After studying this Unit, you will be able to + describe amines as derivatives of ammonia having a pyramidal structure; + classify amines as primary, secondary and tertiary; + name amines by common names and IUPAC system: + describe some of the important methods of preparation of amines; + explain the properties of amines: + distinguish between primary, secondary and tertiary amines: + describe the method of prepara- tion of diazonium salts and their importance in the synthesis of a series of aromatic compounds including azo dyes. LP rPidedin, V ‘re msina AWA wa ee ayes bh Polymer 4 ody eb ou i OF Ga Dn $8.5 and ae in dak ey. CON Akhiatasen tule ¢ sh Bsnd ‘oay Rw avouh “Stucture of aes, PUA gp? Seatac Bnonlion Seo Ke ses Nee. ‘ wp wee BS Mer cet! ) (ad jr“ nahared pair of electrons. Due to the presence of “The oh (sas inlermediates inthe suse gf eciosand fines" Amines constitute an important class of organic compounds derived by replacing one or more hydrogen atoms of ammonia molecule by alkyl/aryl group(s). In nature, they occur among proteins, vitamins, alkaloids and hormones. Synthetic examples include polymers, yestufis and drugs. Two biologically active compounds, namely [a d_ ephedrine, both containing secondary amino group, are used to increase blood pressure, Novocain, a synthetic amino compound, is used as an anaesthetic in dentistry. Benadryl, a well known antihistaminic drug also contains tertiary amino group. Quaternary ammonium salts are used as surfactants, Diazonium salts are intermediates in the preparation of a variety of aromatic compounds Jyfe.)o2,)imchading dyes. In this Unit, you will learn about amines and diazonium salts. 1. AMINES Amines can be considered as derivatives of ammonia, obtained by replacement of one, two or all the three ay hydrogen atoms by alkyl and/or aryl groups. For example: CH, cH, Like ammonia, nitrogen atom of amines is trivalent and carries an unshared pair of electrons. Nitrogen orbitals in amines are therefore, sp” hybridised and the geometry of amines is pyramidal. Each of the three sp? hybridised orbitals of nitrogen overlap with orbitals of hydrogen or carbon depending upon the composition of the amines. ‘The fourth orbital of nitrogen in all amines contains an CH,-NH,,, C,H,-NH,, CH,-NH-CH,, CH,-N unshared pair of electrons, the angle C-N-E, (where E is Scanned with CGMSC or H) Js less than 109,5°: for instance, it is 108 ‘trimethylamine as in Fig. 19.1 sunshared ‘electron pair cn, CH, : cH, cH. cn, 08" cn hae a Mig. 19.1 Pyramidal shape of trimethylamine | 13.2 Classification Amines are classified as primary (1"), secondary (2°) and tertiary (34 depending upon the number of hydrogen atoms replaced by allyl @- cH, ~ 9 azy1 groups in ammonia molecule. If one hydrogen atom of ammong e” 4s replaced by R or Ar , we get RNH, or ArNH,, a primary amine (19) | it two hydrogen atoms of ammonia of one hydrogen atom of FUNH, are replaced by another alkyl/aryl(R) group. what would you get? "You ECE-NHR. secondary amine. The second alkyl/aryl group may be when they are different. NH,—> NH,» Primary(1") —Secondary(2")_Tertiary(3*) 13.3 Nomenclature Scanned with CamScansIn arylamines, -NH, group is directly attached to the benzene ring. C,H,NH, is the simplest example of arylamine. In common system, It 4s known as aniline. It is also an accepted IUPAC name. While naming arylamines according to IUPAC system, suffix ‘e’ of arene is replaced by ‘amine’. Thus in IUPAC system, C,H,-NH, is named as benzenamine. Common and IUPAC names of some alkylamines and arylamines are given in Table 13.1. ‘Table 13.1: Nomenclature of Some Alkylamines and Arylamines Ca eeu CH,-CH-NH, Bthylamine Ethanamine CH,-CH,-CHNH, n-Propylamine Propan-I-amine cH.