Alcohols and Phenols PDF

ebanahn c Alcohots uom Haloal kones K-x + K0H R-0H 4 KX CHI + Reduton < atdehydess ketones Q R-CHO H (NP RCH, OH (Pouinauy LiALH4 CH¡-CHO +H Pt, CH, CH,OH R-R+H, H(Ne/Pe) R-CHR R-H-R' CSeconday alcoh...

ebanahn c Alcohots uom Haloal kones K-x + K0H R-0H 4 KX CHI + Reduton < atdehydess ketones Q R-CHO H (NP RCH, OH (Pouinauy LiALH4 CH¡-CHO +H Pt, CH, CH,OH R-R+H, H(Ne/Pe) R-CHR R-H-R' CSeconday alcoh) Na BH4 CHg CH, CH-=o +H N Pt, cH, -CH-OH Bropan-2-ol 3. Reducicn cabozyhe acids and esters to alcchals R-cooH LiALH4, RCH,OH CHe-coOH LIALH CH, CH, OH LiALHA, R-CHOH +RoH GHsoH CH-e-ocH Na/GHsOH, CH,CH, OH +CHgOH CHg -oc,cHs NalC HsOH LLALH4 CH, CH, OH + CHCH OH H+  alchd todorm Bebxctonaon 3. ---6u H H H--8Ho + + Carbocation on water attack el Nudeophallie d. H H H. Hot H,o+H H Hot edophitlic catuon calbo foum by alkene to Protonauon 1. Mechanun OH Hc-=CH, +H,0 CHg Ht CHg OH tH,0 HC-CH= CH, Ht OH H koukovs uwe * H,0 + alkenes Fronm 5. CHa CHg CHyMgBre +=o CHg- CHg CHs ou H CHg H H CH,OH CH, H MaBr H=04 CH, R ’-c-aMa Reuqhand a frcm 4  Jtyboation Ozrdation Redudin R-CHcH, + H- BH,R-f-çH2 R-CH=CH (RCH,CH2) BH RCH.=CH2 (RCH, CH, la B Ha0 ’ 3cH, CH, CH,- ÔH + B(oH a CHa- CH=CH, BH3. TH F CH CH,-CH, OH Hydrobor ot H,0,,0H CHg (CHa), CH=CH BHa.THE Cy (CHa),CH,-CH,-oH H, O,, OH- CH CHg CHa-= CH BHTHE H,o,,OH CH,-H-CH,0H CHs CH,-CH= CH BH¡ THF 2 H,0,, OH OH H 38  Phytal afeiten Arhelt înternolea'ar as ossociate d ooleoales hoving Aicehcls cnst H-bond R R S.-H---0-H ---0H- R. 1. Beiling Points (bbt) increose in Loex hnembexs have Louo boilimg þoint but oith thisis moleculay mass, bþt dextooas1ual'y Ancreasts be because uncrease un van do waals ces. CHOH < GHs OH < CHa CH,CH, OH Fo isomenic alcohols, having same mumbex Corbon aoms boing þont are n in qo ouoinA order CCH, CH, CH, OH CH, CH, CH-CH Butan- o Butan-2-0l CHg 391 K 373K 2-tmethy þxopan-â-o 356K The above order is dueto thedac that with ban ching sudoce area decrease s, therelore van der oaals orce decreasese consequently bo:ling þoint decreases, 2- Solubility Looex mernbens o alcohols ore highly soluble in but the solubiutu decrea ses ioihhghly oatee nrease fn molealar oeight The soulblty o< owex alcohos isdue to fotthaien bonds betuoeen al cohols and wate As the SIZe the alcohol mnole cule noeases, the oup becenHes be cerHes H-bonds and langen and þxevents foxmaton otky hence soubity deoeasesi  Chemucal Roactiont of Atcolols Alechds behave bolh as mudeobhles ord oterthophales 0) Alcohols as NvCLEOPIfs - bond belween 0-Hubroken H Alcohol Canbocatuon b) Alco hols as ELECTROPHILES - bond between C-0 u broken R-CH,-OH +H*’R-CH, OH, Bx4 "CHa-bH ’ Bu- CHz, + H,0 R R 1. Readion involvinmg cleavage q o-Hbond