09/09/2014

NUCLEAR  SHIELDING  

  CHEMICAL  SHIFT:   Induced magnetic field

screens the nucleus from

Beff  =  Bo  -­‐  σBo    =  (1-­‐  σ)Bo  
NMR   Where  σ  =  shielding    
external magnetic field.

PARAMETERS   constant.

 CHEMICAL  SHIFT  (δ)

THE  SHIELDING  EFFECT  

NMR  Signal  of:    CHBr3  is      90,000,614  Hz  
ν1 = (γ/2π) (1- σ) Bo
       CH2Br2  is  90,000,  441  Hz  
       CH3Br  is  90,000,237  Hz  
Nuclei that are chemically nonequivalent
       TMS    90,000,000  Hz  
are shielded to different extends and give
 
separate resonance signals in the spectrum.
σ(CHBr3)  <  σ(CH2Br2)  <  σ(CH3Br)  <  σ(TMS)  

Αt  1.41  T  magneUc  field,  proton  absorpUon  
frequencies  spread  over  700  Hz.

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Low field
High field

SHIELDING  OF  NUCLEI  

Less shielded
More shielded

TETRAMETHTLSILANE  (TMS)   OTHER  NMR  STANDARDS  

Si(CH3)4  
•  Chemically  inert         Sodium 2,2-dimethyl-2-silapentane-5-sulfonate (DSS)



•  MagneUcally  isotropic   (CH3)2SiCH2CH2CH2-SO3-Na+ Reference for aqueous

•  VolaUle  (b.p.  27oC)  

Solvents.

•  Soluble  in  most  organic  solvents  

•  Gives  a  sharp  single  absorpUon  peak   For 19F, CFCl3 or one of freons






O

•  Absorbs  at  higher  field  than  almost  all  organic   For 13C, TMC, CS2, C6F6 or CH3O-C-OCH3

compounds  
•  Insoluble  in  H2O  and  D2O  

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CHEMICAL  SHIFT  (δ)   CHEMICAL  SHIFTS  OF  1H  

 ν  -­‐  ν  
δ  =    amples       reference  x  106  
               νreference  
 
 
 
 
δ (CHCBr3)  = (641/90 x  106)  106  =  6.82  ppm  
   
 

1H chemical shifts of protons in organic compounds spread over 12 ppm

CHEMICAL  SHIFT  OF  13C   FACTORS  AFFECTING  CHEMICAL  

SHIFT  
•  Local  diamagneUc  shielding  (σdia)  
•  Non-­‐spherical  paramagneUc  shielding  (σpara)  
•  MagneUc  anisotropy  of  neighboring  groups  
(σN)  
•  Ring  current  effects  (σR)  
•  Electric  field  effects  (σe)  
•  Intermolecular  interacUons  e.i.  H-­‐bonding  &  
13C chemical shifts in organic compounds spread over 230 ppm

solvent  effects(σi)  
•  (σ) = σdia  +  σpara  +  σN  +  σR  +  σe    +  σi  

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CHEMICAL  SHIFT  (δ) OF  HYDROGEN  

LOCAL  DIAMAGNETIC  SHIELDING   ATTACHED  TO  CARBON  
1H  CHEMICAL  SHIFTS  OF  HALOMETHANES    

Molecule:  HybridizaUon  Chemical  shif  

Halomethane            δ (ppm)        Elect.  NegaUvity   Akanes:    sp3            0.5-­‐1.5  δ    
 CH3F    4.26      4.00   Alkynes:    sp            2.5-­‐3.1  δ  
 CH3Cl    4.05      3.00   Alkenes:    sp3            4.6-­‐5.7  δ  
 CH3Br    2.68      2.80   Benzene:    sp3            6.0-­‐9.0  δ  
 CH3I    2.16      2.50   Aldehyde:    sp2            9.5-­‐10.5  δ

LOCAL  SHIELDING  (1H)   MAGNETIC  ANISOTORPY  OF  

NEIGHBORING  GROUPS  (σN)  
•  Chemical  bonds  are  magneUcally  anisotropic.  
Thus  induced  magneUc  fields  are  not  equal  in  
all  direcUons.    
•  The  shielding  of  a  nucleus  depends  on  its  
geometric  posiUon  in  relaUon  to  the  rest  of  the  
molecule.  
•  (σN)  =  (1/3r34π)(χpar.-χper.)(1-­‐3cos2θ)

 When  θ = 54.7ο, (σN)  =  0    

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DESHIELDING  EFFECT  OF  DOUBLE  

ANISOTROPIC  EFFECT  
BOND  
The anisotropic effect of a

neighboring dipolar field

is a function of:

a.  Distance of the nucleus


From the point dipole center

b.  The angle θ between the


line joining this center to the


observed nucleus and the


direction of the induced


magnetic field.

