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    10 views9 pages

    Ochem Solution Manual Chapt 7

    Uploaded by

    xiceman0123
    ochem 7e chapt 7 solutions

    Copyright:

    © All Rights Reserved
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    CHAPTER 7 Solutions tothe Problems Problem 7.1 Write the TUPAC name foreach compound. pes ) — © te LOctyne 33-Dimethyl-I-butyne 3-Bromo-3-methyl-I-butyne Problem7.2 Write the common name of each alkyne (a) + (b) (= CQ —_ “NZ Dilsopropylacetylene Cyclohexylacetylene Butylacetyk Problem2.3 Draw a structural formula for an alkene and dichloroalkane with the given molecular formula that yields the indicated alkyne by each reaction sequence, location as the double The key to this problem isto realize that the triple bond in the product is at the sa bond in the starting material (2) CH, C2, cH, c, NINH \ OHsCH.CH=CHCH.cH, C2, cHychec—tuou.cu, 2NaNh, \ (cis oF trans) cl ct Coe CoHy2Cle a, 3, 2NaNH, (6) Gti, Sey cH,,c1, 2 NaN = CH; CH, L Ce Satu tim, 2NANH, ieee — Che-F-G-$ oH, B Sane aa cy, (cis or trans) 7H, Cl, CH. mi Prolem74 Draw a scr formula fora hydrocarbon wih et ghee pa ©** ON wh he en mem ht nds yta 1y 1) (sia).BH Coe > 2) H.02, NaOH ] wee At ert ot bod ct Alkynes Problem 7.5. Hydration of 2-pentyne gives a mixture of two ketones, each with the molecular formula C,H, 0. Propose structural formulas for these two ketones and forthe enol from which each is derived. The two ketones are 2-pentanone and 3-pentanone. Ht Sirnle > erie Ge H.0 Pentanone CH3CH,C=CCH, H2S0, 9 HgS0, CH,CH.C=CHCH, —> cH,cHUcH.cH, 3Pentanone Problem_7.6 Show how the synthetic scheme in Example 7.6 might be modified to give the following. (@) F-Heptanol A reduct indlar catalyst to give am alkene, that ean then be converted to the primary ‘of the double bond using hydroboration. osscu 1-NaNHe __,. cs=c(ct,) Ct He 2. CH3(CH2)3CHBr piaess pd/CaCO3 (Lindlar catalyst) HO __ACH2)4CHs cs 1. BH: py ae ___ = HOCH tGHs) CH;C==CCH;CH2O"Na’ + NHs NH ()) pk, 38 (stronger (weaker (weaker base) base) Oxygen ther to the right on the Periodic Table) than nitrogen, so the hydroxy! group is the stronger acid and equilibrium lies toward the right. i (c) CH,C==C” Nat + CH;COH + CH,CO™ Na* pk, 4.76 (stronger (stronger (weaker (weake hase) acid) iid) hase) Oxygen is more electronegative (farth Table) than carbon, plus t is resonance stabilized. ‘Th -d the right Problem_7.11. Draw the strctral formulas forthe major prout(s) formed by reaction of 3-hexyne with each ofthese erga: (Where you predict no reaction, write NR a) Ha(excess) / Pt (b) Hs / Lindlar catalyst (6) Na in NHs (liquid) CH;CHa __CH,CHs CH3CHa 4H CH3CH,CH2CH2CH,CH3 ne =C H H ‘CHyCHs 3) BH followed by H302 / NaOH (6) BH followed by CHsCOOH (0) BH followed by CHyCOOD 9 CH3CHa ae CHsCHa rtcts CH;CH,CCH2CH2CH3 e ‘A ay > (e) Clz (one mole) (by) NaNHa in NH (guid) (i) HBr (one mole) CH3CHp 1 CH3CH, Br 5 aes NoRé oe ci” YCH2CHs H ‘CH2CH3, j) HBr (two moles) (ky H0 in 2804 /HgSOs Br Clee CH: g CHyCHa¢CH2CH2CHs t icin CH;CH2CCH2CH,CH3 : 4 one Lenng I Rigs Reed May mate camel clo dpe te wits woke a Alkynes 1 Step 4: as cH: Vinyl acetate Syntheses n 7.14 Show how to convert 9-octadecynoic acid tothe following: a3 9 wo all ‘OH 9-Octadecynoie acid (a) (E)-9-Octadecenoie acid (cliadie acid) Chemical reduction ofthe alkyne with to mi Skene’ Nate thatthe carboxy! group i unaffected by these a CH (CH2): H nag, Hae (CH (CHe)/C=C(CH)rCOOH, —= > Yeact death H (CH) ,000H ia converts the alkyne to an E Reduction of the alkyne with one mole of hydrogen with Lindlar’s catalyst gives a Z alkene, The carboxy! froup i unaffected by these conditions. CHs(CHo)z,_,(CHe)7COOH Pd/CaCOs vied CH3(CHz)7C=C(CHe)7COOH 9-Octadeeyn cid (©) 940-Dinydroxyoctadocaoic aid rither the £ alkene or the Z alkene ean be converted to the plycol by oxidation with Os04/I303- CCHy( Clip) CH=CH(CHe) COOH O50» aul epi (202 HO OH 9-Octadecenoie acid (cis or trans) The stereochemistry of the products depends on whether cis or trans 9-octadecanoic acid is used as starting material. (@) Octadecanoic acid (stearic acid) Reduction of the alkyne with two moles Hz or reduction of either the F alkene or the Z alkene with one mole Hz in the presence of a Ni, Pd, or Pt catalyst gives the desired product. 