a. Reaciens with metols 2CHy CH, OH +QNa + Sodium ethode 2CH,CH,0 Na +H, 2CH, CH, OH + Ma ’ (CH, C,O), Mg+ He Magmesiam ethonde CH--0 AL+3H, CHy CHg Aluminiumteut-butoide b. Acduty q alcchas +B-H Alcohdl Base Allbxide On Alcohals showacidic chanacter due to þolannatun q o-t qloup As electon Aeleasing groups (- CHa,-GHs) increase elecron Neleasmndeney density on ozygen,endency to eleose Hfrom o-H bond decyeases which nturn decveases aid strength. OH> R R>¢-oH > R-OH Halcohol Halcohol 6Acidic chaYatex In R 3°alcohol erease s Alcohols are we ake acds than watex  tste'calien Alceholc Yeads oilh cavborytc otds, otd chlondes ond ard CHa-o-GH, +H,0 CHa--cl + H-0-CH,CHg > CHC-oGH, tH Ethaneyl chlorde Hhyelharnoate CH-l-o-cH, t Ho-cycHs CHy-e-ocH,CHyt CHycOOH Acdie anhydxide Ehylethanoate COOH COOH OH + (CHyco),0 -ococky +CH, COOH Salialic Acetic aad anhydude add Q a. Reacten anvolving cleavage Carbon- Oxygen bond *LucasTest 1. Reacuens naith hydogen halides Hi> HBr>Hce o< Rydrogen habdes Cade o< Aeadivty alcohals 3 2 ° Lucas Reagent Oxde o Ae activcty Anhyd Znda+ Conc Hcl CHa CH, OH + HQ Anhyd nd2 CH, CH,e + Hyo Cone HCO Donot hhoduce tuubidity T'alcohal Zodz CHg3~cH-Ce + H,0 CH-OH 4 HC Anhyd Zncd Cenc. Hcl H,c Boduce Hf Euubidity alter Some tne alcohel CHg CHg H,C-(-OH +HO Anhyd Zncla Hc - +Hz0 Conc Hce CH 3°olcehol Tushidity þsoduced imedictd as alcohtu au ee eatune  ehydiatientundugo dehydiatcn to fuam otkones bytabsng Aichet with Cenc. HO I|bene EHhanol ttose qJehydator CH;---H H H 443K >H,C-c=¢- H propene CHe Ht Hac--CH 358K CHs 2methyl þxopene Mechanis : Foxmati on þxotonated alcohol H H H H Protonaed alechol Q. Fozrmation carbocaionH H-¢- slo H H H--¢®+ H,0 H H 3.Elinunaton oa þroton todom alkene EHene 1 CH,-CH-CHy-CHg Conc.H,So4, CH,= CH-CH,-CH, t CHg-CH= CH-CHy But-2-ene OH (80%) 2 CHy-CHy- CH-CH,0H conc. H,S0, CH-CH= CH CHa Oidation Invclves ADmalvon lohond t 0H C-H bord Catled os'dehydgnaften al cohel. nes H. heagnl used. Chdismg ognts such os kMn04, k,Cr,0, 0n du) H, imas Alcchel: a1dised bo al dehyls then Bo oda R-CH,OH o1, R-=o Dy R-o * No.oj Cavbons should ternaun the Same CH, CH,OH +[o] kgCr,ly+ dil H,sot, CHa- CH o [o], CHcooH CH, CH, 0H CrO3, CHC HO *xeagents such as Pcc, Cr0g, Collins reaqent is usedHeaduon oud is st ops &t aldilahd. stage. if K,cr,0, s uted canboylic oblauned Secondany Aleohal:Oxidised to ktone having Same mo C-otoms cH-oH KaCy/H,SO4 C=0 CHg-CH-CH CHyCHy Ht Tetiany Alcchl! Reut Ozudaior  ebaalicn < Phencls halo anenes (hOws Poceas) ONat 306 atm 2. From benzenestlpheno I) 3. Fron dazonu salts Natct OH NH H, 0 Hcl Wann Anihnc Benzene diarnum chlade 4 ropRumene cHg Hc---o-H OH 02 Ht +CH,CoCHg H, 0 Cumene (lsopx cpyl benzene) 5. From Gnignand Reagent