Re on ay (ii) Loss of proton : The basic ion, HSO% abstracts a hydrogen on to yield a substituted product ie, | ritrobenzene, j 0, NO, ‘Fad — 0 +H,S0, / / Inthe above mechanism the rate determining slp ie, slow step) is the formation of carbonium on, (ie, second step. + Physical Propetos (Most of he aromatic ito compounds are yelow enstaine sods, Niro benzene i, however, a qu wih characteristic odour of biter almonds (Abit compounds are insoluble in water bu ready soluble in crganc sovens () They are abvays heavier han water (Aromatic nro compounds ae righ oxi. (On strong heating polyntro compounds explde volenly and hence, are used as explosives. * Chemical Properties The important chemical propertes of aromatic nto compounds (Reduction : Aromat nro compounds undergo reducten unde een! condos prove 2 variety of prodycs. For example, (@) eduction in acidic medium: In acidic conditions such 2s ZnHC! or SHC! mtrobenzane is reduced to ani. ‘NO, NH Ow 2-O)ae j sha eduction: In presence of NiPt nitrobenzene is reduced to ane, QO Reduction with Metal hydrides: Nrabenzane cn reduction with metal hydrides (ie. LAM) iets azobenzene, 6-+-O0x:0 {Reduction in neutral medium: Nicbonzone, on reduction, a nau med (eine dos sa ag, NH! soltonfoms phen hyoxyanine u sue LetNo, 2nd =a Orem) eso O8F-O---O = No, O===© — penean, Ce 0 pen reducti Ooo MY (wosky ate meduny No, NHOH NH, Exec reten, (A Reoranarer at romp OH foramine cae P-amino: phenol (@) _SelgCtive reduction: In case polynitro compounds are treated with sodium polysulphide or ‘azmonium sulphide, one nitro group is reduced to amino group. No, No, ©) 20s —- Osa a8-mK0 mbritroNO, kite NH, acN — a ond te No, No, aert Os — Oo +35 2H0+3NK, Lan’? ne maa a mus benzene ‘ninelectrophitic substitution : Niro group ts deactivating and meta ‘substitution reactions No, No, Nitation: Oo ecmcinn, Spee a ‘NO, oo — ca CYANIDES AND ISOCYANIDES (NITRILES AND ISONITRILES) Ccyanides and isooyanides, the two series of isomeric compounds, ae derivatives of Rycrogen crane (hydrocyanic acid) which exists in the following two tautomeric forms. H—CeN==H-NZC Hence, hydrocyanic acid forms two types of esters (cyanides and isocyant tautomeric forms. R—C=N==2R-NZC General methods of preparation of Nitriles and Isonitri 4. From alkyl hi des) corresponding 10 the tne CHCl +KON-> CH,CN + Kc! ‘cnoomenane manent 2. From arenediazonium salts : Nenci on a +N+ Kon SHS n+Ka Benzene dazonism chloride Bonzonile 4. By sting ammonium sat ofa fatly acd wth phosphonss pentane or ‘alumina (Industrial method). c¥4jc00H—M-»cHCOON, —2OE-» CHACON: —EA>>, CHAN HCOOH — I? Catena | RO) Romande © HO ae ne yCOOH > Ce COONH, FA + CxHCONHa > Case HCOOH Oa et Hoan MO) ree 44. Byte dehyeration of ldoximes with acatcanhyarid. Ci, CH= NOH AER?» CHAN + HA Raine an ocAmines (Grignard reagent and cyanogen choride, ON > CHACN + Mg(ByC on nes : Alkyl and aryl ¢ ry am NY! carbylamin ro reper anne wh chlor an acon se, +e 8 are prepared by carbylamine re ion, ish), + CHC, + KOH(ale) — gy 2 oxo CHC, Y 9 OHCHN ¢ + aK + 9,0 + 3KOHale) —, « apie OHH + MOM) —> cane acts 0 ‘of Nitriles and Isonitriles, i ‘kyl group (hydrocarbon portion ofthe molecule). However. siniries are soluble in organic solvents, enc: evoinparian! chemical reactions of nites and isonites are hytrolysis ad reduction. | tyéoyas: i tor on Hororr R-CRN That R-C-NH, ERO Roo «ni, \sonitriles onthe other hand, are hydrolysed by dilute acids but not by alkalies to form a primary amine and formic acid. sieghigeceee fata, pl {Amine Methanoie acid City NC + 2,0 Calls Ny + HCOOH FCN AP] EHO Rag, Rone Aen Rc, R=CaNe2H, 2", ROHN,—s mame NET > aaa trie wih stannous choi in Brosency 4 spe nto: wet hn a Ty re ihe, CH,CH = NH.HCI CH, — CaN + 2H] + HCI —Sete seataismine hyroririe | seo CHCHO + NHC! her! 3. Reaction with Grignard reagents: Ht ox] R—C=aN+RMQX a—GEN I Mox a tH ADDITIONAL INFORMATION «+ Alkyl nitrites are the esters of nitrous acid, 4% alcoholic solution of ethy tite is called sweet spit of rite. It is used as Vasodilator in medicine forthe treatment of asthama and heart diseases. © On boling with cone. HCI or conc. H,SO,, a primary nitroalkane is hydrolysed to carboxylic acid and hydroxyiamine. On hydrolysis with 25% H,SO,, an aldehyde is formed, ‘Aldol type condensation products are formed when aldehydes and ketones are condensed with primary and ‘secondary nitroalkanes in presence of alkalies. [Niroparatins are used as solvents for os, fats, resins, esters, rubbers and cellulose etc, Niromethaneis Used as high power fue! in racing automobile. «Aly! isocynides are highly reactive because of the presence of lone