DESHILDING  OF  ALKYNYL  HYDROGEN  

DESHIELDING  OF  CARBONYL    

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DESHIELDING  OF  RING  CURRENT  EFFECT   CYCLOHEXANE  PROTONS  

Axial protons

are shielded

Equatorial protons

are dishielded

The difference maybe

between 0.1 to 0.7 ppm

DESHIELDING  IN  [18]  ANNULENE  

C H3

Inner protons:

-1.8 δ

C H3

Outer protons

8.9 δ

δ(CH3) = -4.25

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1H  CHEMICAL  SHIFTS  OF  ARENES  

Mesomeric effects

Mesomeric efffects

AROMATIC  MESOMERIC  EFFECTS  ON   13C  CHEMICAL  SHIFTS  IN  PYRIDINE  

13C  ATOMS  

NH2 NO2 136.0

146.7 148.4 123.5

115.1 123.6
149.9
N

129.3 129.4

134.6
118.5
N N N

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1H  CHEMICAL  SHIFTS  OF  

 -­‐OH,  -­‐SH  &  -­‐NH   HYDROGEN  BONDING  

2.46ppm

CH3 O
Influenced by:

C
-concentration
H 12.05 ppm
14.5 ppm

-solvent
H
-temperature
O
-impurities (mainly H2O)
O O

C H3 C C C H3

CH

CARBOXYLIC  ACIDS   COMMON  NMR  SOLVENTS  

 Since  most  organic  solvents  contain  hydrogen  
O H O atoms,  they  will  inter  fear  with  the  peaks  from  
the  samples.  Thus  NMR  solvents  are  
R-C C-R deutorated  since  D2  does  not  show  any  band.  
 CDCl3  D2O    
O H O  C6H6  CCl4  

             O      
δ = 10.5 - 12.0 ppm

CD3CCD3    
               O  

 CD3SCD3    

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1H  CHEMICAL  SHIFTS  OF  ALKANES  

SOLVENT  EFFECTS  
CCl4 Nonpolar



d6-DMSO Polar



C6D6 magnetically

anisotropic

1H  CHEMICAL  SHIFTS  OF  ALKYNES  

1H  CHEMICAL  SHIFTS    

OF  ALKENES    

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1H  CHEMICAL  SHIFTS  OF  ALDEHYDES   13C  CHEMICAL  SHIFTS  OF  ALKANES  

13C  CHEMICAL  

SHIFTS  OF    
PROPANE    
DERIVATIVES  
α effect: increases with electro


negativity

β effect: always a deshielding


effect

γ effect: increase in shielding

due to steric interactions

13C δ value of CI4 = -292.2

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13C  CHEMICAL  SHIFTS  IN  ALKENES  

13C-­‐CHEMICAL  SHIFTS  

IN  SUBSTITUTED  
ETHYLENES  

+
_

H3C-O=C1H-C2H2

High shielding is due to resonance

effect of the -OR group.

13C-CHEMICAL SHIFTS OF ARENES

13C-CHEMICAL SHIFTS IN SUBSTITUTED
BENZENE DERIVATIVES

δ Range between 120-140

Variations in the chemical shifts values is in accordance

With the inductive and resonance effects of the groups

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13C-CHEMICAL SHIFTS OF ALDEHYDES AND

13C-CHEMICAL SHIFTS OF ALKYNES

KETONES

13C-CHEMICAL SHIFTS OF ACETIC ACID

13C-CHEMICAL SHIFTS OF a- SUBSTITUTED ACETIC ACID
DERIVATIVES

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INTEGRATION HYDROGEN SIGNALS OF

ETHYLBENZENE

INTEGRATING NMR SPECTRUM

The  relaxaUon  Umes  of  hydrogen  atoms  in  

organic  compounds  are  about  the  same.  
Thus,  the  areas  under  the  NMR  signals  are  
proporUonal  to  the  number  of  equivalent  
protons  of  each  type  in  the  molecule.  

H3 C CH3

H3 C CH3
DETERMINATION OF HYDROGEN
DEFICIENCY

Hydrogen deficiency = # of Carbon atoms +

- 1/2 # of hydrogen atoms





- 1/2 # of halogen atoms





+ 1/2 # of Nitrogen atoms

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O
H3 C CH3
CH2

O
CH3-O-C-CH2 Cl

O H3 C H
C=C
H3 C C(CH3)3

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