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Amines Notes and Exercise Questions

Class 12 Chemistry Amines Class notes

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Amines Notes and Exercise Questions

Class 12 Chemistry Amines Class notes

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sanchana.kalaimani
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POINTS TO 1. Introduction Alkyl or aryl derivatives of ammonia are regarded as amines. These are obtained by replacing one or more hydrogen atoms by alkyl or aryl groups. Amines are classified as primary, secondary or tertiary depending ‘upon whether one, two or three atoms of hydrogen have been replaced by alkyl or aryl groups. NH; —Zh— CH,NH, —Zh— (CHy,NH — (CHy)3N i sietganiae °C Dineymine Tusedplinice itaman) PtSecondan) Setenany ‘Thus, characteristic functional groups for 1°, 2° or 3° amines are: I i NH; —Nu Oo + K,COs + 2KBr + 2H,0 Benzamide Aniline 5S. Physical Properties (0 The lower members are combustible gases, members from C; to Cy are volatile liquids and from Cy ‘onwards are solids. Lower aromatic amines are liquids while the higher ones are low melting solids. (ii) Pure amines are almost colourless but develop colour on keeping in air for long time, especially, the ‘aromatic amines. The colouration is due to oxidation of amines by air. (iii) The boiling point increases with the increase in molecular weight. However, primary and secondary ‘amines have higher boiling points than the tertiary amines of the same molecular weight. This is again due to the possibility of intermolecular hydrogen bonding between molecules of primary as well as secondary amines. Amines 405 © scanned with OKEN Scanner ‘The hydrogen bonding between amine molecules is weaker than that between alcohols or carboxylic acids therefore amines have lower boiling points than the alcohols or carboxylic acids of comparable molecular masses. (iv) The lower members are readily soluble in water, the solubility in water decreases and in organic solvents (alcoho! and ether) inereases with the increase in molecular weight. ‘Solubility of all the three classes of aliphatic amines in water is due to the formation of hydrogen bond between amine and water molecules. However, in higher amines, the alkyl group predominates over the amino group with the result that they have less tendency for forming hydrogen bond with water. ‘This explains why the higher amines are insoluble in water. Aromatic amines are insoluble in water. This is because of the larger hydrocarbon part. Thus, aniline is almost insoluble in water. However, all amines are quite soluble in organic solvents like benzene, ether, alcohol, etc. 6. Basie Character of Amines: Amines have a lone pair of electrons on nitrogen atom due to which they behave as Lewis base. Basic character of amines can be better understood in terms of K, and pX;, values as explained below. RLNH, + H,O —= R—NH, + OH 1R—NH,IIOH) RNA] PK, =—log Ky Larger the value of K, or smaller the value of pK, stronger is the base. (a) Amines versus alcohols, ethers and esters: Since nitrogen is less electronegative than oxygen, it is in a better position to accommodate the positive charge of the proton, Therefore, amines are more basi than alcohols, ethers, esters, etc. (b) Alkylamines versus ammonia: In aliphatic amines, the electron-releasing alkyl groups stabilise their ammonium cations by dispersing the positive charge, and in parent amines make the nitrogen unshared electrons more available for sharing with a proton, Thus, the basic character of aliphatic ‘amines should increase with the increase of alkyl substitution. But it does not occur in a regular manner as a secondary aliphatic amine is unexpectedly more basic than a tertiary amine in solutions. Basicity Order: (Et),NH > Et,N > EtNH, > NHy; (Me)sNH > MeNH, > (Me),N > NH, In gas phase, where the solvent effect is missing. the basic trend in nature is as expected, ie. tertiary amine > secondary amine > primary amine > ammonia. Anomalous basic strength of tert-alkylamines: In aqueous solution, the substituted ammonium cations are stabilised not only by electron-releasing effect of the alkyl groups but also by solvation with water molecules. It is a combination of electron-releasing alkyl groups, H-bonding and steric