(Nuclear Magnetic Resonance Spectroscopy, NMR )

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???? ??????? (Nuclear Magnetic Resonance
Spectroscopy, NMR )
2
NMR ? ? ? ?
??????????
NMR ? ?
?????????
13C????????
3

• NMR??
• 1. ????
• NMR?????????????????(Radio-frequency
  Radiation)???,?????????????????????????????????,??
  ?????????
• ?????,?????????(?????1.41T???,??????25?10-3J),??
  ???????(109-1010nm,4-900MHz)?,?????????----????NMR
  ???

4

• ???????(????????)??--????--NMR,??????????,1HNM
  R--??????????????? C????H??????)
• ?UV-Vis????????,NMR???????,??????????????????????
  ?????

2. ???? 1924?Pauli ???NMR ?????,?,??????????????,
????????????
5
1946?Harvard ???Purcel?Stanford???Bloch?????????N
MR??,??1952????Nobel? 1953?Varian????????,??????
???????NMR ? 1956?Knight????????????NMR?????,???
????????????
1970?Fourier(pilsed)-NMR ?????(??????????NMR
??)?
6
??? NMR????
?. ??????
??????? ?????? ? (??????) ?? ?
???????????? P ??, (? ????)????????
?(H??2.68108T-1s-1)?
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?13.1 ?????????????
??? (A) ??? (Z) ??? (N) ?????(I) ??? ??
?? ?? ?? ?? ?? ????? ?? ?? ????? 0 1.2.3 ½,3/2,5/2 ? ? ? 12C,16O,32S 2H,10B,14N 1H,13C,17O,19F,31P,33S
I0??????????,???,??????,???????????,I?0???????,I?
????????,??????????.
8

? ??????????
(?) ?????
?????????,????B0?,?????????????,????????(2I1)
?
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??h?Planck?? (6.624?10-27erg.sec)m?????,?????????
I ??,m ??2I1???,???? P ? 2I1 ???, ???? 2I1
????? ???????????,???????,?????????
?????,I1/2,?m????2?1/212???1/2?-1/2????? H
?????,?????????
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?13.1 (a)?????????? (b)I1/2?????????B0???
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?????????? ???? ???, ??, ?,
12
B0 ???????(T,Kgs-2A-1),1T104 Gauss
????,?????????????????????????????
(?) ???? ????????????H0???,???????????????
?????????????????????,????????????
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?13.2????
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???? a) ??????????,???,???????????????????!
??????Z????N ?????,I0 ? P0,???????????????12C,16
O,32S??????? b) ?Z?N?????,I??,P?0,??????,?NMR
??,?????NMR????2H,14N? c) ?Z?N?????,I???,P?0,????
NMR ??,?1H,13C?
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(1)??????I1/2??????,????????,??h????,???????,????
????????????H0???? (2)??????I1/2???????,?????????
??????,????????????????? (3)???????,??????,???????
,?????,?????????????????
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?.????????????(Relaxation Process) (?) ???????
????????????????,????????????????????,??????????
?????Boltzmann?? ????,????,1H??B0?2.3488
T ????,????????? 1H ??????0.999984???????????????
???????16/1,000,000
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??????????????,???????,?????????????????,?????????
??????,?????????????????????????????????????
????0???????
?2????NMR???????????4.69T????????,?????????????
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?1???25oC?,???4.69T???,??????????????????
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(?)????? ?????????????????????????????????????
???????,?????????????????,???????????????????,???
??????? ?Heisenberg?????,?????E????????????
?(??)???,??????? ???,?
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??,??????????????????,?????????,??????????????
????? ?????1????-?????????????????????????
??(??)?????,??????????????? a)
 ????---??????---?1??---?????---?????? b) ???????
?---??????---?1??---?????---????
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c)  ???????---??????---?1??---?????---????? ?????
????(??????),?1??,????????,????
?????2????-??????????????????,?????,?????????????
??????????? ?????????? a) ???????????????????2?
???????(??)???????
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b) ????????????????????????2?????????????? c
) ?????????????2????????????????? ?????????(?
?????),?2??,????????????????,?????????????,??????
??,??????? ?1 ? ?2 ????,? 0.5-50s
??????????,???????????
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??? ??????????
? ????(Chemical Shift) (?) ???? ??
????????????(1H ?),????????B0??????,??????? 1H
???????,? ?H ???,??????0??,???????????,??NMR??,???
??? ???,??????????B0??,???????? ? ??,???? ?
??????????????????
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????,?????????????????????????,????????????,??????
????!?????????????????????? NMR
?????????? ?????????????,??????????????????,?????
??????????????????,???????
600 Hz
B
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2. ?????????????? ????????????????????,???????B0?
??????????,????????? B?????????,?
?????????????,?????????? ?????????????????,??????
???????,??,?????,????????????,???????????????????(
?TMS),?????
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????????????x ??s,?????????? ?
? ???,????????,??????????
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?NMR?,????????(TMS)????, ?? a) ???????1
2 ?H ????????????,?????? ?????????????? b)
????? ??,?????????????????(??)?
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c) TMS?????????????????
??,?????????????? ????????????? ???????????
(?). ????????? ??? ??,?????????(?????)????
???????,???NMR??????? 1)????(Induction)??????????
?----?????????(???)---???---???????????---????????

