Professional Documents
Culture Documents
Theory of NMR
The positively charged nuclei of certain elements (e.g., 13C and 1H) behave as tiny magnets. In the presence of a strong external magnetic field (Bo), these nuclear magnets align either with ( ) the applied field or opposed to ( ) the applied field.
Bo
The latter (opposed) is slightly higher in energy than aligned with the field.
Energy
DE is very small
Theory of NMR
The small energy difference between the two alignments of magnetic spin corresponds to the energy of radio waves according to Einsteins equation E=hn.
hn
Application of just the right radiofrequency (n) causes the nucleus to flip to the higher energy spin state Not all nuclei require the same amount of energy for the quantized spin flip to take place. The exact amount of energy required depends on the chemical identity (H, C, or other element) and the chemical environment of the particular nucleus.
Theory of NMR
Our departments NMR spectrometer (in Dobo 245) has a superconducting magnet with a field strength of 9.4 Tesla. On this instrument, 1H nuclei absorb (resonate) near a radiofrequency of 400 MHz; 13C nuclei absorb around 100 MHz.
e Nuclei are surrounded by electrons. The strong applied magnetic field (Bo) induces the electrons to circulate around the nucleus (left hand rule).
Bo
(9.4 T)
Theory of NMR
The induced circulation of electrons sets up a secondary (induced) magnetic field (Bi) that opposes the applied field (Bo) at the nucleus (right hand rule).
Bi
e-
Bo
We say that nuclei are shielded from the full applied magnetic field by the surrounding electrons because the secondary field diminishes the field at the nuclei.
Theory of NMR
The electron density surrounding a given nucleus depends on the electronegativity of the attached atoms. The more electronegative the attached atoms, the less the electron density around the nucleus in question. We say that that nucleus is less shielded, or is deshielded by the electronegative atoms. Deshielding effects are generally additive. That is, two highly electronegative atoms (2 Cl atoms, for example) would cause more deshielding than only 1 Cl atom.
H H C H H H H C Cl H
C and H are deshielded
H H C Cl Cl
C and H are more deshielded
Chemical Shift
We define the relative position of absorption in the NMR spectrum the chemical shift. It is a unitless number (actually a ratio, in which the units cancel), but we assign units of ppm or (Greek letter delta) units. For 1H, the usual scale of NMR spectra is 0 to 10 (or 12) ppm (or ). The usual 13C scale goes from 0 to about 220 ppm. The zero point is defined as the position of absorption of a standard, tetramethylsilane (TMS): CH3 This standard has only one type CH3 Si CH3 of C and only one type of H. CH3
Chemical Shifts
Proton Chemical Shift ( ) vs. Electronegativity
5
CH3 F
CH3 O
H1 Chemical Shift
CH3 N
CH3 C
3.5
4.5
Electronegativity
Chemical Shifts
Both 1H and 13C Chemical shifts are related to three major factors:
The hybridization (of carbon) (lai ha ca cacbon) Presence of electronegative atoms or electron attracting groups(s c mt ca cc nguyn t c m in cao v nhm ht in t) The degree of substitution (1, 2 or 3). These latter effects are most important in 13C NMR, and in that context are usually called steric effects. (hiu ng lp th)
1H
Chemical Shifts
C H C C O C X CH3 CH3 CH2 H H Ar CH3 CH TMS
O C OH
O C C H Aromatic H C C H O
C C H 4 3 upfield 2 1 0
12
11
10
8 downfield
7 6 5 1H Chemical shift ()
Classification of Protons
To interpret or predict NMR spectra, one must first be able to classify proton (or carbon) environments. Easiest to classify are those that are unrelated, or different. Replacement of each of those one at a time with some group (G) in separate models creates constitutional isomers.
G CH3CH2CH2CH3: CH3CH2CHCH3 G CH3CH2CH2CH2
These protons have different chemical shifts. This classification is usually the most obvious.
Classification of Protons
Homotopic hydrogens are those that upon replacement one at a time with some group (G) in separate models creates identical structures.
G CH3CH2CH2CH3: CH3CH2CH2C H H CH3CH2CH2C H G H CH3CH2CH2C H H G
Homotopic protons have the same chemical shifts. We sometimes call them identical. Methyl hydrogens will always be in this category (because of free rotation around the bond to the methyl carbon). Molecular symmetry can also make protons homotopic.
Classification of Protons
If replacement of one hydrogen at a time in separate models creates enantiomers, the hydrogens are enantiotopic.
