Nitrogen Containing Organic Compounds ILLUSTRATIONS Section - 4 ED 0 she fotowing conversions. i) Ghelopentene to Cyclopentyl amine (ii)__ Acetic acid to glycine (ceamino acetic acid) (ii) Ethyl cyanide 0 ethylamine (iv) Succinic acid 10 3-aminopropanoic acid (v) Benzene 10 1, 3-dibromobenzene SOLUTION: : 0 Poe Nei of) on ES o SA aera oe ® Hero, LiBHL,CN os NH \ we ae () eIkeooH > crycoo > Cth, Coot Be Nu, can crcren B®, cx,cH,coon M45 cx,cr,—conn, “5 cH,cH.NH, 09) cn } 2. Ni CHCOOH yy, CH= COX 10° CHCOOH oy CHCOOHT @w) | a? NEO cucoon 8 co? cHconH, = CHANH, wier BNO, cons oat, ” THSO, cone.” co = ‘exces CEE bs fining comers ()—Nitrobenzene to m-bromochlorobenzene (ii) Aniline to benzoie acid (iii) Nitrobencene to 1,3, S-tribromobencene (iv) _p-nitroaniline o 1, 2, 3-tribromobencene (0) e-eresol to salieyelic acid NO, NO, wier cl “Oe On. 61, “2. Ol, ©. “ “ees” SC Te” 20 WESTIN, st sey course or with onine Supportieurucumeree NaNoyticl, _cuBr “ore sc? HBr © QO bs “o" oH or 1, Kind, Teal Chloride oO OH group" Note: If deactivating group is present, oxidation is possible, Nitrogen Containing Organic Compounds ier Br Br yypo, BE Br tho? br Br Be 1, Snct Br 2. NaNO,/HCt Br @e-sc) BS Br c= s0), 3. HPO; NO, ASS Rng is destroyed. (When activating group such as ~OH is o/p to-CH,) oo 0 os _o, oo cn, coon oO © oOo 2, @ (yk sare iy - Lal, ci) cHcocr +] NH —> aS a Gy) No ©) cHNH, —2 +a wo ‘are all organic compound) NHOH, y _LiAIy 0 MO A ee? B ©, Ny ol Nit, & Hin, gael, y 0 CH.NH, ———> a Self Study Course for ITJEE with Online Support QUES” 2Nitrogen Containing Organic Compounds TOCA SOLUTION @ (ener ae, Con +N ~ ®) wo) (eo + nnon —+ (enon Hts (vn, ° é Late h-ca, Ly rm rm wii) | NH cHycocl —> | N-c-cH, SEs SH, N-Ethyl ayroligine » ther amine —_(Acetyation) Substituted amide Red 3° amine nm 2 Ope A Opt Onan (2° aly hale) {) (elimination occurs) ©) CHNH, PoH,-CH, > CHNH-cH,~cH, NZ i nines QO (Base cays) by cope co cay» (0 + (ene tit (sc, ‘Note : Inaliphstic ketones, ketimines (R,C=NR) are formed, Whereas in cyeloalkanones ketimines tautomerise to form ‘unsaturated secondary amines. Se ST On HNO, CHNH, OH ono OH 908 ‘CH,NH,, ‘cus Lc, ian rearranged to eve (ateohol +a 22 ESI, sete study course for 113£€ with online Support SOLUTION ne)Acura ed Nitrogen Containing Organic Compounds CEE) Ar organic compound (C,H, on hydrolysis in acidic medium gives another compound B (C,11,0;N). B forms zwitter ion and gives off CO, with NaHICO,, B on heating gives compound C(C,H1,ON). LiAlll, in ether reduces C to pyrrolidine . Identify compounds A, B, C. SOLUTION 0° 4 ACN) 22 BCH,0,N) “4c ‘Since B forms zwitter ion, ithas both acidic and basie groups. B surely has an “COOH group asit gives off CO, with NaHCO, It must have NH, groups also as it forms zwitter ion ° 1 “The structure of ‘B" should be : H,N—CH,CH,CH, —COOH <== H, N-CH,CH,CH, —C-0- 4 B22, w (with one atom less) = Amunbecyanide ew ©", ReOOH Hence he stuctue ofA shouldbe: H,N=CH, Cll CH CN 1 cH, —NH CH, —NH oP oe owe, TY Nei Neu! ‘a cylic amide NH s Pyrrolidine ° © EEE Find the end product (©) in the following reaction sequence. Omm Nig stone, 1B c > A heating” Bag. KOE eat” Coon aos SOLUTION coon cONH, cook, Ni or KOC, = = ‘coon 2,0 ‘CONH, "CON, “ o Phthalic aid "Hoffman's rearrangement” cooH O,, * © a ‘Anthranilieacld © Self Study Course for ITJEE with Online Support UI” 23Nitrogen Containing Organic Compounds rhe magi oy prodsel of ihe reaction a HAC. CO.H NaNO, aqusous HCL Baan esse HCl oC NH, SOLUTION: ‘The given optically pure alpha amino carboxylic acid first forms diazonium salt on reaction with sodium nitrite and HCl, This diazonium ion undergoes intra-molecular nucleophilic attack (Sy2, back side attack) by oxygen atom of neighbouring carboxylic group to form an intermediate having three membered heterocyclic ring. This intermediate further undergoes nucleophilic attack (S,2, back side attack) by water molecule to form alpha hydroxy carboxylic acid with retention in configuration of chiral carbon atom because final product is obtained by two successive Sy? attack on same carbon atom. rie coon esepamens, axon, wy 1, ve oH OH Ne 4 Treatment of compound O with KMaOJH" gave P, which on heating with ammonia gave Q. The compound Q on treatment with BrJNaOH produced R. On strong heating, gave S, which on further treatment with ehyl-2-bromopropanoate in the presence of KOH followed by acidification, gave a compound T. Identify the structures of, Q,R,SandT. (0) cg xs oo CONH, g Ko, ‘ COS a Op Oy Rane OG | pexvon oie , NI w|Ho Cr wo COOH . mn NH, ° Hoffmann’ rearrangement m 2a) NRREEECIC i cy Course orice wits nine Suppor