Citation

 M. Jones, Jr.: ‘ Organic chemistry must be read

with a pencil in your hand……’
 13. Structure Determination:
Nuclear Magnetic Resonance
Spectroscopy 核磁共振光譜

Based on McMurry’s Organic Chemistry, 9th edition

 The Use of NMR Spectroscopy
 Used to determine relative location of atoms
within a molecule
 The most helpful spectroscopic technique in
organic chemistry
 Maps carbon-hydrogen framework of
molecules
 Depends on very strong magnetic fields

Mass spectrometry Molecular size and formula

Infrared spectrometry Functional groups
NMR spectrometry Map of carbon-hydrogen
framework
Why This Chapter?
 NMR is the most valuable spectroscopic
technique used for structure determination

 More advanced NMR techniques are used in

biological chemistry to study protein structure
and folding
The Spectrum and Molecular Effects

CH14

CH12

CH13

=>
(Resonance)
Electromagnetic spectrum
5
13.1 Nuclear Magnetic Resonance Spectroscopy
 NMR is the most powerful tool available for
organic structure determination.
 It is used to study a wide variety of nuclei:
 1H
 13C

 14N

 19F

 31P

 1 H NMR and 13C NMR are the most useful tool.

6
 Nuclear Spin
 A nucleus with an odd atomic number or an odd mass number
has a nuclear spin( 核自旋 ).
 1
H and 13C have a nuclear spin
 C and 16O do not have a nuclear spin
12

 The spinning charged nucleus generates a magnetic field. ( 奇數原

子序或質量數的原子核，可以繞軸自旋轉動，產生磁場，類似一個小磁鐵 )

( 氫核繞自旋軸轉動時，產生磁場，類似一個小磁鐵 )

7
External Magnetic Field(B0)
( 外加磁場 )
When placed in an external field (B0), spinning protons
act like bar magnets.

-spin state -spin state

Nuclear Magnetic Resonance Spectroscopy
 Nuclei are positively charged and interact
with an external magnetic field denoted by B0
 Magnetic rotation of nuclei is random in the
absence of a magnetic field (a)
 In the presence of a strong magnet, nuclei
adopt specific orientations (b)
Nuclear Spins in External Magnetic Field (B0)

(- spin +1/2) (- spin -1/2)

 Nuclear Spins in External Magnetic Field (B0)

a) Nuclear spins are oriented randomly in the absence of an

external magnetic field but
(b) have a specific orientation in the presence of an external
field, B0. Some of the spins (red) are aligned parallel to the
external field while others (blue) are antiparallel. The parallel
spin state is slightly lower in energy and therefore favored.
當氫核置於外加磁場 B0 中時，相對於外加磁場，氫核有兩種排列方向（兩種能階）
：
(1) 與外磁場平行，能量低，自旋量子數＝＋ 1/2;
E between Two Nuclear Spins

-1/2

+1/2
 Two Energy States
 The magnetic fields of the
spinning nuclei will align
either with the external radio-frequency
field, or against the field.
 Radio-frequency ( 無線電射 (spin -1/2)
頻 ) photon with the right
amount of energy can be
absorbed and cause the
spinning proton to flip.
(spin +1/2)
( 在外加磁場中，氫原子核能階產生分裂， α→β ，為能量的吸收，
由低能階向高能階躍遷，需要吸收能量 ( 共 對應無線電射頻的吸收
振 ) 。發生共振，所須吸收能量，對應於無
線電射頻。 )

13
Nuclear Magnetic Resonance (NMR)
 Resonance( 共振 ): the absorption of
electromagnetic radiation by a precessing nucleus
and the flip of its nuclear spin from a lower energy
state to a higher energy state
 氫原子核吸收無線電射頻能量，由低能階向高能階躍遷，
稱為共振。
 核磁共振條件 :
(1) 核有自旋 (1H or 13C ) (2) 有外加磁場 , 能階分裂 (3) 無線
電射頻能量對應於能階分裂能量
 The instrument used to detect this coupling of
precession frequency and electromagnetic
radiation records it as a signal

14
 Nuclear Magnetic Resonance Spectroscopy
 When exposed to a certain frequency of
electromagnetic radiation, oriented nuclei absorb
energy and causes a spin flip from a state of lower
energy to higher energy (Resonance 共振 )
 Nuclear magnetic resonance - Nuclei are in
resonance with applied radiation
 Frequency that causes resonance depends on:
 Strength of external magnetic field
 Identity of the nucleus (1H or 13C )
 Electronic environment of the nucleus
 核磁共振頻率 ( 共振能量 ) 影響因素 :
(1) 外加磁場強度 (2) 不同的核 (1H or 13C ) (3) 核周圍的電子環
境
 E , v and Magnet Strength B0
 Energy difference is proportional to the magnetic field
strength. 産生共振需吸收的能量與外加磁場強度成正比

