N- Bromo Succinimide / NBS Oo f 1 we N—Br N—Br ee \ ‘0 fo} Introduction: romo-2,5-pyrrolidenedione, commonly known _ as_N N- suecinimide,) It is, a convenient source of bromination for both Fac ree | radical “substitution dical substitution and electrophilic addition reaction, mine is carried out with NBS in of allylic or benzylic hydrogen by bro! non polar solvent such as CCl). However (the use of NBS in aqueous solvents, (a mixture of DMS with water) as a source of electrophilic bromination., It has found increasing importance in the formation of bromohydrins, the cyclisation of certain aromatic compounds and in the addition of bromine to alkenes. The oxidation of secondary alcohols to ketone using NBS has been carried out in aqueous solvents. el of NBS It is prepared by action of bromine to-an ice cold solution of succinimide in alkali at 0 °C to form white product, which is washed with water and recrystallised from hot water or acetic acid. It is stored in a refrigerator and protected from moisture to avoid decomposition. It is easier and safer to handle than bromine. f° 7° Peres 0°c Hae \ + Br, —————> | N-Br 4 HBr iy NaOH if C—_! H,C—_¢ S Xo ‘o Succinimide N- Bromo succinimideThe reaction of NBS is catalyzed by peroxide or light. It is believed that function of NBS is to supply a very low concentration of molecular bromine (Br) and trace of HBr is necessary for initiation. The accepted mechanism is, Step-I ne x HAC: co N—Br + tier + Z ad NH + Bry H.C: co HG os By + R——» poo iG r Step —II ——CH,—CH=CH, + py eae 2 ST CH= CH=CH, * +t.Step — HI Br ICH CHS= CH, + Bry ~———_» eo ae Bt Allyl bromide The bromine radical produce in step-IIT can continue chain reaction. The removal of HBr in the step-II is probably due to greater stability of the resulting free radical.=> Further Mechanism :- © 4 eH e -BYr SM yee I Sha ext CHa eo Prova > or ° CHeco moteeted step) Step-Fh+- - : : — CH -eH=CH, + Br ——. eH -ehecn, 4 HBr CNew molecule Frown step-254 otep-tags- er 1 : -cH-ch=on, 4 BY, —— 7 chr ehecH, + Br Frown step dD.Step - I HAC co N—Br;) + HC co Bro + CgHg Step - II CH3 ll \ Br Ss Step - IIT cs . s ‘co HAC \ NH + Br, HBr ——» H,cC——cOo aN Br + Br» — CH, af Ss + HBr CH,—Br lS “+ Br Ss 15%=> Further Mechanism :- —_— “Step-d iG bi a oO eH ~ A 4 eho | Dw 8r 4 ABR os bo SN 8 cH, nH + Bry TAM @ foray eye” CNew molecule) ster-a) » poher > die- uy é cH ——| af 7 "3 + Br —— \l if 4+ HBY CFrom ah ene ee step-dda) SteSynthetic Application: ae i Ae (1) Allylic or benzylic bromination «tie of bowie Seon? NBS is a valuable reagent for brominating ally’ zy) compounds in the ally! position without affecting the double bond. co 7 ~~ N—Br + —CH,—CH=CH, me 0 NBS Allylic group@ NBS tee ace —_— ic NH Ether / 25 °C H,c-——cO Cyclohexene 3-Bromo Cyelohexene Succinimide (50-80%) (Alkenes are brominated at allylic position on refluxing a solution of alkene and recrystallised NBS in anhydrous cc) ‘The reaction is initiated by peroxide or light e.g. reaction of NBS with cylclohexene gives 3-bromo cyclohexene in presence of catalytic amount_of radical initiator such_a benzoyl peroxide: Olefins can be brominated in the allylic position by a number of reagents, but NBS is most common, when this reagent is used, the reaction is known as Wohl - Ziegler bromination. jiy If there are two allylic positions, then two monobromo derivatives 2 may be obtained. Allylic methylene groups are attacked much more rapidly than allylic methyl groups. e.g, In 2 - heptene, a secondary position is substituted more readily “than a primary.Br NBS Hse-cH~cH, | 7 —CH==cH—cy, H,C—CH,—CH,—CH 3 CH CH=CH—cH, cel, 4-bromo-2-heptene 2-Heptene 64% inati s to allylic . Mili) When ever a structure permits, alllylic bromination lead: y! : F i i ixture of ~~ rearrangement ©-&- 1 - Butene on treatment with NBS gives a mix both possible products Br Br NBS 1 Hyo~Gu-cH=cH, + HyC-CH=cH—cH, 3-bromo-2-butene 1-bromo-2-butene v v iv) | The reaction of NBS on i and poly-olefin often leads to abnormal Products by allylic Tearrangement. Thus monobromo product, 1-bromohe; bromo isomer, 1,5-hexadiene give the Xa 2,5-diene with small amount of the 3- But the reaction of 1,5 - hexadiene with 2 moles of NBS give 1,6- dibromo 2,4-hexadiene, NBS i i Br 1,5 hexadine 1~ bromo hexa- 2,5-diene + Br SAH oti con, 3+ bromo 1,5 - hexadiene 2NBS H,C=cH—cu,—cy, CHy—CH=cH, —_2NBS x lg—CH.