CHAPTER 5: ALCOHOL REVIEW REACTIONS PREPARATION OF ALKOXIDES Sy REACTIONS WITH ALCOHOLS sy ta ' ; : rH amon te gp ox + HO id a PREPARATION OF ALCOHOLS VIA REDUCTION, NaBH MeOH Je ene eC, eae Se, F Bs te" BT HD ® s eee ay 7 Nash. MeOH Se soc, te 7 N matam— hp on a ee oe ° 8 elle 1) Excess LAH se aon HO £1 AND Ez REACTIONS WITH ALCOHOLS SL nega 6S thee Le ees an + MoH a ‘ R7 Some 4:0 ROH year! on ton, ob PREPARATION OF ALCOHOLS VIA GRIGNARD 7 z REAGENTS ° on GXIDATION OF ALCOHOLS AND PHENOLS Sk ame aa) ‘With Chromic Aeid i R T see J on eon Te eer dense wn ‘OMe ate Seconda Ketone Sicohat PROTECTION AND DEPROTECTION OF ALCOHOLS | 9M i a? HERS a Non muse a Primary R-o-™s— ° C) wets Bran ok Benzoquinone 13.4 DRAWING A MECHANISM AND PREDICTING THE PRODUCTS OF HYDRIDE REDUCTIONS STEP 1 Drawthe complete stucture | STEP2 Drawtho alkoxide | STEP3 Draw two cured anoy | Gf LAH ancl draw two curved arows intermediate. showing the alkonile intermean, | that show the delivery of hyde to being protonated by the pron the carbonyl group source! 13.12 Draw a mechanism and predict the peste product for each reaction. oO oun , “aR” nua @) HOCUS) Ho” of ° Oo Nao we “WeoH* rk Ho yuan ©) ey 2,0” 9 “xs ta, C oN BHO” ‘OMe NaBH | fe) A WeoH v13.13 Drawa mechanism and predict the major product of the following reaction. O — yExcess tan, xe _ BHO 13.46 Predict the product and draw the mechanism for each of the following reactions: 4 9 auaH a ae? ve “un, o 2H,” 13.5 PREPARING AN ALCOHOL VIA A GRIGNARD REACTION 9 | alpha position. three groups connected installed via a Grignard reaction. | | Ji 2)H,0 Ji 1) MgBr bl A | sone Cintiae= 13.14 Show how you would use a “ee reaction to prepare each compound belo,, FAD SoH BN on Kl oh eo dit? @ RN ne ie ee ye sectnte7 Og a OF oh oH : 3. ae" Two of the compothds (et rotten 13° 2 Yan be ifepared from the reaction between a Grignard reagent and an ester. Identify those two compounds, and greens the other four compounds cannot be prepared from an ester, Bro Ou 13.16 Three of the compounds from Problem 13.14 can be prepared from the reaction between a hydride reducing agent (NaBH, or LAH) and a ketone or aldehyde. Identify those three compounds, and explain why the other three compounds cannot be prepares via a hydride reducing agent. BN 13.17. Draw the mechanism and predict the product of the following reaction. In this case, HO* must be used as a proton source instead of water. Explain why. ch & arsswenaer, D ¢ ng o Dano Oh 13.38 Using a Grignard reaction, show how you could pre- of pare each of the followi alcohols, ape. a oes ey das ey13.6 PROPOSING REAGENTS FOR THE CONVERSION OF AN ALCOHOL INTO AN ALKYL HALIDE SM ay anti | STEP Analyze | STEP2 Analyze | STEPS. Reaction must occur wa 2 eee | the substrate: | thesterecchemistry: | so use reagents that favor Si2 | invenon cn lof}, ce | | x on 13.19 Identify the reagents you would use to accomplish each of the following transforma- tone Oca cot = ot. © SS “Oy hee SES ay t Aw ee13.7 PREDICTING THE PRODUCTS OF AN OXIDATION REACTION EXAMPLE STEP Lsensty whether STEP2 Aprerary akoha canbe oudzed STEPS. Arie wage the alcohols pony or” erher to a slaehyde orte carbonic aces, PCC we to frm secondary Seperding er tereagen's| Cromicoade Oe ok ok Ot Primary Aldehyse Ccarboryie acid 13:23. Propte a synthesis or each ofthe flowing vansformations o Abita. f 4) Sect ° OF hac epg ae sas ee 3 tho f stadt i op ee OG ® Ur ae 4 Hast HO pee. . Nar, THEE “WiS0,.4:0" sae ° 4 ee S @ 0 sexo a wer os _Nasce0> e