E = h =  h B0
2
 E: Resonance energy

B0 :External Magnetic Field 外加磁場
  : Gyromagnetic ratio ( 迴轉磁比率 ), is a constant for
each nucleus (26,753 s-1gauss-1 for H).
  : Radio frequency or resonance frequency of a nucleus
 Low external magnetic field, low resonance energy,
low radio frequency.
• Hertz (Hz) 赫茲 : the unit in which radiation frequency is
reported; cycles per second 每秒周數
MHz: megahertz 百萬 , 1 million cycles per second 兆赫
16
 E, v and Magnet Strength B0
 The energy difference ΔE between nuclear spin states depends on the strength of the applied
magnetic field.
 Absorption of energy with frequency v is depends on the strength of the applied magnetic
field.

In a B0=14,092 gauss field, a E = 60 MHz photon is required to flip a proton.
B0=23,486 gauss, E = 100 MHz
B0=70,459 gauss, E = 300 MHz

 γ 
ν =   B0
 2π  -1/2
-1/2

+1/2
+1/2
 13.2 The Nature of NMR Absorptions
 Absorption frequencies differ across 1H and 13C
molecules
 Shielding effect 電子的遮蔽效應 : Opposing magnetic
field produced by electrons surrounding nuclei to
counteract the effects of an external magnetic field
 Effect on the nucleus is lesser than the applied magnetic
field
 Beffective = Bapplied – Blocal
 Individual variances in the electronic environment of
or Beffective
nuclei leads to different shielding = Bexternal - Bshielding
intensities

NMR 不但能偵測氫核，還可以區別不同氫核因為電子的遮蔽效應
 NMR Spectrum of H and C 1 13

(a) The 1H NMR spectrum and (b) the 13C NMR spectrum of methyl
acetate, CH3CO2CH3.
 Magnetic Shielding ( 電子的磁場遮蔽效應 )
 If all protons absorbed the same amount of energy in
a given magnetic field, not much information could be
obtained.
 But protons are surrounded by electrons that shield
them from the external field.
 Circulating electrons create an induced magnetic field
that opposes the external magnetic field. The result
is that the magnetic field at the nucleus is weaker than
the external magnetic field, we say the nucleus is
“shielded”.
( 氫核受周圍運動的電子影響。在外加磁場作用下，運動的電子産生與外加磁場方向相
反的感應磁場，產生遮蔽效應，使氫核實際受到的外加磁場作用減小 )
 
Beffective = Bapplied – Blocal or Beffective = Bexternal - Bshielding
 Magnetic Shielding

(Bexternal) (Bshielding)

Beffective = Bexternal - Bshielding

 Shielded Protons
Magnetic field strength must be increased for a
shielded proton to flip at the same frequency. 氫
核受電子的遮蔽效應的影響，共振需更強的外加磁場 ( 相
對於裸露的氫核 ) ，來抵消遮蔽的影響。

22
 Shielded Protons in a Molecule
 Depending on their chemical environment, protons in
a molecule are shielded by different amounts. 不同結構
的各種氫核， 周圍的電子雲密度不同，所受到的遮蔽影響也不同。
電子雲密度愈大，遮蔽影響愈大。
shielded H

deshielded H

Bexternal 較強
Bexternal 較弱
 the proton is “deshielded” somewhat by the
presence of the electronegative oxygen atom.
 在有機化合物中，不同結構各種氫核 周圍的電子雲密度不同
遮蔽效應不同吸收共振頻率有差異，即引起共振吸收峰的
位移，這種現象稱爲化學位移可以區別不同的氫 23
 Measurement of an NMR Spectrometer
 Organic sample dissolved in a suitable solvent is placed in
a thin glass tube between the poles of a magnet
 1H and 13C nuclei respond to the magnetic field by aligning

themselves to one of the two possible orientations .

 Constant rf irradiation and varied strength of the applied
magnetic field causes each nucleus come into resonance
at a slightly varied field strength

 Absorption of rf energy is monitored by a sensitive detector

thatNMR
displays signals as a peak h ，改變 B0 ， 讓 1H and 13C
測量，固定無線電射頻的
核在特定値發生共振
Operation of a Basic NMR Spectrometer

