@ Organic il: Extra Problem Set 4 Alcohol Redox Reactions; Epoxides; Ethers Follow the guidelines stated in Extra Problem Set 1 to continue to feach 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 at the back. Note that some problems included in a particular problem section may be referred to for topics covered later. Problems 15.28 and 15.29 in this problem set include problems to be solved with Extra Problem Set 6; use the topic guideline and references shown. Oxidation/Reduction Reactionsof Alcohols: Aldehydes, Ketones, Carboxylic Acids; Alcohol, Epoxide, and Ether Reactions Problems: 15.17, 15.19, 15.23, 15.27, 15.28 (d, e, f,h), 15.29 (a, b, c,d, e, fj, h), 15.32, 15.37, 15.38 Try 15.28 (g, i,j, k) and 15.29 (g, h, 1) with Extra Problem Set 6. Properties, Nomenclature and Additional Reactions of Ethers and Epoxides Problems: 16.21, 16.26, 16.28 - 16.31, 16.33, 16.34, 16.3590 it SC © CaH,Codca in the presence of pyridine 9 * w in the presence of pyridine ° 1528 back of he flowing scons as bien repo inthe chemical eae, Prt eh Pralitin cach exe, showy seeechemisty alee apropcas. OH x, &@ Cl ot As A ceceeng, {NNO 00409, (COCCHI eco bie Cells to Ei ihe Me “Hono © ‘o sat eet, oC Coy © CHEHCRCCH.C pe ca mC CHC, ee j g ow © crdecnenmencian sesguinn, Ty o on ON, 9 on © outa + eu niet £70, 7 wT ow $ p ® + wodew, ° “um, = oer 0) Product ofan @) Sees o p + & ae(as Pri he pac! oman pods of enh of he lowing reasons. Specify Hees operon One cnc, Os Crt ig 6) CCH + NEON oy if Ce Sen.ciy, (6 eauetienen CH CH, CH GMa Nf @ sec + oCpestae Of" \y, BF Gin be be © ae Oe Re ad U o G. © Cpe en cpa cH, ‘CHL as ® w Sac (wo afore RO OTron () CHs(CH) sCHAITs + CH,CH,CH,CB:SNa —> 1/1628 When (8).+)-2-phenyl2-bnaro! is allowed fo stand in metho containing a few drops of aulfre acid racemic 2-mediexy-2-phenylbotane is formed. Suggest a reasonable mechanism far this reaction {716.29 Selestrenetion conditions that would allow you 1o cary out each of the following stereo- speciic transformations: H @ yy + p12 propane " Act oo) > (81,2 propanediol (1630 The last step in the symthesis of divinyl ether (used as an anesthetic under the name Vinethene) involves heating CICH,CH,OCH,CH.C} with potassitma hydroxide. Show how you could srepare the necessary starting material CICH;CH,OCH,CH,Cl from ethylene@ 71547 Write chemical equations, showing all necessary reagents, for the preparation of t-butanol ty tah afte owing eto tate ~on (@ Hydroboraion-oxidation ofan alkene QA Fi20, fou" ttn (2) Use of « Grgnad sagen Heo is (© Ue of eign seagate aay ditsent om put gy ©) Ig re EL AAPA. . het, (Redotin cf weabonic aid <7 (0) Redan ofa mei exer 2 Ngee ST BARTER sayy 4) Reduction of a byt ever = L) aARou hile 2) woo eee? pe (© Hydiogention of an sdehyde 6) Retain ih et yi Row “teas CAs 4) ak, He hy Aa Mabie meee ¢H30H 15.19 Witte chemical equations, showing all necessary reagents, fo the preparation of tet-buty] Be fe Cte sabol by: ZHAO ; 2) CHa ge + (Reaction ofa Grigns