NMRInterpretationGuide Therearethreethingstolookforwhenyouseeaspectrum.First,thesplittingpatternwhichtellsyou whatisnexttotheprotongivingthesignal.Second,theintegrationwhichtellsyouhowmany equivalentprotonsaregivingthesignal.Finally,theshiftwhichtellsyouthetypeofprotonthatisgiving thesignal(wecallthisthechemicalenvironment).Whenyoulookataspectrum,itcanbevery overwhelmingsoweuseatabletoorganizeallofthedata(belowisanexampleofatableandthe analysisofacompound). TheIntegration Theintegrationoftheareaunderthepeakisdirectlyproportionaltothenumberofequivalentprotons givingthatsignal.Therefore,ifyoucalculatethearea,you*know*howmanyprotonsthereare.Usually, weneedtoknowsomethingaboutthecompoundtobeabletousethisknowledgebecausethefirst integrationissetto1protonandeverythingelseisrelativetothatareaunderthecurve.Ifyouknow thatacertaintripletis3protons,youcansetthatareatobeequalto3protonsandeverythingelsewill berelativetothatknown. Importanttothisdiscussionisthetermequivalentprotons.Therearetwoclassificationsofprotons.

. Theyareeitherhomotopicorheterotopic.Homotopicmeanstheprotonsareexactlythesameand indistinguishablefromoneanother(wesubstitutedeuteriumforaprotonandseeifthereisachangein thestereochemistry).

Heterotopicmeanstheprotonsarenotquitethesamebuttherearedifferentdegreesofdifference. First,theycanbecompletelydifferent.Thesearetheeasiesttospotandwillgivecompletelydifferent signalsandsplittingpatterns(whatwecallspinsystems).Anexampleisshownforethanolwherethe

CH2protonsarecompletelydifferentfromtheCH3protons(differentconnectivity).Iftheprotonsare notcompletelythesame(homotopic)orcompletelydifferent,theyareeitherenantiotopicor diastereotopic.Thisismoredifficulttoputintowordssoanexampleisshownbelow.

Intheaboveexamplewithethanol,themethylprotonsarecompletelydifferentfromtheCH2protons andtherefore,heterotopicbecauseofconnectivity(theyarenotconnectedtothesametypeofcarbon). TheCH2protonsareheterotopicbecauseoftheirspatialarrangement(theyseethingsalittle differently). Fordiastereotopicprotons,therehastobeastereocenteralreadyinthemolecule(otherwise substitutingadeuteriumforaprotonwillonlyresultintheenantiomer).Belowisanexampleof homotopicanddiastereotopicprotons.

ProvetoyourselfthattheotherCH2protonsarediastereotopicandbothmethylgroupprotonsare homotopic. Sohomotopicandenantiotopicprotonsgivethesamesignalandtheintegrationwillreflectthenumber ofprotons. SplittingPattern Thesplittingpatternisdependentonthenumberofequivalentprotonsonthecarbonnextdoor (enantiotopicorhomotopic).Iftheprotonsnextdoorarenonequivalent,thenmorecomplexsplitting

patternsoccur(forexample,doubletoftriplets).Thistakespracticetovisualizebutcanbeprettyeasy. Belowisanexampleofanaldehydewithadoubletoftriplets.
SpinWorks 2.5: 1D Proton

O H2 C R H H H

Sees two neighbors on this side so splits into a triplet.

Sees one neighbor on this side so splits into a doublet.

Together it is a doublet of triplets

x 1.924 2.48 2.46 2.44 2.42 2.40

PPM

9.86

9.84

9.82

9.80

9.78

9.76

9.74

9.72

9.70

file: C:\Documents and Settings\Weitu\Desktop\AlkemystNMR\cs-nonanalsm\1\fid expt: <zg30> transmitter freq.: 300.131853 MHz time domain size: 32768 points width: 6172.84 Hz = 20.567092 ppm = 0.188380 Hz/pt number of scans: 16

freq. of 0 ppm: 300.130000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000

Thesetwospinsystemsarerelatedandtheyaresaidtobecoupled(Jcoupled).Ifwereallywantedto makesuretheywerecoupledwewoulddeterminethedistancebetweenthepeaksandseethatthey werethesame(thesmallsplitting). TheShift Theshifttellsyouwhatkindofprotonitis.Intheaboveexamplethetripletat9.77ppmisaprotonon thecarbonyl(aldehydicproton).Thedoubletoftripletsareprotonsonacarbonnexttoacarbonyl (alphatothecarbonyl).Theshiftisprettyconsistentthroughoutorganiccompounds.Therearetablesin booksforallofthedifferentshiftsthatyoucanusetohelpidentifywhichcarbonsaregivingspecific signals.

 TheTable Shift SplittingPattern Numberof Neighbors n1,where nisthe numberof peaks Numberof Protons (Integration) Justthe numberof protonsgiving thepeaks ChemicalEnvironment

Where Whattypeof isthe peaks(s,d,t, setof quart,quint,) peaks Hereisasimpleexample.

SpinWorks 2.5: 1D Proton

Fromthebooks

8.137

1.992

1.984

1.004

1.010

1.004

0.246

1.005

6.006

3.025 0.891

0.392

0.393

PPM

7.2

6.8

6.4

6.0

5.6

5.2

4.8

4.4

4.0

3.6

3.2

2.8

2.4

2.0

1.6

1.2

2.999

0.8

0.4

file: C:\Documents and Settings\Weitu\Desktop\AlkemystNMR\cs-3-18-pnmr\1\fid expt: <zg30> transmitter freq.: 300.131853 MHz time domain size: 32768 points width: 6172.84 Hz = 20.567092 ppm = 0.188380 Hz/pt number of scans: 16

freq. of 0 ppm: 300.130000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000

Thefullspectrumisaboveandtheexpandedspectraarebelow.

