B respectively are (a) benzene diazonium chloride and benzonitrile (b)_ nitrobenzene and chlorobenzene (©) phenol and bromobenzene (@)_ fluorobenzene and phenol Replacement of -N3CI” from benzene diazonium chloride by iodine can be done by using @ HI (bo) Nal (© Phy @ KI Product of the following reaction is CeHs-NgCH*CHs-NH3 —> NH, NH,85. Which of the following are intermediates in Sandmeyer reaction ? © CgHsN’ i) CgHsN* =N Gi) Cats (iv) Cg (@ GandGid) ) @andiv) (©) Givand Gv) (@) @andGiy In the diazotization of arytamines with sodium nitrite and hydrochloric acid, an excess of hydrochloric acid is used primarily to (a) Supress the concentration of free aniline available for coupling (©) Supress hydrolysis of phenol (©) Ensurea stoichiometricamount of nitrous acid (@)_Neutralise the base liberated Which of the following reagent can be used to convert benzenediazonium chloride into benzene? 87. (@) CHOW (b) HPO, (© Bry-H,O (d) LiAIH, 88. When benzenediazonium chloride in hydrochloric acid reacts with cuprous chloride, then chlorobenzene is formed. The reaction is called (2) Gattermann reaction (b) Perkin reaction (©) Btard reaction (qd) Sandmeyer reaction 89. The reaction AWN Cr SH! arc Ny + CuCl is named a (a) Sandmeyerreaction (b)Gatterman reaction (©) Claisen reaction (qd) Carbylaminerreaction 90. Which of the following compound will not undergo azo coupling reaction with benzene diazonium chloride. (a) Aniline (b) Phenol (©) Anisole (d)_ Nitrobenzene 91. Which of the following cannot be prepared by Sandmeyer’s reaction? (@ Chlorobenzene (i) lodobenzene (@) @anddi () Gi) and Giiy (©) Gi) and (iv) (@) @ané (iv) The reagents that can be used to convert benzzenediazonium chloride to benzene are © SnClyHCI (i) HPO, @ @anddi © Gi) and (iv) STATEMENT TYPE QUESTIONS 93. Gi) Bromobenzene (iv) Fluorobenzene 9. (i) CHjCH,OH (iy) LiAlH, (b) Gijand Gi) (@) @and (iii) Read the following statements and choose the correct option. (Nitrogen atom in amines is sp?-hybridised. (i) ‘The geometry of amines is pyramidal 4, 95 96. 97. (ii) The angle C-N-C or C-N-H is slightly more than 109.5". (@) (ii) and iit) (©) (Hand Gi) (©) @and (iii) (4) Giijand (ii) Which of the following statements are correct ? (@ Loweraliphaticamines are soluble in water. (i) Solubility increases with decrease in molar mass of amines. (ii) Higher amines are insolublein water. (iv) Amines are soluble in organic solvents, (@)_ (i, (ii) and (ii) (>) (i), (iii) and (iv) (©) Gi), (iii)and (ivy @) (and (iv) Which ofthe following statements are correct ? ()__Primaryamines show more intermolecular association than secondary amines. (i) Tertiary amines do not show intermolecular association, (ii) Boiling points of isomeric alkenes follow the order Be>2°>1° (@) @and (ii) (>) @andGi) © (@.lidandGii) (@) Gidand ii) ‘Which of the following is/are correct regarding nitration of aniline with cone. HNO, and conc. H,SO,? Nt NH Nit, No, nO 0 one F250, * NO, NH, NH *O-O ‘NO, (ii) The substitution can be explained on the basis of inductive effect (1) (iv) The substitution can be influenced by +M and +E effects (@) @,GiyandGiiy () Giyandciiy (©) Giyand (iv) @_ Gand Giiy Which of the following statements are correct ? (@ In Sandmeyer reaction nucleophiles like Cl-, Br