NMR 測量，固定無線電射頻的 h ，改變 B0

26
26
 NMR and IR Spectrometer
 Time taken by IR spectroscopy is about 10–13 s
(faster)
 Time taken by NMR spectroscopy is about 10–3 s
(slower)
 Provides a blurring effect 模糊效果 that is used in the
measurement of rates and activation energies of vary
fast processes
 13.3 Chemical Shifts
 The relative energy of resonance of a particular nucleus resulting
from its local electron shielding environment is called chemical
shift 化學位移
化學位移是描述遮蔽效應引起的共振頻率差異，所產生的吸收峰位置不同的現象
 The left segment of the chart is the downfield 低磁場
 Nuclei absorbing on the downfield have less shielding as they require
a lower field strength for resistance (deshielded)
 The right segment is the upfield 高磁場
 Nuclei absorbing on the upfield have more shielding as they require a
higher field strength for resistance (shielded)
 Chart calibrated versus a reference point 參考點 ,
set as 0, tetramethylsilane 四甲基矽烷 [TMS]

28
The NMR Chart: Upfield and Downfield

高磁場

低磁場

Chemical Shift (δ)

less shielding H more shielding H

氫遮蔽效應大，共振需要的磁場強度大，信號在高磁場出現
氫遮蔽效應小，共振需要的磁場強度小，信號在低磁場出現
29
 Tetramethylsilane (TMS)
 TMS 四甲基矽烷 is added to the sample as NMR reference
compound (TMS 為相對標準的參考化合物，化學位移 = 0) .
 Since silicon (1.9) is less electronegative than carbon (2.5),
the methyl group of TMS are electron rich, and TMS protons
are highly shielded (upfield).
 TMS signal defined as 0.00 ppm.
 Organic protons absorb downfield (to the left) of the TMS
signal.
 12 proton in TMS give one strong adsorption.

CH3 - 12 個氫等價，産生單一且強烈的吸收峰。
- TMS 氫電子密度大，遮蔽效應大，信號在高磁場區，不會
H3 C Si CH3
CH3 干擾其他的氫信號。
- 化學惰性，沸點低 (270C) ，易去除。
30
Tetramethylsilane (TMS)

31
 The Chemical Shift
 Chemical shift 化學位移 is the position on the chart at which a
nucleus absorbs. Measurement of the difference of the sample
signal and the reference signal
 The delta (δ) scale is used in calibration of the NMR chart
 1 δ = 1 part-per-million (ppm,1/106) of the spectrometer

operating frequency
Observed chemical shift (number of Hz away from TMS)
δ=
Spectrometer frequency in MHz
 Absorptions normally occur downfield of TMS, to the left on the
chart

32
 Chemical Shift
 Chemical shift () 化學位移 : the shift in ppm of an NMR
signal from the reference signal of TMS
 Measured in parts per million (ppm).
 Ratio of shift downfield from TMS (Hz) to total spectrometer
frequency (MHz).
 The delta scale is independent of instrument’s field strength
 Same value for 60, 100, or 300 MHz NMR machine.
 Called the delta () scale.
 TMS is defined as 0 ppm.

 在核磁共振光譜當中，具有不同電子化學環境的原子核由於遮蔽效應的
關係，在磁場中有不同的共振頻率，此共振頻率的差異稱為化學位移。
化學位移是描述遮蔽效應引起的共振頻率差異，所產生的吸收峰位置不
同的現象。

氫遮蔽效應大，共振需要的磁場強度大，訊號在高磁場出現，值小
氫遮蔽效應小，共振需要的磁場強度小，訊號在低磁場出現， 值大
 Delta () Scale
• The chemical shift (in ppm) is independent of the spectrometer
frequency used. 化學位移為一個獨立、不受外在磁場大小影響的數值

60 MHz

sample

300 MHz

sample

Chemical shift ()= 120 Hz = 2.06 = 2 ppm

60 x 10 6 Hz 10
600 Hz 2.0
Chemical shift ()= 300 x 10 6 Hz
=
10 6
= 2 ppm
 電子遮蔽效應和化學位移
• NMR 區別不同氫核 : 對於有機分子的全部氫質子在共同一磁場
強度，吸收本應只有一個信號，但實際不是這樣。
• 因為 H 的環境不一樣，核外電子對核有遮罩作用，電子運動產
生磁場必須抵消外磁場一部分，核磁場不等於外磁場 B0 ，比外
磁場 B0 少一些。其大小取決於電子密度，電子密度大，抵消外
磁場 B0 大 ( 遮蔽效應大 ) ，共振的外磁場 B0 增大，吸收峰出現
在高磁場。電子密度小，抵消小 ( 遮蔽效應小 ) ，共振的外磁場
B0 小，吸收峰出現在低磁場。
 The NMR Spectrum
more shielded proton (shielded) upfield
less shielded proton (deshielded) downfield

TMS

downfield upfield
低磁場 高磁場
 Protons in a Molecule
 Depending on their chemical environment, protons in a molecule are
shielded by different amounts. 結構中不同位置的各種氫核，因電子化學環境的
不同，周圍的電子雲密度不同，所受到的遮蔽影響也不同。電子雲密度愈大，遮蔽影
響愈大。
 The hydroxyl proton is not shielded as much as the methyl protons, so the hydroxyl
proton absorbs at a lower field than the methyl protons.

