NMR=NuclearMagneticResonance

PhysicalPrinciples:
Some(butnotall)nuclei,suchas1H,13C,19F,31Phavenuclearspin.
Aspinningchargecreatesamagneticmoment,sothesenucleicanbethoughtof
astinymagnets.
Ifweplacethesenucleiinamagneticfield,theycanlineupwithoragainstthe
fieldbyspinningclockwiseorcounterclockwise.
N

N
N

spinstate,
favorable,
lowerenergy

Aspinningnucleuswithit'smagneticfield
alignedwiththemagneticfieldofamagnet

S
N

spinstate,
unfavorable,
higherenergy

Aspinningnucleuswithit'smagneticfield
alignedagainstthemagneticfieldofamagnet

Alignmentwiththemagneticfield(called)islowerenergythanagainstthe
magneticfield(called).Howmuchloweritisdependsonthestrengthofthe
magneticfield
Notethatfornucleithatdonthavespin,suchas 12C,thereisnodifferencein
energybetweenalignmentsinamagneticfieldsincetheyarenotmagnets.As
such,wecantdoNMRspectroscopyon12C.

NMR:BasicExperimentalPrinciples
Imagineplacingamolecule,forexample,CH 4,inamagneticfield.
Wecanprobetheenergydifferenceoftheandstateoftheprotonsby
irradiatingthemwithEMradiationofjusttherightenergy.
Inamagnetof7.05Tesla,ittakesEMradiationofabout300MHz(radiowaves).
So,ifwebombardthemoleculewith300MHzradiowaves,theprotonswillabsorb
thatenergyandwecanmeasurethatabsorbance.
Inamagnetof11.75Tesla,ittakesEMradiationofabout500MHz(stronger
magnetmeansgreaterenergydifferencebetweentheandstateoftheprotons)
at no magnetic field,
there is no difference beteen
- and - states.

proton spin state

(higher energy)

Graphicalrelationshipbetween
magneticfield(B o) andfrequency(

E = h x 300 MHz

E = h x 500 MHz

for1 HNMRabsorptions

proton spin state

(lower energy)
0T

7.05 T

11.75 T

Bo

Buttheresaproblem.Iftworesearcherswanttocomparetheirdatausingmagnets
ofdifferentstrengths,theyhavetoadjustforthatdifference.Thatsapain,so,data
isinsteadreportedusingthechemicalshiftscaleasdescribedonthenextslide.

TheChemicalShift(AlsoCalled)Scale
Hereshowitworks.Wedecideonasamplewellusetostandardizeour
instruments.WetakeanNMRofthatstandardandmeasureitsabsorbance
frequency.Wethenmeasurethefrequencyofoursampleandsubtractits
frequencyfromthatofthestandard.Wethenthendividebythefrequencyofthe
standard.Thisgivesanumbercalledthechemicalshift,alsocalled,whichdoes
notdependonthemagneticfieldstrength.Whynot?Letslookattwoexamples.
Imaginethatwehaveamagnetwhereourstandardabsorbsat300,000,000Hz(300
megahertz),andoursampleabsorbsat300,000,300Hz.Thedifferenceis300Hz,
sowetake300/300,000,000=1/1,000,000andcallthat1partpermillion(or1
PPM).Nowletsexaminethesamesampleinastrongermagneticfieldwherethe
referencecomesat500,000,000Hz,or500megahertz.Thefrequencyofour
samplewillincreaseproportionally,andwillcomeat500,000,500Hz.The
differenceisnow500Hz,butwedivideby500,000,000(500/500,000,000=
1/1,000,000,=1PPM).
Itsbrilliant.
Ofcourse,wedontdoanyofthis,itsalldoneautomaticallybytheNMR
machine.
Evenmorebrilliant.

TheChemicalShiftofDifferentProtons
NMRwouldnotbeveryvaluableifallprotonsabsorbedatthesamefrequency.
Youdseeasignalthatindicatesthepresenceofhydrogensinyoursample,butany
foolknowsthereshydrogeninorganicmolecules.Whatmakesitusefulisthat
differentprotonsusuallyappearatdifferentchemicalshifts(.So,wecan
distinguishonekindofprotonfromanother.Whydodifferentprotonsappearat
different?Thereareseveralreasons,oneofwhichisshielding.Theelectronsin
abondshieldthenucleifromthemagneticfield.So,ifthereismoreelectron
densityaroundaproton,itseesaslightlylowermagneticfield,lesselectrondensity
meansitseesahighermagneticfield:
Z
C

This represents the electron density of a C-H bond. How much electron
density is on the proton depends on what else is attached to the carbon. If Z
is an elelctronegative atom, the carbon becomes electron deficient and pulls
some of the electron density away from the H. if Z is an electron donating
group, more electron density ends up on the H.

Howdotheelectronsshieldthemagneticfield?Bymoving.Amovingcharge
createsamagneticfield,andthefieldcreatedbythemovingelectronsopposesthe
magneticfieldofourNMRmachine.Itsnotahugeeffect,butitsenoughto
enableustodistinguishbetweendifferentprotonsinoursample.