-CH-CH, Isopropylamine Propan-2-amine NH, CH,-"'—CH,—CH, Bthylmethylamine N-Methylethanamine H ‘Trimethylamine | -x.v-Dimethylmethanamine cH,—" én, | coupe, -G1, GH, —CH, | NAN-Diethy!butylamine N.N-Diethylbutan-1-amine 1 GH | wii, GH, CH=CH, Allylamine prop-2-en-1-amine HHexane-1,6-dlamine NH, -(cH), —NH. Hexamethylenediamine i O anti one Benzene wt oO -Totuldine |2-aminatouene MH, p-Bromoanine 4-Bromobenzenamine £dromoaniine Br N.N-Dimethylbenzenamine N,N-Dimethylaniline | Scannea with CamScani13,1 Classify the following amines as primary, secondary or tertiary: SNH, NICH), { : “CO “OO (ui) (CHJ,CHNH, (v)(C\H,).NH 13.2 ) Write structures of different isomeric amines corresponding to the molecular = formula, C,H,,N, W) Write 1UPAC names of all the somers, ‘What type of isomerism is exhibited by different patrs of amines? 13.4 Dreparation Amines are prepared by the following methods; of Amines 4 1. Reduction of nitro compounds Nitro compounds are reduced to amines by Passing hydrogen gas _ Wr {i,ihe Presence of finely divided nickel, palladium or platinum Seq t aise by reduction with metals in acidic medium. Nitroalkanes ont | rh also be similarly reduced to the corresponding alkanamines, .NO, NH, *_HL/Pd aor CO ; NO, NH, a oO 220 to initiate the reaction, SX fn RALX > encity 2. Ammonolysis of alkyl halides oe anata voelin a € yx fem nnd ‘ Lynn mobo tube at 373K The ny Fo bebe. Me Itt 214 day 2156 hana nal $ micbaophily if er react with alkyl halid and tertiary amines, and finally quai a fants in Substituted T teltl, 00 6 Steep al, Chem: Scanned With CGMScanIRvH, 3S Rwu BS RW BG RAK Ooo ) ae ‘The free amine can be obtained from the ammonium salt by treatment with a strong base: ° R-NHX + NaOH —> R-NH,+ H,0 + Nax Ammonolysis has the disadvantage of yielding a mixture of primary, secondary and tertiary amines and also a quaternary ammonium salt. ‘However, (primary amine is obtained as a major product by taking large excess of ammonia) The order of reactivity of halides with amines is RI > RBr >RC1) $ Peshiihy peasrQrVienre A ‘Write chemical equations for the following reactions: Example 131 (i) Reaction off lic NH. with C,H,CL. Citenuming + Nell Eirrwinl* NN Die Huy Le () Ammonolysis of benzyl chloride and reaction of amine so formed — * Salome 4 with two moles of CHCl. in Solution ® cee My often, BE operons ML cpienest, Be He CH, Chloroethane Ethanamine _N-Ethylethanamine N.N-Diethylethanamine | Quatempay Wo cat cH Ss 6H,-cH.NH, > 6.H-CH-N-CH, cH, Benzylamine _N.N-Dimethylphenylmethanamine) Ny Noles 3, Reduction of nitriles /=.. o>.) | Nitriles on reduction with lithtum aluminium hydride (LiAIH,) or “* catalytic hydrogenation produce primary amines. This reaction is used for ascent of amine series, Le., for preparation of amines containing one carbon atom more than the starting amine, peg fo R IN tit R- CH; NH, 2 bah fon cai is , ‘ Ramigyesnon 8 CHE NE: ae 4, Reduction of amides Rens tals Romie, The amides on reduction with/lithium aluminium hydride yield amines. ° a é ss WLAN, 662 ny Rn OP R-C-NH,~gpizo R-CH,- NH, Marrs) (GM # Ss on Scanned with UamScani6. Hoffmann bromamide degradation reaction ¥ ae Hoffmann developed a method for preparation of primary amines by treating an amide with bromine in an/aqueous or ethanolic solution of sodium hydroxide. In this degradation reaction; migration of an alkyl or aryl group takes place from carbonyl carbon of the amide J: (o the nitrogen atomyThe“amiine so formed contains one carbon less than that present in the amide. , oF up pow q Ue) Crsoe-) 4 R-C-Ni, +Br, +4NaOH —> R-N1i, + Na,CO, + 2NaBr +2H,0 | Example .2 Write chemical equations for the following conversions: = () CH,-CH,-Cl into CH,-CH,-CH,-NH, (i) C,H,-CH,-Cl into C,H,-CH,-CH,-NH, Solution ® CH,cH,ci EanolleNON, CH CH cen SUH CHLCH-CHNH, Chloroethane Propanenitrile Propan-1-amine () — CHeCH,c EiansieNON, CCH cay MS oH,-CH,-CHH, Phenylethanenitrile 2-Phenylethanamine Chlorophenyimethane (Benzyl chloride) (Benzyl cyanide) Scanned with CamScantCUsenen,- CoH, Write structures and IUPAC names of Se cen ee (0 the amide which gives (propanamine’ by Hoflmann_bromamide (i) the amine produced by the Hoffmann degradation of benzamide. (@ Propanamine contains three carbons, Hence, the amide molecule must contain four carbon atoms. Structure and IUPAC name of the starting amide with four carbon atoms are given below: ? CH,-CH,-CH,-C-NH, Butanamide f ° Ow Benzamide is an aromatle amide containing seven