1. TOPIC 9. STRUCTURE DETERMINATION (chapter 9 and part of chapter 2)

2. OBJECTIVES 1. Use combustion analysis to determine empirical formula.
2. Determine molecular weight (and molecular formula) from mass spectrometry.
2. Calculate number of rings and double bonds from molecular formula.
3. Determine functional groups present from infrared spectroscopy.
4. Use 1H and 13C NMR spectroscopy to identify other structural features.
5. Combine conclusions from individual techniques to determine the structure of organic compounds.
Problems in this section will be restricted to the following classes of aliphatic and aromatic compounds:
Alkanes, alkenes, alkynes, alkyl halides, alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, acyl chlorides, anhydrides, amides, amines, nitriles

3. COMBUSTION ANALYSIS CxHyOz + O2 xCO2 + (y/2)H2O ???
Measure mass of CO2 and H2O formed from a known mass of compound;
data cited as mass% of each element present. Generally do not measure mass%O.
e.g., C H O
Mass%
Mole Ratio =
Empirical formula
Be careful when rounding, elemental analyses provided ±0.4 mass% - do not round by more than 0.05 to 0.1. Multiply ratios before rounding.

4. EMPIRICAL AND MOLECULAR FORMULAS; DETERMINATION OF “SODAR”
Molecular formula is an integral number of times the empirical formula.
C2H4O
Sum of double bonds and rings (“SODAR”)
For C,H,O: (2#C + 2 – #H) / 2
For C,H,O,N,Hal: (2#C + 2– #H – #Hal + #N) / 2
Each Hal replaces a H
Each N adds an extra H
S,O: no effect on calculation
If SODAR calculated from empirical formula is not a positive
integral (or 0), this cannot be the molecular formula.
C2H4O MOLECULAR FORMULA COULD BE:
???

5. If SODAR ≥4: consider the possible presence of a benzene ring

6. MASS SPECTROMETRY Theory and Experiment M + e– (70 eV) M+ + 2e–
M lower mass ions

7. Data Available e.g., mass spectrum of ethane, CH3CH3 abundance
Ions also fragment, which can give further clues about the structure (beyond scope of this course).
Knowledge of molecular weight (from mass spec) and empirical formula (from combustion analysis) allows determination of molecular formula.
abundance
m/e

8. Empirical formula: C2H4O Mass spectrum: M+ m/e = 88
MOLECULAR FORMULA IS:
???

9. SPECTROSCOPY: THE INTERACTION OF LIGHT AND MATTER

10. INFRARED SPECTROSCOPY
Prob: 2.29,43,45,46
Molecular Vibrations: Stretching and Bending
Analogy to masses and springs:
Spring constant (strength) , Frequency, 
Masses  , 

11. Electromagnetic Radiation
E = hn c = ln
For molecular vibrations,
Frequency, n = 6 x 1012 to 1.25 x 1014 Hz
Wavelength, l = 50 to 2.5 mm
Define wavenumber,
= 200 to 4000 cm-1
Instrumentation Spectrum A simple scheme
sample
% transmittance
IR source
reference
detector
4000
600
wavenumber / cm-1

12. Selected Infrared Absorptions
Functional Group Range cm-1 Intensity and shape
sp3C─H medium to strong; sharp
sp2C─H medium to strong; sharp
spC─H about 3300 medium to strong; sharp
C═C weak to medium; sharp
C≡C weak to medium; sharp
N─H medium; broad
O─H (very dilute) about 3600 medium; sharp
O─H (H-bonded) strong; broad
O─H (carboxylic acid) medium; very broad
C─O medium to strong; sharp
C═O (aldehyde,ketone) very strong; sharp
C═O (ester) very strong; sharp
C═O (carboxylic acid) strong; sharp
C═O (amide) strong; sharp
C≡N medium; sharp

13. Validating resonance theory
C═O (ester) cm-1
C═O (amide) cm-1
Which is the stronger bond?
Can we understand this using resonance theory?

