——— » AMINE REVISION MODULE - CLASS -XI (CHEMISTRY } cures § _ MINAY GUPTA -B1 JANAKPURI SHAHGANJ AGRA ~ 7302699469, 9412161447,59 — AMINES uick Revision Points: Amines are alkyl / aryl derivatives of ammonia. In amines nitrogen atom is sp hybridised and contains one lone pair. Primary amine (1°) Secondary amine (2°) __| Tertiary amine | One- H atom is replaced by | Two-H atom is replaced — Three-H atom is R/Ar by R/Ar. replaced by R/Ar. Rone . bc 78 H TUPAC Name: - | Aliphatic amine R | Alkanamines Aromatic amine | Benzenamine/ Aniline | CH-NH | CHNH- CH (CHa - Methanamine N-Methvimethanamine | N, N- CH3-CH- CH; dimethylmethanamine CHa-NH- CH>- CHa MICH, N-Methvlethanamine CHa - CH-NH- CH2- CH3 cq N-Ethylethanamine | SS Aniline/benzenamine N.N- _ Dimethylbenzenamine Preparation of Amines: Reduction of Nitro Compounds gives aliphatic IL/pa eo 1 + NO, NL and aromatic primary amines. (Reducing | q (or Cc m1 Agents): - Ethan? LS + Hydrogen and nickel/ palladium or ol Cr ©. Sener een platinum, 2 orrendt |) + Iron scrap and hydrochloric acid (Fe + HC]) * Tin and hydrochloric acid (Sn + HCI). Ammonolysis of alkyl halides: = Reagent: Ethanolic solution of ammonia. Disadvantage: Mixture of amines formed. Reduction of nitriles Reducing agents: - LiAIH;/Catalvtic hydrogenation. “Reduction of Amides: - CHsCONH, =" — CHCHN Hoffmann bromamide degradation Reaction: An amide is heated with Bromine in aq. solution of NaOH/KOH gives primary amine, R—CONHy + Bry + 4NaOH + R- NH. +NagCOs + 2NaBr + 2H,0 The amine formed contains one carbon less than that present in the amide oe bases tan «primary amines Aromatic primary wuse vl halides do not nl formed by phthalimide Physical properties In Tertiary amines H-Bonding is not possible due to absence of H atoms. Hydrogen bonding 30 <2%« 1° Solubility in water 30 <20«] 0 Boiling Point 30 <2%« 1" Boiling point Alkane < Amine < Alcohol + Miphatic amines + Aromatic amines are weaker bases than nature of the aryl group. Acetylation: (replacement of H-atom of -NH2 />N-H group by the acyl group). Reacting agent: stronger base. Benzovlation: (replacement of H-atom of -NH)/>N-H group by the benzoyl group). Carbylamine reaction (Isocvanide Test) Primary amines react with chloroform and KOH give isocvanides | (Carbylamine} which has unpleasant smell (foul smell), Reaction with nitrous acid (HNO2) Primary aliphatic amines react with nitrous acid to form aliphatic diazonium salts (unstable) which liberate nitrogen gas and alcohols. Aromatic amines at low temperatures | Gabriel Phthalimide Synthesis: Only aliphatic are prepared by this method. amines cannot be prepared | undergo ucleophilie substitution with the anion | HCl | 3 i 7 o> nw Hake (AS ne © Cr 4 IN Nkyénhthaimi| C= ONat © Ona" ° Sareea eee 5 Cr R Le Chemical reaction and Basic Nature NaOH +R NH Amines are Lewis bases due to presence of lone pair. Larger the value of Ke or smaller the value of pK», stronger is the base. NHa< 19< 20< 30 (gas phase) (due to +1 effect) NH2< CoHsNH2< (C2Hs JsN<(C2Hs)2NH [aqueous phase} . NH2. (CHa )aN! CH3CON(C2Hs)2 + ; | | CHaNHp + CsHsCOCl 9CeHs CONH-CH3- HCL - HE. RNH, + CHCl, +3KOH 5 RNC + 3KCI + 3H,0 Secondary and tertiary amines do not show | this reaction. | It is used as a test for primary amines. | 278K CyHeNH, + HNO, > CcHgN}CI” + NaCl + 2H0 | NaNO, +HCI #0, RNH,+HNO, ———> [RN3CI"] — ROH + No + HCI |Rvaction with Benzenesulphony! chloride (Hinsberg's test (CeHsS0:C1) Primary Amine Secondary Amine Dera esae Primary amines form Secondary amines form eee etoitn