CHNG II

PH CNG HNG T HT NHN (NMR-

NUCLEAR MAGNETIC RESONANCE)
GV: ThS. Hong Minh Ho
TI LIU THAM KHO
1. Nguyn Kim Phi Phng (2005), Ph NMR s dng trong phn tch
hu c- L thuyt- Bi tp- Bi gii, NXB H Quc Gia TP. HCM.
2. Robert M. Silverstein, Francis X. Webster (1996), Spectrometic
Identification of Organic Compounds, John Wiley & Sons, Sixth
Edition.
3. James. V. Cooper (1980), Spectroscopic Techniques for Organic
Chemist, John Wiley & Sons.
4. John McMurry (2004), Organic Chemistry, Physical Sciences,
Seventh Edition.
II.1. L THUYT CHUNG
Ht nhn ca mt s nguyn t cng nh ng v c nhng
tnh cht nh th chng l nhng nam chm quay quanh mt
trc. Ht nhn ca hydrogene
1
H v carbon
13
C c tnh cht
.
Khi t mt hp cht hu c (HCHC) c cha
1
H v
13
C
vo mt t trng rt mnh v ng thi chiu x n vi mt
nng lng in t, ht nhn ca chng c th hp th nng
lng qua mt qu trnh gi l: Cng hng t.
S hp th ny c lng t ha v cho ta mt ph c trng
ca hp cht ph Cng Hng T Ht Nhn-NMR.
Mt dung c gi l my ph cng hng t ht nhn cho php
o s hp th nng lng ca ht nhn
1
H hay
13
C.
Ht nhn
1
H,
13
C hp th tn s radio (Radio Frequency-rf).
II.1.1. My ph
II.1.2. Ph -V tr ca tn hiu trn ph
Nu ht nhn hydro
1
H-NMR mt ht eclectron v tch ra
khi cc ht nhn khc th tt c cc ht nhn hydro (proton)
s hp th mt cng t trng mt tn s rf Ph
khng c ngha g.
Thc t th cc proton trong nhng vng c mt
electron khc nhau, v khng b tch loi ra cc ht nhn khc
nn chng s hp th cc tn s khc nhau tn hiu ca
cc proton s xut hin nhng v tr khc nhau trn ph
(C di ha hc khc nhau).
Trc honh: di ha hc (chemical shift) ca cc proton:
H
(ppm)
Trc tung: Cng ca tn hiu (cng mi)
4
2
3
Mt n v bng 1 phn triu (ppm: part per million) ca tn s my.
Th d: Mt my hot ng tn s 500 MHz = 500.10
6
Hz, nh vy 1 s bng
1ppm ca 500.10
6
Hz ngha l 500 Hz.
(ppm)= ( dch chuyn ha hc, Hz)/(Tn s my, MHz)
4
2
3
mnh ca t trng ngoi tng t tri qua phi. Pha
tri l trng thp (downfield), pha phi l trng cao
(upfield).
TMS: Cht chun- (CH
3
)
4
Si c
H
= 0 ppm
II.1.3. Din tch tn hiu hp th. ng cong tch phn
iu ng quan tm khng phi cng (chiu cao) ca tn
hiu m l din tch. Din tch hay ln cho bit s
hydrogen ca mi tn hiu.
Chiu cao ca ng cong tch phn t l vi din tch ca tn
hiu hp th.
4
2
3
II.1.4. S ch tn hiu (signal splitting)
S ch tn hiu cho ta bit cu to ca mt hp cht.
Hin tng ch tn hiu l do nh hng t ca hydrogene k cn.
Mi loi proton trong phn t cho mt mi cng hng (mi n)
nhng trong nhiu trng hp mi cng hng ca proton khng
xut hin mi n, m b ch tch ra thnh nhiu mi.
4
2
3
II.2. SPIN HT NHN-NGUN GC TN HIU
Electron c 2 trng thi lng t spin +1/2 v -1/2. Spin
electron l c s ca nguyn l ngoi tr Pauli.
Ht nhn
1
H,
13
C,
19
F,
31
P c s lng t spin I=1/2.
Qui tc (2nI+1): Nu mt proton kho st c n s proton tng
ng k bn n th proton kho st ny s cng hng cho tn
hiu (n+1) mi trn ph
1
H-NMR.
4
2
3
II.3. S CHN V GIM CHN CA PROTON
Xt trng hp cc electron ca lin kt C-H. T trng
c sinh ra bi cc electron c gi l t trng cm ng.
proton, t trng cm ng i nghch vi t trng ngoi.
iu ny c ngha l t trng thc t m proton nhn c
nh hn t trng ngoi. Cc electron chn proton.
Mc b chn ca proton ph thuc vo mt electron
xung quanh proton. Mt electron ny li ph thuc vo s c
mt ca cc nhm xung quanh (nhm m in).
S chuyn ng ca cc electron linh ng c th chn
hoc gim chn cc proton ln cn.
Proton ca vng thm c gim chn v chng v tr lm
tng cng thm trng ngoi.
Chng ta d on th t khi da vo m in nh sau:
(Trng thp) sp < sp
2
< sp
3
(Trng cao)
Thc t proton ca alkyne u mch cho hp th = 2-3 ppm
v theo th t:
Trng thp sp
2
< sp < sp
3
Trng cao
