NMR ??????????

1
10?
NMR ?????????? Nuclear Magnetic
Resonance Spectroscopy
2
????????????
??
??
??
3
101 ??????????
B (???)
A
? ????????????? ??? ? ????????????
(?????????)
? ????CmHnOxNySz??? ? ??????????????
?????????????
? ????????????
? ??????IR, UV, NMR, ???
4
102 ?????????? ? ???????? (NMR Spectriscopy)
????,??????????????? ???,????????????????
??????????????
????
? c / l? ???????????l? c (c 3 1010 cm
s1) ????????? cps ?????? ????????????????????? ?
????? ,??????????(????????? ???????????????????
??????????????
????
5
????????
??????
???
????
???????
???????
?????
???
???
??????? ????
??
????????
?????????
6
103 1H NMR ???????????
???????????????????????? (????)
?????,????????????,????? ?????????
???,???????????????????? ???
????????? H0 ?????????,????
?????????????(???????? a-? ???? (a-spin state)
?b-????? (b-soin state))
?????????
H0
???????? ??????
a-????? ?b-????? ???
7
hn???? ????
H0
H0
??????
hn???? ????
E
?????
??????? Spin Flip
??????(hn? A?????????????L????
?? Resonance
?????? Spectral Line
8
?10?1
??????? NMR ????????
?????
?????
NMR ??
NMR ??
D, ???????T, ?????
9
?10?6
CH2ClF?70,500G????????NMR?????
H0 70,500G
10
???? NMR ???
??
??
11
???????????????,??????????????????????????(???)
Fourier ???
?????
Solvents CDCl3, CD2Cl2, THF-d8, DMSO-d6, etc
12
???NMR?? NMR Spectrometer
?????????????? ???????????????? ?????????/???????
?? 300MHz NMR Spectrometer
13
? 10-8 1H-NMR ?????
H
C
Cl
CH3
O
H
300 MHz
?????
14
NMR ????????,??????????????
104
H0 ?????? ??????? ?????
?

H0 ?????????? ????????? (local magnetic field)
hlocal
???? H0
???????????? ??????????? ?? H0 ???????
(shielding) ??????
?????????,????? ??????????????
???????????????/???????????
15
? 10-10 ????????????????????????
???????
H ???
C
H ???
Z
???????
????? Shielded ??? higher field
?????? Deshielded ??? lower field
??????????
????????????(Z)??????,????????????? ????,?????????
????????(?)?????
16
? 10-11 2,2-????-1-???????NMR????? (CDCl3,
300 MHz, (CH3)4Si ????
? ????????? ?,??????? ????????? ?????????
????? ? ????????? ?????,??? ?????
?????
?????????????????

• gH0(1 s)/2p

d?
ppm
?????????????
17
? 10-2
?????????????????
d (ppm)
18
??????????????????
? 10-3
???????
??????
??????? ?????
1.73 ppm
d?? 1.03 1.88 3.39 ppm
4.21 ppm
??????????????
19
10?5 ?????????
??????
3??????????
3??????????
2???????
20
?????????NMR ????????
????????? 180 C
NMR ???????? ?????????? ??,NMR ????? ???????????
Hb1,Hb2 ?Hb3 ?????????
???????? ??????
???????
??????????? 10.8 kcal/mol
????????????? 90 C
???????????(1.36 ppm)90 C??????2?(1.12, 1.60
ppm)
21
106 ??
????
???
22
(No Transcript)
23
10?7 ????????????????????
? 10-17
??? t
??? d
??? q
??? d
????????? spinspin splitting ?????????
spinspin coupling
??? m(multiplet)
24
?????????????????????
? 10-17
hlocal
H0
H0 hlocal
Ha ????????
??????
hlocal
H0
??????
H0 hlocal
Ha ????????
????? ??
?????????????
?????
25
? 10-18
???????? couplinng constant (J)/Hz
? ?????????????????????????????? ?
???????????(NMR???????????????)
26
???????? couplinng constant (J)/Hz
? ?????????????????????????????? ?
???????????(NMR???????????????)
? ???????????????(??????????? geminal
coupling) H?C?H ? ?????????????????????
H?C?C?H (?????????? vicinal
coupling) ? ???????????????????????,?????????????
????????? H?C?C?C?H ? ???????(??????????????)
?,??????????? ??????? CH3?CH3
27
? 10-1920
?????????? ?????????? ??????
N 1 ?
1 3 3 1
1 2 1
28
?10?4
N ??????????????? NMR ????????(Pascal????)
????? (N 1)
???????? ?????
????? ???? (N)
??????? ???
??? ??? ??? ??? ??? ??? ???
Pascal????
29
H??? ????
H??? ????
?105
? 10-21
??
? 10-22
30
108 ?????????????
? 1024
? 1023
90 MHz
ClCH2CH2OCH2CH2Cl
500 MHz
?
Pascal????????? Dn gtgt J ??????? ????????(first
order)
?
Dn J ??? ?????????(non-first order)
31
? 1025
??????????????????????N 1?????
32
? 1027
???????????????????
CH3CH2CH2Br
a b c
Jab Jbc N 1 ?
? 1028
33
??????103
??????????????????????
?????CH2????? ????????????
34
J1a,1b
J1a,1b
J1a,1b
J1a,2
J1b,2
J1a,2
a
b
J1b,2
doublet of doublet dd
C(2)?????????? Ha? Hb????????
A?B?C?????????Ha? Hb??????????????
35
??????????????????????????
??????????????????105 ?
?????????
? OH????????D2O???????????? ?
OH??D2O???H?D?????? ( D ??????? H ????????)
36
???????????????,??????????????????????????(???)
Fourier ???
?????
Solvents CDCl3, CD2Cl2, THF-d8, DMSO-d6, etc
37
109 ???13 ?????(13C NMR)
CH3CH2Br
????????????? 13CH 13CCH N 1 ?
????????????? 13C13C ???????
????
????? ???????
38
? 106
???? 13C NMR ?????
39
DEPT 13C NMR ?????
??????? normal spectrum
40
?????? 104
????? 1H
????? 13C
????? COSY
???????? HETCOR
????? 1H
????? 1H