factors that determine the stability of the ammonium cations in solution and thereby resulting in the basic strength order of aliphatic amines as secondary > tertiary > primary amines. (¢) Aromatic amines versus ammonia and aliphatic amines: Aromatic amines are weaker bases than ammonia and aliphatic amines. Since resonance stabilises an aromatic amine more than it stabilises its ammonium cation, the proton acceptability and thereby basic strength of aromatic amines would be less. It may also be argued that due to resonance, unshared electrons on nitrogen in aromatic amines are less available for sharing with a proton—a feature opposite to that in alkyl amines. 406 Xam idea Chemistry-Xil © scanned with OKEN Scanner (@ Effect of substituent on the basicity of aromatic amines: (@ Electron-donating groups such as —CH,, —OCH, -NH,, etc., increase the basicity while electron-withdrawing substituents such as —NO;,—CN, halogens, etc., decrease the basicity of amines. The effect of these substituents is more at p- than at m-positions.. (i) Among the isomeric toluidines, the basic strength with respect t0 a NH, NH, NA, CHy ii) The order of basic strength of some amino compounds: Ortho-substituted anilines are weaker bases than aniline irrespective of the nature of the substituent. This is called ontho-effect and it is probably due to a combination of steric and electronic factors. NH, NH, NH, NH, NHCH, NH, NH, Q . O . O . o . O . O . O NO, Br a CH OCH; 7. Chemical Properties of Amines: (@) Alkylation: CH=CH Nl “Oa (CHy—CH,):NH yamine corer (CHy—CHy),NBr 22 CH, —CH,)sN “Teeth Tiictylamine scene bromide (b) Acylation: i i R-NH, + R’—C—cl R—NH—C—R’ + HCI Newbee amide i ase CH,—CH, (CHy—CHy_NH + CHy—C—cl + cH, CoN CH Diethylamine Acetyl chloride 'CH;—CHy NNDietiyacetmide + HCI i CH—Cw I CH;—CH;—NH; + >>0 —— CH;—C—NH—CH;—CH; + CH;—COOH Ethylamine cus N-Ethylacetamide Acetic anhydride i 9 NH—C—CH, Amines 407 © scanned with OKEN Scanner g cl H—-CHy CH;-NH, + — + HCl Methylamine pentoyl chloride N-Methybenzamide i i NH, cc ¢—nn-{O) O +O BQ era Asiline Benzoy/ chloride Benzanilide (c) Reaction with chloroform (Carbylamine reactior RONH; + CHCh + 3KOH (ale) —“~ RNC + 3KCI + 34,0 cabyiine NH, NC o + CHCl; + 3KOH (ale) —A_. oO +3KCl + 3H;0 Aine Prenylisocyanise (@) Reaction with nitrous acid: Reaction with nitrous acid helps in distinguishing between amines. Primary amines react with nitrous acid to form alcohols. + HONO “SO ROH + Nz + H20 Secondary amines react with nitrous acid to form a yellow green oily layer of N-nitrosoamines. N-nitrosoamines on warming with a crystal of phenol and a few drops of conc. HSO, form green solution which when treated with aqueous NaOH, turns deep blue and then red on dilution. This reaction is called Liebermann’s nitroso reaction. R,NH + HNO; ——~ R,N-N=O + H. Amine N-Niuonoamine tert-Amines readily dissolve in nitrous acid forming crystalline tialkyl ammonium nitrite. RN + HNO, —- __RsNHNO} ‘eiatyl ammo ite (@) Diazotization: NH, Nenci o +NaNO, + 2HC] —2-278K oO +NaCl + 2H,0. Asiline erediao0i ‘honde (P Electrophilic substitution reactions: Due to resonance, electron density increases at ortho and para positions as compared to meta positions. ‘Therefore. NH; group directs the incoming group to ortho and para positions. INH; Ay fy chit iit Gf 85 408 Xam idea Chemistry-Xil © scanned with OKEN Scanner (1%) In strongly acidic medium, significant amount of meta isomer is obtained. This is due to the formation of anilinium ion which is meta directing. However, the p-nitro derivative can be vu iS pa =| W | e) v2] tm < im < les) a (tao) PNitroaniline (i) Sulphonation: Nn, NHHSO, NH, NH, Gea OG 226 a seine sine ee (0) Friedel-Crafts renction: ta) An,aici, oO + AIC; = ———> oO toe tie Due to salt formation, nitrogen of aniline acquires positive charge and thus acts as a strong deactivating group and hence does not allow Friedel-Crafts reaction to occur. Amines 409 © scanned with OKEN Scanner 8 Diazonium Salts (@) General formula: RN;X™ where R stands for an aryl group and X" ion may be CI”, Br’, HSOj, BF;, etc. The No(—N = N) is called the diazonium group. (6) Stability of diazonium salts: Arenediazonium salts are much more stable than alkyl diazonium salts. The stability of arene diazonium salt is due to the dispersal of the positive charge over the benzene ring as shown below. (©) Preparation of diazonium salts NH, NX oO 4+ NaNO, + 2HX —2=278K, oO + NaX + 2H,0 Aniline Denzene axon ‘ak This process of conversion of a primary aromatic amine into its diazonium salt is called diazotization. 