14. Infrared spectroscopy indicates the presence of particular bonds in a sample. The combination of bonds indicates which functional groups are present.
You do not need to memorize the data in Table 2.7 (or the previous slide) for this class. However, you must develop experience at interpreting IR spectra to be able to determine the presence of particular functional groups.
O-H
C=O
C-O 
Alcohol
Ether
Aldehyde or ketone
Ester
Carboxylic acid
4000
600
Wavenumber / cm-1

15. 4000 3000 2000 1500 1000 500 Hexane 100 50 Transmittance (%)
Wavenumber (cm-1)
Transmittance (%)
100 50

16. 4000 3000 2000 1500 1000 500 1-Hexene 100 50 Transmittance (%)
Wavenumber (cm-1)
Transmittance (%)
100 50

17. 4000 3000 2000 1500 1000 500 1-Hexyne 100 50 Transmittance (%)
Wavenumber (cm-1)
Transmittance (%)
100 50

18. 4000 3000 2000 1500 1000 500 Toluene 100 50 Transmittance (%)
Wavenumber (cm-1)
Transmittance (%)
100 50

19. Butyl methyl ether
Wavenumber (cm-1)
Transmittance (%)
100 50

20. 4000 3000 2000 1500 1000 500 1-Hexanol 100 50 Transmittance (%)
Wavenumber (cm-1)
Transmittance (%)
100 50

21. 4000 3000 2000 1500 1000 500 2-Hexanone 100 50 Transmittance (%)
Wavenumber (cm-1)
Transmittance (%)
100 50

22. 4000 3000 2000 1500 1000 500 Hexanoic Acid 100 50 Transmittance (%)
Wavenumber (cm-1)
Transmittance (%)
100 50

23. Methyl Propionate
Wavenumber (cm-1)
Transmittance (%)
100 50

24. Draw eight possible structures consistent with this data.
Wavenumber (cm-1)
Transmittance (%)
100 50
C4H8O2
Structure contains:
Draw eight possible structures consistent with this data.
???

25. Problem: C8H8O2. What functional group(s) is(are) present
Problem: C8H8O2. What functional group(s) is(are) present? What other structural features?
Wavenumber (cm-1)
Transmittance (%)
100 50
P-TOLUIC ACID

26. Problem: Determine the structure of the compound with the following empirical formula and IR spectrum.
Empirical formula: C4H8O
IR; peak at 1720 cm-1; no broad peak at 3300, no strong peaks at 1000 to 1200 cm-1, no strong peaks at cm-1

27. Important infrared adsorptions
COOH
3100
sp2C–H
1600 C=C
3500, O-H
C–O
2900 sp3C–H
1700
4000
600
Wavenumber / cm-1

28. HYDROGEN (PROTON) NUCLEAR MAGNETIC RESONANCE (1H NMR) SPECTROSCOPY
Nuclear Spin (1H, 13C, 19F, 31P) N S N N S S

29. The Energy of the Spin States of Hydrogen Nuclei in a Magnetic Fieldβ E
Bo=0 α Bo
The frequency ν required to flip the spin state from α to β is called resonance frequency

30. ...not much chemical information
An early 1H NMR spectrum
...not much chemical information
A modern 1H NMR spectrum
…lots of chemical information
absorption
E=hν
E=hν

31. If the applied magnetic field is held constant, the protons Ha and Hb absorb irradiation with different frequencies. Ha Hb E
The spectrum
absorption B hν

32. Preview: Types of Information available from a 1H NMR spectrum
A 1H nuclear magnetic resonance spectrum contains information about the:
(a) number of different types of proton
(b) relative number of each type of proton
(c) proximity to functional groups
(d) the number of adjacent protons

33. (a) The number of signals in the spectrum is the number of types of proton.
1H NMR spectrum of methane CH4
one peak  one type of proton
1H NMR spectrum of ethane CH3–CH3
absorption hν
absorption hν

34. Protons that are related to each other by a rotation or plane of symmetry are identical (chemical shift equivalent)

35. 1H nuclear magnetic resonance spectrum of methanol…
CH3–OH
two peaks  two types of proton
absorption hν

36. (b) The relative area of each peak (the integration) corresponds to the relative number of each type of proton
1H NMR spectrum of methanol
integral ratio :  ratio of types of proton
1H NMR spectrum of p-xylene
absorption hν
absorption hν