TheHardPartInterpretingSpectra
LearninghowanNMRmachineworksisstraightforward.Whatisless
straightforwardislearninghowtousethedatawegetfromanNMRmachine(the
spectrumofethylacetateisshownbelow).ThatsbecauseeachNMRspectrumisa
puzzle,andtheresnosinglefactthatyousimplyhavetomemorizetosolvethese
spectra.Youhavetoconsiderlotsofpiecesofdataandcomeupwithastructure
thatfitsallthedata.WhatkindsofdatadowegetfromNMRspectra?For 1H
NMR,therearethreekindseachofwhichwewillconsidereachoftheseseparately:
1) Chemicalshiftdatatellsuswhatkindsofprotonswehave.
2) Integralstellsustheratioofeachkindofprotoninoursample.
3) 1H1Hcouplingtellsusaboutprotonsthatarenearotherprotons.

ChemicalShiftData
Aspreviouslymentioned,differentkindsofprotonstypicallycomeatdifferent
chemicalshifts.Shownbelowisachartofwheresomecommonkindsofprotons
appearinthescale.Notethatmostprotonsappearbetween0and10ppm.The
reference,tetramethylsilane(TMS)appearsat0ppm,andaldehydesappearnear10
ppm.Thereisapageinyourlabhandoutwithmoreprecisevaluesforthischart.
Notethatthesearetypicalvaluesandthattherearelotsofexceptions!
R
R

NH

OH
R

Ph
OH
R

O
H

10

Downfield region
of the spectrum

R
7

(R)
HO CH3

R
OCH3

H
5
ppm

H
TMS = Me

Ph CH3
NR2 O

Cl

CH3

CH3

Me
Si Me
Me

R
CH3

CH3
TMS

Upfield region
of the spectrum

Integrals
Integralstellustheratioofeachkindofproton.Theyarelines,theheightsofwhich
areproportionaltotheintensityofthesignal.Considerethylacetate.Thereare
threekindsofprotonsinthismolecule,theCH 3nexttothecarbonyl,theCH2nextto
theOandtheCH3nexttotheCH2.Theratioofthesignalsarisingfromeachof
thesekindsofprotonsshouldbe3to2to3,respectively.So,ifwelookatthe
heightoftheintegralstheyshouldbe3to2to3.Withthisinformation,wecan
knowwhichistheCH2signal(itsthesmallestone),buttodistinguishtheother
two,wehavetobeabletopredicttheirchemicalshifts.Thechartontheprevious
pageallowsustomakethatassignment(theCH 3nexttotheC=Oshouldappearat~
2PPM,whiletheotherCH3shouldbeat~1PPM).
3H'S

O
O

O
O

CH3

O
H 3C

H
3H'S

2 H'S

H1HCoupling
Youllnoticeinthespectrathatweveseenthatthesignalsdontappearassingle
lines,sometimestheyappearasmultiplelines.Thisisdueto 1H1Hcoupling(also
calledspinspinsplittingorJcoupling).Hereshowitworks:Imaginewehavea
moleculewhichcontainsaproton(letscallitH A)attachedtoacarbon,andthatthis
carbonisattachedtoanothercarbonwhichalsocontainsaproton(letscallitH B).
ItturnsoutthatHAfeelsthepresenceofHB.Recallthattheseprotonsaretinylittle
magnets,thatcanbeorientedeitherwithoragainstthemagneticfieldoftheNMR
machine.WhenthefieldcreatedbyHBreinforcesthemagneticfieldoftheNMR
machine(B0)HAfeelsaslightlystrongerfield,butwhenthefieldcreatedbyH B
opposesB0,HAfeelsaslightlyweakerfield.So,weseetwosignalsforH A
dependingonthealignmentofHB.ThesameistrueforHB,itcanfeeleithera
slightlystrongerorweakerfieldduetoH Aspresence.So,ratherthanseeasingle
lineforeachoftheseprotons,weseetwolinesforeach.
1

For this line, H B is lined up

with the magnetic field
(adds to the overall
magnetic field, so the line
comes at higher frequency)

For this line, H B is lined up

against the magnetic field
(subtracts from the overall
magnetic field, so the line
comes at lower frequency)

HA
HA is split into two lines because
it feels the magnetic field of HB.

HB
HB is split into two lines because
it feels the magnetic field of HA.

HA

HB

More1H1HCoupling
Whathappenswhenthereismorethanoneprotonsplittinganeighboringproton?
Wegetmorelines.Considerthemoleculebelowwherewehavetwoprotonsonone
carbonandoneprotononanother.

Note that the signal produced

by HA + HA' is twice the size
of that produced by HB

HA + HA'
HA and HA' appear at the same
chemical shift because they are
in identical environments
They are also split into two lines
(called a doublet) because they
feel the magnetic field of HB.