9. Chemical Properties of Diazonium Sal ‘The reactions of diazonium salts can be divided into two categories, namely (a) Reactions involving displacement of nitrogen. (b) Reactions involving retention of diazo group. (a) Reactions involving displacement of nitrogen: @ Replacement by halide or cyanide ion: ArNyX” S28 rc + Ny) ArN,X” —S2B2B_ arpr + Ny { Sandmeyer's reactions AIN2X” SSRN. ACN + Ny on cunt AMX ArCl + No + Cux Gatterman’s reaction AN, x” —Sut ArBr + Ny + CuX (ii) Replacement by iodide ion: ANCE +KI—- Ad + KCI + Ny Benzene diario Iadoberene ‘orde Gi) Replacement by fluoride ion: AIN,CI” + HBF) — ArN,BF7 —“— Ar—F + BF; + No iv) Replacement by H: AIN,CI” + H3PO; + HzO —— ArH + Ny + H3PO3 + HCL AWN,CI” + CHy—CH,—OH — Ar +N, + CH)—CHO + HCI 10 Xam idea Chemistry-Xil © scanned with OKEN Scanner (©) Replacement by hydroxyl group: AmN2Cl' + H20 —*~ ArOH + Nz + HCI Pew < (vi Replacement by —NO, group: [Link] [Link] NO; z — NNO © + HBF, sn + NaBR, + Nz ; luoroberie acid IitoBarene () Reactions involving retention of diazo group: Coupling reaction: The reaction of diazonium salts with phenols and aromatic amines to form azo compounds of the general formula, Ar—N=N—Ar is called coupling reaction. The mechanism is basically that of electrophilic substitution where the diazonium ion is electrophile. In this reaction, the gen atoms of the diaz0 group are retained in the product. The coupling with phenols takes place © in mildly alkaline medium while with amines, it occurs under faintly acidic conditions. For example, ©pnvancr + (O)-on BES. (O)-n=n{O)-oH + HCI r ‘Bentenediazoium Phenol ‘Pygoxyarobensene Ghonde ‘orange dye) uy tence “max (Opntencr + (Ow, BSR (O)-n=n{O)-NHy + HEI Bentene dizoniam Aine ‘-Aminasobensene J Chott ‘Gelow . Na0,8-{O)-Nte=Ncr + (O)-NCHy) FB2BKON, AD area N-Dimetyanitine cu na 5 Nz0,8-{O)-W Cou, Ct Matylorange 13 Coupling generally occurs at the p-position, w. it takes place at the o-position. 10, Some Important Name Reactions (a) Gabriel phthalimide synthesis: This reaction is used for the preparation of aliphatic primary amines. In this reaction, phthalimide is first of all treated with ethanolic KOH to form potassium phthalimide. Potassium phthalimide on treatment with alkyl halide gives N-alkyl phthalimide, which on hydrolysis with ae hydrochloric acid gives a peiary ‘amine as the product. Orbe sate +Kowatey oe tio, * Spe the hydroxyl or the amino group, if free, otherwise Pitatnie coon Ni + ‘COOH Phahalic ac @) foffmann bromamide reaction: When a primary acid amide is heated with an aqueous or ethanolic solution of NaOH or KOH and bromine (ie., NaOBr or KOBr), it gives a primary amine with one carbon atom less. R—CONH, + Bry + 4NaOH —~ R—NH) + Na;COs + 2NaBr + 2,0 ‘Acid amide Manine Amines 411 | © scanned with OKEN Scanner "ONH; NH, + Bry + 4KOH ——> O + K,COy + 2KBr + 2H,0 Benzamide Aniline (©) Sandmeyer’s reaction: The CI’, Br" and CN“ nucleophiles can easily be introduced in the benzene in the presence of Cu (I) ion. This reaction is called Sandmeyer's reaction. a cucynict a +N Chlorobenzene Sener Br Benzene diazoniom Bromabenzene ‘hide oN NIKCN cucnxer an, Benzonirle (@) Gatterman’s reaction: Chlorine or bromine can be introduced in benzene ring by treating the diazonium salt solution with corresponding halogen acid in the presence of copper powder. cl #2. GO) ems ac Chlorobenzene Br a) +Ny + CuCl Bromobenzene X,cr (@) Carbylamine reaction (Isocyanide test): Aliphatic and aromatic primary amines when heated with chloroform and alcoholic solution of KOH give isocyanides (carbylamines) which have extremely unpleasant smell. RNH, + CHCl; + 3KOH (ale) —~ R-NC + 3KCI + 3H,0 Vramie re weynie NH, Ne o + CHCls + 3KOH (ale) —S+ Oo + 3KCI + 3H,0 aloe Phenyl isyae IL, Uses of Amines: (@ The quaternary ammonium salts of long chain aliphatic amines are used as detergents, e.g. cetyltrimethyl ammonium chloride. ii) Low molecular mass aliphatic amines are used as reagents in organic synthesis and as intermediates in the manufacture of drugs. (ili) Aniline is used in the manufacture of dyes, dye intermediates and sulpha drugs. 