carbon atoms. lence, the amine formed from benzamide is aromatic primary amine containing six carbon atoms. oo oo 13.3 How will you convert y Deny 5 ( Benzene into aniline (ii) Benzene into N, N-dimethylaniline (ii) CL{CH,),-Cl into hexan-1,6-diamine? | | wo. ym 13.5 Dhysical ‘The lower aliphatic amines are gases with fishy odour. Primary amines Driperti with three or more carbon atoms are liquid and still higher ones are TOperAIES solid. (nlline-andl_other arylamines_are usually, colourless but get coloured on storage dué to atmospheric oxidation. > r aliphatic amines are soluble in water because they can form hydrogen bonds with water molecules. However. solubility decreases Rs Syighan lve increase in molar mass jue to increase in size of the fe IS cts ae garter anes ar ese oli wate _-- Considering the electronegativity of nitrogen of amine and oxygen of “alcohol as 3.0 and 3.5 respectively, you can predict the pattern of ¢-2°e solubility of amines and alcohols in water. Out of butan-1-ol and , butan-1-amine, which will be more soluble in water and why? Amines oe. _. are soluble in organic solvents like alcohol, ether and benzene. You P may remember that\alcoh than amines and for stronger int lar hydrogen: bo1 F “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 there are two hydrogen atoms available for hydrogen bond formation in it. Tertiary amines do not have intermolecular association due to the al rogen pp Wee Sion available for hydrogen bond formation. Therefore, the order of (he dA ying points of isomeric amines is as follows: pc Lee AO a gael (38Z, Amines ane Scanned with canteena Secondary > Tertiary Bp Soret Coa THTOEET DOMAINE Be ay bond Fig. 13.2. x in primary amines is shown jy, Sete RON-H-7-GN-H-ye NOR \n fee Fig. 13.2 Intermolecular hydrogen bonding tn primary amines Boiling points of amines, alcohols and alkanes of almost the same pp> Alehel) Prive) filk.molar mass are shown in Table 13.2. Comparison of Boiling Points of Amines, Alcohols and Alkanes of Similar Molecular Masses Table 13.: freee n-C,H.NH, 73 (CH),NH Ue C\HNICH), 73 C,H,CHICH), 7 2-C,H,0H 7 13.6-Chemical __Dilference in electronegativity between nitrogen and hydrogen atoms and Reuctions. _-giatner renctver Phe nenvoce ot ydengen slams attached to ited Pram Popcrioe (ort aise decries th reac 5: mary Pe d les the course of reaction-of amines; that is why ASpenionsn om X N a (2iH), secondary ( > N—H1) and tertiary amines (> N—) diferin many DRA pA Cea reactions. Moreover, amines behave as nucleophiles due to the presence ~ Sioa eatin of unshared electron pair. Some ofthe reactions of amines are described below: R—NH+HX = R—NH, X (Sal) F +s Re NHI + HCl == Src ay Anilinium chloride } fe! sé@nnea with CamscaniPiratine LOlublan gr late Cobaaaiat E rtmetll (ans eoll ant tid. Te entiney ¥ Solute Fa water. salts' {ne th he Regen aoe 4 RNHLX+ 0H —> PAHO. nine salts are sol n Shows that these are basic in nature, of electrons on nitrogen atom dis Lewis ¢ to which they behave as Lewis base.) Basic character of amines ean be beter Understood in terms of their K, and pK, values as explained below: 2 : j R— NH +HO => R— Ni, Sew Z xo RM fon) 1R=F 9) | wang) Amon _ Wn, [on] —JR-NH__ | + OH or \K, [PK, = log K, } Larger the value of K, or smaller the ie base THE DR eet oF smaller the value Df pK, stronger is thi nase. The pK, values of few amines are given in Table 13.3. PK, value of ammonia is/4.75, Aliphatic amines ase isangerhases shan-ammonia due to +1 effect of alkyl groups Teading to high electron density on the nitrogen atom. Their PK, values. fie In ti-ramge or te e ~4.22, (On the other hand, aromatic amine: esa Table 13.3: pK, Values of Amines in|Aqueous Phase Methanamine C1, \o¥\, N-Methylmethanamine cn-6WJ-CMy 22>} Pe PBeorihy wa jethylmethanamine @ ,).en Ethanamine 9? N-Ethylethanamine 2% rf4d pea benemins NN-Diethylethanamine scanned with UGMScanlTa Satis fet .