and (CN. are indroduced in benzene ring in the presence of Cu" ion (i) InGattermann reaction nucleophiles are introduced in benzene ring in the presence of copper powder and HC. (ii) The yield in Gattermann reaction is found to be better than Sandmayer reaction, (@) @andGi) (>) @.G) andGii) (© GiandGii) @ @andiii)MATCHING TYPE QUESTIONS 98. Match the columns Column-t (Column-I (A) Gabriel phthalimide (p) CjH,CH,NH, reaction (8). Reduction with (@ CyHsNH, LiAIH, (© Reaction with (8 CCN alc. KOH + CHC1, () 1° Amide with Br, +KOH (@) A=(p,3);B=(p,3); C-(0, 43); D-@.4,3) (0) A~()B-(P);C-(@)sD-(P,9) (©) A-(p,8);B-();C-(q);D-(s) (@)_ A~(,4);B~(); C-(p, 4); D-) 99, Match the columns Column-T (A) Ammonolysis (8) [Link], Column (p) Amine with lesser number of carbon atoms 8) Gabriel phthalimide (q) Detection test for primary synthesis amines, nbromamide () Reactionof Phthalimide with KOH and RX (8) Reaction of alkythalides with NH, a) A-(s), B-(r),C-(p), D-(q) () A-(©,B-(p),C-(,D-6) (© A-@),B-(9,C-(), D-(p) @ A~(),B-(p),C-@),D-() 100. Match the columns oO (©) Carbylamine reaction Column Column (A) Benzene sulphonyl — (p) Zwitter ion chloride (8) Sulphaniticacid ——_(@)_Hiinsberg reagent (©) Alkyl diazoniumsalts (©) Dyes (©) Aryldiazonium sats (8) Conversion to alcohols @_A-(),B-(@,C-O,D-(P) (b) A-(@),B-(p), C-(s), D-() © A-(,B=(3),C-(p), D-(@) @ A-(),B-(p),C-),D-(@ 101, Match the columns Column-t Column-tt (A) ArN$Cr— ArH (p) HBR, / NaNO, (8) ArNjCr—+ Arno, @) H,0 © amnicr— ArH © HBF, ©) ArN}Cr—+ArF (8) CH,CH,OH (@) A-(@), B-(p), C—@),D-© (b) A-(s), B=(p), C-(@),D-@) (© A-@,B-(),C-(),D-©) @_ A-(@),B-(s), C-(),D-(p) ASSERTION-REASON TYPE QUESTIONS Directions : Each of these questions contain two statements, Assertion and Reason. Each of these questions also has four alternative choices, only one of which is the correct answer. You have to select one of the codes (a), (b), (©) and (4) given below (a) Assertion is correct, reason is correct; reason is a correct explanation for assertion (b) Assertion is correct, reason is correct; reason is not a correct explanation for assertion (©) Assertion is correct, reason is incorrect (d) Assertion is incorrect, reason is correct. 102, Assertion : Aromatic I°amines can be prepared by Gabriel phthalimide synthesis. Reason : Aryl halides undergo nucleophilic substitution, with anion formed by phthalimide 103. Assertion : Onlya small amount of HCI is required in the reduction of nitro compounds with iron scrap and HCI in the presence of steam. Reason : FeCl, formed gets hydrolysed to release HCI during the reaction. Assertion : Amines are basic in nature. Reason : Amines have lone pair of electrons on nitrogen atom. 105, Assertion : Acetanilide is less basic than aniline. Reason : Acetylation of ani electron density on nitrogen 106, Assertion : Nitration of aniline can be conveniently done by protecting the amino group by acetylation Reason : Acetylation increases the electron- C3HsNH3 > (CpHs),NH > (C;Hs)3N) o (©) (CoHs)NH > CyHsNHy > (CyHs)sN > NH, (@)_(CgH)y NH > Cy HsNHy > (CHs)3 NH> NH, ‘The correct order ofthe increasing basicity of methyl amine, ammoniaand aniline is, (CoHs)3N > (CyHs),NH > C3HsNH) > NH, 119, @ (b) © @ Arrange the following amines in the decreasing order of