412 Xam idea Chemistry-Xil © scanned with OKEN Scanner 12. Test for Amines (a) Hinsberg’s test: In this test, the amine is first treated with Hinsberg’s reagent (benzenesulphonyl chloride) and then shaken with aqueous KOH solution when the three amines behave in different ways. @A 1° amine gives a clear solution which on acidification gives an insoluble N-alkyl benzene H Rn +HOu ote ; Benzene N-Alkylbenzenesulphonamide Peon | sulphonyl chloride (soluble in KOH) (ii) A 2° amine gives an insoluble N, N-dialkyl benzene sulphonamide which remains unaffected on addition of acid. Ole. uks — Of hae ul 2 Amine - Benzene — = sulphor chloride sulphonamide r (insolubie in KOH) £ iii) A 3° amine does not react at all. nt [Link] + RN No reaction os) Benzene mipbony! amine am ‘lerde () Isocyanide test (Carbylamine test): Primary amines (aliphatic as well as aromatic) react with — chloroform in the presence of alcoholic KOH to form foul smelling carbylamine. a R-NH; + CHCl, + 3KOH (ale) —*- R—NC + 3KCI + 3H,0 Famine yt eyside NH, Nc oO + CHCl, + 3KOH (ale) —4—> oO + 3KC1 + 3H,0 aniline Phenyl izocyanie Secondary and tertiary amines (aliphatic as well as aromatic) do not give this test. (©) Azo dye test: It involves the reaction of any aromatic primary amine with HNO; (NaNO, + dil. HCI) at 273-278 K followed by treatment with an alkaline solution of 2-naphthol, where a brilliant yellow, orange or red coloured dye is obtained. Opn + HONO + Hcl —2275K (O>N=xcr + 2H,0 Asiline Benzene diazonium ‘chloride OH — _DiLNAOH = Orinner Gy sya. Gren «se Benzene dszoniam mae ©) ©) [Link] 1-Phenyaco-2-napnbl (Grange ye) Aliphatic primary amines under these conditions give a brisk evolution of Ny gas with the formation of primary alcohols, i-e., the solution remains clear. RNH, + HONO 273K. R_oH + Nyt + HO ‘aol C)HyNH, + HONO 228K __ C,H,OH + Not + H)O Eylamine Eyl! Amines 413 © scanned with OKEN Scanner Ans. Classify the following amines as primary, secondary or tertiary: NH, N(CHiy2 (@) @) (©) (Cylg,CHNH, ——@) (CHy;NH (@) Primary (©) Tertiary (©) Primary (@ Secondary (a) Write structures of different isomeric amines corresponding to the molecular formula, CHiN. () Write TUPAC names of all the isomers. (c) What type of isomerism is exhibited by different pairs of amines? (a) and (by Primary amines: ( CH,CH,CH,CH,NH, (ii) CHyCH,— CH—CH, Butanamine I NH, Batn-2-amine CH, 2 2 (i) CH;—CH—CH,—NH; 2 Met ropananice Secondary amines: (v) CHy—CH)—NH—CH,CH, (vi) CHCH,CH,—NH—CH, N-Bihyletanamine [N-Methylpropanamine ‘CH, on dy 2dt—ne—cay, SSenlpopn amie Tertiary amine: CH; (viii) CH: tones, NN Dineyenamine (c) Chain isomers: (i) & (iv Position isomers: (i) & (ii), (vi) & (vii) Metamers: (v) & (vi), (v) and (vii) Functional isomers: All primary amines are functional isomers of secondary and tertiary amines and viceversa, How will you convert: (Benzene into aniline, (ii) Benzene into N, N-dimethylaniline, (ii) CKCH,),—C1 into hexan-1, 6-diamine? cme 80, cone SO NO> remica o™ oO S- CO TES eee een) Me sie cn ss iy se i : » © vane ae a wSecptate 414 Xam idea Chemistry-XIl © scanned with OKEN Scanner Ethanole NC (ii) CL-(CH)4—C1 Dichlorobutane C—(CH).—C EN Hans H;N—CH;—(CH;),—CH:—NH; Hexane1,6daming or \—(CH)¢—NH3 Q.4. Arrange the following in increasing order of their basic strength: (a) CyH NH, , CNH, NH, « [Link], , (CyH9),NHL (6) CgHNU, , (Cyl) NHL, (CH), CHANT (©) CHNHL , (CHL),NH, (CH) Ny Cll NH,» Cll sCHNH Ans. (a) CgHgNH < NHy < CgHsCH,NH, < C3HsNH, < (C3Hy);NH (b) CgHgNHy < C3HsNHp < (CHy)3N < (CoH) NH (0) CgHyNHz < CgHsCHaNHy < (CH3)3N < CHNH, < (CH,);NH Q.5. Complete the following acid-base reactions and name the products: (® CHyCH,CH,NH; + HCL —- (i) (C:H93N + HCL — <—™, fh tar Ans. (i) CHjCH:CH:NH2 + HOC! ——+ CH,CH;CH:NH3CI ropyamine ‘Popjlamonimehonise oN Suer di) CHyN + HOC. ——- — (GHy,Nucr “hethylamine ‘Toeglammonium ere Q.6. Write the reactions of the final alkylation product of aniline with excess of methyl iodide in the presence of sodium carbonate solution, NH; + Malt ——> [GH [Link]” NMethyaniiium odie 2ICGHsNH CHy] I + NagCOy ———> 2CHsNHCHy + CO: + 2Nal NMethylaiine « ony carstinich Ee cyyNicH): N,N-Dimethylanitine CHSN(CHy), + ni. CoHN(CH,).I” [Link] 2CHNICH)5 + Ne;CO——> _[CQHACHIg:COF + Nal nih Tinea