Nuclear Magnetic Resonance 1 NMR spectrum PPM
PPM X: X X:
1.5 1.5 1 1 1 1 : 1: 1 : 1.5 : 1.5 2 : 2 : 2 : 3 : 3 1
13 NMR spectrum BM PPM BM
13 NMR spectrum DEPT
OSY a b c d a c 1 NMR spectrum PPM a-c a b c d d c b a 1 NMR spectrum PPM
- OSY a a b c d c 1 NMR spectrum PPM a-c d c b a 13 NMR spectrum PPM
OSY
- OSY
O + 3 O + ( O 3 + 2 O O O
IR O
MS
NMR
NMR : 1, 12, 13, 14 N, 15 N, 19 F, 31 P,... : I 0, I = 1/2, 1, 3/2, 2, 5/2, 3,...
or
: : ΔE N /N = e E/kT : B0 = 2.35 T 1 N > N N - N = 10-5
NMR NMR ΔE ΔE = hν
ΔE = 2µB 0, γhi µ = 2π (μ:, : ( ), B0:, h: ) I = 1/2 ( 1, 13,...) ν [z] = ΔE = h γb 0 2π B0 = 2.35 T 1 ΔE = 3.99 x 10-2 (J mol -1 ) ν = 100 x 10-6 (z)
: Beff = B0 Bind Bind = σb0 Beff = (1-σ)B0 B0 Bind γb ν [z] = 0 (1-σ) 2π σ:
σ = σdia + σpara + σ σdia: ( σpara: p (1/ E, p, 1/r 3 ) σ : (
z z ν χ ν standard = ν Δν ν [ppm] (perts per million) Mz 1. 2. 3. 4. 5. singlet 3 3 Si 3 3 3 3 Si D 2 D 2 O 2 Na 3
deuterated solvent formula mp ( ) bp ( ) δ δ c (multiplicity) acetone (D 3 ) 2 O 95 56 2.04 29.3 (7) 206.3 acetonitrile D 3 N 45 82 1.93 1.3 (7) 117.7 benzene 6 D 6 6 80 7.27 128.0 8(3) chloroform Dl 3 64 61 7.24 77.0 (3) dichloromethane D 2 l 2 97 40 5.32 53.5 (5) dimethylsulfoxide (D 3 ) 2 SO 19 189 2.49 39.7 (7) methanol D 3 OD 98 64 3.35 49.3 (7) 42 4.78 pyridine 6 D 5 N 0 115 7.19 125.3 (3) 7.55 135.5 (3) 8.71 149.5 (3) water D 2 O 100 4.65
X 2 2 3 X = F: 4.30, 1.68, 0.97 X = l: 3.30, 1.61, 0.89 N( 3 ) 2 O 3 < < o 6.59 o 6.80 < 7.27 N + ( 3 ) 2 o 7.98
< < < 1.43 5.66 5.89 7.34 B0
[10] 0.51 ppm 2.63 ppm
[18]アヌレン 9.28 ppm 非遮蔽領域 低磁場シフト -2.99 ppm 遮蔽領域 高磁場シフト
B0 Alkenes arbonyl Groups
1.30 ppm 4.93/4.97 ppm 1.94 ppm B0 Alkynes
ax. eq. δ (ax) > δ (eq) ( 0.5 ppm) - bond B0
RO aromatic R R 2 3 10 9 8 7 6 5 4 3 2 1 0 OR l NR 2
: 4-methylenzaldehyde D A B B O 3
: benzaldehyde A B D B D O
: 2-hydroxy-4-methoxy-benzaldehyde A B F D E D E O 3 O O
a b Jab Jba a b Jab = Jba : z
a b a(β)b(α) a b a(α)b(α) a b a(β)b(β) a b a(α)b(β) a b
a ν0 ν1 a ν0 ν2 B0 b β b α b a (Jab = Jba)
a b ν 0 J ab J ba ν 1 ν 2 or :
singlet 2 doublet 1 100 Mz 200 Mz (1 ppm = 10 cm) 1 cm 2 cm doublet 2.10 2.00 1.99 2.10 2.00 1.99 singlet 2 cm 2.10 2.00 1.99
100 Mz 200 Mz 10 z 10 z 10 z 10 z 2.10 2.00 1.99 1.98 2.10 2.00 1.99 1.98 2.10~1.985 ppm (m, 2) 2.00 ppm (t, 1, J = 10.0 z) 1.99 ppm (d, 1, J = 10.0 z)