their basicity w Y methyl amine 3>2 1>2>3 @ © (by 3>2>1 (d) 2>1>3 (Opn sna wo 121. (ny) uae «a0 The basicity order of I, Hand IIT is— @ m>I>m (b) Isom (9 Ment () U>u>t Which of the statement is true regarding the basicity of the following two primary amines? é CH,NH, ° CH;NH, 122. (@ b) © @ Both are equally basic because both are 1° amines, 1> Il because itis an aromatic amine I> I because itis an aliphatic amine 1< I because of difference in the nature of -carbon,123. The correct order of decreasing basic character is CoHsNHa, CoHsCHaNH2 To " : (CoH) NH CoH NH m > Vv (@) I> 1>1I>IV (b) IV>11> 111 (©) >t >m>1 (@) I> 01> 1>1 124. Aniline when treated with cone. HNO gives (a) p-Phenylenediamine (b)_m-Nitroaniline (©) p-Benzoquinone —(d)__Nitrobenzene 125. The correct increasing order of basic strength for the following compounds is NH, NH, NH, 2 CH, © ay cm @ Wemle © @ ‘NO> NO, NH 128. CUSCOC, ¢ _BE-H2O, y_ HO" C (major product) is ~ NH NH Br (@) () Br NH, © (d)_ None of these Br 129, Towards electrophilic substitution, the most reactive will be (@) Nitrobenzene (b) Aniline (© Aniline hydrochloride (@)_ N-Acetylaniline 130, ‘The most reactive amine towards dilute hydrochloric acid is HC (@) CHy-NH, © cr NH, HCN >N-CH, © ne @ 131. Nitration of nitrobenzence is carried out than obtained product is reduced with Fe/HCI, product so formed on reaction with HNO, and than with H,0, forms (@)_1,3-4ihydroxybenzene (b) 3-nitrophenol (©) 2-nitrophenol (@_1,2-dihydroxybenzene132. A compound of molecular formulae CsH,N shows following, ‘The structure of C would be: characteristics (Get dissolved in acidic medium. @) © N=N-CH,-N Neu, NaNO, 4 oY 8» — gc AM ; -On-O Neu,FACT/DEFINITION TYPE QUESTIONS 1 © =~ RNH, R,NH RN Primary amine Secondary amine Tertiary amine 2 © 2@ 40 S (© _1°amineshave-NH, group in their structure. 4 primary amines are possible by CH, 1N. CH; ~CH2 ~CH) ~CH NH 0) CH; -CHy -CH-CH; | NH, wi CH; CH; CH, -C -CH-NH3 CHls ~C-CHs H NH, (iii) y) ‘The compound contains longest chain of 6C atoms and amino group. Hence it is analkanamine. 7 @ & @ % @& 10. (©) CHNC (methyl isocyanide) on reduction with LiAIH, gives secondary amine 0 I CH, ~ CH) -C-NH) + Br) + KOH 1.) 4 crty—ctty-Nty 1 @ R-Nec —4", eH-cH, alkyl isoevanide cvcondary sine ° f KOH n B. © NH NK Phuhalimide -Potassium phtbaimide (@ rucleopie) ° rar ee o Nealky! phthalimide ° OH + mN-R OH Pamary Phtnalic 2c HINTS AND SOLUTIONS 4. 18. 21. 2. © © © © @ © 26. 29. 30. 31. 32. 3M 35. 36. 37. 38. 39 42. a. © © @ @ @ ©) @ @ © ® © © @ o © (CHsl+ NH3 —+C3HsNH) +H Baby! ide CaHsOH + NH; —> CHsNH +11,0 16. @ For the preparation of Me,CNH, the required alkyl halide is Me,CX which will react with potassium phthalimide, a strong base, to form alkene rather than substituted product. For preparing CgH,NH, CgHsCl will be the starting halide in which Cl is non-reactive. 19.@ 20.) Reduction with iron scrap and hydrochloric acid is preferred because FeCl; formed gets hydrolysed to release hydrochloric acid during the reaction. Thus, only a small amount of hydrochloric acid is required toinitiate the reaction 23.0 24. (a) Amines possess fishy smell. 