Organic lt: Extra Problem Set 3 Organometallic Reactions; Grignard Reactions Follow the guidelines stated in Extra Problem Set 1 to continue to teach yourself the important procedures for problem solving. The problems from another text are listed in numerical order based on the text chapter Configuration, Answers to the problems are included on separate pages a he back Nofe that some problems included in a particular problem section may referred to for topics covered /ater. Problems 14.17 (n}, 14.21 (b), and a .24 in this problem should be solved with Extra Problem Set 6. Preparation and Properties of Organometallic Compounds; Nucleophilic Addition and Addition/Elimination: Alcohol Formation from Carbonyls Organo-zinc and Organo-mercury Etectrophilic Addition Reactions Problems (all concepts): 14.15, 14.17 - 14.24, 14.26,14.27, 14.29 Try 14.17 {n), 14.21 (b), and 14.24 with Extra Problem Set 6.(AA.15 Suggest appropsiate methods for preparing each of the following compounds from the sart- mas ing material of your ctoce DAV The (2) CHCH,CHCH,CHMgT (9 CHCHCHCHACHL aa @) CHCH.C=CM gl HO cHoncHcHOLcLi — B) “Scagd + CHaMgh > Dvn Sb ra: Wits the sirctreof the principal onpaic product of rach of the fullowing reactions: ” ~ (©) Bromopropane wits liam in diel ether (©) 1-Bromopropane with magnesium in diethyl ether CL) 7 he (6 ‘odopropane with ithium in diethyl eter & mn, ger (6 Dindopogane wih maps in detyt aber) EB 8) Aa Bs {@) Product of part (a) with copper) iodide «= 2) UN Chi 9) . (0 Pret of pt) wi oad EE BY AA By) EI (@) Product of par (@) with iodobenzene = 42.) 7D () Prove of par (2) with D,O and DCL 5 A 4) Aon Product of pare (¢) with D0 and DCT 4 oH ) Product of par (a) with formaldehyde in eter, followed by dite acid R) e D Or (8) Product of prt (0) with benzaldehyde in ster, followed by dite acd ), Product of par (¢) with eycloheptanone in ether, followed by dilute acié 3 rm) ” (0m) Product of part (¢) with CHsCCHCHs in ether, followed by dilute acid 9 1 (0) Prodvt of pre) with CHsCOCH, (2 mal) in ete, flowed by ate acit ©) (©) LOctene with disdomethane and zinc-copper couple in ether PE oa ss owt ng CH KK (@) (2)-2-Decene with diiodomethane and zine-copper couple in ether (@) @3-Decene with diodomethane and zine—copper couple in ether 7.38 Using omens an any mesa cage spe fet ya Lig TSS RE mt ad any cesar ran inane age pp icienteyms — O.) AA. wher @ PRewmoi (©) 3 Metny--heptaol 1. Ceo (©) 2Hexanot (©) 1-Butyleyclobutasol Zc ASIO Be (©) PbeayL- 1 pentanal \ ise tagrecnnt tyne wpe gan napeacaesn ©) ~~ ppg “Sein thes fen of lowing a Tae (@) BemsyLatcbol “YS Seg {aot (@) 1-Phenyht-hexanol © pe ) AAO feo EY € Brasdiphnyntne {09 tmertsioin | eaptecs {siomnec 5 © tenet Peyote eat i. “20 Analyze the following structures so as wo determine sll the practical combinations of Grig- t ge ‘atone lk pom sy gemntemsiumetees if SE @ oe (@) 6Methyl-S-heptea2al . a Had feck p i A page L NIB Lee g apple eee = oe wt ° (0 (@i),CCH.OH 4) ~Siiggr bk avo1428 Addition of phenylmsgnesiam bromide to 4-ter-btyicyclobexanone gives two isomeric ex- {iy slobols as product Boh lho ld to same lene wien sjee o acif-aaly 5 Seton Sopp resomble srocwes free we sod ye eg NO axon cccts}g on. oo A ‘teere-Boyglobeancne maze i fonmate (HCOCH,CH,) yields a different class of alcohols on restment with Grignard ‘eagents. What kind of alcohol is formed in this cxse and why? I (b) Diethyl carbonate (CHjCH,OCOCH,CH;) reacts with excess Grignard reagent to yield ; ‘cobs ofa pasicolar type. Wat i the sructua felue that characterizes alcohols 1 orngs ‘Prepared in this way? —, 5. Double ester givee alcofate with £9. ~O7 oS SD <™O7 NON thre idemhcak erie grows Pa o{¢ 1426 Suggest reasonable stuctares for compounds A, B,,and C in the following reactions: SEe 3} ‘! 3 OTe ican, (cx LJ O™ PAS compound A + compound Bp . (as (Cuz) Coty BS Gud, eis % ee sn (ors ny fa ccunse compound B + compound C (Can) Compound C is more stable than compound A. OTs stands for tluenssulforat, = DB = E2 product (eae 14.27 ‘The following conversion has been reported in the chemical literature. It was casied oot in two steps, tbe first of which involved formation of a p-toluenesuifonate ester. Indicate the reagents for this step, and show how you could convert the p-toluenesulfonaze to the desired product. LO Tstl 2 Kon AAS Geren, 1429 Dipherolmethane i significantly more acidic than benzene, and tiphenylmetane is more acidic han either Mentfy tbe most acidic proton in esch compound, and suggest a reason for the trend in seily: Ci (Colig.Cth, (Cell sCH Bearene,, Diphenylmetbare nee Re 10 oy ® CTS fake henee tes form Otani Bier is Steer Lieed ky ¥ dbth, foen pine ml vrela 14, 20° 9. b 4 =) 5 2) ie ~ ~~ et. Oe OS £5) 1. Ba He Brig CH CH (cH), HG —CHe CHGHS) i 2 Exum Gs) e-cHeot t lg oitig Be + HEH = CH), Bolg eae, seg Grae e ig 5 Fo 5A421 A number of érugs are prepared by reactions of the type described in this chapter. Indicate what you belie would bea reatonable last sep inthe steals of eats of te folowing. LHeseNa on —_—__ ) cHycayocence Meparfynol,¢ mild hypoatic or secppiaducing agent 4) _¢ 2. K20 bn . 98, g -Taeey r > Grgiees, 3.40 ws catge)tntpmt natin nn eos of or Hig S- maple. hh \CH,O" with aldehde “1422 Predict the principal organic product of cach of the following reactions: OH i : 1 2. gid ai CF @ - + NaCency + 4Etaeete, Cc > ~<) 7H i 2 CH w HE) - as . on nen Meme, ca omy ake cHcR—cR, nee He eich . 4 cH nm eal Pe © Nome’ "St &)y cHe 4 _y 14 Licw(cHy, > Saty en is a One SN % © cud e Ham CHACHCH, a @ sat Scr + LiCu(CH,CH,CH:CHs), —> os od a o =OTS