conse Q.7. Write chemical reaction of aniline wth beneoy hlarde and write the name f the product obtained, H H O5 fo) Aca roLy wonwn, [Pryeh iP itt ans, )-n: 4 cotptc Ld Noten, Oan-c—cotts 1-C—Cglly I Zi 4 & 1 TN Pheytenzmide Aviline Benzoyl NeAllgl benzene Benzaniie) chlo Ssulponamise Q.8. Write structures of different isomers corresponding to the molecular formula, CyHl,N. Write IUPAC names of the isomers which will liberate nitrogen gas on treatment with nitrous acid. ‘Ans. Inall, four structural isomers are possible. These are as follows: Primary amines: CH;CHCH2NH, CH;—CH—CH; Propan “famine NH; Progen Amines 415 © scanned with OKEN Scanner Secondary amines: CHj;—NH—C>Hs N-Methledanamine ors Tertiary amines: CHy—N—CH, NN-dimetyinethanamine Only primary amines react with HNO, to liberate Ns £28, CH;CH,CH,NH, + HNO; —~ CH;CH,CH,OH + H,0 + Nz Props taiee Fropea- deol jer roe) cH, cH, “SCH-NH, + HNO, ——* ~ > SCHOH + N; + H,0 Hy cHy Propan-2amine Propan-2-01 (ar produc) Q.9. Convert: (@ 3-Methylaniline into 3-nitrotoluene i) Aniline into 1, 3, §-tribromobenzene Hy cH. NaNOWHDE, Ans. (i) & 23218, Q, BaNowCu a Nig Das Heat No, 2 = 3-Methylaniline [Link] NH NH Nicr Br NNOYHC! By Br Br. Br «i Bao, “or T3-28K HPO, 3,0 IOs “Bromination™ ‘Diazotsation)” Br Br Br 2.4, 6Tribromoanline 13,5 ‘Tribromabenzene Q.1. Write IUPAC names of the following compounds and classify them into primary, secondary and tertiary amines. @ (CHy,CHNH, i) CHACH).NU, (ii) CHANHCHICHY: (iv) (CH) CNH () CH NHCH, (vi) (CH CH,).NCHy (ii) m-BrCgHNHy Ans. (i) Propan-2-amine (primary) Gi) Propan-1-amine (primary) (iti) N-Methylpropan-2 amine (secondary) __({v) 2-Methylpropan-2-amine (primary) (v) N-Methylbenzenamine or N-Methylaniline (secondary) (vi) N-Ethyl-N-methylethanamine (tertiary) (vii) 3-Bromobenzenamine or 3-Bromoaniline (primary). Q.2. Give one chemical test to distinguish between the following pairs of compounds: () Methylamine and dimethylamine (ii) Secondary and tertiary amines (ifi) Ethylamine and aniline (iv) Aniline and benzylamine (0) Aniline and N-methylaniline ‘Ans. (i) Methylamine is 1° amine, therefore, it gives carbylamine test, ie., when heated with an alcoholic solution of KOH and CHCl; it gives an offensive smell of methyl carbylamine. In contrast, dimethylamine is a secondary amine and hence does not give this test. 416 Xam idea Chemistry-Xil © scanned with OKEN Scanner CH,NHs + CHCl + 3KOH CH,NC + 3KCI + 31,0 Mea ine Mat etpbnine (anne) (conve me) (CH) ,NH —SHURONIE) No reaction. inet aine eat (Canine) (ii) By Hinsberg's reagent (benzenesulphonyl chloride). The amine is treated with benzenesulphony! chloride and shaken with alkali solution when the two amines behave in different ways: (@) Secondary amines form dialkyl benzenesulphonamide which does not react with alkali and hence it remains insoluble. (&) Tertiary amines do not react with benzenesulphony! chloride at al. oH CsHsSO2Cl + HNR, ——~ CgHsSO2NRz No reaction Secondary Dally ‘amine Berseseslphonsmise CsHsSO2Cl + R3N ——~ Noreaction TTentry i) Ethylamine is primary aliphatic amine while aniline is a primary aromatic amine. These may be distinguished by the azo dye test: Refer to Points to remember 12(). (iv) Benzylamine reacts with nitrous acid to form a diazonium salt which being unstable even at low temperature, decomposes with evolution of Ny gas. CoHsCH;NH, —4 Bensyiamine ICotiCHA = NCI] t= [Link] + Not + HCI Hs 1 —Greonpoas~ CHlsCHs01 Hy ‘Aniline reacts with HNO, to form benzene diazonium chloride which is stable at 273-278 K and hence does not decompose to evolve Ns gas. HNO HEL ee Se ON ener Benzene diazoniam chloride (») Aniline being a primary amine gives carbylamine test, ie., when heated with an alcoholic solution of KOH and CHCl, it gives an offensive smell of phenyl isocyanide. In contrast, N-methylaniline, being secondary amine does not give this test. CgHsNH; + CHCl, + 3KOH —*. CyH NC + 3KCI + 3H;0 s ‘nine Phenyl nny aide (nine) (eter) cuiciyeontate i CeHy—NH—CH, —SSHMONEE) No reaction. N-Medaniline 2 amine) Account for the following: ( pK, of aniline is more than that of methylamine. (ii) Ethylamine is soluble in water, whereas aniline is not. (ii) 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. (CBSE 2020 (56/5/1)] (vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines. (vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines. ‘Ans. (i) Inaniline due to resonance, the lone pair of electrons on the N-atom are delocalised over the benzene ring, Due to this, electeon density on the nitrogen decreases. On the other hand, in CHNHs, +I-effect of CH, increases the electron density on the N-atom. Consequently aniline is a weaker base than ‘methylamine and hence its pX, value is higher than that of methylamine. Amines 417 © scanned with OKEN Scanner dissolves in water because it forms H-bonds with water molecules as shown below: { H I H na a —? GHs GH; H In aniline, due to the large hydrocarbon part the extent of H-bonding decreases considerably and hence aniline is insoluble in water. Gil) Methylamine being more basic than water, accepts a proton from water, liberating OH” ions. a fy ‘ . cHNH, + HOH CHA, + OF ‘These OH” ions combine with Fe”* ions present in HzO to form brown precipitate of hydrated ferric oxide, FeCl; ——- Fe + 3¢17 2Fe* + 60H” ——- 2Fe(OH); or Fe;03.3H,O yd ri oie ‘Gown (iv) Nitration is usually carried out with a mixture of conc. HNO, and cone. H3SO,. In presence of these i, most of aniline gets protonated to form anilinium ion. Thus, in presence of acids, the reaction mixture consists of aniline and anilinium ion. The —NH, group in aniline is 0, p-directing and activating while the NH; group in anilinium ion is m-directing and deactivating. Nitration of aniline mainly gives p-nitroaniline. On the other hand, the nitration of anili ‘menitroaniline. NH, NH, NH, O#O - Oo Ailing NO) ‘pNitroailine (51%) ao + + Nu, NH, NH, © = O. oy " NO, HT ‘NO, Anitinium fon ‘m-Nitroniline (57%) ‘Thus, nitration of aniline gives a substantial amount of m-nitroaniline due to protonation of the amino group, ine being a Lewis base, reacts with Lewis acid AICIs to form a salt. CgHsNHz + AICI; —— CsHsNH,AICIy Lewitbase Lewisacid ine acquires positive charge and hence it acts as a strong deactivating group for substitution reaction. Consequently, aniline does not undergo Friedel-Crafts reaction. (vi) The diazonium salts of aromatic amines are more stable than those of aliphatic amines due to dispersal of the positive charge on the benzene ring as shown below: (vii) Gabriel phthalimide reaction gives pure primary amines without any contamination of secondary and tertiary amines. Therefore, itis preferred for synthesising primary amines. 418 Xam idea Chemistry-Xil © scanned with OKEN Scanner Q.4. Arrange the following: (@ In decreasing order of the pK, CHAN, , CHNHCHY (C, (i) Ininereasing order of basic strengti “INH, , CN(CH yy, (Cyl), NH and CIN, (ii) In increasing order of basic strength + p-nitroaniline and p-toluidine NH,» CUNHICH, . CH CHNI, (iv) In decreasing order of basic strength in gas phase: CAINE, (CjM,),NH, (CH),N and NH, (®) In increasing order of boiling point: CyH,OH, (CHy), NH, CNH (vi) In increasing order of solubility in water: CelgNHy, (CyH1p):NH, CzHNH, (®) CgHgNHy > CgHsNHCH; > CoHsNH2 > (C3Hs)NH (ii) CgHsNH, < CgHjN(CH,), < CH NH; < (C;Hs);NH Gii) (a) p-niteoaniline < aniline < p-toluidine. (B) CcHsNHz < CcHgNHCH, < CHCH.NH3 (iv) (CsH)5N > (CsHy);NH > C)HsNH, > NHs (0) (CHy):NH < CpHsNH, < CsHsOH (vi) CgHNH, < (C,H.).NH < C,H,NH, Q.5. How will you convert (@ Ethanoie acid to methanamine (ii) Methanol to ethanoie acid Ans. (ii) Hexaneni (v) Ethanami itrile to 1-aminopentane jine to methanamine (v) Ethanoic acid to propanoic acid (vi) Methanamine to ethanamine (ii) Nitromethane to dimethylamine (viii) Propanoic acid to ethanoic acid? Ans. (@ CH,COoH 2 cHycocl SH. cH,CONH, eae CHNH; Titanic aid Etaryl clone hnaide "Were ome Nene Gi) CH (CH,) CN —"8°—.. cH, (CH) ,CooH —— CH,(CH,),COCI Heweninle vein Hecaci acid Uexaoylelonde Se. CHy(CH,),CONH; —2"°". CH, (CH,),.NH Avinopenane Gi) CHjoH 2 cHycr ~™. cHyen —Y°— cH,coon Meteo Eeesie Tatu acd G) CHycHaNH seta CH;CH,OH 10-1504 xu aencont edison) CH3COOH 2 (CH;CONH> Wotimana 7 CHSNH: secomise reaction) al © cH;coon 4+ cHycH,0H 8 cHycH) — (CH;CH;CN itanac wid Re al Bipinde“ iptoyide 0M" __ CH,CH,COOH. Projemaic acid () CH,NH, CH,CN #80" _ CH, CH,NHy Metaranine Ha hsanile Ehsan (i) CHNo, cHyNC —N#C#598_. CH,NHCH. ivoetne Maint PRION” Semen tene Amines 419 © scanned with OKEN Scanner ni Heat (ili) CHyCH:COOH CHsCH2COONHs —y,9~ CH3CH2CONH2 Propane