37. (c) The chemical shift indicates the environment of the proton
1H NMR spectrum of methanol
absorption
chemical shift,  /

38. Shielding and DeshieldingBo
Bind Ha
Bo-Bind Bo
shielded B
absorption hν

39. The d-scale d = x 106 [ppm] nproton - nTMS nTMS
The frequency at which a proton resonates is measured relative to the frequency for the protons of tetramethylsilane, TMS (which resonates at a relatively low frequency), and cited on the d (delta) scale in parts per million of the frequency at which TMS resonates.
d = x [ppm]
nproton - nTMS
nTMS

40. β α E Bo Field Strength TMS / Hz CH4 / Hz CH4 / ppm B / T
,000, ,000,100
,000, ,000,200
,000, ,000,300
- The resonance frequency (in Hz) depends on magnet strength.
- The chemical shift () is independent of magnet strength.

41. Effect of Structure on Chemical Shift (d scale, ppm)
CH3-CH3 CH3- N(CH3)2 CH3-OCH3 CH3-F
CH3-Cl
3.1
CH3-Br
2.7
CH3-I
2.2
CHCl3 CH2Cl2 CH3Cl hν E Ha
Bo-Bind Bo
Bo-Bind
shielded
deshielded B

42. You will be provided with a copy of Table 9. 1 on exams
You will be provided with a copy of Table 9.1 on exams. This provides approximate ranges for values of chemical shifts for particular types of protons. Remember that protons adjacent to two (or more) electron withdrawing groups will appear further downfield than a proton adjacent to only one.

43. δ=7.3 δ=5.3

44. Other peaks in spectrum:10
d / ppm 5
CDCl3
H2O
TMS

45. (d) The multiplicity of a signal indicates the number of adjacent protons
1H NMR spectrum of ethanol
S:9.8

46. Spin-Spin Coupling E Ha B
The magnetic field experienced by a proton is effected by the magnetic field generated by each adjacent proton. Bo
If Hb spin , need to apply larger E (=hn) to achieve resonance of Ha
If Hb spin , need to apply smaller E (=hn) to achieve resonance of Ha E
Bo+↓ Ha
Bo+ B

47. Bo
To achieve resonance of Ha
If Hb spins  + , need to apply higher n
If Hb spins  + , or,  +  signal appears at a
If Hb spins  + , need to apply lower n

48. Coupling is only observed between non-equivalent protons.
The signal for a proton with N adjacent equivalent protons will be split into a multiplet consisting of N+1 lines.
The relative area of each peak within a multiplet can be determined from Pascal’s triangle

49. Some Common Sets of Multiplets
Et–X a b
i-Pr–X a
t-Bu–X a X X X

51. Problems: How can you get a pentet?

52. Multiplets of Multiplets
Jab = Jbc Jab > Jbc

53. Geminal protons
Rings
Vinyl groups

54. Summary: Types of information available from 1H NMR spectrum
Number of signals Number of types of proton
Integral of signals Relative number of each type of proton
Chemical Shift Electronic environment
Multiplicity Number of adjacent protons

55. Problems: Predict the appearance (chemical shift, integral and multiplicity) of the 1H NMR signals of the following compounds.
(a) 2-butanone, CH3COCH2CH3
(b) methyl 3-chloropropanoate, ClCH2CH2CO2CH3

56. Problems: Provide structures consistent with the following data.
(a) Compound A: C2H4Cl2, one singlet in 1H NMR spectrum
(b) Compound B: C5H12O2, two singlets in 1H NMR spectrum

57. C4H6O2 SODAR = 1 IR: 1720 cm-1 » C=O no peak at 3300 cm-1 » no O-H
???
1H NMR

58. 13C NMR SPECTROMETRY Introduction 13C (not 12C) has nuclear spin
However, 13C is only present at 1.1% abundance
- Signals are weak
- Spectra usually acquired without multiplicity information
- Larger range of chemical shifts (0 to >200 ppm)