__, You may find some discrepancies while trying to interpret ee values of amines on the Sant sih 4 e on the beats of, 1 or 1 elect of the BC vebsted to ker She fpiaton effet sternite Wie affect ppc iowa " Ax amines. Just ponder over. You may get the answer in the “SS =n 2 bt thebty sr} Fe enacts relationship of amines 2 Basicity of amines is relatéd to their structure. Basic character of, amine depends upon the estof formation of the cation by accepting i ae ae hae nett The tre stable the Eation is relative amine, rore basic is the Se Geo Cs (a) Alkanamines. ugrsus ammonia) Let us consider the reaction of an alkanamin ammo a proton to compare thelr basicly. ae H RN +H" == H x AG en H H Due to the electron releasing nature of alkyl group. it (R) pushes electrons towards nitrogen and thus makes the unshared el pair more available for sharing with the proton of the acid. Moreover, the substituted ammonium ion formed from the amine gets stabilise due to dispersal of the positive charge by the +1 effect of the allyl group. Hence, alkyl bases than_ammonia, ‘Thus, the basic nature of aliphatic amipes should increase wih increase in the number of alkyl groups. This trend is followed in the gaseous phase. The order of basicity of amines in the gaseous phase follows the expected order: tertiary amine > sec: > Primary amine >NHy ‘The trend Ts pt Tegullar_in_the aqueous state as evident by their pK, values given in Table os quent place, the substituted ammonium cations get stabilise fot electron releasing effect of the alkyl group-(+)-but als iy by solvatior les. The. greater the size ot ha lessei and the less stabilised is the ion, The order of stability of ions are as follows: . | yn. with. wat oH by Leh H R, | /H~ OH, a aot RNA ou, > << > SR-H~ Off x Rr’ SH on, on, a pes 1° 2 Decreasing order of extent of H-bonding in water and stability of fons by solvation. p— scotty otions Py Se Scanned with CGMScan>Greater is the stability of the substituted ammonium cation, stronger should be the corresponding amine as a base. Thus, the order of basicity > weep amines should be: primary > secondary > tertiary, which » is to the inductive effect based order. Secondly, when the Prbualve ints Sroup is small, like -CH, group, there is no steric Se (olachie (fol H-bonding. In case'the alkyl group is bigger than CH, group, there Bee testuctitlate c H-bonding. Therefore, the change of nature of the alkyl group, e.g., from ~CH, to ~C,H, results in change of the order J )of basic strength. Thus, there is a subtle interplay of the igductive v effect, whi decides the bas: the aqueous state. The - order of basic strength in case of methyl substituted amines and ethyl Substituted amines in aqueous solution is as follows: (C,HJ.NH > (C,H,).N > CjHyyH, > NH, (21° (CH),wH > CH,NH, > (CH, n > NH, ’ (®) Arylamines versus ammonia Ps PK, value of aniline is quite high, Why is it so? It is because in a ene or other arylamines, the -NH, group is attached directly to “the benzene ring. It results in the unshared electron pair on nitrog . __ atom. tg be in conjugation with the benzene ring and thus making ars it less available for protonation. If you write different resonating structures of aniline, you will find that aniline isa-resonance PB 1.%he0 hybrid of the following five | at Ovo (As, A = On the other hand, aniljnium ion obtained by accepting a proton ivi om can have only two resonating structures (kekule) We know that greater the number of resonating structures, greater is the stability. Thus you can tat aniline tive resonat S.more stable than aniliniumcTor. Hence, the proton /) would be less a ._In case of substituted aniline, it 18 observed that electron releasing groups like -OCH,, -CH, ineregec basic strength whereas electron withdrawing groups like NO," “oes -COOH, -X decrease tt..