ProblemSet2Answers

CHEM30203.0F14
Proposestructuresforeachofthefollowing 1.
(a) C
4
H
8
O
4
O
H
H
H
3.9 ppm
4.05 ppm
6.4 ppm
3.7 ppm
1.15 ppm
weak
coupling
large J
less
large J
intruth,therewasnoneedtoconsiderthesplittingpatternat all,usingthefollowinglogic:
(1) theformulacallsfor1e.u.
(2) theNMRclearlyshowsaCH
2
CH
3
pattern(quartet+triplet at2:3ratio),andtheCH
2
signalisshiftedto34
regionbyO(nootherpossibility,asC=Owouldnotbepowerfulenough),hencethereisaOCH
2
CH
3
fragment
(3) therest,C
2
H
3
,canonlybeavinylgroup(CH=CH
2
)
thesplittingpatterninexactlyasseenearlierwithstyrene,thoughthechemicalshiftsaredifferenthere(owing
toverydifferent and situations)
(b) C
7
H
7
NO
2.2
0.9
5.0
1.8
8.0
2.2
1.8
8.0
5.0
0.9
J valuesinthearomaticregion:
This oneisabittricky andtherearetwoacceptableanswers.
(1) The formulashows5e.u.
(2)
13
Cand
1
HNMRspectrashow oneCH
3
andoneC=O(1e.u.).
(3) The rest,C
5
H
4
N(4e.u.),showing5aromatic
13
Csignals(4withH)and4downfieldshiftedaromatic
1
H
signals,isconsistentwithanumberofstructures,buttheobviousoneisasinglysubstitutedpyridine.
(4) It ispossiblefortheretobeanaldehyde group(CHOfragment),butthiswouldbedisconnectedfromthe
CH
3
groupandwouldleaveC
4
H
3
Ntoaccountfor4e.u.andtwositesofsubstitution(forCHOandCH
3
)
thisisnotreallypossible,soanacetylgroup(COCH
3
)seemslikelyandwouldfitwithasinglysubstituted
pyridine.
(5) In pyridines,theHCCHfragmentsnexttoNshowweakerthanusualcoupling(seeTableattheendofthe
CourseKit),andweakercoupling (here,5.0Hz)is indeedevident inthecloseup.
(6) Thesplittingtreesofquestion2applyhereaswellandqualitativelyfit.Thereisadditionalfinesplittingin
thisexample(even
5
J coupling).
(7) 4Acetylpyridinehastoomuchsymmetrytofitthespectra.Both 2 and3acetylpyridineareacceptable
answers.3Acetylpyridine isthebestanswer,asitaccountsforthechemicalshiftsandcoupling constants
best(seediagramsbelow).
(contd)
Inexaminingthesplittingshere,itisusefultotemporarilysetasidetheverysmall(
4
J and
5
J)couplingsandconsider
onlythelarger3bondcouplingstodecideonconnectivity;hencethepatternsare (lefttoright)asinglet,narrow
doublet,widerdoubletanddoubletofdoublets,andthisisconsistentwith3acetylpyridine(andnot2
acetylpyridine).
N
CH
3
O
H
H H
H
2.67 ppm
9.18 ppm
8.8 ppm
7.42 ppm
8.12 ppm
N
CH
3
O
H
H H
H
2.2 Hz
8.0 Hz
5.0 Hz
0.9 Hz
1.8 Hz
Athighresolution,rigidsystems(aromatics,conjugatedalkenes,etc.)canshow
4
J couplingsas
veryfinesplittings.Fornicotinicacid(atright),drawcompletesplittingtreesforeacharomatic
1
HNMRsignal,usingtheindicatedcouplingconstantsandinorderofdecreasingchemicalshift,
toshowhowthesignalsareexpectedtolookonanactualhighresolutionspectrum.Itsusually
easiesttostartwiththelargercouplingswhendrawingasplittingtree,butdecidefirstonthe
chemicalshiftorder.
2.
N
COOH
2
4
5
6
3
J
4,5
=8Hz
3
J
5,6
=4Hz
3
J
4,6
=1Hz
3
J
2,4
=2Hz
3
J
2,6
=0Hz
Thechemicalshiftorderisthesameasin3acetylpyridine(seeproblem1b).
H
2
H
6
H
4
H
5
1
2 4 8 8
4
2
1
N O
H
3
C
H
3
C Ph
R H
RCHO
NH OH H
3
C
H
3
C Ph
N O
H
3
C
H
3
C Ph
R H
+
Whenaldehydes aretreatedwithLephedrine,twodiastereomeric oxazolidines result.Theseareanaloguesofacetals.InthecasewhenR
=CH
3
,thechemicalshiftofthealdehydic hydrogenisat5.5ppm forthemajorproductand6.2ppm fortheminorone.Whichisomeris
themajorproduct?Youwillneedareasonableconformationalpictureforthisquestion.
3.