—CH,. Sheth ia eth | Bede A3in eae HCH cH cy dae 6 Bru, 17 dibromo 2,4-hexadiene(vy) Allylic bromination with NBS is very useful for converting a monounsaturated compound into diene and_a diene into triene e.g. cyclohexadiene. 3-bromo cyclohexene NBS a “HBr BS H Triene \e/Benzylic bromination: ue Ethyl benzene give 38% yield of the a-bromo compound in the ‘Yabsence of initiator and 45% yield in the presence of an initiator. er NBS C pre—ore — CH,—cH, 38% 145%(Vili) Another examples of benzylic bromination are the conversion of {-pheylbutane to 1-bromo-1-phenyl butane) and 1-methyl-naphthalene to 1-bromomethyInaphthalene and foluene to benzyl bromide: Br C \cr-ctieons-on as CN -by—en,-on-o ‘a 1-phenylbutane 1-bromo-1-phenyl butane % CH, CH,—Br NBS/ CCl, — Benzoyl peroxide CO CH; CH. -Br NBS/ CCl, ————_. — Benzoyl peroxide Benzyl bromideCiv) Brornimation of aromatic compound — The arcwautic compounda act coith NAS under joie cond ito: +o _aive nuclear substiution prodvedt. — Bi woe cohen treated coith NAS and sone, Has and eter eta) gi _bromabenzene iv oy ied. ér NB OO 3 e— 21 CTT a7. = Hederocyelic compounds ssithout alkyl substituents ave brominated by NBS in hetero rine gy. NB, sicts itn thiophene to give. 2-hramothioph — Nun rH Le — oa H,caoH = CHel. 2-browmo thiophene — N-substituted yan les are brominated ooith NBS in THE olyent to give 2-bromopaysyrole und Wibromevyyrole saith Neo of NBS evith high selectivity. f aot a! wes TtAE EL Lay + en SOr nN " be V ey 3 a Bi Rewethgt 25 aibrs N-methyl 2-browe nS Neynethyl pyyrele- os ae oe 7aration of 9 ai Chat= > CHS eH— Oe amethy) erotonete(oe tcesa tsi, f Retinol into Dehydrovetinel :=- Role nay amints Seas ia AA ae i oo Qedinol Cvitewin A, oe Alephemsl wv pholii L Hos Li AH, aT Cor a wee ede tin I ECT Lo DehydroreHwel Cvitawie Az?Pege—— +) en DNAS as oxidizing agent: Ce) owidation of ulchohols = NAS oxidizes primary ulehohal: silclehydes cond | sadary alehshaloto edo ied, | =. THACH,oH 4 For = TH, EHO FBR F Sana | nes ‘ Con, CHOH ———— fo eso + HAY succiviinn idle. oxidation of cholic ecid at oy cath Na yi deoney chal sicid on oranE a oa syd etl hes (eam nbz, Pas saya aaa ’ ¥ lope elie 25 holic _cteid decry ohalic oid. Ch) Degradative: oxidudion of hydroxy curbortslia aid: — NAS ds edith o-hydvoocy acid in hot yteo4s solution do give aldehydes or Wels pith toss of wbora_oite wa. ow FBS a R-eH-cooh = rere = IBS reacts nith leche acid to give sicedea\ dehyde. on cH,-¢-wor ——— CH,CHO = i Ho | A BS Luctic Acid BS earls coith crlyeolic ucid fo give forynaldehyde ou was n= = won —_——_— HeHo H Ho | A Crlyealic acid NBS veseds eaith mnandelicecid cicid do ~yive. benzal dehy de. on AS C(Hs- ©= won CH CHO A Ho | e Mandelicacid eid—~ (. wienilavly, oh cimine anid ive: decarhouylated saith Nias im actdeous mediaen ae flocs a Bob eoon % = Be. pecno + NHy+ Oa vid Addition regetion:- cud Formation of dibremo rompeind 165 ia often eed os the source of electrophilic braxainetion in polar solvent NOS er yi = a anes TEAST, Br 12 dibromoeyola hessely Ch) Format of brawnohydvin = Nb wets coith alkenes im prenence of enccess caciter adily achieved do_give browmhydrin, Preparation of epaside i by reactina bromohydein eoith Sadium hydride. a) ae) es fF be browohdy J 2 epaces yo (oheocuwen