¢§ —____- Sa, ar Scanned with CGMSCanIa Salat rr the following order: A Cestanit> Coy, > Ni, > CNH, = Gener) 3 ¢ } Soe A halides (pefer Ung ndergo alkylation on reaction with alkyl halides ae nso ‘acylation § vcs Shas b%! hoslayeveact to vijt ad r es Aliphatic and ardnatc primary and secondary amines react wil By b@al/ eid chlorides, anhydrides and esters by nucleophilic substi a ), teactiont This reaction is known as acylation. ¥ of NH, ood et ‘this reaction as the replacement ¢ of hydrogen at oom of NE 1. ({. eroup by the acyl group. The products obtained by acylation reactig © ° are known ag amides) The reaction is carried out in aht presence sue Ser than the aming, like pyridine, which removes HCIy s the rium to the right hand side H CH, — f si. T H,-N-C-CH, + H- ees Rye oa TT Fs \ 1 ,HO mH Oe Av Chby: N-Ethylethanamide or gaan, + cH c—ey E> cK —o— cH, Hg I bg y CHO N.N-Diethylethanamide C=0}-c—CH, ——> 64,— i 1 {i = Oo Jo Ethanoic anhydride N-Phenylethanamide or Acetanilide Amines also react with benzoyl chloride (C,H,COC). ‘This react 1s known as CHGNH, +. “CoH C06] > CHSNHCOC,H, +H¢j Methanamine Benzoyl chloride N=Methylbenzamide What do you think j. reac iie ee ee uy see hast and potassium hydeaxie form isoeyanides or carbylamines which are foul smelling substances. Secondary and tertiary amines 5 PTR] De Re took ew thts teactions "Thua restr Keown os | i yo! reaction or isocyanide test and is used as (Test for primary { R=Ni + CHOL+ s+ SHOW ASH ee Ne + 3KCl+ 3H,0 fvk Mokor| 6: Réaction with nitrous seid DS sotepanti I fan om f 13 ‘Three classes of amines react differently with nitrous acid which ——— prepared in-situ from a mineral acid and sodium nitrite. (a) Primary aliphatic amines react with nitrous acid to form aliphatic diazonium salts which liberate nitrogen gas quantitatively and alcohols Quantitative e evolution of nitrogen 1s. used in estimation of amino acids and proteins RH, ¥ HINO, NNQ* HC w4 HQ, QOH s +Ho ) ‘(b) Aromatic amines react with nitrous acid at low temperatures (273-278 K) to form diazonium salts, a very important class of “compounds used for synthesis of a variety of aromatic compounds discussed in Section 13.7. _ NH, NaNO, + 2H 273 -278K p42 f Ani Benzenediazonium aX we ‘hioride Secondary and tertiary amines_react with nitrous acid in a * different manner. -a,¢ 6. Reaction with arylsulphonyl chloride \ ° Benzenesulphonyl chloride (C,H,SO,Cl), which is also known as Be njend bal ‘out Hinsberg’s reagent) reacts with primary and secondary amines to // orm sulphonamides. CH, cH, — NC! + NaCl + 21,0 oy 82, (@) The reaction of benzenesulphonyl chloride with primary amine c iphony! ELA yields N. pees amide. ? He g a 4 eo tou OF rans ne t Line a 9 Pr . N-Ethylbenzenesulphonamide i 0 tho Seng 6201 ulplonal sD 4 ia Wignly eS stachuble in ala sae The hydrogén attached t stro acidic due to the presence of strong electron withdrawing ae 1 _ group. Hence,,it is soluble in alkali, (b) In the reaction with secondary amine, N,N-diethyl- te —C rt benzenesulphonamide is formed. OM. +nnoH a. t ees | ‘a eh, Fou, + Het 3 Nrerty CH, + CAN, 2 NN-Diethylbenzenesulphonaniide or eile bac bho! i] Yasin na ¥ 4 athe i Pa sepond on Bins enlace De 0 vaflace Oy q sans t5 Cee 4 ehh igkg Scanned With CGMSCanIPid) fleas a Lphrolsioiliowt — sysrgen ea mehed to nitrogen atom itis not acidic in alkali. jhonyl chl orf, 1 fo rea teria ane donot east wi ng ‘This. ‘of amines tion of a mH for the distinet primay Paty 24!4. 18n a diferent manner 1s used for Oe Tre separation of, + Rene hye secondary and tertiary amines a © ays benzenesullphoy, _mixture-of_amines. However, iIphony! chloride. t tion sum el ity) Lah vehi pArastructures. Where do you find the maximum electron density ¢. ese structures? Ortho- 7 2 aos et ten ayo A oo E CZ fisindice ait ro see anda power ectaing UD. _ gamers Bromi |bromine water) at a : Aniline reacts_with {t 2 water] at rom) ES sere Penney ve a white precipitate of 2,4,6-tribromoanilg & 16ND A gy AobbtoNH zoe Dy Pe z NH, lethylbenzene sulphonamide does ee aod ha ae Br nob 4 gr, BELIS, + SHBr 4 opimwono® on) 7 ote Br out yromoaniline LL hee 1 19h conch OPE Ee eel tase 20 z pre cH" “The main problem encountered during electrophilic substi ) 5 ~ reactions of aromatic amines is that of their very high rea Y Protnujltly Substitution tends to occur at ortho: and para-positions. 