S hp th ca proton alkyne u mch xy ra trng cao l
do s quay ca electron ni ba lm chn cc proton .
II.4. DI HA HC (CHEMICAL SHIFT)
di ha hc (
ppm
) c tnh da theo s hp th proton ca
cht chun TMS: Si(CH
3
)
4
II.5. PROTON TNG NG V KHNG TNG NG
Proton tng ng v mt ha hc th cng tng ng v
di ha hc trong ph
1
H-NMR
II.5.1. Nguyn t hydro Homotopic (Homotopic hydrogene atom)
bit 2 hydrogene c tng ng (c cng di ha hc)
hay khng, ta th ln lt mi Hydro bng nhm th khc.
Nu sau khi th m ta thu c cc hp cht mi ging nhau
th cc proton th c coi l tng ng ha hc c cng
di ha hc cho mt tn hiu trn ph .
C
H
H
C
CH
3
CH
3
(b)
(a)
(b)
(a)
C
H
Cl
C
CH
3
CH
3
(b)
(a)
(b)
(a)
Thay H (a) ba ng Cl
Thay H (b) ba ng Cl
2-Metylpropen
1-Cloro-2-metylpropen
C
H
H
C
CH
3
CH
3
(b)
(a)
(b)
(a)
2-Metylpropen
1-Cloro-2-metylpropen
C
Cl
H
C
CH
3
CH
3
(b)
(a)
(b)
(a)
(A)
(B)
(A) tru ng (B)
Vy: H(a) v H(b) l 2 hydrogene homotopic v hp cht
2-Metylpropen cho 2 tn hiu ph trn ph
1
H-NMR: Mt ca
H(a) H(b) v CH
3
(a)CH
3
(b)
II.5.2. Nguyn t hydro enantiotopic v diastereotopic
Nu th mt trong hai hydro bng mt nhm to thnh hai
cht l enantiomer th hai nguyn t hydro gi l
enantiotopic. Cc nguyn t hydro enantiotopic c cng di
ha hc v ch cho mt tn hiu trn ph
1
H-NMR.
C
Br
H
CH
3
H
Thay H hoa c H ba ng Cl
C
Br
H
CH
3
Cl C
Br
Cl
CH
3
H
Etylbromua
Enantiomer
Vy: H v H l hai hydro enantiotopic c cng di ha hc
(khng o trong dung mi th tnh) v ch cho mt tn hiu trong
ph
1
H-NMR.
Ch ra nguyn t Hydro enantiotopic trong hp cht
2-phenyletanol?
C
6
H
5
CH
2
CH
2
OH
2-Phenyletanol
Nu th mt trong hai hydro bng mt nhm th khc to thnh
hai hp cht l diastereomer th hai hydro c gi l
diasterotopic. Proton diastereotopic khng c cng di ha hc
v cho tn hiu khc nhau trn
1
H-NMR.
Thay H hoa c H ba ng Cl
C
Br
H
C H
CH
3
OH
H
C
Br
H
C H
CH
3
OH
Cl
C
Br
H
C Cl
CH
3
OH
H
Diastereomer
sec-Butyl alcol
Vy: Hai proton (H v H)ca nhm CH
2
- trn l
diastereotopic v cho hai tn hiu ph
1
H-NMR.
II.6. S CH TN HIU: TNG TC SPIN-SPIN (SPIN-
SPIN COUPLING)
S ch tn hiu c gy ra do nh hng ca t trng ca
cc proton ln cn. S ch tn hiu ny xy ra l do hin tng
tng tc spin-spin.
nh hng ca tng tc spin-spin c truyn ch yu qua
cc electron lin kt v thng khng ng k nu 2 proton
cch nhau qu 3 lin kt .
S ch tn hiu khng xy ra vi cc proton tng ng ha
hc (Homotopic hoc enantiotopic).
Khi t trong t trng, cc proton c 2 nh hng: Cng hoc
ngc vi t trng ngoi Moment t ca mt proton c th nh
hng ln proton k cn theo mt trong hai cch.
S tc ng ca hai nh hng khc nhau rt nh ny gy ra s
xut hin ca mt mi nh hn v pha trng cao (so vi v tr m
tn hiu xut hin nu khng c s tng tc) v mt mi khc v
pha trng thp.
C
H
C
H
a
b
H
a
B
0
Two magnetic
orientations of H
b
Applied field
J
ab
H
a
: two peaks with equal
intensity (1:1): doublet
Qui tc (2nI+1): Nu mt proton kho st c n s proton tng
ng k bn n th proton kho st ny s cng hng cho tn
hiu (n+1) mi trn ph
1
H-NMR.
C
H
C
H
a
b
H
a
B
0
Two magnetic
orientations of H
b
Applied field
J
ab
H
a
: two peaks with equal
intensity (1:1): doublet
Hng s ghp (coupling constant): Khong cch gia 2 mi, tnh
theo n v tn s, c gi l hng s ghp (J
ab
), Hz.
V s tng tc l do nhng lc bn trong, ln ca hng s
ghp khng ph vo cng ca t trng ngoi (khng ph
thuc vo tn s my).
Cch tnh hng s ghp:
J
ab
(Hz) = (V tr mi th hai V tr mi th nht) (ppm) x
Tn s my (MHz)
Mi i
J = (4,753-4,738) x 500 = 7,5 Hz
ng dng ca hng s ghp
Trn ph c nhiu tn hiu, cc mi no c cng hng s
ghp th s suy bit c rng hai loi proton ghp vi
nhau, ngha l 2 proton gn vo hai carbon k cn.
5
3; 5
3
2; 6