G CH3CH2CH2CH3: CH3CH2 C CH3 CH3CH2 H H C CH3 G
Classification of Protons
If replacement of hydrogens in separate models creates diastereomers, the hydrogens are diastereotopic.
H CH3 C H C CH3 H G C C CH3 G CH3 C H C CH3
CH3
H Br
H Br
H Br
Diastereotopic protons have different chemical shifts. Usually, in order to have diastereotopic protons, there has to be a stereocenter somewhere in the molecule. However, cis-trans alkene stereoisomers may also have diastereotopic protons.
1H
NMR Problems
2 environments
CH3 CH3OCH2CH2CHCH3
CH3 CH3OCH2CH2CHCH3
5 environments
CH3
CH3
H H C C
CH3 C C H C C H
4 environments
H
1H
NMR Problems
CH3 C C CH3 H CH3 CH3 CH3 C C H CH3
4 environments
CH3CH2 C C H
CH2CH3 H
CH3CH2 C C H
CH2CH3 H
O CH3CCH3
OCH3
CH3
O CH3COCH3
Multiplets
Consider the ethyl group in chloroethane CH3CH2Cl. The methyl protons experience a magnetic field that is somewhat influenced by the chlorine on the adjacent carbon, but is also affected slightly by the nuclear spin states of the adjacent methylene (CH2) protons. The two CH2 protons can have the following possible combination of spins: magnetic field
two spin up (1 way) one up and one down (2) two spin down (1)
Multiplets
The magnetic field experienced by the CH2 protons in chloroethane (CH3CH2Cl) is mainly influenced by the electronegative chlorine. However, it is slightly perturbed by the spin states of the three methyl (CH3) protons on the adjoining carbon They have four possible combinations of spins:
Three spin up (1 way) Two up and one down (3) Two down and one up (3) Three spin down (1)
Spectrum of chloroethane
Putting the multiplets together gives the predicted spectrum. CH The pattern of a downfield quartet CH and an upfield triplet is typical of the presence of an ethyl group in the molecular structure. Note that the triplet is larger than the quartet. That is because 4 3 2 there are 3 protons giving rise to the triplet, and only 2 protons CH3CH2Cl giving rise to the quartet. The integrated signal areas are in a 3:2 ratio.
2 3
TMS
1H
NMR Problems
singlet singlet
Predict the splitting patterns (multiplets) for each proton environment in the following:
CH3CHBr2
doublet doublet
CH3OCH2CH2Br
ClCH2CH2CH2Cl
O CH3 CH3CH2COCHCH3
The Integral
Integration is performed to determine the relative number of protons in a given environment. The number is set at 1, 2 or 3 for a given peak, then the areas of the other signals are reported relative to that one. The integral should be rounded to the nearest whole number; after all, there is either 1, or 2, or 3 protons in a certain environment, never a decimal fraction. Our spectrometer prints the integral below the spectrum written sideways and in red.
CH3
CH3
O CH3COCH2CH3
OCH2
CH3
(2H)
(3H) (3H)
CH3
OCH2
CH3 CH3
O CH3CH2COCH2CH3
OCH2 CH2
CH3 CH3
OCH2
CH2
.
ethylC butanoate 6H12O2
O CH3CH2CH2COCH2CH3
CH3
CH3
CH3
CH3
O CH3CCH2CH3
CH2
CH3
CH3
CH2
CH3
H O
H H H
H H
CH3C H H
CH3
H C
H H H
C C H
C C
H H
CH3CH2CH2OH
CH3
CH2 CH2 O
OH
CH3
CH2 CH2 O
OH
CH3
CH3CH2CH2CH2OH
CH2
CH2 CH2
OH
CH3
CH2
O CH2
OH
CH2
CH3CH2CH2CH2CH2OH
CH2
CH2
OH
CH2
O CH2
OH
CH3
CH3
CH3 H H H H H
H H H other Hs
CH3
H H H
other Hs
CH3
CH3CH2CH2Br
CH2 CH2
CH3 CH2
CH2
2-methyl-1-hexene
CH2 CH3
CH2
CH3 CH3
CH2CH2CH2CH3
CH2 CH2 CH2
CH3
1-octene
CH2CH2CH2CH2
CH2
C8H16 CHCH2CH2CH2CH2CH2CH3
H H H
C10H14 (sec-butylbenzene)
H Aromatic Hs
CH3 CHCH2CH3
H