1f Grave’ oad have to prepare monosubstituted aniline derivative, how the activating effect of -NH, group be controlled ? ‘This can done by protecting the -NH, group by acetylation with anhydride, then carrying out the desired substitution follow by hydrolysis of the substituted amide to the substituted amie ty + by 9 9 Oe HCN-C—cH, H-N-C-cH, NE O seuso9 os, a | Prridine marco ees , | Br Br Aniline _N:Phenylethanamide “ecard (9) am ‘The lone Pair of electrons on nitrogen of acetani lide vith oxen atom due to resonance we shen 20: : 5M a NOS cH es Sh . >Ree_ cy, Newer : 4 AU canned wihtamScano y Hence, the =p, lone pair of electrons.on.nitrogen is less available for “C~12"% | donation to benzene ring by resonance. Therefore, activating effect of -NHCOCH, group is less than that of amino group. s () Nitration: ee tie Milibe, ylelds_tarry oxidation oho? products in addition to the nitro derivatives. Moreover, in the Sang tre B Strongly_acidic_medium,_anline-1s-protonated to form the MH, Sh, anilinium ion which is meta directing. That is why besides the A? 4A (ie ortho and para derivatives, significant amount of meta derivative ¥ © “oh vet’, )is also formed. Sap yw, Ya H, thes fe uss Be 4 HNO,,H,S0,, 288K, PYMo|? & SES Me % . = err NO, \ No, (1%) (4796) 2%) pont bap om However, by protecting the -NH, group by acetylation reaction with acetic anhydride, the nitration reaction can be controlled and the p-nitro derivative can be obtained as the major product. NHCOCH, NHCOCH, eae) HNO,, H,SO,, 288K, QO OH or HY Pyridine ee =e NO, NO, Acetanilide pNitroacetanilide — p-Nitroaniline (c) Sulphonation: Aniline reacts with concentrated sulphuric acid to form anilinium hydrogensulphate which on heating with \¢ sulphuric acid at 453-473K produces p-aminobenzene sulphonic 7 acid, commonly known as\sulphanilic acid) as the major product. — NH,HSO, 1H, Nu, O22 0 = O SOW SO, Pitcacaulve 4.¢ es Anilinium ¢ ‘ Ene hydrogensulphate _¢ Sulphanilic acid Zwitter ton fin, i, high Man % Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due to salt formation with aluminium chloride, the Lewis acid, which is used as a catalyst. Due to this, nitrogen of aniline acquires positive charge and hence acts as a strong deactivating group for further reaction. Amines Scanned With CGMSCanI19.4 Arrange the following in increasing order of their basic strength: () C,H,NU,, C,H,NH,, NH,, C,H,CH,NH, and (C,H,),NH (ti) C,HNH,, (C,H,),NH, (C,H,),N, C,H,NH, (ii) CH,NH,, (CH,),NH, (CH,),N, CJH,NH,, CsH,CH,NH,. 13.5 Complete the following acid-base reactions and name the products: () CH,CH,CH,NH, + HCl > ¢5(t) (CH,N + HCL > CY 13.6 Write reactions of the final alkylation product of aniline with excess of methyl iodide in the presence of sodium carbonate solution. a 13.7 Write chemical reaction of aniline with benzoyl chloride and write the name of the product obtained. 13.8 Write structures of different isomers corresponding to the molecular formula, C,H,N. Write IUPAC names of the isomers which will liberate nitrogen gas on treatment with nitrous acid. “yl ase at Il, DIAZONIUM SALTS ee ei e PR WX | you aMowl the duazpnium sats have the general formula RNa X where R stand Jando Dnsoja ty dra : a (ai, ) ahi tahoe ebay group/and x ion may bd Cr Br, HSO,+ BF, | etc. They an “pu oe S named by suffixing diazonium to the name of the parent hydrocarba “N N erage Basis Gort. from which they are formed, followed by the name of anion such a PRX Raghly & \e chloride, hydrogensulphate, ete. The_N,\ soup 18 called dlazoniun 4 Bs led diazonite ee group. For example, C,H, N2Cl #8 named as benzenediazontun Chioride and C,H,N;HSO, is known as benzenediazontug 4 oa Clourtoss oi Cxuctalhi weQoledk —_hydrogensulphate. ] evornpese in dey SH Ar-N,oR, > Ar-P+ OR+ N, 4. Replacement by H: Certain! ‘mild reducing agents like hypophosphorous acid (phosphinic acid) or ethanol reduce diazonium salts to arenes and themselves get oxidised to phosphorous acid and ethanal, respectively. BLdq Amines wd scanned with CGMS cant| Eee ng, onitnd Logie’ Ard. | paolo Cm ; opecipiatne RP Anil H,PO,+ HO. — ‘ArH + N, + H,PO;+ Hel / + CH,CH,OH ArH + N+ CHcHo + Hel Arn xt Replacement by hydroxyl group: If the perature of the diazonium salt solution is allowed to rise ¢iupto 283 K. the salt gets hydrolysed to phenol Ang + H.0 spe AH + N, + Het 6. Replacement by -NO, group: When diazonium fluoroborate 1s _ parted ith aqueous sodium nitrite solution in the Presence of copper, the diazonium group is replaced by -NO, @rouP- Pry 5 hol BF Iw NO, + HBr, ——> = . +N, + NaBr, Fluoroboric a= acid B. Reactions involving. retention of diazo grouP s& coupling reactions i ‘The azo products obtained have an extended conjugay jem having Toh the cromatic rings joined through the-NeN—band. These compounds {isec Benzene diazonium chloride are often coloured and are fised as dyes. reacts with phenol in which the phenol molecule at its para position is coupled with the diazonium salt to form, { p-hydroxyazobenzene) This type of reaction is known as coupling reaction. Similarly the reaction of diazonium salt with aniline yields p-aminoazobenzene. ‘This is an example of electrophilic substitution reaction. Cp : a pron oa, Cppver{provieet +10 s _p-Hydroxyazobenzene (orange dye) Cpe + a{ rn ea SS Okt pm cr+ HO Smcenmene OaM J RS - f ano Pzobejeel 13.410 Importance From the above reactions, its clear that the anf hcer sheeted of Di ch good intermediates for the introduction of -F, -CT, -Br, =I, -CN, -O, een - “NO; Groups into the aromatic ring. AryrMuorides and iodides cant p ; repared by direct halogenaliom) Synthesis __ The cyano group cannot be introduced by nucleophilic substitution of Aromatic chlorine in chlorobenzene but cyanobenzene can be easily obtained vercunde from diazontum salt. oe ‘Thus, the replacement of diazo group by other groups is helpful | PA Scanned With CGMScanIpreeating those sub Prepared stituted aromatic compounds which cann by direct Substitution in benzene or substituted Ft cH, Solution HCI Nt no) 00 | 00H CH | KMno, oo rts Ou ars 13.9 Convert aX ). 3-Methylaniline into 3-nitrotoluene. Gi) “Aniline into 1,3,5 - tribromobenzene. : Summary. Amines can be considered as derivatives of ammonia obtained by replacement of hydrogen atoms with alkyl or aryl groups. Replacement of one hydrogen atom of ammonia gives rise to structure of the type R-NH,, known as primary amine. Secondary amines are characterised by the structure R,NH or R-NHR’ and tertiary amines by R,N, RNR'R” or R,NR’. Secondary and tertiary amines are known ay simple amines if the alkyl or aryl groups are the same and mixed amines if the groups are different. Like ammonia, all the three types of amines have one unshared electron pair on nitrogen atom due to which they behave as Lewis bases. Amines are usually formed from nitro compounds, halides, amides, imides, etc. They exhibit hydrogen bonding which influence their physical properties. In alkylamines, a combination of electron releasing, steric and H-bonding {actors influence the stability of the substituted ammonium cations in protic polar solvents and thus affect the basic nature of amines. Alkyl amines are found to be stronger bases than ammonia. In aromatic amines, electron releasing and withdrawing groups. respectively increase and decrease their basic character. Aniline is a weaker base Scanned with CaMScantthan ammonia, Reactions of amines are governed by availability of the unshared patr of electrons on nitrogen. Influence of the number GF rgarogen atoms at nitrogen atom oe type of reactions and nature of products is responsible for identification and distinction between primary, secondary and tertiary amines. ‘p-Toluenesulphonyl chloride tused for the identification of primary, secondary and tertiary amines. Presence of ibid group in aromatic ring enhances reactivity of the aromatic amines. Reactivity of fromatie amines can be controled by seylation proces, fue., by treating with acety? ect, ‘acetic anhydride. any amines like trimethylamine are idiazdaium salts, usually obtained from arylamines, undergo replacement of the diazontum group with a variety of nucleophiles to provide advantageous methods producing aryl halides, cyanides, phenols and arenes by reductive removal of the diazo group. Coupling reaction of aryldiazonium salts with phenols or arylamines Cass rise to the formation of azo dyes ) 18.1 Write IUPAC fames‘of the following compounds and classify them snto Primary, \ secondary and tertiary amines. wd () (CH,),CHNH, (i) CH(CH,),NH, iit) CH,NHCH(CH,), X iv) (CH,)CNH, (©) CyHNHCH, (ei) (CH,CH):NCHs (vii) m-BrO,H,NH, 13.2 Give one chemical test)to distinguish between the following pairs of compounds, () Methylamine and dimethylamine (i!) Secondary and tertiary amines J&Nii) Ethylamine and aniline (i) Aniline and benzylamine (v) Aniline and N-methylaniline. 