shielded H Bexternal 較強 upfield deshielded H

Bexternal 較弱

• the proton is “deshielded” somewhat by the downfield

presence of the electronegative oxygen atom.
在有機化合物中，不同位置各種氫核 周圍的電子雲密度
不同遮蔽效應不同吸收共振頻率有差異，即引起共振
37
吸收峰的位移，這種現象稱爲化學位移
 Chemical Shift
•A 300-MHz spectrum of methanol. The methyl protons absorb
at 3.4 (or 3.4 ppm), and the hydroxyl proton absorbs at 4.8
(4.8 ppm).
•Proton signals range from  0 to  10. 1H 訊號通常出現在 10
ppm 以內

intensity

Downfield 低磁場 Upfield 高磁場

less shielded more shielded
 值大  值小 38
 Analysis of NMR Signals
1
H NMR 能提供有機物的氫結構資訊
 The number of signals (peaks) shows how many
different types of protons are present.
吸收峰的數目：分子中氫的種類
 The location of the signals shows how “shielded”
or “deshielded” the proton is. 吸收峰的位置：吸收峰的
位移，每種氫所處的化學環境，遮蔽或去遮蔽。顯示官能基
 The intensity of the signal shows the number of
protons of that type. 吸收峰的強度 ( 面積 ) ：每種氫的數
目 ( 相對 )
 Signal splitting shows the number of protons on
adjacent atoms. 吸收峰的裂分數：相鄰碳原子上氫數
• 核磁共振光譜主要是判斷有機物的結構
•注意 : (1) 氫吸收峰的數量， (2) 吸收峰的位置， (3) 吸收峰的强度和 ( 4)
吸收峰的分裂 4 個重要資訊
 Number of Signals 氫吸收峰的數目
 Chemically Equivalent( 化學等價 ): equivalent hydrogens have
the same chemical shift.
 The same NMR signal

若分子中兩個氫，處於相同的化學環境，它們是化學等價，有相同的化學位
移。相同的 NMR 訊號。

H H
H C H O
C C
H H
H
C C
H H3C CH3
C
H H
H H
 Number of Signals

Methyl acetoacetate: three signals, three types of protons

 Number of Signals

Methyl t-butyl ether: two signals, two types of protons

13.4 Chemical Shifts in 1H NMR Spectroscopy
 Chemical shifts are due to the varied magnetic fields
produced by electrons surrounding nuclei
 Proton signals range from  0 to  10. 1H 訊號通常出
現在 10 ppm 以內
 Protons bonded to saturated, sp3-hybridized carbons
absorb at higher fields
 Protons bonded to sp2-hybridized carbons absorb at
lower fields
 Protons bonded to electronegative atoms absorb at
lower fields
 Regions of the 1H NMR Spectrum

 7 regions

downfield upfield

less shielded more shielded

Chemical Shifts in 1H NMR Spectroscopy

(alkane) 0~2
α
3~4
* (alcohol, ether, ester)

4~6
* (alkene)

 2~3
* (aromatic) 7.0~8.0 7~8
*
(ketone)
(aldehyde)
9~10
* *

*

3~4 * (acid) 11~12


7 regions
 Chemical Shift 影響化學位移的因素

 Chemical shift are affected by neighboring

substitutent
 Depends on (1) electronegativity of nearby atoms, (2)
diamagnetic effects from adjacent pi bonds

影響化學位移的因素 :
1. 相鄰原子的電負度
2. 相鄰 pi 電子產生誘導磁場
 Chemical Shift- Electronegativity
 More electronegative atoms deshield more and give larger shift values.

.
X in CH3-X
F OH Cl Br I
EN of X 4.0 3.4 3.2 3.0
2.7
Chemical shief of CH3-X() 4.3
與氫相連元素的電負度越強，拉電子作用越強，氫電子雲密度減 3.4 3.0 2.7 2.2
小，遮蔽作用減小，信號峰在低磁場出現，化學位移值變大。
electronegative  deshield  shift to downfield 
• Effect decreases with distance
CH3–CH2–CH2–CH3 CH3 – CH2 – CH2 – CH2 – Br
chemical 0.9 1.3 1.3 0.9 0.9 1.3 1.7 3.4
Shift
deshielded by Br : 0.0 0.0 0.4 2.5
當電負性元素與氫距離增大時，遮蔽作用大，化學位移值變小。
 Chemical Shift

• Additional
electronegative
atoms cause increase
in chemical shift
碳原子上拉電子基團越多，
信號峰在低磁場移動，則化
學位移值越大。