59. 200
150
100 50
d / ppm

60. Types of Information available from a 13C NMR spectrum
A 13C nuclear magnetic resonance spectrum contains information about the:
(a) number of different types of carbon
- Each peak corresponds to a different type of carbon
(b) type of carbons and proximity to functional groups
- Chemical shift provides information about the type of carbon present
Unlike 1H NMR spectra, simple 13C NMR spectra do not provide information about the:
relative number of each type of proton or
number of adjacent protons or carbons

61. USING DATA TO DETERMINE STRUCTURE
1. Write down conclusions from each individual technique
- Use combustion analysis to determine empirical formula, and mass spectrometry to give molecular weight (and molecular formula)
- Calculate number of rings and double bonds from molecular formula (SODAR)
- Determine presence of functional groups present from infrared spectroscopy.
- Use 1H and 13C NMR spectroscopy to identify other structural features.
2. Use these conclusions to determine the structure
3. Check your answer (predict the spectra; do your predicted spectra match the data provided?)

62. WORK PROBLEMS!!
In the remaining lectures we will cover problem solving approaches for determining organic structures from spectral (and other) information. Additional problem appear in the following sources:
Solomons
(just do the “easy” problems from this site. The answers to these problems are NOT available from this site; do not bother Prof. Smith. The answers to the easy problems, along with answers to the problems in these notes are posted on the “Notes and HWebs” page of the course web site)

63. USING SPECTRAL INFORMATION AND OTHER DATA TO DETERMINE THE STRUCTURE OF AN UNKNOWN COMPOUND
Elemental Analysis: C, 54.51; H, 9.09
Mass spectrometry: m/e M+, 88

64. Infrared Spectrum 100 50 absorbance - % 4000 3000 2000 1500 1000 500
absorbance - %
frequency – cm-1

65. 100 50
absorbance - %
frequency – cm-1

66. 13C NMR Spectrum
d / ppm

67. 1H NMR Spectrum

70. Bringing it all together

72. WORK AS MANY PROBLEMS AS POSSIBLE…

73. Elemental Analysis: C, 54.51; H, 9.09IR
100 50
Mass Spec
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
Methyl propionate

74. Elemental Analysis: C, 90.38; H, 9.47 Empirical Formula: C4H5
100 50
Mass Spec
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
2-lines
Ethyl benzene

75. Empirical Formula: C5H7 Mass Spec: M+ m/e= 134 IR 13C NMR 1H NMR
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
P-diethylbenzene

76. Empirical Formula: C5H5O Mass Spec: M+ m/e= 162
100 50
H2O
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
P-diacetylbenzene

77. Empirical Formula: C5H10O2 Mass Spec: M+ m/e= 102
100 50
H2O
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
Propyl acetate

78. Empirical Formula: C4H10O Mass Spec: M+ m/e= 74
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
1-butanol

79. Empirical Formula: C6H14O Mass Spec: M+ m/e= 102
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
1,3-propanediol

80. Empirical Formula: C3H8O2 Mass Spec: M+ m/e= 76
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
1,3-propanediol

81. Empirical Formula: C8H9Cl Mass Spec: M+ m/e= 140 and 142 (3:1 ratio)
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
2-lines
1-chloro-2-phenylethane

82. Empirical Formula: C7H9N Mass Spec: M+ m/e= 107
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
P-toluidine

83. Empirical Formula: C7H9N Mass Spec: M+ m/e= 107
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
N-methyl aniline

84. Empirical Formula: C4H4O Mass Spec: M+ m/e= 136
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
2-lines
P-toluic acid

85. Empirical Formula: C8H9Br Mass Spec: M+ m/e= 184 and 186 (1:1 ratio)
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
2-lines
1-bromoethylbenzene

86. Empirical Formula: C4H5O Mass Spec: M+ m/e= 138
100 50
transmittance
Wavenumber / cm-1
13C NMR 1H NMR
P-methoxy benzyl alcohol

87. CHAPTER 9 ON EXAM 5 Types of Questions
- Use data from elemental analysis, infrared spectroscopy and nuclear magnetic resonance spectrometry (1H and 13C) to determine the structure of organic compounds.
- In class assignment
- Take home assignment (more complex problems)
Preparing for Exam 4:
- Work as many problems as possible.
- Work in groups.
- Do the “Learning Group Problem” at the end of the chapter.
- Work through the practice exam