Organic Il: Extra Problem Set 4 Alkynes; Conjugated and Allylic Systems; Diels-Alder Cycloadditions Use the extra practice problems to continue to teach yourself the important procedures for problem solving. If you get stuck while attempting a problem, go back to the text or notes to find the key information which will allow you to continue the solution. Do not go directly to the answers! Simply reading the answer will convince you that: | could have done the problem if | had to.” However, during an exam you may find out that you never really understood how to solve the problem type. After you finish a section of problems, use the text or notes again as a reference to confirm (or deny) your answers. This wil allow you to reinforce the concepts and correct problem areas. At this point, your answers should be identical to the answer pages. if problems cannot be solved through the text, make certain you ask in or out of class to clear up any difficulties. ‘These problems are taken from another text; the problems 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. Use the topic guideline and references shown. Bonding, Properties, and Nomenclature of Alkynes Problems: 9.18 - 9.22 Alkyne Acidity and Reactions Problems: 9.25 — 9.28, 9.30- 9.33 Bonding and Nomenciature of Dienes and Polyenes Problems: 10.17, 10.18 Allylic Position Chemistry: Electrophilic Addition to Dienes; Diels-Alder Cycioaddition Problems: 10.22 - 10.24; 10.30, 10.26 — 10.29; 10.35, 10.369a8 Provide the IUPAC rane foreach of the foiowing alkynes: (@ cHCHCACecA | pentyne Moncucecey, A- Pentene 9 Biememtanem, 4,6 -dimebnee-a-hexyne a, @ D-craicnc=ce S~ tuclopRepyh -I ~ perrtyne ez © _fnemcd, . cloteidee: Ae gre © crrernctnce inti beac, 4 butye-2~ mongne SHE ®iHComccct 2,2, 5,5 - Eotmmettiyl ~3-hexyne yon ‘Weito s srucroal formula or build 2 molecolir model of each of the following: @) Loewe BD ALANA by Anw 2 ~ ev © 20ey0e © 30aymne A) NRAY gy aay £) Qo (8) 40ctyne (e) 2,5-Dimethyl-3-hexyne () 4BahyLt-heryre Q ot hy as (2) Eahynyleyciohexane (¢h) 3-Ethyl-3-methyl-L-pentyoe 2.20 All ihe compounds in Problem 9.19 are isomers except one. Which one? (Q-) 921. Write structural formulas for all dhe alkynes of molecular formals CyHy« that Ge Seehylhexane on catalytic hydrogenation. : . 7. AL 3 3 922 An unknown acctylenic amino acid obtained from the seed of # tropical fit has the mo- lecular formula CjH,,NO,. On catalytic hydrogenation over platinum this euuino acid yielded hhorncleacine (an aminoacid of known structure shown here) as the only product. What is the ssructore of the unknown amino acid? oO ok a ons persiste J Biingrengator OL _ 4 0 Soxeriyci Oo) FC =C (CHa, . Wp (cen, Te @ Product of pat () E> = int 4 ia Luis) nate kone pn sen coin ti er ef eee ay rect inling cone milk cheddar cos. Deter & eerrepmere em ag len and aay neces or inorgenisreagenis, . recy Yen emi arbors BO ae ° Iie a4 gs Hs = HH aa Engen, cscy, a ~ e anon t a if seons Caucbuns, Nanila 2 Vaa2_ 9Tieve (25H) GACH) Chew phrnene oe female He=cH > He=tnP ow: Sythe 9c it toed tlt 0 he me fs to wap ta soma eet le. Using scenes sd letols af your choice as sting ates, lang ily pores ~ L ‘inorganic reagents, show ow you cold prepare (2) S-icotene. meee ek Cyr OTs A Aa Sc BS ALAA ots / i, é 7 2. | Wane watt Ake AL On Tc AAA AYA 1433" Show by wag «nabs series of eacaions how you cold reper cach of te flow 3. Cyr ots | ing compounds from the designaied staring mateils and any necessary organic or inorgenis feagente (@) 22-Dibromepropane from [,t-ditromopropane () 22-Dibromopropane from 1,2-éibromopropane (©) 11.2.2-Tetachloropropane from 1,2-dichloropropane (@) 22-Dilodobutane from acetylene and ethyl bromide (©) 1-Hexene from I-butene and acetylene CH, CCH.),CH SCH CHEM, : Lindley Eo Ha [Linde | product (D Decane from I-butene and acetylene B ® tr LNawits ag Be A ey 2 Fao” 2 olen Be L Nandy kia 1) Se ame “Ss —rat ai ct Nats ct © « ALA ange? ss —Ster “OX, CYS Hz He He==cH 1 Netils 2, CH CH, B _ . | : L 4 sug HCERC—CHaCH, “Sa hinlew @2 oO : o —COOCH: lensticarbonylate, (CEOCC=0CO { i —> acetyl late, ( ICH) 8 conch Cocks, 410.27 ‘Two constitutional isomers of molecalar formula Cyfiy,0 are in the following reac- arial 5. ij . — oO = ne Net enema on ‘ «tai, — CR 