27.0) 28.6) Basic nature of amines arises duc to presence of lone pair of e's on the N-atom, which can be shared with an electron deficient species ‘Secondary amine ismore basic than primary amine, Amines are basic in nature (CH,)N 18>3°>NHy €S-ar-st, mpd stb tolocalized lone pair of electron on nitrogen atom while other compounds have delocalized lone pair of electron. .@) 41.) Amines give alcohols only on reaction with HNO, and not on hydrolysis. ~ Aniline gives dyes on coupling reaction with phenols and p-amines. Aryl amines do not produce phenol on treatment with nitrous acid45. ©) 46, (a) 47. ©) 49. @) 50.) ©) @) ‘Methyl amine is a stronger base than ammonia due to +Leffect. The alkyl groups which are electron releasing groups increase the electron density around the nitrogen thereby increasing the availability ofthe lone pair of electrons to proton or lewis acid and making the amine more basie NH CHNH, Ky=18 «10 44 10% Any primary amine means both aliphatic as well as aromatic but monoalkylamines means enly 1° aliphatic amines. Therefore, option (a) is correct while (4) is wrong. RNH,+CHCI,+3KOH—> RNC +3KC1+3H,0 alkyl ssocyanide We know that CHIN, + CHC, +3KOH —> HH NCedKEts 31,0 In this reaction, bad smelling compound ethyl isocyanide (CH CH, NC) isproduced. This equation isknown ascarbylamine reaction. Acylation occurs in one step only because lone pair of nitrogen is delocalized with acyl group. QP , G @ t R-NH2C>CH; <—>R-NH-C-CH3 R-NH,+CHCI, _aie. KOH, sc xowt cys “< = RNH, —™®2 5 ROH+H,O+N, t wo ® © ‘Since the organic amino compound on reaction with nitrous acid at low temperature produces an oily nitrosoamine so the organic amino compound is a secondary aliphatic amines, (C)HsNH) + HNO) Ethyl amine Nitrous acid ee R-NeC 27-278K [Link] +N, +H,0 Ethanol Note : This reaction is used as. test for aliphatic amines since no other class of amines liberates N, gas on treatment with HNO}. 1° amines (aliphatic and aromatic) react with CHCl,/KOH to yield isocyanide (foul smelling) This is known as carbylamine test which is not given by 2° and 3° amines. 54. @ Nitrous acid reacts differently with aliphatic and 7. n. n 73. 74. © © © @ @) © © @) @ aromatic amines in cold. (CoHsNHp+HONO—+CHsOH+ No 1 Amine Alcobo! e Ni 2 cr Benzene diazonium chloride O-O-O~--O) ‘The compounds containing active H-atoms (H atoms attached to N, O or S) react with CH,COCI to form acetyl derivatives. 59.0) 60.) 4. @) Hinsberg’s method is based on the use of benzene ssulphonyl chloride ‘The inclusion of CHjCO gp in a molecule is called benzoylation Aniline is insoluble in water, because its—NH, group can’t form H- bond with water due to bulky phenyl group, 0.0) 70. @) Pyridine is a stronger base than the amine, pyridine removes HCI formed in acylation reaction ofamines and shifts the equilibrium to the right hand side. ‘The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of strong electron withdrawing sulphonyl group. Hence, itis ‘soluble in alkali. In case of substituted aniline, electron releasing groups like -OCH,, ~CH, increase basic strength whereas electron withdrawing groups like -NO,, -SO;H, —COOH, —X decrease it. NH) oO + Hono» (NaNO + HC), 61.) 62. @) NH, R-Na® Nanio,/ttct ve Disa © cubuite Sandmeyer reaction15. 