qualitative organic analysis – ch 351 nmr...

74
Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela Torok Department of Chemistry University of Massachusetts Boston Boston, MA

Upload: vandieu

Post on 04-Oct-2018

223 views

Category:

Documents


1 download

TRANSCRIPT

Page 1: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

Qualitative Organic Analysis –CH 351

NMR Spectroscopy

Bela TorokDepartment of Chemistry

University of Massachusetts BostonBoston, MA

Page 2: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

2

Page 3: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

Theoretical base of NMR spectroscopy

General Aspects

3

Page 4: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Theoretical base of NMR spectroscopy

4

Page 5: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Theoretical base of NMR spectroscopy

Page 6: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Schematic diagram of an NMR spectrometer

6

Page 7: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Handling

7

Page 8: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Magnetic field

8

Page 9: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Pulsed NMR

9

Page 10: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Relaxation

Spin-Lattice Relaxation (longitudinal or T1)

10

Page 11: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Relaxation

Spin-Spin Relaxation (T2)

11

Page 12: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

Shielding

12

Page 13: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects

NMR active nucleii (elements)

Odd number of protons and/or neutrons

(strongly depends on natural abundance)1H , 2H (3H)13C15N18O check!19F31P

and many others

13

Page 14: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Equivalent vs. Nonequivalent nucleii

14

Page 15: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Equivalent vs. Nonequivalent nucleii

15

Page 16: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Equivalent vs. Nonequivalent nucleii

16

Page 17: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Equivalent vs. Nonequivalent nucleii

17

Page 18: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Equivalent vs. Nonequivalent nucleii

18

Page 19: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Equivalent vs. Nonequivalent nucleii

19

Page 20: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

Chemical Shift

General Aspects – 1H NMR Spectroscopy

20

Page 21: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shiftδ = dist. down field from TMS (Hz) / op. frequency (MHz)

21

Page 22: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

22

Page 23: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

23

Page 24: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

24

Page 25: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

25

Page 26: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – Mass Analyzers General Aspects – 1H NMR Spectroscopy

Chemical Shift

26

Page 27: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

27

Page 28: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR SpectroscopyChemical Shift

28

Page 29: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

29

Page 30: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

30

Page 31: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

Diamagnetic anisotropy

31

Page 32: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift

Diamagnetic anisotropy

32

Page 33: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift Diamagnetic anisotropy

33

Page 34: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift Diamagnetic anisotropy

34

Page 35: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Chemical Shift Diamagnetic anisotropy

35

Page 36: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Integration

36

Page 37: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Integration

37

Page 38: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Integration

38

Page 39: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Integration

39

Page 40: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling splitting of the signals

40

Page 41: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling splitting of the signals

N+1 rule

(2I+1 in general)

41

Page 42: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling splitting of the signals

42

Page 43: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

43

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

Page 44: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

44

Page 45: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

45

Page 46: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

46

Page 47: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

47

Page 48: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling long range splitting

48

Page 49: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

49

Page 50: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

50

Page 51: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

51

Page 52: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

52

Page 53: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

53

General Aspects – 1H NMR Spectroscopy

Geminal Coupling Spin-Spin Coupling

Page 54: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

54

Page 55: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

Page 56: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

Page 57: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

Page 58: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling

Page 59: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling – Coupling Constant

Page 60: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling – Coupling Constant

Page 61: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling – Coupling Constant

Page 62: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling – Coupling Constant

Page 63: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling – Splitting Diagram

Page 64: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling – Splitting Diagram

Page 65: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling – Splitting Diagram

Page 66: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Spin-Spin Coupling – Splitting Diagram

Page 67: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Enantiotopic hydrogens

Page 68: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Diastereotopic hydrogens

Page 69: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Diastereotopic hydrogens

Page 70: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Time dependence - slow method

Page 71: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Time dependence - slow method

Page 72: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Time dependence - slow method

Page 73: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

Effect of the medium

General Aspects – 1H NMR Spectroscopy

Page 74: Qualitative Organic Analysis – CH 351 NMR Spectroscopyalpha.chem.umb.edu/chemistry/ch351/files/Overheads/NMR... · Qualitative Organic Analysis – CH 351 NMR Spectroscopy Bela

General Aspects – 1H NMR Spectroscopy

Resolution of spectra