NMR solvent: CDCl3

Impurity CHCl3:  7.24
 Chemical Shift
• Electronegativity
electronegative  deshield  shift to downfield 
Electroneg- Chemical Shift ( ) of
C H3-X ativity of X Methyl Hydrogens

C H3 F 4.0 4.26
C H3 O H 3.5 3.47
C H 3 Cl O3.1 3.05
C H 3 B rR-CH2-O-C-R
2.8 2.68
C H3I 2.5 2.16
( C H ) Si
3 4
1.8 0.00 (by definition)

alcohol ester α to carbonyl

 O
  O
R-CH2-OH R-CH2-O-C-R
R-CH2-C-R

more electron-
3.5 4.0 2~3
withdrawing
 Aromatic Protons, 7-8
 The induced magnetic field of the circulating aromatic
electrons opposes the applied magnetic field along the
axis of the ring. The aromatic hydrogens are on the
equator of the ring, where induced field lines curve
around and reinforce the applied field (deshielding).

B0 =10092 Guass
60 MHZ

BI =0.5 Guass
B0 =10091.5 Guass
BI
60 MHZ
Absorbs at a lower field

pi 電子產生誘導磁場，氫位於誘導磁力線上的方向，與外磁場方向一致時 ，產
生加成作用，共振所須外加磁場減小 去遮蔽效應，低磁場區， 值大。
 Aromatic Protons, 7-8

• aromatic protons at 7.2

• methyl protons at 2.3
 Vinyl Protons, 5-6
Vinyl protons (– CC–H) are positioned on the
periphery of the induced magnetic field of pi
electrons. In this position, they are deshielded by
the induced magnetic field.

>

BI
>
 Aldehyde Proton, 9-10
The aldehyde proton are deshielded(1) by the induced
magnetic field of pi electrons and (2) by the electron-
withdrawing effect of the carbonyl group (C=O).
Electronegative
(2) oxygen atom

(1)

BI
 Acetylenic Protons, 2.5

The acetylenic (– CC–H) proton lies along the axis of
this field, which opposed the external field (shielding).

BI
B0 =10092 Guass
60 MHZ

BI = -1 Guass
> B0 =10093 Guass
60 MHZ
Absorbs at a higher field

pi 電子產生誘導磁場，氫位於誘導磁力線上的方向，與外加磁場方向相反時，產
生抵消作用，共振所須外加磁場增大 遮蔽效應，高磁場區， 值小。
 O-H and N-H Signals

 Chemical shift depends on concentration.

 Hydrogen bonding in concentrated solutions
deshield the protons, so signal is around 3.5
for N-H and 4.5 for O-H.
 Proton exchanges between the molecules
broaden the peak.
Carboxylic Acid Proton, 10+

• carboxylic protons at 

• methyl protons at 2.1
Common chemical shifts in the 1H-NMR Spectrum

(acid)
C H

CC–H

TMS

(alkene) (ketone) (alkane)

(aromatic)
C—H (sp3)
(aldehyde)
(alcohol, ester, ether)

Downfield upfield
(more shielded)
(less shielded)
13.5 Integration of 1H NMR Absorptions: Proton Counting

58
 Integration of 1H NMR Absorptions:
Proton Counting

• Methyl 2,2-dimethylpropanoate. Integrating the peaks have a

1:3 ratio, corresponding to the ratio of the numbers of protons
(3:9) responsible for each peak.

C6H12O2 4 spaces/12 H = 1 space / 3 H

59
* How Many Hydrogens?
When the molecular formula is known, each integral rise can be
assigned to a particular number of hydrogens.
a area= 6
O CH3
C6H12O2 area=3 b c  1.2
 2.2 CH3 C CH2 C CH3

OH
d
area=1
6 spaces/12 H = 0.5 space / 1 H area= 2
 2.6  3.8

吸收峰面積與同類氫數成正比，同時能知道不同類氫之間的相對比例。
當分子式已知時，可由吸收峰積分面積計算出吸收峰含氫的數目
 Analysis of NMR Signals
1
H NMR 能提供有機物的氫結構資訊
 The number of signals (peaks) shows how many
different types of protons are present.
吸收峰的數目：分子中氫的種類
 The location of the signals shows how “shielded”
or “deshielded” the proton is. 吸收峰的位置：吸收峰的
位移，每種氫所處的化學環境，遮蔽或去遮蔽。顯示官能基
 The intensity of the signal shows the number of
protons of that type. 吸收峰的強度 ( 面積 ) ：每種氫的數
目 ( 相對 )
 Signal splitting shows the number of protons on
adjacent atoms. 吸收峰的裂分數：相鄰碳原子上氫數
• 核磁共振光譜主要是判斷有機物的結構
•注意 : (1) 氫吸收峰的數量， (2) 吸收峰的位置， (3) 吸收峰的强度和 ( 4)
吸收峰的分裂 4 個重要資訊
 13.6 Spin-Spin Splitting in 1H NMR Spectra
 Multiplet 多重線 : Absorption of a proton that splits into
multiple peaks

