4 NMR 4.1 Zeeman 1, 13 C, 19 F, 31 P NMR 1 13 C 1/2 4.1 7%&'- 89:;'<= 7%&':#$>?@ 89)A89B.+ " %&' 23456,#$-./01 #$( )*+! %&'!"#$ #E = h $ 2% B 0 B 0 4.1 α β ΔE B 0 ΔE B 0 γ gyromagnetic ratio T 1 γ = 2.675 10 8 T 1 s 1 13 C γ = 6.688 10 7 T 1 s 1 h Planck ΔE = h(γ/2π)b 0 = hν 1
ΔE ν NMR Fourier FT γ NMR 4.70 T 1 200 Mz 13 C 50 Mz NMR 4.70 T XX200 1 13 C NMR NMR 0.5 ml CDCl 3 5 mm 4.2 NMR 1 100 1 NMR 1 m 300 Mz NMR 2
4.2.1 NMR 4.2 NMR NMR 4.2 2,2 1 1 NMR 1/10 6 TMS Si(C 3 ) 4 ppm (parts per million) 3
NMR chemical shift NMR ppm δ = TMS / TMS 10 6!"#$ 4.1 C 3 C 2 C Ar C 3 C 2 0.9 ± 0.2 1.3 ± 0.2 1.5 ± 0.2 2.5 ± 0.2 2.1 ± 0.3 5.0 ± 0.5 6.0 ± 1.0 6.8 9.0 1.9 ± 0.3 %&3)45* C= %&'()* 7.0~8.2 6.0~7.4 4.4~5.9 6.1~7.4 C 2 C 2 C 2 C 2 CN 2.1 ± 0.3 2.2 ± 0.2 2.2 ± 0.2 2.8 ± 0.3 2.3 ± 0.3 N 2 C 2 C 2 C C 2 N C 2 X C 2 4.3 ± 0.1 3.5 ± 0.3 4.2 ± 0.3 N C 2 2.4 ± 0.4 X 3.3 ± 0.3 (X=F: 4.1 ± 0.1) +,-./#$ 012%&#$ R R Ar 9.6 ± 0.2 10.2 ± 0.6 Ar C N 2 CN 2 2~5 4~9 9~13 1~4 5~9 4
4.2 2,2 1 1 NMR δ 0.91 1.48 ppm 3.29 ppm C 2 4.1 4.3 C C C Z C C (Z =, N, X) 10 9.0 6.5! (ppm) 4.5 2.5 0 4.3 C 3 C 2 C sp 2 diamagnetic anisotropy 4.4!"# ()&' ()&' ()&' $%&' $%&' $%&' (a) *+,- (b).-/- (c) *+0-4.4 5
ring current 1 1.9 ppm 4.2.2 NMR 4.2 9 1 2 4.2.3 1 2 2 1,1 4.5 1 NMR C Br C C 3 C 3 4.5 2 1,1 1 NMR (270 Mz) 6
δ 3.47 singlet 2 δ 3.42 1 2 doublet 1 δ 4.61 2 2 triplet 6 2 1 4.2.4 4.13 spin spin splitting spin spin coupling spin spin coupling constant J J = 5.5 z J z N N 1 4.6 1 NMR C 3 CC 2 C 3 4.6 1 NMR (270 Mz) 7
3 δ 2.02 3 δ 1.25 2 quartet δ 4.12 C 2 2 3 C 3 3 4 J = 7.0 z 1 2 1 2 2 2 1 2 1 1 3 3 2 1 3 3 1 4 4.7 A!"#$ X %$&'()*+,-./0 1./ -"#$ X %$&'()*+,1./0 1"#$ X %$&'()*+,2./0 2./ J J J 4.7 2 1 αα, (αβ, βα), ββ 3 3 1 ααα, (ααβ, αβα, βαα), (αββ, βαβ, ββα), βββ 4 1 1 3 3 1 (C 3 ) 2 CCl C 6 C 1 6 15 20 15 6 1 8
1 1 4.2 4.2 z X C Y 6~18 C C 6~8!"#$%& 8~12 2~3 2~3 0~2 X X X 6~12 12~18 7~10 2~3 0~1,-./0123 0~1.3 0.6~2 0~1.5 'W()*+& < 7 geminal 2 J 3 J C 90 0 3 J = 9~12 z 180 3 J = 10~15 z Karplus A, B, C Karplus 3 J = Acos 2 + Bcos + C 3 J 4 J < 1 z 4.2.4 1 NMR 1 NMR 4.8 3 2 1 NMR 9
