CP203 LecLure 13

CcLober 8, 2014

vlclnal coupllng
MeLabollc prollng, meLabolomlc and meLabonomlc procedures for nM8 specLroscopy of urlne, plasma, serum
and ussue exLracLs Claf 8eckonerL, PecLor C keun, 1lmoLhy M u Lbbels, !acob 8undy, Llalne Polmes, !ohn C
Llndon & !eremy k nlcholson naLure roLocols 2, 2692 - 2703 (2007)
Pow much lnformauon have we gouen ouL of Lhe nM8 so far?
1. 1he locauon of Lhe hydrogen resonance ln ppm. 1ells
us Lhe local elecLronlc envlronmenL of Lhe hydrogen.
2. 1he number of dlerenL hydrogen resonances. 1ells
us how many seLs of nonequlvalenL hydrogens are
presenL.
3. 1he number of hydrogens ln each nonequlvalenL seL
by lnLegrauon.
1he nexL blL of lnformauon we can geL ls Lhe number of
hydrogens ln nelghborlng seLs.
lnLeracuon of vlclnal hydrogens
C C
H H
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
vlclnal (from Lhe Laun for nearby) hydrogens are separaLed by Lhree bonds.

Pa and Pb are nonequlvalenL hydrogens ln Lhe parual sLrucLure above.

Pa looks over aL Pb and sees lLs uny llule magneL nelghbor ln one of Lwo
quanuzed spln sLaLes, up or down, because Lhey boLh llve lnslde a blg 8
o
.
lnLeracuon of vlclnal hydrogens
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
C C
Ha Hb
lmaglne a blg populauon. Pa are all Lhe same. 1hey see Lhe same 8
o
and Lhe same 8
e
.
1he only dlerence ls LhaL now half of all Pa see 8
o
plus 8
e
plus 8
P
and Lhe oLher half
see 8
o
plus 8
e
mlnus 8
P

Palf of Lhe populauon of Pa ls now ln a sllghLly dlerenL magneuc envlronmenL Lhan
Lhe oLher half.
lnLeracuon of vlclnal hydrogens
Palf of all Pa see 8
o
plus 8
e
plus 8
P
and Lhe oLher half see 8
o
plus 8
e
mlnus 8
P

Palf of Lhe populauon of Pa ls now ln a sllghLly dlerenL magneuc envlronmenL Lhan
Lhe oLher half.

Palf of Lhe populauon of Pa now absorbs energy aL a sllghLly dlerenL energy.
1he resonance slgnal of Pa
lnLeracuon of vlclnal hydrogens
Palf of all Pa see 8
o
plus 8
e
plus 8
P
and Lhe oLher half see 8
o
plus 8
e
mlnus 8
P

Palf of Lhe populauon of Pa ls now ln a sllghLly dlerenL magneuc envlronmenL Lhan
Lhe oLher half.

1hls ls called vlclnal coupllng, or spln-spln coupllng, or spln spllmng.
1he resonance slgnal of Pa
C C
Ha Hb
lnLeracuon of vlclnal hydrogens
1he chemlcal shl of Pa ls dened as ln beLween Lhe spllL
slgnals.

1he spllL slgnal ls called a doubleL.
1he resonance slgnal of Pa
C C
Ha Hb
Chemlcal shl of Pa
lnLeracuon of vlclnal hydrogens
Cf course, Pb also sees Pa ln Lhe same way, so Lhe Pb resonance slgnal ls
spllL by Pa Lhe same way LhaL Pa was spllL by Pb.

Pa and Pb show as Lwo doubleLs. 8emember LhaL Pa and Pb musL be
nonequlvalenL.
C C
Ha Hb
lnLeracuon of vlclnal hydrogens
lf Pa has Lwo nelghbors Pb, x of Pa sees boLh up, x of Pa sees one up and one down
or one down and one up, and x of Pa sees boLh down.