called spin-spin splitting 自旋 - 自旋分裂

Caused by coupling of neighboring nuclear spins
 Coupling 偶合作用 : interactions between

nonequivalent protons on adjacent carbons

 The splitting is into one more peak than the number of
H’s on the adjacent carbon (“n+1 rule”)
 The set of peaks is a multiplet (2 = doublet, 3 = triplet, 4 =
quartet)
氫吸收峰的裂分數 (n+1) ：相鄰碳原子上氫數 (n)
氫吸收峰的分裂原因 : 自旋磁偶合，相鄰兩個氫核之間因自旋產生的磁
偶合作用
 Origin of Signal Splitting
 When the chemical shift of one nucleus is
influenced by the spin of another, the two are
said to be magnetically coupled 自旋磁偶合
 Consider nonequivalent hydrogens Ha and Hb
on adjacent carbons
 the chemical shift of Ha is influenced by
whether the spin of Hb is aligned with or
against the applied field

The two hydrogen on adjacent

Ha Hb
carbons, Ha and Hb , are coupled
C C
 Origin of Signal Splitting
 The signal of Ha is split into two peaks of equal
area (a doublet) by its nonequivalent neighbor Hb.

Ha
B’ Ha is influenced by the spin of Hb

ⱱ Ha signal split 
become a doublet
B0+B’ B0- B’

 ⱱ : Coupling constant 偶合常數 (Jab , Hz)

Proton NMR of 1,1,2-tribromoethane shows a triplet
of area 1 at 5.7 and a doublet of area 2 at 4.1.
Doublet: 1 Adjacent Proton

1 : 1
Triplet: 2 Adjacent Protons

22=4

1 : 2 : 1
 Simple Spin-Spin Splitting
Bromoethane

1 2
quartet triplet

2 1 1:3:3:1 1:2:1
Simple Spin-Spin Splitting
1 2

23=8 22=4

Bo

69
 Simple Spin-Spin Splitting

An adjacent CH3 group can have four different spin
alignments as 1:3:3:1
 This gives peaks in ratio of the adjacent H signal

An adjacent CH2 gives a ratio of 1:2:1
 The separation of peaks in a multiplet is measured
is a constant, in Hz
 Coupling constant (J) 偶合常數 : the distance

between peaks in a multiplet

多重峰的峰間距：偶合常數（ J ），用來衡量偶合作用的大小

70
 Coupling Constant
偶合常數
當自旋氫核存在自旋 - 自旋偶合時，核磁共振氫
吸收峰發生分裂。分裂峰間的距離稱為偶合常
數 ( 以 J 表示 ) 。單位為 Hz 。偶合常數顯示兩
個氫核間作用力大小，與外加磁場無關。
Spin-Spin Splitting in 1H NMR Spectra
 n + 1 rule: Protons that exhibit n + 1 peaks in
the NMR spectrum possess
 n = number of equivalent neighboring protons

5 Sextet 6 1:5:10:10:5:1
 Rules of Spin-Spin Splitting
1) Chemically equivalent protons do not show spin-spin
splitting

singlet singlet

2) The signal of a proton with n equivalent neighboring

protons is split into a multiplet of n + 1 peaks with a
coupling constant J
 Protons separated more than two carbon will not couple
 Rules of Spin-Spin Splitting
3) Two groups of photons coupled together have
the same coupling constant, J

para-methoxypropiophenone C10H12O2

J J
 Spin-Spin Splitting in 1H NMR Spectra
 It is possible to identify multiplets in a complex NMR
that are related
 Multiplets that have the same coupling constant can be
related
 Multiplet-causing protons are situated adjacent to each
other in the molecule
2-Bromopropane C3H7Br

septet doublet

J J
 Splitting for Ethyl Groups
NMR of ethylbenzene
-CH3 at 1.2, triplet
-CH2- at 2.6, quartet
The aromatic protons near 7.2, multiplet.
C8H10

76
 Splitting for Ethyl Groups
triplet
quartet

• The hydrogens on the CH3 are affected by the two neighboring hydrogens on the
adjacent CH2 group. According to the N+1 rule, the CH3 signal will be split into (2+1)
= 3. This is a triplet.
• The hydrogens on the CH2 group are affected by the three hydrogens on the
adjacent CH3 groups. The N+1 rule for the CH2 signal will be split into (3+1) = 4.
This is called a quartet.
 NMR of Ethyl Acetate 乙酸乙酯
 
