SpecLropscopy lnvolves measuremenLs of lnLeracuon beLween llghL energy and

mauer. We focus on C and P, because Lhese are Lhe elemenLs found ln all organlc
compounds.
1
A magneuc momenL creaLes a magneuc eld.
2
3
lf Lhe LoLal number of proLons and neuLrons ls even, Lhen Lhe aLom wlll noL have a
magneuc momenL aL all, and lL wlll noL be aecLed by Lhe exLernal magneuc eld.
4
lL ls more sLable for Lhe nucleus Lo allgn wlLh Lhe magneuc eld.
3 6
When Lhe magneuc eld sLrengLh ls less, (because lL has been canceled or reduced by
Lhe magneuc eld of Lhe clrculaung elecLrons) Lhere ls a smaller energy gap
7
1he sLrucLure LhaL Lhe molecule ls connecLed wlLh deLermlnes Lhe elecLronlc
envlronmenL for each aLom and Lhus whaL energy gap wlll be observed for each aLom
ln Lhe magneuc eld. So, lf cerLaln energy gaps are observed, concluslons can be
made abouL Lhe sLrucLure of Lhe molecule.
8
9 10
11
ueuLeraLed solvenLs are necessary, because a solvenL wlLh any number of proLons
belng ln large excess would glve a huge slgnal. Slgnals for Lhe soluLe ln comparlson
would be lndlsungulshable above Lhe nolse ln Lhe slgnal.
12
13 14
13 16
17
8ecause of Lhe chlral cenLer LhaL Lhe CP group ls auached Lo, lf one of Lhe labeled P
ls replaced wlLh a u and Lhen Lhe oLher labeled P aLom ls replaced wlLh a u, Lhe
resulung compounds wlll be dlasLereomers. 8esulung dlasLereomers shown above
18
19 20
21
Axlal and equlLorlal proLons have dlerenL elecLronlc envlronmenLs. lf Lhe chalr were
noL lnLerconverung, Lwo slgnals would be observed.
22
lf Lhe LemperaLure were lowered, and Lhe lnLerconverslon were slowed down, Lhen
Lwo slgnals would be observed.
23 24
23 26
27 28
LlecLronegauve aLoms auracL elecLrons away from Lhe P aLoms Lhrough lnducuon.
WlLh fewer elecLrons around Lhe h aLom, Lhe exLernal magneuc eld aecLs Lhe P
aLom more causlng a larger energy gap beLween alpha and beLa spln sLaLes. 1haL
means a greaLer energy wlll be necessary Lo puL Lhe P aLom ln resonance, and Lhe
slgnal wlll appear on Lhe hlgh energy or downeld slde of Lhe specLra.
29 30
31 32
33 34
Some reglons are more shlelded Lhan oLhers, because Lhe elecLron denslLy around
LhaL area ls greaLer, can be aecLed by Lhe shapes of orblLals and by Lhe presence of
pl bonds versus slgma bonds, and Lhe proxlmlLy Lo elecLronegauve aLoms.
33
1he nonequlvalenL P aLoms on Lhe rlng (should see Lhree slgnals) are shled Lo very
slmllar posluons, so Lhey overlap creaung a slgnal LhaL appears as lf lL ls one slgnal.
36
1he P aLoms on Lhe ouLslde of Lhe sLrucLure appear aL 8 ppm, whlle Lhe proLons
polnung lnLo Lhe pl cloud appear around -1 ppm.
37 38
39 40
41
1erL-buLyl meLhyl eLher would glve Lwo slgnals. Cne slgnal for Lhe meLhyl group aL
approxlmaLely 3.3 ppm wlLh an lnLegrauon of 3. 1he oLher slgnal for Lhe LerL-buLyl
group, whlch has Lhree equlvalenL meLhyl groups. lLs shl would be approxlmaLely 1
ppm wlLh an lnLegrauon of 9.
3-penLanone would have Lwo slgnals because of symmeLry. Cne slgnal for Lhe Lwo
CP2 groups on elLher slde of Lhe carbonyl wlLh a shl of approxlmaLely 2.2 ppm and
an lnLegrauon of 4. 1he oLher slgnal would shl Lo approxlmaLely 1 ppm wlLh an
lnLegrauon of 6.