2H, CHs(CHe)rC=C(CHz),COOH) (CH, (CHz2)7CH2—CHo (CHz)7COOH 9-Octadecynoie acid CH (CH2)7CH=CH(CHz)7COOH = ClH3(CHz)7CHe-CH2(CH2)7COOH i 9-Octadecenoie acid (cis or trans) ©2014 Cengage Learning All Rights Reserved May ot es ee Looking Ahead Probleme 7/26 Alkyne anions ect wit te cron lasted by the felling soc 9 I = Naty HE! —CH,OH CHyCmc?~ Nat + HOH ——> [CH,C=EC—CH,0~ Nat] G> CHs C=C An alkynyl alcohol Propose a mechanism forthe formation of the bracketed compound, using curved aows to show the flow of electron p im the course ofthe reaction. uucleophile and attacks the electrophilic carbonyl carbon atom (make a new bond between a nucleophile and an electrophile). The carbonyl pi bond is broken, generating the alkoxide anic the species inthe bracket. The carhonsl carbon atom is electrophilic bec tom that provides for a rather polar C=O, Problem 2.27 Following is the structural formula ofthe tranquilizer meparfynol (Oblivon, FO Obtven ‘HO’ yess fr this compound sartng with acetylene anda Ketone. (Notice they and theo nano hi compoun cans tht ton aya sn pnt gag me tin ck Acetylene The synthetic strategy for the construction of me anion with a carbonyl species as described ig followed by protonation ‘examples in which the carbons! ea 8 You will see many other W carbon-carbon bond, Must be primary haloalkane to avoid E2 Mates « carbon-carbon bond Reaction 74 2X, Adding only ove equivalent of J ives an (E)-dihaloalkene Reaction 7.74 1.BH, 2.11,0,,NaOH Little ‘regiochemical preference Reaction involves enol formation followed by Keto-enol tantomerism Reaction 78 1.H,0,1,S0,,HgS0, Markornikov repiochemisiry for terminal alkynes Reaction involves enol formation followed by Ketosenol tantomerivm Reaction 7,9 H,, Lindlar catalyst Sym addition Great way 10 make (2) alkene Radical mechanism involving two cycles of ‘one electron reduction followed. by protonation ‘Great way to make (E) allene \lem.7.30 Write the products ofthe followin ns allow you t reaction sequence rest 1. Hy/ Lindlar catalyst Reaction 795 > @ —= n » —=— An alkyne YF Reactiove.t Am alkene DA An alkene section) 2NaNH, in NH, (D alten ast sep in converting an through ie tpcios! dihaloetkane 3 teen flowed by protonation Jor terminal alkyne into an alkyne istry (with terminal alkynes) Markornikov_resioche Adding only one equialent of HX gives a haloalkene Non-Markovnikor ‘regiochemisiry for terminal alkynes Reaction involres nol formation oll by: ketorenal.tantomerism Reaction does not stop at the alkene but continues ‘on to the clkane Reaction 7.10 1 R,BH 2. Protonolysis (ie, CH,CO,H) Can give Markornikor regiochemistry depending on R Sym addition Alternative way 10. make (Z) alkene eqquences of reactions. Refer to your roadmap to see how the combine navigate” between the differen functional ret how ie oad roups. For example, in fan alkyne into a haloalkane in two steps. 2. HBr mixture Br &r A haloalkane 201 Reaction A vicinal dihaloalkane Alkynes ONS ) Saas \ alent of NaNH, Ce 2.CHyI ate “Reaction 72 An alkyne Cr. 3. acess Hy Pd Ca 1, Reaction 7.9a An alkyne (new C-C bond) Am alkane 1.1 equivalent of NaNH. 2. Reaction 72 An alkyne (new C-C bond) C mixture aalyst 4.Br Br Br a Reaction 63 An alkene Br* ‘er A vicinal dihaloatkane a a ; 2,3 equivalents Roa of NaNH in cl NH (0 i 3. Mildacid ion 73 51,0; / NaOH n alkyne Amalkyme “Reaction 7.7 An aldehyde Multistep Synthesis Multistep Svat 1 convert acetylene a bromoethane into L-butene All ofthe carbon stoms ofthe BS) Problem 23 Show bow fom the given ating materials. Show all intermediate molecules synthesized slong ihe way ee eae Acetylene Bromoethane 1-Butene NaNH, He Pd/CaCOs ee catalyst) nests, recognize that a carbon-carbon bond must be formed between both (wires n starting srecognize Wat roduct, ‘The best way to accomplish this to deprotonate sesttene 12 cee spate daction with bromoethane. Reduction with hydrogen and the hesis of 1-but sodiui completes t ne carbon stoms ofthe target molecule must be ablem 7.32 Show how to convert ethylene into I-butene. lof the fom tyne. Show aie neces sytesed akong 2 Ethylene He Her Pd/CaCO (Lindlar eatalyst) “Se a be wm / “Nal NaNH, Acetylene The last three steps a extension of the previous synthesis (Problem 7.3 c ne then hydi n of acetyl jon with bromoet! tylene ation followed by reaction with NaNH; lkyne, using 3 equivalents of NaNH; followed by reprotonation in is generated by reaction of ethylene with HBr. Problem 7.33 Show how to convert 3-hexyne into propanal. All ofthe carbon atoms of the tar get molecule must be

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