aid z Proporamide — Balk. CHyCH,NH2 CH;CH,0H Ehanarine hard iOS CHycHO 22052. CH,COOH Aestlehye arc aid Q.6. Describe the method for the identification of primary, secondary and tertiary amines, Also write chemical equations of the reactions involved. ‘Ans. Refer to Points to remember 12(a). Q.7. Write short notes on the following: (@® Carbylamine reaction (i Diazotisation (ii) Hofmann’s bromamide reaction (iv) Coupling reaction (») Ammonolysis (vi) Acetylation (vif) Gabriel phthalimide synthesis ‘Ans. (i) Refer to Points to remember 10(¢) (ii) Diazotisation reaction: When a cold solution of a primary aromatic amine in a dilute mineral acid (HCI or H;S0,) is treated with a cold solution of nitrous acid (generated in situ by the action of dil. HCI or dil. H,SO, on NaNOz) at 273-278 K, arene diazonium salt is formed. This reacti called diazotization reaction. For example, NaNO, + HCl —- HONO + NaCl NH, Nencr oO + HONO + HC) RK. Oo + 2H,0 Aniline Benzene diazoniam ("Aromatic amine) ‘hide NH) WN =NHsoz oO + HONO + H,s0, —22## + 2H;0 Ienzenedazonium yarogen sulphate (iii) Refer to Points to remember 10(6). iv) Refer to Points to remember 9(6). (v) Ammonolysis: The process of cleavage of the C—X bond by ammonia molecule is known as ammonolysis. ie NH, + REx ——+ RONHX” Nucleophile Substituted ammonium salts R—NH; ®=*_, R,NH —®* RN + RN'X 0 @ eo Quatemary ‘ammonium salt i (vi) Acetylation: The process of introducing an acetyl group (CH;—C—) into a molecule is called acetylation. CHy H Gt Cots +G-c1 ee cH bc Cats —N—6—Cy + HCL H uty Aceyl N-Ethyl amine chloride acetamide 420 Xam idea Chemistry-Xil © scanned with OKEN Scanner NH, : NH—C—CH, 1H: ine Oo 4 HCN _ pri CHE“ Asiline Acetaniide ‘Acetic anhydride (vil) Refer to Points to remember 10(a). Q.8. Accomplish the following conversions: (0 Nitrobenzene to benzoic acid (ii) Benzoie acid to aniline (») Ben: (il) Aniline to p-bromoaniline (éx) Aniline to benzyl alcohol + CHy—C—OH (di) Benzene to m-bromophenol (iv) Aniline to 2, 4, 6-tribromofluorobenzene chloride to 2-phenylethanamine (vi) Chlorobenzene to p-chloroaniline (viii) Benzamide to toluene No, Rencr coon oO oremer anaes, xaxowci O cucyen seca, Gn, nor O “toxson” “asa” Tati die enenedazonium Benzoitie Benzoi acid Sond No, cone HNO, i + cone I OSB 6 = G = jr Denzene Niobenene mm Bromonirbentene NH, N,cl oH ©. avon ©. ing ©. be EIR Br ~aLHSO, ‘Br Bromine 1m Bromophenal COOH ‘OC ‘ONH NH, 1 = Be-KOH a a 2 Benzoie acid seein Benzamide Aritine NH, A=npe, Berto Sar NaNOMOr, | Bro wea aK Ailing 2..6Titonamtne ee cH.C. CH,CN ¢H, CH, NHy ete Lamy > couse, Sa Phenyethnenitite 2-Phenyethanaine Sa/Hct Redaction) NO; NH, _p-Nitochlorobenzene -Chloranitine ‘bisorisomer| Amines 421 © scanned with OKEN Scanner NHCOCH; (CH,CO,0/ ~cH,coon NH) ow © Aniline Acetailide BryCH,COOH, 9 Hor jr ‘p-Bromoacetanlide NHCOCH; NH, jr p-Bromoanitine (Major isomer) ‘ONH, NH, r CH, 7 Bry 20H (witty a (0) ee. cH Benzamide Toluene Ni Nc" NaNoynict ‘ 2heK HPO, H,0Cu, cucu 38 & Wiazotization) ear “Rata. aichy aniline Benzene dizoniam Benzene Toluene ‘hone CH,CI HOH oO KOM (a) ‘Cyeroiyss) Benzyl corde exyl lesbo Q.9. Give the structures of A, B and C in the following reactions: @ CH,CH,I SS A aati BSH Ba (i) CoHsN,C1 2 4 Fg ND . © ii) CHyCH,Br SS 4 HAN. gp EO. (iv) CHsNO, EM 4 SOHNE. gp toa (») CHyCOOH M4 S08. g —NeNoynta | ¢ (i) CoHsNO, =". 4 2. gp —SetON_ G r Ans. (i) CHsCHst —“— cH,CH;CN (CH,;—CH,—C—NH, indent Propane (A) nn Propane (2) —f0Hlt86 CH, —CH,—NH, Eanamise (0 GO CgHgN2Cl CoHCN EOE CoHycooH MO Benzene iia cysteine 4) HBOYE Braet aid @) chloe (CHsCOONH, —“~ C,H,CONH, Bensaie(C) ii) CH;CH,Br “SS cH,cH,cn “*~ cH,CH,CH)NH) Bromoetane Prope tile Propan-Ianine (5) oy a [CH,CH,CH,N=NCI1 CH;CH,CH;OH "ropana () (6) CgHyNO, 2. CgHyNH, OO. CH Nencr OH. C.H,OH trotensene ‘aloe (4) Bens datoton Pret) ‘haie (8) 422 Xam idea Chemistry-Xil © scanned with OKEN Scanner () CH;CooH SB cHyconH, —“°—~cHyNH, 2 cH,oH Tatu aid Thane 8) Maasamiae() Metal (©) (i) CoHsNO, "2, CH NH, SES Nitrobenzene Aniline (A) Benrenediazonium chloride (B) ae Onnan \-on ‘P-Hydroxyazobensene(C) Q.