0.28 tiene can bs covered to tier (compound A) of molesslr formula Ca. Compound ‘A reacts with dimethyl actylenedicasborjate wo give compound B. Dade te suucure of eom- 020 We floving retin ge ay pode ie, By Ha arn es is Sono ty “no -reerrangpent nts those 2 atkybre carbon cation comics Cpa ntam ) MM Ao3s Sarma i nee i nn O-O+ o> thse were) 5 Sty sO Ah) Diels~ Alder) = —» rast bry gp miro lets re ih hei ey 6 Ave tf Dares ee ce ts ey 4 ‘ge of Dicls-Alder reactions, predic the constitution ofthe Diels-Alder adduct that you would OCH; by RR-O-0-H expect to be formed fom the following combiations of dienes and a Co cts COCA» . OCH @ + cH0,CC 000, cI, a J Logis” Gigi (CHy,sio €ANSS 0 OS + croscomcco.as @ + CGy=CHNO, / CHLOCH,828 Wits sci of to naj oni prosutsled hon te macon of Leama wis (A Aly ——> ) (9) Hoytioges @ mod, platinem, DANY © Hodges Ome, Lar pany AO) NE (Same aren) as) (6 iti in qi ammonia Souk Na. Nig (@) Sodivm amide in liquid ammenia (© Prodotin pat) weted with Voowbume — OL) NAGE NE 0) ANBN~ GND) (©) Product in past (Q) reatod with sere butyl bromide le (© Hiydogen chloride (1 mal) £) G2! = Angst A cia Py ® Who Ape G) Chlorine (2 mot) Aqsoos slic aid eesy( sul) ko ) —~ 2) fet ® Ozone followed by hydeelysis San S27 hi sac fe ir eon tn he asin hexyne with (@) Hydrogen (2 mo}, platioum QAM. 4 C ~e —>) (©) Hydrogen (1 mol), Lindlar palladium ) ; «| © Lithium in tiguie aermonia 4 4 AS nent) eo a aah cc {€) Hydrogen cilorde (2 mol) 9) one © Cena (me) “A AL (@) Chlorine (2 mol) » (" hy (i) Aqueous sulfuric acid, mercury(I) sulfate 6 Crone followed by hydrolyse O ygor + ao A s28. When Ltepyne wes wesied wit gicous alfa ai somtining mieary ste, two prodecu, each having the moteur formoia C3440, were obtained in oppeoxiaately equal mons, What a these fa compounds? : ae! RGA, ie AAS + ANA, CSE er w¥ Ja2e ‘a1 80 tag aston hehe eit in te seal en a pce in ‘good yield. In some eases sie reactants are more complicated than those we have so far encoun- ‘ered, Nevertheless, on the basis of what you have already leamed, you should be able to predict the principal provinct in each case (@) NeC=CH + CICHLCH,CH.CHLCH.CH,I > G[CHa CHa CH, CHCH, CH CCH (LD better vatnitstamunm, 1.23.4 5.4 leaving gparp) (0) BrCHACHCHACHSCHCHBE Sy” HC SEC CHa CH C= CH Bo Bk © pte ocr, Doc=ecn a — OTs = STS = leaving group o€ Scam + csoul Co (By-cs0 CHC ; “Bg ©) Cyeloseeyne 357,57 ‘1 2 es ° zs 44 fe wr AAA . . HOE NEC 3 oT °\a6.17 Write steerural formulas fr each of the folowing: (@ 34-Octadione (@) @.B)35-Ocndione © G2)-13-Cyclooctadiene © E2yA1,ACyctooetadione © EBS Cyclocetasiene t1.¢4,2,) () QEAZ6E)-246-Octatriene a NANI oa \ t@stiniscrmanear ‘by AD ae} Uten/, (i) drans-1,2-Divingleyelopeopane 3 Ereme @) 24-Dimethyl-1,3-pentadiene ¢) /0.18 Give the IUPAC names for each of the following compounds: G x Org a OH + 49 24 2) o wetowinrn — olt hye, 9 Cc epg 1,8 nonad iene, Y ele ~ dichioro—|,3,5~ " hon ‘ saat hexetbiene ) * © Cydnthiddey, ocm-cqoeco, 1 EY a eG SIGNS He aime a 12,4 “hexatriene Letrmethye= Fs " aa is amet ae 1,54 exelo~ hy ~ OH =Crle © CHh=CHy.CH @, , dodecateiene 3- athengt—),4 - . B cotaddene MAY. da z 4 Fag nub Be, (ey So re yts OH, Cnc Ly nege- © Ke | cy hexadvene gua SCs s ein 4 =nethyg~),3— pow (ey 3 -elhyge~ fo) ues oe /4a:22 Show how you could prepare each ofthe folowing compounds fom propene aad any nee Q) 2 BR eccary organs o inorganic reeset Be. e (©) Ally bromide See (9 123tibvemopropane bb A Se, (@) 12-Diwemopropmne “USE CH Ally alcool Be, (© L3Dibromepropme ——PAGR 4 (g) s-renten tyne (CHy—CHCHC=CHD z ues i (©) 1-Brome-2-chloropropane () 1,4 Pentadiens i ane Ae A023 Show, by writing a suitable seqoenes of chemical equations, how you could prepare exch 2 Be Rew] ata flowing campeunds fom eylopeucee and my necatary orgie or wore wagons: BE ALY we {@) 2-Cyclopenten-L-o1 (° 15.oshytine YO wl (0) ate Dawes (© 3-Cymocyetopentene te \ boca, (rom abo) _fo28 civ te seme, extant ppl ape put meson SM @ —F fenction of 23-daveiyl13 botdiene wits cach of the following: a o AR ky ty¥ d) Be 2) Be cavaee, aA ak (@) 2 mol H;, platinum catalyst 1st roa fae hn) (2 1 wal HE Geos tengo ti) (@ 1 ol ge fet 88) tml eae ener in amis ° » ot 5' Be. o Ss. 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