1he Pa slgnal wlll appear as Lhree peaks ln Lhe rauo 1:2:1. 1hls ls a LrlpleL.
lnLeracuon of vlclnal hydrogens
lnLeracuon of vlclnal hydrogens
(! + 1) rule: lf a hydrogen has ! hydrogens
nonequlvalenL Lo lL buL equlvalenL among
Lhemselves on Lhe same or ad[acenL aLom(s),
lLs
1
P-nM8 slgnal ls spllL lnLo (! + 1) peaks.
lnLeracuon of vlclnal hydrogens
lnLeracuon of vlclnal hydrogens
Pa has one vlclnal nonequlvalenL hydrogen. 1he Pa slgnal ls spllL lnLo n+1 = 2
slgnals, a doubleL.

Pb has Lwo vlclnal nonequlvalenL hydrogens. 1he Pb slgnal ls spllL lnLo n+1 = 3
slgnals, a LrlpleL.

Pb ls closer Lo more elecLronegauve aLoms and ls Lherefore more deshlelded.
lamlllar pauerns of slgnal spllmng - Lhe eLhyl group
H
3
C
O
C
H
2
CH
3
2-buLanone
H
3
C
H
2
C
OH
lamlllar pauerns of slgnal spllmng - Lhe eLhyl group
C
4
P
8
C
2
O
O
undersLandlng vlclnal coupllng and recognluon of slmple resonance
pauerns llke LhaL of Lhe eLhyl group makes sLrucLure deLermlnauon go
fasLer.
2P, quarLeL
3P, slngleL
3P, LrlpleL
lamlllar pauerns of slgnal spllmng - Lhe lsopropyl group
nM8 of 4-lsopropylbenzaldehyde
1he coupllng consLanL, !
1he resonance slgnal of Pa
C C
Ha Hb
"
ab
1he dlsLance beLween Lhe Lwo halves of Lhe doubleL ln Lhe Pa resonance slgnal,
measured ln Pz, ls dened as "
ab
, Lhe coupllng consLanL beLween Pa and Pb.

1he magnlLude of "
ab
ls a reecuon of how eecuve Lhe Lransfer of Lhe
magneuc eld 8
P
ls Lhrough Lhe Lhree bonds connecung Pa and Pb.
1he coupllng consLanL, !
1he vlclnal coupllng beLween Pa and Pb ls exacLly Lhe same as LhaL beLween Pb and Pa.

So "
ab
= "
ba
. 1hey are usually boLh referred Lo as "
ab
.
1he coupllng consLanL, !
1he vlclnal coupllng beLween Pa and Pb ls exacLly Lhe same as LhaL beLween Pb and Pa.

So "
ab
= "
ba
. 1hey are usually boLh referred Lo as "
ab
.
1he coupllng consLanL, !
1he coupllng consLanL, !, and Lhe karplus curve
1he karplus curve predlcLs LhaL vlclnal P-P coupllngs wlll be greaLesL beLween proLons wlLh
180 and 0 dlhedral angles and LhaL coupllng wlll be leasL for proLons LhaL are 90 from
each oLher.
1he coupllng consLanL, !, ln a benzene rlng
1he proLon-proLon coupllngs ln benzene are Lyplcally 7-9 Pz for "
orLho
, 2-3 Pz for "
meLa

and <1 Pz for "
para
. Coupllng ls observed ln Lhls aromauc sysLem even Lhough only Lhe orLho
proLons are Lhree bonds away from one anoLher.
H
H
H
H
H
H
orLho, 7-9 Pz
meLa, 2-3 Pz
para, 0-1 Pz
ueduce Lhe sLrucLure
ueduce Lhe sLrucLure
MaLch Lhe specLrum Lo lLs sLrucLure
O
O
O
O
MaLch Lhe specLrum Lo lLs sLrucLure
O
O
O
O
ueduce Lhe sLrucLure
1.0P
4.63P
C
3
P
11
Cl
ueduce Lhe sLrucLure
1.0P
4.63P
C
3
P
11
Cl
CH
3
C H
3
C
CH
3
H
2
C Cl