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 CgH1,N. Write the structures and IUPAC names of compounds A, B and C. Ans. (i) To find out the structures of compounds *B" and *C’. (a) Since compound ‘C’ with molecular formula CgH,N is formed from compound *B” on treatment ‘ith Br, + KOH compound “B* must be an amide and °C’ must be an amine, the only amine having the molecular formula CgHyN is CsHsNHy (aniline). (4) Since °C” is aniline, the amide from which it is formed must be benzamide. Thus, compound ‘B’ is benzamide. ‘The chemical equation showing the conversion of ‘B" to °C" is CsHsCONH> KOM CoHsNH> enamie() ‘rine tr C80 OF = Cat) (i) To find out the structure of compound ‘A. ‘As compound ‘B" is formed from compound ‘compound ‘A’ must be benzoic acid. CeHsCOoH 228 OH CONH, ensicacdta) Hest enti 2)” Q.11. Complete the following reactions: (@ CoHsNH, + CHCl; +[Link] —- (ii) CHsN,C1+ HyPO, + H;0 — with aqueous ammonia and heating, therefore, ii) CgHgNH, + HzSO,(cone.) —- (iv) CgHgNzCl+ C;Hs0H — () CoHyNH + Bry(aq) — (vi) CgHsNH;+(CHsCO) 0 — Wii) CHSN3Cl—ayxinoytng Heat Ans. (i) CgHsNH; + CHCl, + 3KOH ———“" —__._ CHsN EEC + 3KCI + 3H,0 “aaline 9 (dey Catan raion) ~ eal iscpanide . (Oemsive sel) (ii) CgHsN2Cl + HyPO, + H,O —"*" . CyH, +N, + HyPO; + HCI Brazen zona Benzene ‘aide (ili) CgHsNHz + HSO, (cone) —- _ CgHsNHjHSOz ‘aiine Aino hydrogen whe CoHsN2Cl + CsHs0H =" Cyl + CHsCHO + Nz + HCL Benzene atin Bensene Exam ‘odie NH NH, Br Br ” + 3Brx(ag) ——> + 3HBr Ailne Br 2,4, 6Tribromoanitine (vi) CeHsNH; + (CH)CO),0 —~ CsHsNHCOCH; + CH;COOH ‘ailing ‘Acaatiise Amines 423 © scanned with OKEN Scanner Qn Ans, Q.13. Ans. QM. Ans. (i) CoHsNaCl SONY CgHNO, + BR + NaF Dees anion ‘Nirortene ‘horde ‘Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis? [CBSE 2020 (56/5/1)] ‘The success of Gabriet phthalimide reaction depends upon the nucleophilic attack by the phthalimide anion on the organic halogen compound. oO oO Tf I cht — ob {| oO Phtstinige aon [Neathyp baie t C—O CcC¥ +ArLX e+ — Noreaction ce Any halide 8 Pratine aion ‘Aryl halides do not undergo nucleophilic substitution reactions easily because the carbon-halogen bond acquires partial double bond character due to resonance, therefore aromatic primary amines cannot be prepared by Gabriel phthalimide reaction. Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous acid. Aromatic primary amines react with HNO, at 273-278 K to form aromatic diazonium salts. NH, Nencr o + HNO, + 2H) 228K, Oo + 2HCI + 21 aniline Benzene dao ‘horde Aliphatic primary amines also react with HNO, at 273-278 K to form aliphatic diazonium salts. But these ae unstable even at this low temperature and thus decompose readily to form a mixture of compounds consisting of alkyl chlorides, alkenes and alcohols, out of which alcohols generally predominate. CH;CH,NH; + HNO, + HC] ""**_.. (CHyCH;—N = N)CIl- #2. CHyCH;OH + Ny + HCI ‘ihae disor clei Enhancl (enaable) Give plausible explanation for each of the following: (i) Why are amines less acidic than alcohols of comparable molecular masses? Gi) Why do primary amines have higher boiling point than tertiary amines? ii) Why are aliphatic amines stronger bases than aromatic amines? [CBSE 2020 (S6/S/1)] (@ Loss of a proton from an amine gives amide ion while loss of a proton from alcohol gives an alkoxide ion as shown below: R—NH; —~ R—NH™ + H* Amine ‘Amide ion R—O—H —~ R—O"+ H* ‘Also ‘Aoi fon ‘As O is more electronegative than N, RO™ can accommodate the negative charge more easily than the RNH™ can accommodate the negative charge. RO™ is more stable than RNH™. Therefore, amines are less acidic than alcohols. (ii) In primary amines, two hydrogen atoms are present on N-atom and they undergo extensive intermolecular hydrogen bonding which results in association of molecules while in tertiary amines, 424 Xam idea Chemistry-XIl © scanned with OKEN Scanner no hydrogen atom is present on N-atom. Hence there is no hydrogen bonding in tertiary amines. As a result of this primary amines have higher boiling point than tertiary amines. (iii) Aliphatic amines are stronger bases than aromatic amines because: (a) due to resonance in aromatic amines, the lone pair of electrons on the nitrogen atom gets delocalised over the benzene ring and thus is less easily available for protonation. (b) the aryl amine ions have lower stability than the corresponding alkyl amines, i.e., protonation of aromatic amines is not favoured. © scanned with OKEN Scanner

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