N-alkyibenzene sulphonamide N, N- ; reba reagent which is soluble in alkali due dialkylbenzenesulphonamide —_ Hinsberg : to presence of acidic hydrogen which is not soluble in alkali at N-atom. due to absence of hydrogen atom at N-atom Ce a son meat Pt eae | ; < . > ; L ue L bn poe ee < eee No Reaction Electrophilic substitution: —-NH2 group is ortho and para directing and a powerful activating group: nity ATH, U Er, be ie ce MN | | m In direct Nitration meta product is formed due to formation of aniliniurm ion which is meta directing. NH Nea Nea ita No2 HNO. . . Oo esr Noz Noz am ed 1% (m - proauer) te - preaucy Electrophilic substitution: Aniline is converted into acetanilide by acetylation with acetic anhydride and then the desired substitution is carried out followed by hydrolysis the lone pair on nitrogen is less available for donation to benzene ring by resonance. Therefore, activating effect of - SAUDIS grote Whe ae Reneepe rine ey reo tel, i — nl on, ee ere = a eee a = om Br a ‘Benzene Diazonium Chloride Preparation and Reactions: © KI Noy Sane C3 seman Cc ae 3 Sandmeyer Reaction Br - io Sandmeyer Reac ON Sandmeyer Reaction Gattermann ReactionjreVISION MODULE Q.L Classify the following amines as p secondary or tertiary: (i) (i) (iii) (C2Hs)2CHNUP Q.2 How will you convert? (i) Benzene into aniline (ii) Benzene into N, N-dimethylan (iii) CI-(CHa)s-Cl into hexan-1, 6-diamine? Q.3 Arrange the following in inereasing order of their basic strength: (i) CHsNH2, CoHsNH2, NHB, CoHsCH:NE2 and (CaHs):NH Ha, (C2Hs)2NH,, (CaHs)3N, CoHsNH2 (iti) CHsNHb, (CH)2NH, (CHs)3N, CoHsNH2, CoHsCH2NHa. 0.4 Complete the following acid-base reactions and name the products: (i) CHsCH2CH2NE2 + HCI (ii) (C2Hs)3N + HCL> Q.5 Write reactions of the final alkylation product of aniline with excess of methyl iodide in the presence of sodium carbonate solution. Q.6 Write chemical reaction of aniline with benzoyl chloride and write the name of the product obtained. Q.7 Convert (i) 3-Methylaniline into 3- nitrotoluene. (ii) Aniline into 1,3,5-tribromobenzene. (Q.8 Write IUPAC names of the following compounds and classify them into primary,secondary and tertiary amines. (i) (CH3p2 CHNH2 Gi) CHa(CH2)2NH2 (iii) CHsNHCH(CH3)2 (iv) (CH3)sCNH2 (¥) CoHsNHCHS (vi) (CH3CH2)2NCH3 (vii) m-BrCoHaNHz Q.9 Give one chemical test to distinguish between following pairs of compounds. (i) Methylamine and dimethylamine (ii) Secondary and tertiary amines ylamine and aniline (iv) Aniline and benzylamine (vy) Aniline and N-methylaniline, Q.10 Deseribe a method for the identification of primary, secondary and tertiary amines, KIB SCIENCE SCHOOL A PREMIER INSTITUTE Pe aaaeoeaee OF EDUCATION CLASS - XII [CHEMISTRY] Bl JANAKPURI SHAHGANJ AGRA - 7302699469 941216144 LAAT, 2259363937) _ CHAPTER -AMINES, Also write ch reactions involved. Q.11 Account for the following: (i) pKoof aniline is more than that of methylamine. (ii) Ethylamine is soluble in water whereas aniline is not. (iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide, (iv) Although amino group is o, p~ directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m-nitroaniline. (v) Aniline does not undergo Friedel-Crafts reaction. (vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines. Gabriel phthalimide synthesis is preferred for synthesising primary amines. Q.12 Arrange the following: (i) In decreasing order of the pKsvalues: CoHsNHb, CoHsNHCHs, (C2Hs)2NH and CoHsNH2 (ii) In increasing order of basic strength: CéHsNH2, CsHsN(CH3)2, (C2Hs)2NH and CH3NH2 In