Ove ore Oo o Oe wee? re =13.48. Identify the reagents you would use to accomplish each ofthe following transformations on Mam 0 ak ML Gil 6 On Nate, Rh 9 Ayah OH YY Lat oe Hie <8 fe 13.37 _ Starting with 1-butanol, show the reagents you woul 48 © prepare each of the flowing compound i ABB i 6m. oy () 4 OH BAKag o ~AONX13.8 CONVERTING FUNCTIONAL GROUPS Functional groups canbe interconverted using the following reagents. which should be commited 19 memory sayoee | -——teeeseiet ___aneres c ee 6 Bhat MO nage ne A vig0, 40 RS, Row Maga wsogima) BRS) «erm ont gree | BO oy BB Bnet “ ax or S09 oF PR aconots | “ey Taciby. DNR sot 2) eer Ketones! slsenyses (a) 13.25 Show at least two different mgthods for preparing 1-methyleyclohexene from I-methylcyclohexanol. oe oe 4 13.26 Using any reagents of your chobsing, show how you would convert tert-butyl alcohol into 2-methyl-1-propanol ih 45H THE UNE43.39. Each of the followin reduction of a ketone or ald aldehyde or ketone that would be required | 13.51 Identify the rea, ‘accomplish | ° 4, 9-68N A tfyOk aoe 13.9 PROPOSING A SYNTHESIS. ESTEP1 tetheres ‘change in the carbon sheleton? Keop track of the CC bond-ormng feclone that you ve learned STEP2_ Is there a change Inthe functional groups? The chart rm the previous Shiavider summarzes many of he important {inconal grue 'g alcohols can be prepared via lehyde. In each case, identify the gents that would be necessary to each of the transformations shown here: as STEP. Aker proposing 2 Syren, analyte your arewer ahha fowng te quests: athe regiochemicl outcome tfeach ep correct? ste the stereochemical outcome ofeach step correct? MORE TIPS. Rornember thatthe ered prtuct shuld batho major product of you proposed sya Always thnk backwards fete ‘rays a wel ae ere, an thon tye bridge the aap Most syethetis problems wil ive multiple tolind the "one" coret air13.40 What reagents would you use to perform each of the following transformations? 13.43 Consider the following sequence of reactions, and identify the structures of compounds A, B, and C. compound M2. Compound 8 (Oey (CoH 4180) 13.44 Consider the following sequence of reactions, and identy the reagents a-h 4 my Bite, 4 © SneEaO On One 2 eae Smet |p ae oH 20 NURS oth wy wees Sleeeee 10one « ty PED AS ae 13.45 Using 2-propanol as your only source of carbon, show ae how you would prepare 2-methyl-2-pentanol. os IAM OH wage POO 13.35 Predict the major product of the reaction between i ae AHO ‘1-butanol and: (a) PBr3, (b) SOCK, py (9 HCI, 2ncl, (@) H,S0,, heat a fee (@) PCC, CHCly (6) NagCr07, HaSOx, HzO : Noir . Lah @) ui () Na » Noy, AN @ TMSCI, EQN OTechpyidne hy (Na {) Potassium tert-butoxide C ah, we ING 13.49. Predict the products for each of the following: ZO Be. Ns ols Bm, oA I @ ‘ canon” f : \ a ae jet 4) in ES _hes LP it 1305 MeN 0 oJ Ses 2 AAD On aay ANE EF | ie B Aixs Lit AA~ANu Not» ae no OMS, Bp i, Ny AWN,1)03 aks 5 ee AION NIE 3) Excess LAH 4 © Ay Heo a xSLAN Lads o) DOF AOS egal oe 20 r TS RaGerIHO. RO? Rare ae sy @ Vener Sie ag gor \ ‘aes SA 2)H,0 2) TsCi, pyridine ‘0 a a tes a tne SQ. Se att 13,21. Prodict the Qa§ for each of the following transformations. an, By noe QD ol @) ees “RyNaOET” male minor et 13.52 Propose. plausible synthesis for each of the following ? Cele transformations: ° Ay Metab HON ®) inusep,, Nari 2Cer ES 0a se ky st yc, eae » Cig icon oe 4y o BO aise enh pile 0 sat © Hi xy epee Astor Ay Bey 4 hares bb hee aD rele PS oe - ge io he ee i l en OE IIT oa bebe ne Ne of yh onesee