6
O
H
3
CO
OH
OCH
3

1
2
3
4
5
6
1
'
2
'
3
'
4
'
5
'
6
'
2'-Hydroxy-4, 4'-dimetoxychalcon

= J

= 15,5 Hz
H

v H

ghp
cp vi nhau
Hng s ghp H-H v cu trc ha hc
a) Ghp hai ni (
2
J)
S ghp 2 ni cn c gi l ghp gem (geminal coupling) xy
ra gia hai proton ca mt nhm CH
2
- vi iu kin 2 proton ny
khng tng ng v mt ha hc.
Hng s ghp gem thng c gi tr m,
2
J (H,H) < 0.
C
H
H
-9 e n -15 Hz
C
H
H
0 e n 3 Hz
H
H
Cl
2
J = 12-18 Hz
b) Ghp 3 ni (
3
J)
Ghp H-C-C-H cn gi l s ghp k bn (ghp vic: vicinal
coupling). S ghp k bn s to nn cc kiu ghp spin tun theo
qui tc (n+1).
C
H
H
C
Hnh chiu Newman
Hng s ghp
3
J
trans
v
3
J
cis
C
H
R
C
H
R'
Cis
3
J
cis
: J = 4-12 Hz
3
J
trans
: J = 13-19 Hz
C
H
R'
C
R
H
Trans
Hng s ghp ca cc proton trong nhn benzen
Trong benzen, cc proton orto, meta, para c th tng tc
ln nhau, tng tc para khng phi lc no cng thy.
H
a
H
b
H
a
H
b
H
a
H
b
orto meta
para
3
J = 6-10 Hz
4
J = 1-3 Hz
5
J = 0-1 Hz
II.7. PH
13
C-NMR
II.7.1. S lc
Ph
13
C-NMR gi l ph cng hng t Carbon. Mc d
13
C ch
chim 1,1% carbon trong t nhin nhng n cho tn hiu NMR l
iu rt quan trng trong vic phn tch cu trc cc hp cht
hu c.
II.7.2. Mt mi cho mt loi nguyn t Carbon
Khng c hin tng tng tc Carbon-Carbon lm ch tn
hiu thnh cc mi.
ph
13
C-NMR: Tng tc
1
H-
13
C b loi b (kh ghp:
decoupling) nh vo chng trnh ca my o.
Trong ph
13
C-NMR, phn ln mi Carbon cho mt tn hiu
trn ph (c trng hp 2 Carbon chng ln nhau).
II.7.3. Ph
CH
3
CH
2
CH
Cl
CH
3
2-Clorobutan
II.7.4. di ha hc
13
C
II.7.5. Ph DEPT
DEPT 135: Cc nhm CH
2
cho mi m (hng xung), cc mi CH
v CH
3
l mi dng (hng ln), carbon bc 4 khng cho mi.
DEPT 135
DEPT 90
DEPT 90: Cc nhm CH cho cc mi dng, nhm CH
2
, nhm
CH
3
v carbon bc 4 khng cho mi.
DEPT 90
DEPT 135