C4H8O2

triplet
3
quartet
2
 Splitting for Isopropyl Groups
The isopropyl group appears as a characteristic pattern
1. a strong doublet at a higher field and a weak multiplet
(a septet) at a lower field.
C5H10O

septet doublet

79
Ethyl and isopropyl groups are
common. Learn to recognize
them from their splitting patterns.
 13.7 1H NMR Spectroscopy and Proton
Equivalence
 Proton NMR is much more sensitive than 13C and the
active nucleus (1H) is nearly 100 % of the natural
abundance
 Shows how many kinds of nonequivalent hydrogens
are in a compound
 Theoretical equivalence can be predicted by seeing if
replacing each H with “X” gives the same or different
outcome
 Equivalent H’s have the same signal while
nonequivalent are different
 There are degrees of nonequivalence
若分子中兩個氫，它們是等價的氫，有相同的化學位移。
若是不等價的氫，有不同的化學位移。
81
 Equivalent H’s 等價氫
 Two H’s that are in identical environments (homotopic 同類
) have the same NMR signal
 Test by replacing each H with X
 if they give the identical result, they are equivalent
 Protons are considered homotopic
6 equivalent H

82
 Nonequivalent H’s 不等價氫
 Replacement of each H with “X” gives a different
constitutional isomer
 Then the H’s are in constitutionally heterotopic
異類 environments and will have different
chemical shifts– they are nonequivalent
(unrelated) under all circumstances

83
Enantiotopic Distinctions
 If the hydrogens are homotopic but not identical,
substitution will form a new chirality center
 Hydrogens that lead to formation of enantiomers upon
substitution with X are called enantiotopic
 The H’s have the same NMR signal (in the
absence of chiral materials

* *
 Diastereotopic Distinctions
 If the hydrogens are neither homotopic nor
enantiotopic, substitution of a hydrogen with X at
C3 would form a second chirality center
 Diastereotopic hydrogens are distinct chemically
and spectrocopically, and show different NMR signal

* * *
* *
13.8 More Complex Spin-Spin Splitting Patterns
 Spectra can be more complex due to overlapping signals,
multiple nonequivalence
 In the spectrum of toluene (methylbenzene), the five aromatic ring
protons produce a complex, overlapping pattern though they are
not equivalent

C7H8

86
More Complex Spin-Spin Splitting Patterns
 Splitting of a signal by two or more
nonequivalent kinds of protons causes a
complication in 1H NMR spectroscopy
trans-cinnamaldehyde

1 3

1 3

2 2
Tree Diagram for the C2 proton of trans-cinnamaldehyde
 13.9 Uses of 1H NMR Spectroscopy
 The technique is used to identify likely products in
the laboratory quickly and easily
 NMR can help prove that hydroboration-oxidation of
alkenes occurs with anti-Markovnikov regiochemistry
to yield the less highly substituted alcohol

anti-Markovnikov product
89
H NMR Spectra of Cyclohexylmethanol
1

Fig(a) a –CH2- group shows a two-proton peak at 3.4

Fig(b) a –CH3 group shows a three-proton peak near 
90
 13.10 13C NMR Spectroscopy: Signal
Averaging and FT–NMR
 Carbon-13 is the only naturally occurring carbon isotope that
possesses a nuclear spin, but its natural abundance is 1.1%
 Signal averaging and Fourier-transform NMR (FT–NMR 傅立
葉轉換 NMR) help in detecting carbon 13
 Due to the excess random electronic background noise
present in 13C NMR, an average is taken from hundreds or
thousands of individual NMR spectra

 13C NMR 能提供有機物的碳結構資訊

 C-13 的含量相當小，故其訊號較弱，利用多次脈衝波方法，增強訊號
，才能產生明確的圖譜。此訊號信號是隨時間衰退的一個時間函數，
再經傅立葉轉換成頻率信號。
 Carbon-13 NMR Spectra of 1-Pentanol
Carbon-13 NMR spectra of 1-pentanol, CH3CH2CH2CH2CH2OH. Spectrum (a) is a
single run, showing the large amount of background noise. Spectrum (b) is an
average of 200 runs
 Interpreting 13C NMR
 The number of different signals indicates the
number of different kinds of carbon.
峰的數目：分子中碳的種類
 The location (chemical shift) indicates the type
of functional group. 峰的位置：峰的位移，每種碳所
處的化學環境，遮蔽或去遮蔽。顯示官能基