pair of electrons on carbon atom, fa-fied: th rections gery ivove nucleophilic adaitons. ‘Some important altrating agents are conc HNO,, HNO, + glacial acetic acid, fuming HNO, in acete annyeride, miture of cane. HNO, + conc. H,S0, (nitrating mixture), acety nitrate, benzoy! nate etc 1+ Nitobenzene is called ol of mirbane or artificial oll of bitter almonds. Nitrobenzene is a good solvent in Friedel-Crafts reaction because it dissolves AICI, «+ In dy state, ciazonium sats are explosive and explode violently on warming. When dilute aqueous solution of NaOH is added to C,H,N,C in benzene, diphenyl is obtained. This is an extension of Gattermann's reaction. ‘On reduction with Na,SO,, the benzene dazonium chloride gives pheny! hydrazine. ‘On reduction with Zn + HCI, C.H,N,Cl forms aniline as the main product. (On catalytic reduction with H,/ Ni, benzene diazonium chloride forms aniine ‘+ () With phenols and naphthols, coupling always takes place in the para-position to the -OH, but if pare position is already occupied then inthe ertho-position (i) Aniline couple more readily than do phenols. (i) in alkaline solution, the coupling will be directed by the -OH group and in acidic solution, the reacton wil take place vi.rt. ~ NH, group, if compounds to be coupled possess both -NH, and ~ OH groves. {jw} Electron.ttracting groups inthe rng of dazonium salt facitate coupling, while the presence of eecror- donating group (-NH,, -OH) especaly inthe meta-position ofthe xiginal ~OH or -NH, group, aso fcitate coupling. Thus resorcinol (m-Dihydroxy benzeno) couples more readily than phenol with a given diazonium salt. (v) A halogen or nitro group in the ing of aromatic amine of pheno! lowers the eestor density in the ring. Hence, such compounds do not undergo couping with diazonium sats, Corporate Oifce : Aakash Tower, 8, Pusa Road, New Delhi-110006. Phone : 011-47623456Amines § 1 ao at of onmarin ST=GR Stet tacreasing tang N ge RUN NH, GHCHNH,, CH Neat Rui i 17 cet BN. NH, GoHsCHANM,, CH, ly Ce \ ty Mature are (CH,).N* OH-, (CH,), eMGNH,. (CHy).NH, CH,CONH,, oo elds pure prima 4 in rearrangement Ny amines. The eduction of certain types of nitr an compounds ett maton of PAMOTY AMINeS relatively fee of si noone Te etoine wary amine, wet an gies may arco oper of amines tha ably to fon wi Salts of picric aci, \ go ron ants yl se 'Y 10 form salts with acids. The salts of picrc ack rates, ff ines, and in fact all-NH, arya ‘ompourds ine oman gon The yield of hydro, mre Sin amides, react with HNO, at ordinary temperature *Y Compound (alcohols) Touton of iS Quantitative and itis the ba 1 Vane) YEtY low in case of aliphatic primary amines "8 of Van-Siyke amino nitroge is. Aromatic amines, ee anne 180 react inthe same manner fe arn nrogen cay ae activity of tertiary amines of the type RAR.RN : A tertiary amine like NH, fone al of eCONS Present in p° arbi We ctbital containing th "Wer 35 the fourth diferent substituent, hee {he tertiary amines of the type oral shapes bored a Renee resolvable. But, in actual, Practice, such type of tertiary amines foereverbeen resolved, This is due to the reason neg {he energy diference between the enantomore of eo amines it Very Smal 25 kJ ma} and he ‘pialyinterco Ses niogen inversion oF amine inversion” vento one another by a process ergs non InWeS.on, the state of hybridization not rca terse the rat ofthis inversion is very high (23 x 4gto 5), therefor re, tertiary amines of RRRN sou itl en 25 racemic mitures wich canna resolved, ag ee Y's method for separation of 49, 2° yoffmann’s met 4 32 and 3 amines : The reaction "Seat rie ceric Te td Uiteacted teriary amino eve Properties of amines) is distiled when Stary ami pe me NA containing the substi ‘xamide (Solid) and the oxamic 1a 6 Serarated by simple tration, Bema oo ne 2nd the oxamic ester when boiled separately ponding amines, Thus, has @ pyramidal shape lone pair of electrons is R,R,RAN because of their IMPORTANT NAME REACTIONS + Hofmann Mustard Oi! Reaction Onwarming with 8. prime tothe aky isothiocyanate, ar amines form dthioearbamic acid, which is ‘fecomposed by mercuric chlorideNEET (ent | ‘Amines Coupling Reaction In alkaline soktion, 1-and 2-naphthols couple with diazonium salt in the 4-and 1-posions respectively H | ‘phil +OH N=N-GH, HN, Ct NEN-GiH oH Peale (©range-red dye) Hoffmann-Martius Rearrangement |When trimethyl anilrium chloride is heated under pressure: NH, “HCI Aicry,cr N(CH), - HCI NH(CH,) - HCl O ‘ HK cH, CH, CH, cH, Benzidine Rearrangement Hydrazobenzene undergoes rearrangement when heated in the presence of acid to yield benzidine (4, 4-iaminodpheny, OO Owner Ot goa