3 13.3 Account for the following: ( pK, of aniline is more than that of methylamine. MEQ) ob Best's sae im wer wheres ant eo (yy Methylamine in water reacts with ferric chloride to precipitate hydrated 2 “ferric oxide. } @ Although amino group 1s o- and p- directing in aromatic electrophilie ibettation reactions, aniline on nitration gives a substantial amount of menitroaniline. (¥) Aniline does not undergo Friedel-Crafts reaction. (jf Diazonium salts of aromatic amines are more stable than those of aliphatic amines. (vit) Gabriel phthalimide synthesis is preferred for synthesising primary amines: 43.4 Arrange the following: (i) In decreasing order of the pK, values: C,H,NH,, CyH,NHCH,, (C,H,),NH and C,H,NH,, (1) In increasing order of basic strength: CiH,NH,, CgHN(CH,),, (CzH,),NH and CH,NH, (11) In increasing order of baste strength: {a) Aniline, p-nitroaniline and p-toluidine * Chemistry Scanned with CGMSCanI(b) CcH.NE,, C.HNHCH,, CyH,CH,NH. (iv) In decreasing order of basic strength in gas phase: CAHNH,, (CjH,).NH, (CjH),N and NH, {v) In increasing order of boiling point: C,H,OH, (CH,),NH, C,H,NH,, (vi) In increasing order of solubility in water: CcHsNH,, (C,H,),NH, C,H,NH,. 13.5 How will you convert: () Ethanoic acid into methanamine (i) Hexanenitrile into 1-aminopentane Mn (ii) Methanol to ethanoic acid pe hse is ata Oe {v) Ethanoie acid into propanoic acid th Ae (vi) Methanamine into ethanamine U por (vit) Nitromethane into dimethylamine Vs (vili) Propanoic acid into ethanol acid? 13.6 Describe a method for the identification of primary, secondary and tertiary amines. Also write chemical equations of the reactions involved. 13.7 Write short notes on the following: ( Carbylamine reaction (i) Diazotisation (ii!) Hofmann's bromamide reaction iv) Coupling reaction (¥) Ammonolysis (vi) Acetylation (vii) Gabriel phthalimide synthesis. » Sil 18.8 Accomplish the following conversions: fe e ( Nitrobenzene to benzoic acid @ Benzene to m-bromophenol Gi) Benzoic acid to aniline (v) Aniline to 2,4,6-tribromofluorobenzene Zw) Benzyl chloride to 2-phenylethanamine F ny (vi) Chlorobenzene to p-chloroaniline 5 (vii) Aniline to p-bromoaniline Jun 7 cm (vili) Benzamide to toluene go te ) Aniline to benzyl alcohol. A the structures of A, B and C in the following reactions: / | si cHicHi) M+ A pe ott se v CoHiN,C1—2* 5 AHO _yp My an: CH,CH,Br —> A—M_5 B—8O_4¢ @ a 6 (iv). CgH,NO, —2H > atest p_ HOM _.@ 7a ue (v) CH,COOH M1» a M08" B—MANOA/HC ps 2 (vi) CoHlgNO, EH Oe mh Peers ae NM any BD § gat \ 6 e4Om Amines ai ye we oie oy \ f ft : Neel 4 ft h td scanned with CaMScani-ompound ‘A’ {ment yueous ammonia and "Crm compound "which on heating with Br, and ROH forms a compound of molecular formula C,H,N. Write the structures and IUPAC names of compounds A. Band C. 13.11 Complete the following reactions: () CgHgNH, + CHCl, + aleKOH -> (i) CoHgNoCl+ HPO, + H,0 > (it) CgHgNH, + 11,80, (conc.) > (§) CyHN,C1+ C,H,OH > (©) CgHNH, + Br, (aq) > (01) CoHgNH +(CH,CO), 0+ (oi) CHNC— 48.12 Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis? 18-18 Write the reactions of (i) aromatic and (i) aliphatic primary. amines with nitrous acid. 18.14 Give plausible explanation for each of the following: (i) Why are amines less acidic than alcohols of comparable molecular masses? {t)'Why do primary amines have higher boiling point than tertiary amines? - (ti) Why are aliphatic amines stronger bases than aromatic amines? Answers to Some Intext Questions 18-4 (0) CcHNH, < NH, < C,H,CH,NH, < CH,NH, < (C,H,),NH (i) CyHNH < O,H,NH, < (C,H),N < (CzH,),NH (00 CeHNH, < CoH CH,NH, < (CH,).N < CH,NH, < (CH,),NH Scanned with CamScans