0) aniline 76. (a) Azo dye is prepared by diazo coupling reaction of phenol with diazonium salt 5-6-O--© — P-trdroxyambenzene chleide (-N=N_-) group iscalled az0— group, NH, Nenct 7. CO) ase, NaNO, HCL Oe Cucn, “vc Anne (azotisaton) ee uaronum chloride “N HNH, O Lill O (B) « Cymotentens benaylarsine 78. (b) The given reaction is known as Sandmeyer’s reaction. Ny scr ot, 80.) 7 =NCI + © Benzene diazonium chloride — Ope p-llydroxyazobenzene (orange dye) 81. (©) Primary aromatic amines react with nitrous acid to yield arene diazonium salts ArNH, + NaNO, + 2HX —SM4y 1° Aromatic amine ArN=N*X- + NaX + 2H,0 Aree diazoniam salt The diazonium group can be replaced by Nuorine by treating the diazonium salt with fuoroboric acid (HB,). The precipitated diazonium fluoroborate is isolated, dried and heated until decomposition occurs to yield the aryl fluoride. This reaction is known as Balz-Schiemann reaction. Ar—N;*X- HEL ar—n,*BF,-+ ty ‘Ar—F + BF3+Ny NH, N3cr Nant ¢ HO,278K Diazotzation 82. (@) Benzene daazonium “hlonde aw Benzonitile 8) Sandmeyer reaction 83. 86. © — 84) 85. (a) (a) Excess of HClis used to convert free aniline toaniline hydrochloride otherwise free aniline would undergo coupling reaction with benzenediazonium chloride. 87. 88.) 89.6) 90.) ) o. ) o STATEMENT TYPE QUESTIONS 93. (6) The fourth orbital of nitrogen in all amines contains an unshared pair of electrons. Due to the presence of unshared pair of electrons, the angleC-N-E, (where E isC or H) is less than 109.5°. Lower aliphatic amines are soluble in water solubility decreases with increase in molar mass of amines. Higher amines are essentially insoluble in water. 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 more in primary amines than in secondary amines as thereare two hydrogen atoms available for hydrogen bond formation in it. Tertiary amines do not have intermolecular association due to the absence of hydrogen atom available for hydrogen bond formation. Therefore, the order of boiling points of isomericamines is as follows Primary > Secondary > Tertiary6. 7. o (@) ‘The yield in Sandmayer reaction is found to be better, than Gattermann reaction, MATCHING TYPE QUESTIONS 98. (a) 99. (a) 100. (b) 101. (e) ASSERTION-REASON TYPE QUESTIONS 102. (a) 104. (a) 105. (@) 106. (@) 107. (a) 109. (@) 103. (@) Amines are basic due to the presence ofa lone pair of electrons on nitrogen atom. The lone pair can beeasily donated. Acetylation decreases the clectron-density in the benzene ring thereby preventing oxidation, 108, (¢) HNO; +2H)S04 === 2HSOj + NO} +H30* CRITICAL THINKING TYPE QUESTIONS 110. (a) M1. © 12. © 113. (a) 114, @ Hy 7 —~ an Hs He- cHy Calls N, Ne diethyl propan - 2-amine ‘The compound is derivative of aniline. The positions of groups are shown by numbering the nuclear C- atoms, cxycontt, 2 crits (Hofmann bromamide reaction) Aniline cannot be prepared by this method because aryl halides do not undergo nucleophilic substitution with potassium phthalimide under ordinary conditions to give N-phenyl phthalimide (i.e., cleavage of C-X bond in haloarenes is quite difficult) CAO “o> afira.o COOH + RNHL, ‘COOH 115. @) 116. @) 117. @ 118. @) 119. @) 120. @) ‘The reaction is Hoffmann bromamide reaction 1 R= Ny By +40 — R= NH) + 2NaBr + NayCO3+2H20 oO R—NH, contains one carbon less than r-b-nn Secondary amines are more basic than tertiary amines due to stabilisation of 