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Chemistry233Chapter9ProblemSet

Nomenclature1) ProvidetheIUPACnameforeachofthealkynecontainingcompoundsbelow.

2) ProvidetheIUPACnameforeachoftheenynecompoundsbelow.

3) Providethecommonnameforeachcompoundbelow.

Cl

Br

Ie z

s 6 Sg y z 8chloro 5,6 diethyl Inonyne

ornon tyne

9 76 s 48 32 G tert butyl 2methyl 3nonyneor

non 3 yne

6 y7 s z l

s z 3,7 dimethyl lis octadiyneorOcta1,5digne

37 y a 1 9 methyl 8decen 1,4 digne9 s

to 8 6 or

9methyldec8 en 1,4 diyne

z 4 8p g 8,8dimethyl 1,3nonadien G yne

s s 6 or8,8dimethylnona1,3DienGgree

Zs t g

gS isopropyl 2nomen 7 yne

or

S isopropylnon Z en 7 yne

gethylbutyl Ofcom Propyl

cyclobutylmethylisopropyl propylacetylene acetylenebutylisopropylacetylene bromoethylacetyleneH CEC Hacetylene

Answer Key

Chem.233–Chapter9ProblemSet

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StructureandPropertiesofAlkynes4) Foreachindicatedcarbonatomdetermineitshybridization.

5) Thesmallestcycloalkynethathasbeenisolatedandstorediscyclooctyne.Explainwhyalkynesdonotexistinsmallerrings.

6) ConsiderphomallenicacidC(shownbelow),aninhibitorofbacterialfattyacidsynthesis.

7) Thinkingbacktoourdiscussionofacid/basechemistryinChapter2,explainwhysodiumamide

(NaNH2)isastrongenoughbasetodeprotonateaterminalalkyne.

8) Drawtheproductsfromtheacidbasereactionshownbelow.Labelthenucleophilicsiteintheproduct.Showcurvedarrowstodemonstratetheflowofelectrons.

9) Showhowthenucleophilegeneratedabovewouldreactwithiodoethane.

H

+ Li

C

HO

O

a. Circlethemostacidicposition.b. WhatistheshortestC-Csinglebond?c. Howmanysphybridizedatomsarepresentinthe

molecule?d. Forthebondsindicatedwitharrows,determine

theorbitalsthatmakeupthebond.

Spa SpSP SP SP Sp

Alkyne C'sare sphybridized Constraining a alkyne in a ring results inand want a 1800bondangle substantialdeviationfrom the 1800bondask

soo Ringswith 8ormoreCatomsarelargeenough to containtheR I R alkynewithout seriousanglestrain

CspCspshortest c cf CspGp2

sp sp spspsp 5

Gp3Gp2

yes you should still knowthisR Ij Hft NFL R I 0 t NB

acid conjugateacidHere the acid is a strongeracid than the conjugateacid so the rim lies tothe right sideopposite thestrongeracidwe learned the exception that alkyne C H is more acidic than amine N H

nto M t t Lito

N

Nucleophiliccarbon

METTE my I 0

Chem.233–Chapter9ProblemSet

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ReactionsandMechanisms10) Predicttheproduct(s)foreachhalogenadditionbelow.

11) Predicttheproductsforeachhalogenationreactionshownbelow.

HBr(xs)

HCl(2 equiv)

HCl(1 equiv)

PhHBr(xs)

HBr(xs)

Ph

HBr(1 equiv)

Br2(2 equiv)

Cl2(1 equiv)

PhBr2

(1 equiv)

Cl2(2 equiv)

BjBrT

a

th

f BrMph t mph

Br Br

Bi t the

ph tPh

Bj Brf BrCl

THdiBr

PhBr

thcaCI

Chem.233–Chapter9ProblemSet

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12) Drawtheelectronpushingmechanismforthereactionshownbelow.

13) Drawtheelectronpushingmechanismforthereactionshownbelow.

14) Drawtheelectronpushingmechanismfortheacidcatalyzedtautomerizationof(Z)-2-penten-2-ol.

PhHBr

(2 equiv) Ph

Br Br

Ph PhBr2

(1 equiv)

Br

Br

OH H+, H2O O

HBR provides a sourceofBroHBr T Ht t Br

HPh H Ph t BBP

HBurPh BF Ph

db

ph phyjbrg.io Phx

OH H

newor IOH

µ t 11300net

Chem.233–Chapter9ProblemSet

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15) Drawthealdehyde/ketoneformforthefollowingenoltautomers

16) Predicttheproductsfortheacidandmercury(II)catalyzedhydrationreactionsshownbelow.

17) Drawtheelectronpushingmechanismfortheacidcatalyzedhydrationreactionbelow.

OH

OH

Ph

OH

OH

H

HgSO4H2SO4

H2O

H2SO4

H2O

Ph

H2SO4

H2O

HgSO4H2SO4

H2O

HgSO4H2SO4

H2O

Ph PhH2SO4

H2O PhPh

O

Although Hg2+ isn’t necessary, it can be used to catalyze the hydration of internal alkynes.

at

X to

O

n

pn n t pn rfE't

O

dy t It

Hm iii into

LHtoPhy µ Phy HHT 2 HTO Ph H 00 Ph

Chem.233–Chapter9ProblemSet

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18) Predicttheproductsforthehydroboration-oxidationreactionsshownbelow.

19) Determinethenecessaryreagentstocarryouteachoftheinterconversionsshownbelow.

Ph

1. BH3•THF

2. NaOH, H2O2

1. BH3•THF

2. NaOH, H2O2

1. BH3•THF

2. NaOH, H2O2

1. BH3•THF

2. NaOH, H2O2

1. BH3•THF

2. NaOH, H2O2

O

O

Br Br

Cl

Cl

it s

own

ph n t phO

H

O

dy t It

Hg504I 04Heo

1BitsTHF2 NaOH1h02

HBR Xs

It 2equiv

U21equiv

Chem.233–Chapter9ProblemSet

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20) Predicttheproductsforthealkynereductionreactionsshownbelow.

21) Predicttheproductforeachalkylationreactionbelow.

Ph

H2

Pd/C

H2

Lindlar Cat.

Na

NH3(l)

H2

Lindlar Cat.

H2

Lindlar Cat.

Na

NH3(l)

1. NaNH2

2. CH3Br

1. NaNH2

2. I

H H

1. NaNH22. CH3CH2Br

3. NaNH24. PhCH2Br

1. BuLi

2. CH3Br

in

IL

rn

Ph

EfIn

Ctb

Ctb

norPh

Chem.233–Chapter9ProblemSet

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Synthesis22) Providethemissingreagentsinthesyntheticsequenceshownbelow.

23) Provideareasonablesynthesisforeachofthefollowingcompoundsusingtheprovidedstartingmaterial.

Br

O

H

O O+ en

?H H

H?H H

O

?H H

Ph

O

?H H

Cl Cl

Cl Cl

?H3C H

BrHO

NaNitsch

1k1 Nank Pdk

HC H2 Br If

Nank LindlerHgS0yHzSO4140

BBTHF MCPBA2NaOHHz0z

okaytoswitchorderis1 Nank 1 NaN1k IL2 CBI 2 I y Lindler

Cle Brokaytoo1 NaNK 1 Blb THE2 c 2 NaOH Hoz

1 Nantz Hg50y125042 PhakI 1h0Kayto swapsteps

1 Nantz 1 NANK Ck2 CBI 2 I Xs

4,491 litho Fifa 758 SakhodhempTd

Soeitherreduction isfine