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2)????(Conjugated)?????????,????????????? ?
C2H4 ? a)??????C2H4???? p-? ??,CH2??????????,???
?? b)????? C2H4 ?-???,CH2??????????,?????
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3)????????????????????????(????),????????????????
?,????????????????????????????????,?????,?????????
3
2
1
?13.3 ????????
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?1C2H4 ?? ??????? ????????,????????????()?????(
-), ??????????,?C2H6(?0.85)??????(?5.28)?
2C2H2 ??? ? ???????C-C?????????,???????,????????
? (?1.8)? 3????C2H4 ?????,?????????(?7.27
)???????,??????? ???,???????????????,??O
?????,??????(?7.27)?
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4)?????????????,?OH?SH????????????????,??????????
?????? ????????????????,??????????? ???????????
???????????
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? ????J
(?)????????? ??CH3CH2OH???????????,??????????????
??,???? NMR ?,CH2?CH2???????????,????????
???????
?13.4?????????
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?????????????,????????????????????,??????????
??,???????????????!???,?????,??????????????,??,???
???????????????,??,?????????????????????????????
??????????-???????????????????????????-?????
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????????????? nJ ??(n?? H ?????)?????????????????
??????????????,???? nJ ????????????????????????
B0,????????????????
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?????????? ???????????????????????????????????? ?
??????????????,?????????????,???????,????????????

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1 CH3CH2X?CH3????????????,?????? 2
?????Ha?Hb??????,?? JHF(??)?JHF(??),??Ha?Hb?
?????? 3 ?-?????,Ha?Hb?????,??????(3Jac?
5Jbc)? ??????,??????,??????????????
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• ????????????
• 1 ????(2J)
• ???????,J ??,????????????,???????????
• 2 ????(3J)
• ???????,J ??,??????????????????.????????Karpl
  us??
• ????,???????,???????????,???????????????????

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?13.5????
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?????????????,????????? 1)??(?)???????????n??????
??,???n1??? ?,CH3CH2OH(21311) 2)??(?)????
???????????(???m??n???)??,???????????????,????mn
1??,?CH3CH2CH3???????,????(m1)(n1)??,?CH3CH2CH2
NO2 3)?????????(ab)n????????? 4)????????,??????
?????
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5)?????????????????,?ClCH2CH2Cl,?????? 6)?????????
?????????????????????????,????????????,???????(??A
B/JAB??20,????????????????????????)??????????,????
?????????,???????????
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???? 1) ClCH2CH2CH2Cl ??????????,3(121)-5(146
41)-3(121) 2) CH3CHBrCH3 ??????????2(11)-7(1
615201561)-2(11) 3) CH3CH2OCH3 ??????????3
(121)-4(1331)-1
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(?)???
?13.6 ??????
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??? NMR??
? ???????
?13.7 ???NMR????
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1)??????????????????????,??????
??????0.7046T(30MHz)?1.4092T(60MHz)?????????,???,
????,?????????,????????????,????????????????????,?
????????????23?! ?????2.3T???,?????????????,
????????????????,???????,?????,????,??????
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??????5.8T???,????12T,???(?Nb?Ta??)?????(??)?????
???????????,???????,?????,???????,????????????????
?,???????,???????????????10-9-10-10??---??????????
?? 2)??????????????????????????????Hz?????,??????
??????????????????,???????
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?CW-NMR?,??????10-5T????????????? 3)?????????????
????,???????10-8,????(??1W)?????1? 4)
?????????? ???? ?????????????????? ?????60MHz?9
0MHz?200MHz.. ????????NMR?(CW-NMR)????????NMR
?(PFT-NMR)
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(?) ???????? ?????????????????B0,???????????
??,?????????????,????B0??????,??????
???(Continuous Wave ,CW)????????????????????,??
?????,???????????????????? ??
??,??,?????,?????,?????,???????????
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(?)???????????? (Pulsed Fourier Transform NMR
,PFTNMR)? ???????,?????????????? ?,?????????,????
?????
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??? ?????????

• ????????????
• (1)???????????????
• (2)?????????????
• (3)???????????????????
• (4)??????????????????
• (5)??????,??????????????
• (6)??????????,?????????,
• ??????(-OH?-NH-?-SH?-COOH)????

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(7)????n1???????,??J?,??J ????????? (8)??????????
???,?????? (9)??UV?IR?MS???????????? ???? (10)????
????????????
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??? 13C????????

• 13C?????????
• 1. 13C?????????
• 2. ?????
• 3. ????T1?????????????
• 4. ?13C-NMR?????????????????
• ????

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? 13C???????? (?)???? ? ??????????13C????????
?????????????,????????????200? 1.????
2.???? 3.???? 4.???? 5.????
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• (?)????J
• 1. 13C13C??
• 2. 13C--X??
• 3. 13C--1H??
• ????
• (?)??????
• (?)?????

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?13C???????? (?)?????? (1)?????? (2)?????? (3)????
???????? (?)??????
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????
1.?????I1/2?????????,?????????
?????????I1??????? ???? 2.?????????,??????
???????,? ,????????????
???? (????2001?) 3.?????????,??????
?????,????? ???????? (????2002?)
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4.??60MHz?????,?????????????????????180MHz,???????
?__________? 5.?????????,??????______???????????
????,???CH3CHO?CHO????????____??,?????_______? (??
??2003?) 6.?????????___________,?????_______,???
_________? (??????2000?)
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7.??????????????????,???????????( ) A ???????
B ??????? C ??????? D ??-????????? 8.1H?19F?13C?
15N???????2.79?2.63?0.73?0.3????,?????????????,???
????????,???????(H)??????( )
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A HHgtHFgtHNgtHC B HFgtHHgtHNgtHC C
HNgtHCgtHFgtHH D HNgtHCgtHHgtHF (????2001?)
9.?????????????????( ) A?????
B????? C??????? D????? (??????2002?) 10.??
???I1????,??????????????( )
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A ,1 B,2 C,3
D,4 (????2002?) 11.??????C4H8O?????,????1H-NMR?,??
????? 12.???????1H-NMR??????????????(???????)
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13.?????????C8H10,?????????A?B????,???????6.8cm?
10.2cm?????????A?_____?,B?_____?? (??????2001?)