HB
HB is split into three lines
because it feels the magnetic
field of HA and HA'

HA'

HA

HB

WhyareThereThreeLinesforHB?
HBfeelsthesplittingofbothHAandHA.So,letsimaginestartingwithHBasa
singleline,thenletsturnonthecouplingfromH AandHAoneatatime:
HB

If uncoupled, HB would appear as a

singlet where the dashed line indicates
the chemical shift of the singlet.
Now, let's "turn on" HB - HA coupling. This splits
the single line into two lines
Now, let's "turn on" H B - H A' coupling. This
splits each of the two new lines into two lines,
but notice how the two lines in the middle
overlap. Overall, we then have three lines.

HA'

HA

HB

Becausethetwolinesinthemiddleoverlap,thatlineistwiceasbigasthelineson
theoutside.Moreneighboringprotonsleadstomorelinesasshownonthenext
slide.

SplittingPatternswithMultipleNeighboringProtons
Ifaprotonhasnneighboringprotonsthatareequivalent,thatprotonwillbesplit
inton+1lines.So,ifwehavefourequivalentneighbors,wewillhavefivelines,
sixequivalentneighborswell,youcandothemath.Thelineswillnotbeof
equalintensity,rathertheirintensitywillbegivenbyPascalstriangleasshown
relative intensities
pattern
example
below.
no. of neighbors
0

1
2
3

1
1
1

singlet (s)
1

2
3

doublet (d)
1

triplet (t)
1

quartet (q)

4
5

1 4

1 5 10 10

1
5 1

pentet
sextet

1 6 15 20 15 6 1

septet

H
H

Wekeepemphasizingthatthispatternonlyholdsforwhentheneighboringprotons
areequivalent.Whyisthat?Theansweristwoslidesaway.

MoreAboutCoupling
Earlierwesaidthatprotonscoupletoeachotherbecausetheyfeelthemagnetic
fieldoftheneighboringprotons.Whilethisistrue,themechanismbywhichthey
feelthisfieldiscomplicatedandisbeyondthescopeofthisclass(theydontjust
feelitthroughspace,itstransmittedthroughtheelectronsinthebonds).Itturns
outthatwhentwoprotonsappearatthesamechemicalshift,theydonotspliteach
other.So,inEtBr,wehaveaCH3nexttoaCH2,andeachprotonoftheCH3
groupisonlycoupledtotheprotonsoftheCH2group,nottheotherCH3protons
becausealltheCH3protonscomeatthesamechemicalshift.
The blue protons all come
at the same chemical shift
and do not split each other

H H

H C

H H

Br

The red protons both come

at the same chemical shift
and do not split each other

H H
H H
H C

H H

H C
Br

H H

Br

NotallCouplingsareEqual
Whenprotonscoupletoeachother,theydosowithacertainintensity.Thisis
calledthecouplingconstant.Couplingconstantscanvaryfrom0Hz(which
meansthattheprotonsarenotcoupled,eventhoughtheyareneighbors)to16Hz.
Typically,theyarearound7Hz,butmanymoleculescontaincouplingconstants
thatvarysignificantlyfromthat.So,whathappenswhenamoleculecontainsa
protonwhichiscoupledtotwodifferentprotonswithdifferentcouplingconstants?
Wegetadifferentpatternasdescribedinthediagrambelow.

So,iftheprotonsarenotequivalent,theycanhavedifferentcouplingconstantsand
theresultingpatternwillnotbeatriplet,butadoubletofdoublets.Sometimes,
nonequivalentprotonscanbeonthesamecarbonasdescribedonthenextslide.

CouplingConstantsinAlkenes
Couplingconstantsinalkenescanalsodifferdependingonwhethertheprotonsare
cisortranstoeachother.Notethatinaterminalalkene(i.e.,analkeneattheend
ofacarbonchain),thecisandtransprotonsareNOTequivalent.Oneisonthe
samesideasthesubstituent,theotherisontheoppositeside.Thecouplingoftrans
protonstoeachotheristypicallyverylarge,around16Hz,whilethecouplingof
cisprotons,whilestilllarge,isalittlesmaller,around12Hz.Thisleadstothe
patternshownbelow,andanexampleofamoleculewiththissplittingpatternis
shownonthenextslide.
HA
If uncoupled, HA would appear as a
singlet where the dashed line indicates

12Hz coupling

HA

HM

16 Hz
12 Hz

HX

16 Hz coupling

Now, let's "turn on" HA - HX coupling. This splits

the single line into two lines that are 16 Hz appart
12 Hz

Now, let's "turn on" HA - HM coupling. This

splits each of the two new lines into two lines
that are 12 Hz appart for a total of four lines

Thereareothertimeswhenprotonsonthesamecarbonarenonequivalent,which
wellseelater.

HO

A molecule with a terminal alkene

HO

CH3

H
H

HO

HO
H

H HO

CH3

H
H

H HO

HO

H
H

A molecule with a nine line splitting pattern

Me

OH
Me

Nine lines, you just can't

see two of them because
they are so small.

Me
OH

Me
H

Me
Me

OH

H
Me

Me
OH

OH