4.8 3 2 1 NMR 400 Mz 1.11 2.15 ppm 2 2.60 ppm 6 7 N + 1 1:6:15:20:15:6:1 6 J = 7.2 z 7 4.8 3 2 1.11 2.15 ppm 1.11 ppm C 2.15 ppm 10
4.9 2 1 NMR (400 Mz) 4.9 2 3.70 3.95 ppm J = 5.8 z 4.08 4.23 ppm 6.48 ppm 3 2 4 2 J trans = 14.4, J cis = 6.8, J gem = 2.4 z 4 4.2.3 NMR 2 2 4.10 1,2 1 NMR 11
3 C C* C Br a b Br 4.10 1,2 1 NMR (270 Mz) C2 4.11 C1 2 3.55 3.85 4 Br Br Me Br Br Br Me a Me b a Br b a 1 2 3 b 4.11 1,2 2 2 2 4.12a 2 J 4.12 12
J J (a)!" J > 10 " A " # (b)!" J = 5 " A " # (c)!" J = 2 " A " # J J (d)!" J = 1 " A " # (e)!" J = 0 " A = " # 4.12 ν z p 4.13 7 ppm 13
4.13 p 1 NMR (400 Mz) 4.13 p 1 NMR 2.28 3.76 6.80 7.07 J = 8.4 z 3 2 4.2.5 a. 5.2 2,2 1 C 2 C 2 14
C 2 CDCl 3 2,2 1 1 NMR 4.14 1.44 ppm J = 6.2 z 3.29 ppm C 2 2 NMR 4.14 2,2-1- 1 NMR CDCl 3 400 Mz NMR J z 1~10 4 NMR 15
b. irradiation NMR 4.15 (a) (b) 1.9 ppm (b) (a) 4.15 1 NMR 4.3 13 C NMR 12 C NMR 1.11% 13 C NMR 1 16
1/6000 13 C NMR 1 1 broad-band proton decoupling 13 C 4.4 NE FT NMR 2 13 C 13 C 13 C 13 C NMR 200 ppm 5.3 13 C 13 C NMR TMS (C 3 ) 4 Si R C 3 R C 2 R R R C R R R C R 4.3 13 C NMR ppm 0 8~35 15~50 20~60 30~40 C I C Br C Cl C N C 0~40 25~65 35~80 40~60 50~80 R C Y R C 65~85 C 100~150 C 110~170 R C R R C 165~185 195~205 195~215 NMR 13 C 1 1/4 NMR 1/64 1/5800 NE 17
13 C sp 2 sp 1 4.16 4 3 2 13 C NMR 20.57 27.55 31.58 154.83 198.35 124.30 4.16 4 3 2 13 C NMR 4.17 CDCl 3 13 C NMR 10% 13 C 30.06 50.11 61.29 200.67 167.24 14.13 89.79 59.93 21.12 14.30 175.55 172.72 18
4.17 13 C NMR CDCl 3 13 C NMR 4.4 4.4 4.4.1 NMR saturation relaxation 2 spin-lattice relaxation 19
T 1 T 2 T 1 > T 2 NMR T 1 T 1 13 C NMR 4.4.2 NE NMR verhauser nuclear verhauser effect, NE 1000 13 C NMR NE 3 13 C NMR NE 1 NMR 4.5 NMR 2D NMR NMR 20
NMR 2D NMR 2D NMR NMR 2D NMR 1 1 CSY correlation spectroscopy 1 13 C 1 13 C 13 C 2D NMR C C C NESY nuclear verhauser effect difference spectroscopy NE 1 1 CSY 3 4.18 x y 1 NMR CSY a b 3 C 7 3 C b' 1 2 3 5 6 4 a' C 3 c c' 3!"#(3-Carene) 6 3 C 7 1 eq ax ax eq 2 C 3 5 C 3 4 3 21
4.18 3 CSY a a δ 1.7~2.3 ppm 2, 2 5, 5 4 1 1 6 b b 2 5 1 6 c c 4 5 3 4 5 5 6 1 7 3 2 (ax), 5 (ax), 2 (eq), 5 (eq), 4 22