b b ' a a b b ' α α β β α β α β β α β α β α β α up-field shift no shift down-field shift 1 2 1 b b : ( + 1 )
1 singlet 1 1 doublet (1 : 1) 1 2 1 triplet (1 : 2 : 1) 1 3 3 1 quartet (1 : 3 : 3 : 1) 1 4 6 4 1 quintet (1 : 4 : 6 : 6 : 4 : 1) 1 5 10 10 5 1 sextet (1 : 5 : 10 : 10 : 5 : 1)
' ' ' geminal ( 2 J) 9~15 z vicinal ( 3 J) 0~18 z : 7~8 z long range ( 4 J) 0~3 z φ φ ' Karplus 3 J = A cos 2 φ + B cos φ +
ax ax eq eq eq eq ax ax 3 J (~12 z) >> 3 J (2~3 z) ~ー 2 J (2~3 z) cis geminal trans 3 Jtrans (11~18 z) > 3 Jcis (6~14 z) >> 2 Jgeminal (~3 z)
o m : 3 J (6~9 z) : 3 J (1~3 z) : 2 J (~0 z) p 4 J = 2~4 z
O 3 2 2 2 3
l O 2 3
a O 3 b AnMmXl A (m+1) (l+1) JAM = JAX (m+l+1) a b dd: double doublet (AMX) t: triplet (AX2)
Allyl Ethyl Ether 2 O 2 3
~17 z ~10 z ~6 z
AA XX a b Br O a ' b ' νa = νa νb = νb Ja,b Ja,b Ja,b Ja,b
90 Mz AA BB Br Br l 1 2 1 2 l Br l 1 2 ν1 = ν2 enantiomers p1 p2 p3 Br 3 4 B B' Br l 3 B B' 4 Br l 1 2 1 2 A A 1 2 l 4 A 3 A' A' A' B' B (P87) J1,3 = p1jab + p2jad + p3ja J1,4 = p1jab + p2ja + p3jad J1,3 J1,4
JAB JAB JAB JAB ν1 ν2 ν3 ν4 νa νb νa - νb > 10 JAB ν1 ν2 ν3 ν4 νa νb νa - νb < 10 JAB
A2X2 90 Mz O N 2.61 ppm 3 J = 7 z AA XX
ax. eq. eq. very fast at rt slow below 100 ax. ax. eq. ax. eq.
(ABX 3.08 ppm JAX = 8.6 z O 2 JAB = 17.1 z A B X 4.52 ppm 2.89 ppm Br O 2 JBX = 6.4 z A O 2 B O 2 O 2 A B O 2 O 2 Br X Br X Br O 2 B A X A B
O O 3 N 3 N 3 E/Z 3 cf. 3 N 3 3
1 { 1 }NMR A cf. - OSY X hν A X A X
13 { 1 }NMR (~ 1%) (99.99%) 13 1 1 J(, ) = 125~250 z 2 J(, ) = 70 ~ 20 z 3 J(, ) = <15 z cf. 1 J(, X): X = D, 19 F, 31 P 3 BM
O δ R O < Ar O < R OO O + fast O 2 O + 2 O quartet (α) O a singlet b + fast O a b a + fast O b (β)
O cf. in DMSO cf. dq O a t 3 O - S+ 3 O O
N 14 N: I = 1, 3 δ 1.98 O δ 6.7 N δ 3.26 5.6 z 7.2 z δ 1.14
S 7.7 z 7.7 z S t 7.7 z q sex t
O fast + D O D 2 O + DO 3 O N fast O + D 2 O + DO 3 N D
O 2 3 O O 3 3
O 3 2 2 2 3
13 NMR spectrum 1. 13 99% 2. 13 γ 1 1/4 γ 3 3. 1 J(, ), 2 J(, ), 3 J(, ) 400 Mz ( 1 NMR vs. 100 Mz ( 13 NMR) 1. FT-NMR 2. 1 NOE J(, ) : 1 J(, ) : DEPT -OSY, MQ, LR--OSY, MB
13 NMR spectrum 119.0 135.5 O 129.9 112.7 170.2 161.8 117.6 O O 61.4 14.2 : 0~220 ppm : 0~50 ppm : 40 100ppm sp 2 : 100~160 ppm =O: 150~220 ppm : singlet
13 NMR OR R 3 X R 2 X R 2 X aldehydes aromatics alkynes X 3 ketones carboxylates alkenes NR 2 2 3 220 200 180 160 140 120 100 80 60 40 20 0