SpinWorks 2.5: 1D Proton

7.3874 7.3817

7.3589 7.3564

7.3400 7.3345

7.3274

7.3124

7.2861 7.2803 7.2771 7.2713 7.2621 7.2558

7.2364

7.2288

7.2142

7.1149 7.1091

7.0896

8.137

1.992

PPM

7.36

7.32

7.28

7.24

7.20

7.16

7.12

7.08

7.04

7.00

6.96

1.984

6.9571

6.92

file: C:\Documents and Settings\Weitu\Desktop\AlkemystNMR\cs-3-18-pnmr\1\fid expt: <zg30> transmitter freq.: 300.131853 MHz time domain size: 32768 points width: 6172.84 Hz = 20.567092 ppm = 0.188380 Hz/pt number of scans: 16

freq. of 0 ppm: 300.130000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000

SpinWorks 2.5: 1D Proton

5.0178

4.8307

4.7771

4.6113

1.004

1.010

PPM

5.04

5.00

4.96

4.92

4.88

4.84

4.80

4.76

4.72

4.68

4.64

4.60

1.004

4.56

4.5577

4.52

4.48

file: C:\Documents and Settings\Weitu\Desktop\AlkemystNMR\cs-3-18-pnmr\1\fid expt: <zg30> transmitter freq.: 300.131853 MHz time domain size: 32768 points width: 6172.84 Hz = 20.567092 ppm = 0.188380 Hz/pt number of scans: 16

freq. of 0 ppm: 300.130000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000

SpinWorks 2.5: 1D Proton

4.1567

4.1329

3.8781 3.8717

0.246

PPM

4.24

4.20

4.16

4.12

4.08

4.04

4.00

3.96

3.92

3.88

1.005

3.8545 3.8481

3.84

3.80

3.76

3.72

3.68

file: C:\Documents and Settings\Weitu\Desktop\AlkemystNMR\cs-3-18-pnmr\1\fid expt: <zg30> transmitter freq.: 300.131853 MHz time domain size: 32768 points width: 6172.84 Hz = 20.567092 ppm = 0.188380 Hz/pt number of scans: 16

freq. of 0 ppm: 300.130000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000

SpinWorks 2.5: 1D Proton

2.6718

2.3153

2.2407

6.006

3.025

0.891

PPM

2.68

2.64

2.60

2.56

2.52

2.48

2.44

2.40

2.36

2.32

2.28

2.24

2.20

2.16

2.12

2.08

0.392

2.0655

2.04

2.00

1.96

file: C:\Documents and Settings\Weitu\Desktop\AlkemystNMR\cs-3-18-pnmr\1\fid expt: <zg30> transmitter freq.: 300.131853 MHz time domain size: 32768 points width: 6172.84 Hz = 20.567092 ppm = 0.188380 Hz/pt number of scans: 16

freq. of 0 ppm: 300.130000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000

SpinWorks 2.5: 1D Proton

1.3090

1.2852

1.2614

1.0731

0.393

PPM

1.52

1.48

1.44

1.40

1.36

1.32

1.28

1.24

1.20

1.16

1.12

1.08

2.999

1.0494

1.04

1.00

0.96

0.92

0.88

0.84

0.80

file: C:\Documents and Settings\Weitu\Desktop\AlkemystNMR\cs-3-18-pnmr\1\fid expt: <zg30> transmitter freq.: 300.131853 MHz time domain size: 32768 points width: 6172.84 Hz = 20.567092 ppm = 0.188380 Hz/pt number of scans: 16

freq. of 0 ppm: 300.130000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000

Shift Splitting Pattern d t s broads s s dquart quart d d Broads s mult mult Numberof Neighbors 1 2 0 0 0 0 1and3 3 1 1 0(?) 0 ? ? Numberof Protons (Integration) 3 0.39 0.39 1 3 6 1 0.24 1 1 1 2 2 8 ChemicalEnvironment

1.061 1.29 2.07 2.2 2.3 2.7 3.86 4.14 4.58 4.80 5.02 6.96 7.067.13 7.187.42

CH3CH Unknown(maybeCH3CH2) Unknown(maybeCH3C=O) ProbablyHOC(broadsingletshereare usuallyOHprotons) Oddbutprobablyamethyl Oddbutprobably2equivalentmethyls CH3CHCH Unknown(probablyCH3CH2O OddbutlookslikeaABpattern OddbutlookslikeaABpattern NotreallyanOHsounknown Aromatic Aromatic Aromatic

First,wecanthrowoutthesignalsthatdonothaveintegrationsthatlookgood(youshouldseethe ethylacetatepeaksasbeingthe0.39,0.39and0.24integrations).Nowthetableiscompleteandshould helpyourealizethereareatleasttwoaromaticrings(aromaticprotonsequal12),atwoCHgroups,an OHand4methylgroups(threenonequivalent).Thiswouldbeagoodstarttoidentifyingthe compoundandtherearepeoplewhocanlookatthisdataandcomeupwiththecorrectcompoundbut wereallyneedmoreinformation.Thisistheproductfromthefollowingreaction:

(R) (R)

OH
(S)

OH
(S)

Ph Ph Br

N SO2

HN SO2

Ph

Ph

Youshouldbeabletoidentifythesignalsfromthetableandthereactionwiththeexceptionofthe broadsingletat5.02ppmbutyoucanusetheprocessofeliminationtoidentifyeventhat.