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SolutionstoProblemsAldehydesandKetones
BuildingBridgestoKnowledge
PhotooftheHuanpuRiverCruiseBoat’sgangplankinShanghai,China1. SuggestIUPACnamesforthefollowingmolecules.
(a)
6-phenyl-3-hexanone
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(b)
7-phenyl-4-oxohexanal (c)
5,7-diphenylheptanal2. Suggestamechanismforthefollowingconversion.
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(1)
(2)
(3)
(4)
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(5)
3. Suggesttheproductexpectedfromthereactionofbenzaldehydewitheachofthe
following.
(a)
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(b) dilutesodiumhydroxide
Noreaction
(c) concentratedsodiumhydroxide
(d) propanalanddilutehydroxide
(e) butanalanddilutesodiumhydroxide
(f)
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4. Suggestasynthesisforthefollowingmoleculefromtheindicatedstarting
materialandanynecessaryorganicandinorganicmaterials.
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5. Writeamechanismforyoursynthesisoftheesterinproblem4.(1)
(2)
6. Using1-propanolastheonlysourceoforganiccompoundsandanyother
necessaryinorganicreagents,suggestsynthesesforthefollowing.
(a)
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9
(b)
7. Suggestasynthesisforthefollowingmoleculefromtheindicatedorganic
compoundandanyotheravailableinorganicmaterials.
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8. Suggestasynthesisforthefollowingfromtheindicatedstartingmaterialand
anynecessaryinorganicandorganiccompounds.
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9. CompoundIexhibitsthefollowingprotonmagneticresonancespectrum.10.
1HNMRofcompoundI
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AconstitutionalisomerofcompoundI,compoundII,exhibitsthe followingprotonmagneticspectrum.
1HNMRofcompoundII WhencompoundIwastreatedwithlithiumaluminumhydride followedbyhydrolysis,thenaqueousacidatabout200oC, compoundIII,C10H12wasproduced.CompoundIIIhastwo isomers.
FollowingistheprotonmagneticresonancespectrumofcompoundIII,C10H12
1HNMRofcompoundIIIWhencompoundIIwastreatedwithlithiumaluminumhydridefollowedbyhydrolysis,thenaqueousacidatabout200oC,compoundIV,C10H12wasproduced.FollowingistheprotonmagneticresonancespectrumofcompoundIV,C10H12.
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CompoundIVhasoneisomer.CompoundsIIIandIVarealsoconstitutionalisomers.ThestructureofcompoundIis
ThestructureofcompoundIIis
CompoundIIImayhaveacisconfigurationoratransconfiguration.Thesestructuresare
CompoundIVdoesnothaveanonsuperposable/nonsuperimposablemirrorimage.
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1HNMRofcompoundIV 10. Acertainbiologicallyactiveterpene,C10H16Ofollowstheisoprenerulewillform
anoxime,asemicarbozide,anda2,4-dintrophenylhyradazide.Uponozonolysis,theterpenesproducesthefollowingcompounds
Suggestastructureconsistentwiththeexperimentaldataandtheisoprene rule.
11. Aterpenethatfollowstheisopreneruledecolorizesadilutesolutionof
potassiumpermanganate,and,upon,treatmentwithhotconcentratedpotassiumpermanganateinsulfuricacid,producesthefollowingtwoorganicacidsacids:
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Suggestastructurefortheterpenethatisconsistentwiththe experimentalevidence.
12. Suggestasynthesisforthefollowingconversionusingappropriateinorganic
reagents.
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13. Suggestaseriesofelementarystepsthatwouldrationalizethefollowing
observations.
(a)
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(b)
(1)
(2)
(3)
14. Predicttheproductorproductsexpectedinthefollowingsequenceofreactions.
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15. CompoundIistreatedwiththereagentsoftheClemmensenreductionto
producecompoundII.TreatingcompoundIIwiththereagentsforhydroboration-oxidationproducescompoundIII.CompoundIIIupontreatmentwithpyridiniumchlorochromateproducescompoundIV.
CompoundI ClemmensenReduction:
compoundII
Hydroboration-Oxidation:
compoundIII
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OxidationwithPyridiniumChlorchromate
compoundIV16.Considerthefollowingsynthesispathway:
C9H16O4 + LiAlH4H2O
C9H18O3
C9H18O3H3O
+C6H12O2
C6H10O2C6H12O2 + PDC
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17.Treatingcompound17A,C6H12O,withiodineinsodiumhydroxide,resultsintheformationayellowprecipitateandcompound17B,C5H9O2Na.Acidificationofcompound17BformedC5H10O2,compound17C.Treatingcompound17CwithLiAlH4followedbyhydrolysisproducescompound17D.Theinfraredspectrumofcompound17Dexhibitedaprominentstretchingtransmittancesignalat3333cm-1.Followingaretheprotonmagneticresonancespectrumandcarbon-13magneticresonancespectrumofcompound17D.1HNMRCompound17D
13CNMRCompound17D
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Sulfuricacidconvertedcompound17Dtocompound17E.Ozonolysisofcompound17Egavecompound17Fand17G.Prominentmassspectrumpeaksforcompound17Foccuratm/e29and43.Prominentmassspectrumpeaksforcompound17Goccuratm/e43and58.Usethesedatatodeterminethestructuresofcompounds17A,17B,17C,17D,17E,17F,and17G.Pleasesupportyouranswerswithchemicalequationsandanygivenspectradata.Provideadetailedmechanismfortheconversionof17Dto17Ewithsulfuricacid.
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Mechanismof17Dto17E: (1)
17D (2)
(3)
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(4)
17E