ExamName___________________________________

MULTIPLECHOICE.Choosetheonealternativethatbestcompletesthestatementoranswersthequestion.
1) Thechemicalshiftsforprotonstoacarbonylgroup:
A) aresimilarforallacidderivatives.
B) fallbetween1.3and1.8(ppm).
C) arefarthestdownfieldforcarboxylicacids.
D) arefartherdownfieldthanthose toanitrile.
E) fallbetween3.1and4.2(ppm).
1)
2) Startingwithanacidchlorideandanyotherchemicalreagentyouvelearnedinorganicchemistry,
whichofthefollowingfunctionalgroupscanbesynthesizedinthreestepsorless?
A) aldehyde B) tertiaryalcohol
C) amine D) ester
E) primaryalcohol F) onlyAandC
G) onlyC,DandE H) alloftheabove(A- E)
2)
3) Acidscanbereducedtoaldehydesby:
A) conversiontotheesterfollowedbytreatmentwithLiAlH
4.
B) conversiontotheacidchloridefollowedbytreatmentwith
LiAlH[OC(CH
3
)
3
]
3.
C) treatmentwithLiAlH
4.
D) conversiontotheanhydridefollowedbytreatmentwithMgandH
3
O
+.
E) conversiontotheamidefollowedbytreatmentwithNaBH
4.
3)
4) Whilethecarbonylstretchingfrequencyforsimplealdehydes,ketones,andcarboxylicacidsis
about1710cm
-1
,thecarbonylstretchingfrequencyforamidesisabout?
A) 1735cm
-1
B) 1660cm
-1
C) 1800cm
-1
D) 1700cm
-1
E) 2200cm
-1
4)
5) Acidscanbeconvertedtoprimaryaminesby:
A) conversiontothenitrilefollowedbytreatmentwithLiAlH
4.
B) conversiontothediazoniumsaltfollowedbytreatmentwithNaBH
4.
C) conversiontotheprimaryamidefollowedbytreatmentwithLiAlH
4.
D) bothAandB.
E) bothAandC.
5)
6) Whichofthefollowingisthemostreactivecarboxylicacidderivative?
A) nitrile
B) acidchloride
C) anhydride
D) amide
E) ester
6)
7) Acorrectorderofreactivityofacidderivativestowardsnucleophilicattackis:
A) anhydrides>acids>acidchlorides.
B) esters>acidanhydrides>amides.
C) carboxylates>esters>amides.
D) anhydrides>amides>carboxylates.
E) anhydrides>amides>esters.
7)
1
8) Anitrilecanbemadebydehydratinganamide.However,forthisreactiontooccur,theamide
mustbe:
A) N-methylated.
B) tertiary.
C) secondary.
D) primary.
E) partofalactam.
8)
9) ThemostcharacteristicIRstretchofbutanenitrileoccursatapproximatelywhatwavenumber?
A) 3100cm
-1
B) 1750cm
-1
C) 2200cm
-1
D) 3500cm
-1
E) 2600cm
-1
9)
10) Typically,amideswillhydrolyzeunder__________conditionsthanesters.
A) moresaline
B) stronger
C) moredilute
D) lessvigorous
E) milder
10)
SHORTANSWER.Writethewordorphrasethatbestcompleteseachstatementoranswersthequestion.
11) Whatarethemajororganicproductswhen1equivalentofaceticformicanhydridereacts
with1equivalentofmethanol?
11)
12) Providethemajororganicproductinthereactionshownbelow. 12)
13) Providethemajororganicproductinthereactionshownbelow. 13)
14) Arrangethefollowingcompoundsinorderofincreasingboilingpoint:aceticacid,
propanenitrile,butane,andacetamide.
14)
15) ProvidetheIUPACnameofthefollowingcompound. 15)
2
16) Providethestructureofo-bromobenzoylchloride. 16)
17) Providethestructureofcyclohexylformate. 17)
18) Providethemajororganicproductofthefollowingreaction. 18)
19) Predicttheproductthatresultsfrom2-methylamino-1-ethanolbeingtreatedwith
phosgene.
19)
20) Whatcompoundresultswhenethylbenzoateisstirredinmethanolcontainingatraceof
HClandbywhatnameisthisprocessknown?
20)
21) Providethemajororganicproductinthereactionshownbelow. 21)
22) Providethenameofthecompoundshownbelow. 22)
23) Namethecompoundwhichresultswhenpropylbenzoateisheatedinalargeexcessof
ethanolinthepresenceofcatalyticacid.