N O
H
3
C
H
3
C Ph
R H
deshielding
O
N
H
H
R
CH
3
CH
3
Indrawingtheringsubstituents,onerealizesthatthe
methylgroupnexttothePhgroupforcesthePhgroupto
facetheringedgeon.BecausethePhisedgeon,itis
expectedtodeshield theHwhenitisonthesamefaceof
theoxazolidine ring. The minorisomergivingthedownfield
signal(6.2ppm)hastheCH
3
(R)grouptrans toPhwhilethe
majorisomergivingtheunshifted signal(5.5ppm)hasthe
CH
3
groupcis toPh.
4.
OH
Cl
Cl H
H
H
A
C
B
Cl
Cl
Cl
H H
H
A
B
C
Here,thefinesplittingseenin
signalsBandCmustbefrom4
bondcoupling,absentwithA.
Asinthecaseatleft,thefine
splittingseeninsignalsAand
Cmustbefrom4bond
coupling,absentwithB.
AllHheresufferadeshielding effectfromone
ortho andonemeta Cl.BothH
B
andH
C
alsosufferthe
shielding effectfromOH(H
A
doesnot),butH
B
also
suffersthestrongest deshielding fromO.
SignalAleansstronglytowardsignalC,moresothan
signalB,eveniffurtherawaythansignalB,andthisis
becauseofitsstrongerJ value.
AllHheresufferacombinationofdeshielding effects
fromCl neighbours,againstweaker effects.The
orderingofchemicalshiftsresultsprimarilyfrom
2 ortho +1meta effects(H
A
)
> 1ortho +2meta effects(H
B
)
> 1ortho +1meta +1para effects(H
C
)
SignalBleansalittlemoreherethanatleftbecauseitis
closertosignalC,andsignalAispracticallynonleaning
becauseitisfurtherawaythanisthecaseatleft.
7
CHCl
3
7
CHCl
3
B C A
Thediagrams atrightare closeups ofthearomatic
1
HNMRregions of2,5dichlorophenoland 1,2,4trichlorobenzeneat 300MHz.Thetwo
compoundsdifferonlyinonesubstituent.Determinewhichspectrumbelongstowhichcompound,assign thesignals, draw splittingtrees
andaccountfortheleaning.
Thedifferencebetweenthetwocompounds(strongdonating OHasopposedtotheweakerdonating Cl)is
expectedtoshowupinupfieldshiftedsignalsinthe2,5dichlorophenolcase,andthisisthebasisofassigningthe
spectra.
A B C
TheleaningoftheCsignalsissomewhatlessclear,butthegreaterproximityofstronglycoupledsignalBatright
isconsistentwithstrongerleaningofsignalCatright.
5. Thediagramatrightisacloseupofthealkene regionoftrans1phenyl1propeneat
300MHz.
(a) Assignthesignalstoeachalkene H.
(b) Accountforthealkene chemicalshifts.
(c) Drawasplittingtreeforthissystem.
(d) Estimatethe3couplingconstants(usearuler).
H
CH
3
H
7 6
H
CH
3
H
A
B
H
A
H
B
(a)seediagram
(b)H
B
isnotmuchaffectedbytheCH
3
effectnorbyanyPh effect,butis
downfieldshiftedbythePhring
currenteffect(magneticanisotropy).
H
A
islessaffectedbytheringcurrent
andmoreaffectedbytheCH
3
and
Ph effects.Withrespecttothe
latter,Phcanbeeitherdonating
(shielding)orwithdrawing
(deshielding),withnoclear
preference,sincethesecondary
(d)At300MHz,1ppm =300Hz.Dependingonyourprinter,thewidthof1ppmonthechemicalshiftsscalewill
vary.Onmyprinter,this is10cm(100mm),sothatwehave3Hz/mm.Wewouldthereforechoosesomeofthe
peakpairssuggestedbythesplittingtreetoestimatewitharulerthat
4
J
AMe
is2Hz,
3
J
BMe
is6.5Hz,and
3
J
AB
is16.5
Hz.
anionorcationresultingisnotthebestnortheworstpossibilityineithercase.
As aresult,wewouldnotpredictmuchofaneffect.Inanycase,thestrongercouplingoftherighthandsignal
makestheassignmentclearandwouldrevealthatthemagneticand effectsarestrongerthanany effect.
(c)Seediagram.WehaveaABsystem,eachbranchsplitintoquartets.
6. Thediagramatrightisacloseupofthealkene regionoftrans3hepteneat300
MHz.Accountfortheappearanceofthissignalandattempttodrawasplittingtree
forthissystem.
H
B
H
A
CH
3
CH
3
H
A
H
B
TheassignmentofthedownfieldsignaltoH
A
isuncertain,butisbased
onthegeneraltrendofhighersubstitutioninalkanes leadingtomore
downfieldpositions.
Inanycase,wearedealingherewithanABsystem,eachbranchof
whichissplitintoa1:2:1triplet,owingtocouplingtotheneighbouring
CH
2
grouping,withasimilarcouplingconstantoneachside.
Notetheverystrongleaningduetotheverysmalldifferencein
chemicalshiftsandastrongJ
AB
.