OH Y0, Dry ehex, T HtH,0. + Mg(oa) Brn Acduty o Phenols Phenols are stvongex auds thon olcohels (D0-! (00 Phenols ovc constdexed tobe esonance hymd o ieltuing otuura afe ocquires þaitol þoshu charge asa MeSutt el thu the oxygen afon wfhch weakens 0-H bond, hus joctating uelease d þototon. þroton stabiied Also þheno ide Lon 0-hitro þhenol > m-nutro þhenol OH -NO NG -NO, qroup at 0- þ- þositon withd aws ele cron s 0-H bond y -Reffet whie-N group at m-þositen withdaws stelererige tns weake - I eflet * -Retfect þxedominates ovee-I etfet untamole 0-mitroþhenol vs less audicthanb-ntrophenol due to culax H- bondung OH  -ntophenol + H0 # Gxeatx mo. ol EW od o-8þ-þosadion hghe The oudiy 2,4,6-Trinitobhenol > 2, 4-dinctobhenol>4-huophenol>a-ntophen b)EAetaon Donating Gnoups (EbG) -NH, -0R, -R megaluie charge Decacase acdity ol þhenol as they destabilkse the xel alie o þhenol Phenol > m-cresol þ-Cresal > 0-Cresol OH OH  Readens oj heocls 1Eledcphllc Substutution Reotions a Nbafion 0-nlrohhenol Mo, þ-ntrophenol (mojor) NO conc. HNOg NO3,T bcic oid NO, 2,4,6 tunitro þhenol b. Halogenaton OH OH OH B + Q13K 2- Bromoþhend Be 4-bromophendl 0H (majoi) B B +3Ba4’ B 2,46-bubnomoþhenol C. kolbes Reaction pH CO0H ONa Na0H (Deo,1-hydnoybenzaic (u) Ht Saliyie aud aod d. Reime-Tiernann Readion oNat -CHO CHCe Cne CHd2 NaoH. CHO aq-Nao4 Intemediate Saliafaldehyde a-hydrobenxaldehy e. Reacion wth Zn dust +Zn > +Zn0 benzene No,,O1 benzoquinone Hy604  EHhers Pvepavath on o EHhers 1. Wilianmson s synthesis R-oNa +RX R0-R+Nax Diethylethe HC-c- ONa + CH, Bx> H C-C-0-CH +Na G CHa ÒNa oCHg + Na BL +CHa Bx ’ ONat 0-CHy CH= CH, + CHa= CH-CH-Bs ||) CHsCH,0H conc HaS04(ecce ssaH,: =CHytH,0) 433 443 K E hene 2CH,CH,OH conc HgS O4, CHCH,-0-CB fH (excess) 413K Ehoxyethane CHg CHs CHg Conc HgS O4 QCH-H-o-H-cH, 413k Disopropyl ether Mechanismi 1. CH-CH,-6H ++ Mt CH¡-CH, Botonalion o alcchd 2. CHcH,--CH CH + H,o Nudeophitlic attock H unpiotonted al cohol orn 3. CHg-CHy -CH- CHg >CHe- CHy-0-CH- CHg t He þrotonated Las boton to alcohd foum'the  Physital Propextuos CH, (CH;), CHa CH,(CH,)a-04 309.1 801.6 g40 he taxge d|]exence n bh olcohds 3ethers i dueto þresence c Hbendmg in alcchol!' Chmcal Readions ctheas d Cleavage ol -0 bond tn R-0-R4 HX R-x 4ROH R-CH 4 HX Rx + H,0 0-R OH +R-X CHgCH, OCH,CHgS CHg CHh1 + CH,CH, OH R-0-R tHÍ-’ R-I +H,0 CH CH,0 CH,CHg táQHI’ CH,CHaI + H,0 CHa CHa CHy-¢-oCHg +HI’ CHg-c-I +CHg0H CH CH9 a. Electaophllec Substttuti on a. Halogenation a. Honc3 C H3 B Br Ehanorc Ani'sole þ-bromo O-bromo anisole anisole ) b. Fiedel-Crafts Reaction pcH tkylationpcpeHs CHg +CH,a Anhyd. Aicls S toluenY H, 4-methoy Loluene Acylstion OCHg ocHg +CHCoa Anhyd. Al dy, C 4-methoy Q methoy acetophenone cocHg acetophenone