42
43 44
43 46
When one nelghborlng proLon ls shleldlng and Lhe oLher ls deshleldlng, Lhe eecLs
cancel ouL.
47
1he LrlpleL resulLs when one nelghborlng proLon shlelds and Lhe oLher deshlelds half
Lhe ume (glvlng Lhe cenLer peak wlLh a lnLegrauon Lwlce LhaL of Lhe ouLer peaks).
48
nelghborlng P aLoms LhaL allgn Lhelr spln wlLh Lhe magneuc eld have dlerenL
shleldlng eecLs Lhan nelghborlng P aLoms LhaL allgn agalnsL Lhe magneuc eld.
49
lnLegrauon rauos should be 1:3:3:1
30
31
n+1 rule means Lhe spllmng should be equal Lo Lhe number of P aLoms on Lhe
ad[acenL carbon +1. Lxplalned more Lhrough examples on subsequenL slldes.
32
1,2-dlchloroeLhane should be a slngleL
33 34
33 36
37 38
39 60
61
lf nonequlvalenL P aLoms spllL wlLh Lhe same coupllng consLanL, Lhen Lhey acL as lf
Lhey are equlvalenL, and Lhe spllmng pauern wlll follow Lhe n+1 rule. See analysls for
(!)-penL-2-en-4-ol on followlng sllde.
62
lf nonequlvalenL P aLoms spllL wlLh Lhe same coupllng consLanL, Lhen Lhey acL as lf
Lhey are equlvalenL, and Lhe spllmng pauern wlll follow Lhe n+1 rule. See analysls for
(!)-penL-2-en-4-ol on followlng sllde.
63 64
Mechanlsm on nexL sllde
63 66
1he solvenL wlll be ln a large excess, so Lhe equlllbrlum creaLed where someumes Lhe
molecule has a P aLom and someumes a u aLom wlll favor replacemenL of Lhe P aLom
wlLh u aLoms.
67 68
Lach molecule has slmllar funcuonal groups, so Lhe sLreLchlng vlbrauons wlll be very
slmllar pracucally lndlsungulshable. 1he proLon nM8 for each would glve a dlerenL
number of slgnals (from le Lo rlghL 3 slgnals, 4 slgnals, 2 slgnals).
69
1he rlghL hand slde of Lhe molecule ls Lhe same for boLh, buL on Lhe le hand slde
oLher Lhe molecule, Lhe spllmng pauers wlll be dlerenL. Movlng from le Lo rlghL,
Lhe molecule on Lhe le has a doubleL, quarLeL, slngleL, eLc. 1he molecule on Lhe
rlghL has a LrlpleL, quarLeL, slngleL, eLc.
70
71
Pul = 1. 1he slngleL lnLegraung Lo 6P suggesLs Lwo meLhyl groups.
72
1he doubleL of quarLeLs shled Lo 3.3 ppm suggesLs a CP auached Lo a C=C double
bond wlLh a meLhyl group auached Lo Lhe carbon and a slngle P on Lhe oLher carbon
of Lhe C=C double bond. 1he peak aL 3.4 ppm suggesLs LhaL Lhere ls a carbon wlLh 2
P aLoms auached Lo Lhe Cl and nexL Lo a carbon wlLh no P aLoms on lL. 1he molecule
works ouL Lo be cls or Lrans 3-chloro-4,4-dlmeLhyl-2-penLene.
73 74
73 76
2 slgnals
77 78
79 80
81
ln Lhe molecule on Lhe le, Lhe CP2 ls shled farLhesL downeld. ln Lhe molecule on
Lhe rlghL, Lhe CP ls shled farLhesL downeld, and ln uL1 CP and CP2 are
dlsungulshable.
82
Some ussues have more waLer versus oLher molecules LhaL may have more carbon or
oLher elemenLs. A 3u lmage resulLs from Lhe dlerenL slgnals glven ln dlerenL
ussues. no known slde eecLs Lo radlo waves or magneuc elds.
83