注意：碳吸收峰的數量，和吸收峰的位置
93
 C NMR Spectroscopy: Signal Averaging
13

and FT–NMR
 Spin-spin splitting is observed only in 1H NMR
 The low natural abundance of 13C nucleus is the
reason that coupling with adjacent carbons is
highly unlikely 13C 相鄰碳 - 碳的偶合不會產生
 Due to the broadband decoupling method 寬頻去氫
耦合方法 used to record 13C spectra, hydrogen
coupling is not seen
 each different kind of carbon gives a single, unsplit
peak
(broadband decoupling method 去除所有碳 - 氫的偶合， 每個
碳原子呈單一、未分裂吸收峰 )
13.11 Characteristics of 13C NMR Spectroscopy
 13C NMR provides a count of the different
carbon atoms in a molecule
 13C resonances are 0 to 220 ppm downfield

from TMS

13
C NMR 能提供有機物的碳結構資訊
Characteristics of 13C NMR Spectroscopy

 General factors that determine chemical shifts

 The electronegativity of nearby atoms
 The diamagnetic anisotropy of pi systems
 The absorption of sp3-hybridized carbons and
sp2 carbons

影響化學位移的因素 :
1. 相鄰原子的電負度
2. 相鄰 pi 電子產生誘導磁場
3. 原子的混成軌道
 Hydrogen and Carbon Chemical Shifts
 Most of 13C-NMR values for a carbon atom are
about 15 - 20 times the chemical shift of a proton
if it were bonded to the carbon atom.
H 10 ppm width
1

C 200 ppm width(15 - 20 times as large)

13
 Carbon-13 Spectra of 2-butanone

 Spectrum of 2-butanone is illustrative- signal

for C=O carbons on left edge

98
Carbon-13 NMR spectra of para-bromoacetophenone.
 Chemical Shift in Carbon-13 NMR

Ethyl acrylate

actural absorption:  14.1; 60.6 ; 128.5 ; 130.3 ; 160.0

13.12 DEPT 13C NMR Spectroscopy
 Improved pulsing 脈衝 and computational methods
give additional information
 DEPT-NMR (distortionless enhancement by
polarization transfer 無畸變極化轉移增强 )
 Normal spectrum shows all C’s then:
 Obtain spectrum of all C’s except quaternary (broad band
decoupled)
 Change pulses to obtain separate information for CH 2, CH
 DEPT method for determining the presence of
primary, secondary and tertiary carbon atoms

DEPT-NMR 區分一、二、三級碳

101
(tertiary carbon)
(secondary carbon)
(primary carbon)
spectra for 6-methyl-5-hepten-2-ol.
Part (a) is an ordinary broadband-decoupled spectrum, which shows signals for all
eight carbons.

3
8 7
2 4
5
1

7 6

6 5 4 3 2
8 1
DEPT–NMR spectra for 6-methyl-5-hepten-2-ol.
Part (b) is a DEPT-90 spectrum, which shows only signals for the two CH carbons

5 2

7
OH C2,C5  CH
6 4 2
5 3 1
8

H
H
DEPT–NMR spectra for 6-methyl-5-hepten-2-ol.
Part (c) is a DEPT-135 spectrum, which shows positive signals for the two CH and
three CH3 carbons and negative signals for the two CH2 carbons
8 7
1
5
2

4 3

7
OH

6 4 2
C2,C5  CH, positive
8
5 3 1 C1,C7,C8  CH3 , positive
H
C3,C4  CH2 , negaitive
H
13.13 Uses of 13C NMR Spectroscopy
 Helps in determining molecular structures
 Provides a count of non-equivalent carbons
 Provides information on the electronic
environment of each carbon and the number
of attached protons
 Provides answers on molecule structure that
IR spectrometry or mass spectrometry cannot
provide
13
C NMR Spectrum of 1-methylcyclohexane

• 7 carbon signals
• 1-methylcyclohexene has five sp3 resonances ( 20-50)
and two sp2 resonances  100-150

methylenecyclohexane
• symmetry
• 5 carbon signals
• three sp3 resonances ( 20-50) and two sp2 resonances  100-150
 Summary
 Nuclear magnetic resonance spectroscopy or
NMR is the most important spectroscopic
technique used in the determination of molecular
structure
 Magnetic nuclei such as 1H and 13C spin-flip from
a lower energy state to a higher energy state
when they absorb radiofrequency waves
 Each 1H or 13C nucleus possesses a unique
electromagnetic field that causes it to resonate at
different values of the applied field causing peaks
whose exact position is termed a chemical shift
Summary

 Delta (δ) is the unit of calibration in NMR

charts
 Tetramethylsilane (TMS) is a reference point
on the NMR chart
 TMS absorption that occurs at the right-hand
(upfield) side of the chart is assigned a value
of 0 δ
 Fourier-transform NMR (FT–NMR)
spectrometers are used to obtain 13C spectra
using broadband decoupling of proton spins