increasing order of basic strength: (a) Aniline, p-nitroaniline and p-toluidine (b) CoHHsNH2, CoHsNHCHs, CoHsCH2NH2. (iv) In decreasing order of basic strength in gas (vii) phase: CaHsNHb, (C2Hs)2NH, (C2Hs)3N and NH3 (v) In increasing order of boiling point: C:HsOH, (CH3)2NH, C2HsNH2 (vi) _ In increasing order of solubility in water: CoHsNEb, (C2Hs)2NH, C2HsNH2. Q.13 How will you convert: i) Ethanoie acid into methanamine (ii) Hexanenitrile into 1-aminopentane (iii) Methanol to ethanoic acid (iv) Ethanamine into methanamine (v) Ethanoie acid into propanoic acid (vi) Methanamine into ethanamine (vii) Nitromethane into dimethylamine (vili) Propanoic acid into ethanoie acid Q.14 Write short notes on the following: (i) Carbylamine reaction (ii) Diazotisation (iti) Hofmann’s bromamide reaction(iv) Coupling reaction (v) Ammonolysis (vi) Acetylation (vii) Gabriel phthalimide synthesis. Q.15 Accomplish the following conversions: (i) Nitrobenzene to benzoic acid (ii) Benzene to m-bromophenol (iii) Benzoic acid to aniline (iy) Aniline to 2,4,6-tribromofluorobenzene (v) Benzyl chloride to 2-phenylethanamine (vi) Chlorobenzene to p-chloroaniline (vii) Aniline to p-bromoaniline (viii) Benzamide to toluene (ix) Aniline to benzyl alcohol. Q.16 Give the structures of A, B and C in the following reactions: > iy CHI S54 SB pte ow ve (iy CHN.CI oA they BoM jig) CUCUBr SS 4 ett, ppt. ii) 2 < CIULNO, 2" 4 (iv) * (vy C1 COOH 4 4 te gsr nt COHLNO, eth f wp >A Lett g Q.17 An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms compound ‘B’ which on heating with Broand KOH forms a compound ‘C” of molecular formula CsH>N, Write the structures and IUPAC names of compounds A,Band C. Q.18 Complete the following reactions: w CAMANIL + CHCI, tale KOH (iy OHNO HPO. + H.0 5 (ii) CHENH. FH.SO ,(cone.) > (ivy GHEN.CL- CHLOH (yy) CHNH, + Brtagy > (vi) CHINE. H(CH,CO),0 > ia Coll Cl— (vii) . Q.19 Why cannot aromatic primary amines be Prepared by Gabriel phthalimide synthesis? Q.20 Write the reactions of (i) aromatic and Gi) aliphatic primary amines with nitrous acid. Q.21 Give plausible ex; following: (@ Why are amines less acidic than alcohols of comparable molecular masses? (ii) Why do primary amines have higher boiling point than tertiary amines? (iti) Why are aliphatic amines stronger bases than aromatic amines? planation for each of the 1 NCERT Intext Examples Q.1 Write chemical equations for the following reactions: (i) Reaction of ethanolic NHs with C2HsCl, (ii) Ammonolysis of benzyl chloride and reaction of amine so formed with two moles of CH3Cl. Q.2 Write chemical equations for the following conversions: (i) CH3~CH2-Cl into CH3~CH2-CH2-NH2 (ii) CoHs~CH2-Cl into CoHs-~CH2-CH2-NH2 Q.3 How will you convert (i) Benzene into aniline (ii) Benzene into N, N-dimethylaniline (iii) CL{CH2)<-Cl into hexan-1,6-diamine? Q.4 Arrange the following in decreasing order of their basic strength: CsHsNH2, C2HsNH2, (C2Hs)2NH, NH Q.5 How will you convert 4-nitrotoluene to 2- bromobenzoic acid ? Q.6 In the following reaction chart identify A, B, C, D and E. Write their IUPAC name and rewrite the following reaction ni By A “ Ron” | r sir Q.7 (i) An amine “X” with formula C3HON re: with benzenesulphonyl chloride to give a precipitate which is insoluble in alkali. Give the structure and IUPAC name of amine “X”, Write the chemical reaction ii) How will bring out the following conversions: acts ine to Todobenzene. Q8 Complete the following reactions: U\CH:CONH + Bry+ NaQH9...... + NayCOy+ 10 4 Ul) nso tH CH3-CHNH (it crLconr A,