2° amine by hydrogen bonding with solvent molecule. Aromatic amines are less basic than aliphatic amines. Among aliphatic amines the order of basicity is 2° > 1° > 3°. The electron density is decreased in 3° amine due to crowding of alkyl group over N atom Which makes the approach and bonding by a proton relatively difficult, Therefore the basicity decreases, Further Phenyl group show ~ I effect, thus decreases the electron density on nitrogen atom and hence the basicity. dimethylamine (2° aliphatic amine) is strongest base among given choices. ‘The correct order of basic strength is Dimethylamine> Methyl amine > Trimethy! amine> Aniline. All aliphatic amines are stronger bases than NH; and among different ethylamines order of basictity is 2°> 19> 3°. Thus, the correct order is (d)i.e., (C,H), NH> C,H,NH, > (C,H,),N>NH, ‘This anomolous behaviour of tertiary ethyl amine is due to steric factors i.¢., crowding of alkyl groups cover nitrogen atom from all sides and thus makes the approach and bonding by a lewis acid relatively difficult which results the maximum steric strain in tertiary amines, The electrons are there but the path is blocked resulting the reduction in its basicity. Inaniline the lone pair on Nisinvolved in delocalization with benzene ring and is not available for protonation. Methyl amine isa stronger base than ammonia because +L effect of methyl group increases electron density ‘on N making it more basic than NH,. ®nn, 6-8 ‘Cannot be protonated. least basic CH, > NH, “fet increases fase125. 121. @) (Oy™« _{a1xCO,,O.F yi, . 126. @) C)-a o 11, compound is most basic due (Liat to localized lone pair ofelectron on nitrogen atom while NH 6 —CHs 0 cts cman tne elaine deste (hy 90 NH-CO-CH, ab Product (II) is Op ~C~—CH, and (III) is ll NH -CO-CH; oO i) Oya -CH)-CH; (ub NO *, I> 1> IL, As + Leffect increases the basic strength : and — R, ~ I effect shown by ~ COCH; reduces the {ne basic strength. 122. (@) Here again the two amines differ in the nature of B-carbon atom NH 123. b) Gieaterthedelocaistion of lctron pair on N, lesser is its availability for protonation leading to lesser basic NED NO, character, Vv m oO agent, aaa, to mu I Ia ‘rekcirnlang ‘lean erbarwing It anin Father Clap NH-C-CH NH-C-CH3 124, (b) Although - NH, group is op - directing but in presence of conc. HNO, it undergoes protonation to Bry-Hz0 form NH, which, being electron - deficient, becomes m- directing, Br NH, “wn, (a) (B) cone. HNO, cone. HNO, NH Nil; group is = NU} group is 0, p- directing m- directing 20" Sn, ©129. ) 130. ) nitrobenzene Aniline Nucl I-N-C-CH, ‘Aniline hydrochloride N+ Acetylanitine Nitrobenzene and aniline hydrochloride haveelectron- withdrawing (-NO, and NH) groups, hence these will undergo electrophilic substitution with difficulty. Aniline and N— acetylaniline (acetanilide) have electron~ releasing groups, however -NHCOCH, is less electron- releasing than - NH due to delocalisation of lone pair of electron on N toward carbonyl group. Hence aniline (having ~ NH) will No; Fettcl ‘NO; ‘NH NO, No, 10 oH N,CI 132. (a) 133. (@ The reaction can be completed as follows: Itisa tertiary amine hence shows above observations. NH, _NaNOvHCy, azetsaton) OOO“, NNedmethylaniine artim nie |: OnOrKor edithlamnoussbenens