reaget witha ketone > Lethe (© Reaction ofa Grigaré reagent with an ese of de ype RLOCH, 6) cg -octs + Ag Mghe 2 FPALO \As23 Wie equuins showing How I phenylethanol (CQI:CHCH) could be prepared fm each ingle WOK, fetfrn Gm: err _aw Nig cf te foowing sang mauris a toy fe SF z. Hae (6) Bromobenzene (@) Acctophenone L coe gg (©) Benzaidchyde @ Bane — bY oye Tae Save : (c) Benzyl alcohol, cH. xn) 9 oe Qs Dehr0, oh 45.27 Show how each of the following compounds can be synthesized from ¢yclopen sy necessary ergs or Snags teats In ay cases fe Sate congound a be rade d) ON el Mote Leva) owes ae Tee Nee bes Br Oa S \ sexe (9) 1-Preylecopensno (b) 1-Phenylcyclopentene l nee 1 Or, @ see lage Ey» - C se “ © cavhenonnde a (©) srans-2-Phenyleyelopentano LG srpeny 5 petmetit 5.28 Wile the sructare ofthe penepal organic product formed in tbe reaction of I-propanal 4 wih each ofthe following reagents: me (© Pyridiniom chiorochromate (PCC) in dichloromethane © Resi eine 009 nae aeinme 2) YH ay oe Sodium amide (SNH) 4) Sue 4) Q xo ee ee agen chloride CHC OA, w am \ soe ‘in the presence of pyridine JX CH, = Nols + ~e o> 3 o o cno-€ \-ba inthe presence of pyridine dy au. orn, AY ES|As28 Pe pnp orp pot of cath of te felon mao Sty seme ‘chemistry where appropriate, me CHACH, ¢ ROHS o Dee cuca — A T 3. “—f OD CH: crc, Gh tty SF Sb Siva > St—oensctts (no chenge af, chivas castes) (0) CCH + © CCHCCH BE CHa CHa QHZ CH Oo” oo) Cy t Chasis J _. Se oe plo NG os OH ~Oeh= Chi, Bt ® Ge Berm ne (OH, eo cnn wort OE aan OE ‘CHACeHs oH 5 CH—CH,- OH CHa CoH: eS on Matas bi w Ros SIE ) CAYCE) CLOTS + CHCHLCHCHNA—> CHSC CHa} ig CHa SCHACHaCHaCHs BU Dw D ene 116.28 When (R){+)-2-phenyi-2-butanol is allowed to stand in || containing a few drops ® “een te i anny Totes ome. Sgpe + Rel an hema one o (R)_OH team plucte eine sain ttn awe ananttcttmaccrme —@ gs Jono A Vig a Haosbx® ck Gents (By) AES —> crys 2-propanedtiot fo chown be chine & Yo one no eae B by H26/ He oK © (9).1,2-propanediol Thvergion ak Chirat © Roe S e \/r630 Tho tas step in the symhess of divinyl cher (used as an anesthetic under the mame Vnethene) elves hesting CICH,CH,OCH,CH,CI with poasum hyaroxide. Show how Yow could prepare the necessary starting material CICH,CH,OCE:CH,CS fom ee owseeet ' 50% O- CHG Chis, “ee C= tig Ch OH —HeS28, C1 cHlaCHe 2 " [acid eodensetion. 9, alcohols)®) a. : 030 ROD 2 QO ymio) Fetio i 9 9 yy e OH Hei ey) ON { ore Ore Tae ry, Othe29 ° s : : $0 cagboleyt, ine prsene of prize 2) Cute bo Uo non ke ub . oi EO 5 * 08 [7 in te presence of pyetine +) Hosa ‘ °° V/4529 Bach of the fllowing reactions has been reported in the chemical literate. Prediet the product in etch case, showing steeechomisy where appropsin. @ cme 259,(€ 1) cit { pHs Gis) = 4CH3)2 bu OH 0 CHcmc(cty, ACOH. OOseD, (CH gsCOH, FIO” ° O- ne ction Cre exn at double bond) © emquomciniv, gaahOOaae CHa PW SCC) HS I on A i “ 9H tno Rawat © catercrmcucrten, “ME, OL OOH CHEECH HZ CHCHs — oloulle bend) ON : . ‘I cide — @ cH + ( Nyy zai omy a 3y hos Ce The in. stereochenistiey : 90 / 9 ° rm it LS * {COCCH _ = no ten,) oe omc, C " W PN og a0) 5 é é dz (+ H20) oe Con fee at &—OCHs on’ oun? 9 9 si gaa, goon CH CH,OH ASC, ly ® hua, a cg A SxSHs04 sy g ad aS + oy “GoweeAS.32, Suggest reaction sequences and reagents suitable for carrying out exch ofthe faowing con- versions. Two syuthesi operations are required in each ease, y MabHe, gon THE, (en) “CHSOK 30H Oo ates Cou He ) or HO. Cena . Cr as why + y ®) CHAO [20 trod” ed on g oH ‘ H Heso. CuHs (Re ca oho » Ch oi rit gatas (fete on len 2 2 “ott #837 Colo living ee gatos y wing ttt fra ferconpemnes A [A= Q,, {sk QQ, ‘through @ O® one caer = cao fee coupon Tisacno” CHO ie Q Compas + {oe Oe ° — Ga, Es cpr ES caco MMS cot, .c10 Compound DMP Compound E compesnar L2)= Ray lew A) On » Oa Compound G Y&.&E°%> conpomnttt > ess Viena ie ome 9 oe ens tig ter cette UD se flowing ce fe S 6d. “CH Br ot om OF SO oso tle caugenen, HS cate, es « 9 CHy-OH {zs on OCHACH, Sh Bee Ou OF CO ‘Sugeest # reasonable mechanisin for this reaction based on the observation that the ether produced Met (3, Sh peal eve dahl rn ant eres can be on m9 be eee cake) [F] = wine (Compound er i Re Hasoy Gis Gus cnacon) \ FS Cos pote Cote ny iChb > CellaGcHacHs TF" (Cts cect ox, wis0 CH aan tn 2282 a po ma geet ‘ethers are quite Hammable, their place in medical practice has been taken by highly halogenated nonflasroabl eters. Two suc general anesthe agents te ufone and enfurane. These com Pounds are fomeic: isfurane is shlovo-222-mifuoroeiy]duoromet ether eairane fe 2-chor-i ifoercehyditueromediyt sts, White the smuctal formulas of fsoforae aad fens. a F Hq isoflurane = Fo entlarane = Yoh ode ~ F-o5o5 0-8 eos (goer i ro) i eH z F e® “is Soe sh fin cen eat uh fr rp ach fe owing rele ne eee . Ne . _ Boon tt Luana on + cto Ae Bue ©) a wom | » “RAGS ca PBrs or ae LO yt oC tom tom ae Jpenzene and cyclohexanol OH Cros? oO S imo? Calls ) cr es Tie thee (©) CQHCHACHCH, from bromobenzene and isopropyl aleabol i Wah. [2 He bn See tat BOGE er > ve (@) CgHSCH{CH,CH,OCH,CH; from beazyl alcohol and ethanol 2 2S; oH See, (eet Pose Root SS Keats ce) from 1,3-cyclohexadiene and ethsnol Celis See (aot one Cc xe, & . Cots / 16.3 Deduee the identity of the missing compounds in the following reaction sequences. Show sereochemisny in parts (b) through (@). A= Ch=CHcH-GHe OH mcucirsie EM» Compound A Bs, Compound B YO) Hemcucesbs ritse Chino, © (akan) a , sto" |rwwe BS .<€51 Compound © 7 “bee (CaHr0) (Compound D Vio, compeina (ep) 220, compamssiesiyos TL * — Jowscowoe (alianis) CH. CH “3g, Compound L (C7803) (mp 995-101°C} (sa et pen cf exp ib barely a Cee ee ee racks more OHs Dave the structure of cingoe. (635 The poluenesutfonate shown undergoes an intremolecular Williamson reaction on test- ‘ment with base to give 2 spirocycli ethes- Demonstrate your understanding of the terminology seine neg sence hy wing eres ing eocheni oe pret 3 Ley OD, = 2 CHLCHEHLOTs > Cyto 7 Cos Cute