23)
24) Providethemajororganicproductofthefollowingreaction. 24)
3
25) Providethemajororganicproductinthereactionshownbelow. 25)
26) Providethemajororganicproductofthefollowingreaction. 26)
27) Providethestructureof(R)-4-ethoxypentanenitrile. 27)
28) Usingthetwokeyresonancestructuresforanester,showhowresonancestabilizationis
lostwhenanesterisattackedbyanucleophile.
28)
29) Providethenameofthecompoundshownbelow. 29)
30) Drawtheproductresultingfromthefollowingreaction.Indicateanyrelevant
stereochemistry.
30)
31) Whataretheproductsfromthereactionofexcessmethylmagnesiumbromidewithethyl
acetatefollowedbyH
3
O
+
?
31)
32) Providethemajororganicproductofthefollowingreaction. 32)
4
33) Whatreagentsareusedtodehydrateamidestonitriles? 33)
34) Distamycinandderivativeshaveexhibitedantiviral,antibiotic,andantitumoractivityby
bindingtotheminorgrooveofDNA(J.Med.Chem.2004,2133).Placealinethrougheach
bondofdistamycinthatwouldbecleavedbyacidhydrolysis.
34)
35) Providethemajororganicproductinthereactionshownbelow. 35)
36) ProvidetheIUPACnameofthefollowingcompound. 36)
37) Providethestructureoftrifluoroaceticanhydride. 37)
38) Providethestructureof-butyrolactam. 38)
39) Arrangethefollowingthreeamidesinorderofincreasingboilingpoint:propanamide,
N-methylacetamide,andN,N-dimethylformamide.
39)
40) Providethemajororganicproductinthereactionofcyclopentanecarbonylchloridewith
sodiumformate.
40)
ESSAY.Writeyouranswerinthespaceprovidedoronaseparatesheetofpaper.
41) ProvidetheproperIUPACnameforthecompoundbelow.
42) Proposeasynthesisofmethylthioacetatefromonecarboncompoundsandanyothernecessaryinorganic
reagents.
43) Providethestructureof2-bromo-2-methylbutanoylchloride.
5
44) Providethemajororganicproductinthereactionof3-methylpentanoicacidwithCH
2
N
2
.
45) CarbonatedbeveragestypicallyhavepHsbelow7.0.WhatacidispresentwhichlowersthepH?Showthe
reactionbywhichitisformed.
46) ProvidethestructureofN,N-diethylbutanamide.
47) Usingresonancestructuresandpicturesoforbitals,explainwhyresonancestabilizationofthioestersisless
thanthatofesters.
48) Namethecompoundwhichresultswhen-valerolactoneisheatedinalargeexcessofmethanolinthe
presenceofcatalyticacid.
49) Ethyleneglycolwillreactwithphosgenetoproducewhatorganiccompound?
50) Whatcompoundresultswhenbenzoicacidreactswithmethylamine,andwhatcompoundultimatelyresults
whentheinitiallyformedcompoundisheatedat140C?
6
AnswerKey
Testname:12BACIDDERIVATIVES
1) A
2) H
3) B
4) B
5) E
6) B
7) D
8) D
9) C
10) B
11) aceticacidandmethylformate
12)
13)
14) butane<propanenitrile<aceticacid<acetamide
15) N,N-diethylformamide
16)
17)
18)
7
AnswerKey
Testname:12BACIDDERIVATIVES
19)
20) methylbenzoate;transesterification
21)
22) ethylhexanoate
23) ethylbenzoate
24)
25)
26)
27)
28)
29) N,N-dipropylbutanamide
30)
31) t-butanolandethanol
8
AnswerKey
Testname:12BACIDDERIVATIVES
32)
33) P
2
O
5
orPOCl
3
34)
35) HOCH
2
CH
2
CH
2
CO
2
-
Na
+
36) ethylhexanoate
37) (CF
3
CO)
2
O
38)
39) N,N-dimethylformamide<N-methylacetamide< propanamide
40) C
5
H
9
CO
2
CHO
41) 3,3-dimethylcyclobutanecarbonitrile
42) BeginningwithCO
2
,
1.CH
3
MgBr
2.H
3
O
+
3.CH
3
SH,H
+
catalyst,
43) CH
3
CH
2
CBr(CH
3
)COCl
44) CH
3
CH
2
CH(CH
3
)CH
2
CO
2
CH
3
45) carbonicacid,CO
2
+H
2
OH
2
CO
3
46) CH
3
CH
2
CH
2
CON(CH
2
CH
3
)
2
47) SeeFigure21-12onp.989.
Theoverlapbetweenthe2porbitalofcarbonandthe3porbitalofsulfarisweakandrelativelyinefficient.
48) methyl5-hydroxypentanoate
49)
50) PhCO
2
-
CH
3
NH
3
+
;PhCONHCH
3
9