Review for the Examinations: Sample Midterm

Winter, 2003

Spectral Interpretation

Given a proton nmr, a carbon nmr, or both, you should be able to suggest complete or partial structures which are consistent with the data. In addition to drawing these compounds or structural fragments, you should be able to write a coherent paragraph explaining the reasoning you used in your deduction. The exam will include the appropriate tables from the appendix of your text necessary to answer the questions, but you should know the general chemical shift regions shown in Figure 4.21.

Theoretical Background

Theory of nmr:
What are the four major pieces of information obtained from a proton nmr spectrum?
Why can't you obtain nmr spectra of ¹²C or ¹⁶O?
Why is the magnetic field necessary for nmr?
How does the nmr frequency vary with magnetic field strength?
How does the magnitude of the magnetogyric ratio affect the nmr spectrum?
What are three reasons that large magnetic fields are preferrred for nmr?
How does the energy difference in nmr compare with the energy of molecules at room temperature, and what are the consequences of this?
What is meant by "saturation?"
What is meant by precession of a nucleus, and what determines the precession frequency?
What is meant by "resonance?"
What is the origin of diamagnetic shielding of nuclei by surrounding electrons?
Why is the magnitude of diamagnetic shielding dependent upon the electronegativities of neighboring atoms?
What is the "chemical shift?"
What is the advantage of expresssing chemical shift in terms of d, rather than Hz? How can you calculate one from the other?
What are the typical ranges of d in carbon and in proton nmr?

Instrumentation:
Why are internal standards such as TMS added to samples?
What is the structure of TMS, and why is it a good standard?
Why is CDCl₃ the most common nmr solvent?
Why does a superconducting cryomagnet produce such a strong magnetic field?
What temperature is the magnet? How is it maintained at that temperature?
What is the temperature of the sample when it is in the magnet?
Why is the magnet filled with liquid nitrogen every week?
What are shim coils, and why are they necessary?
Why is the sample tube spun?
What frequency does our nmr use for proton spectra?
How can a monochromatic transmitter excite all of the protons at once?
What is meant by a "90^o pulse?"
What is meant by "relaxation?"
How does relaxation of nuclei generate a signal in the detector?
What is the FID, or interferogram?
Why does the detector substract the carrier frequency from the detected FID?
Why does adding multiple scans increase the signal-to-noise ratio?
How does the signal-to-noise ratio vary with the number of scans?
Why is it necessary to lock onto the solvent?
How does the solvent lock actually work?
What does a Fourier transform accomplish? Be rather specific about the inputs and the outputs.
What does the integration of the spectrum do?

Interpretation of Proton Spectra:
Where do “normal” methyl, methylene and methine protons occur? Why do they come in this order?
How does an electronegative substituent affect the chemical shift?
How does distance away from an electronegative substituent affect the chemical shift?
Why do alkene protons appear downfield?
Why do aromatic protons appear even farther downfield?
Why are aldehyde proton farther downfield than aromatic or alkene protons?
Why are alkyne protons farther upfield than alkenes?
Why are OH or NH chemical shifts variable?
What is the N+1 rule, and when does it apply?
What is the origin of spin-spin splitting?
Why do split peaks have intensities corresponding to Pascal’s triangle?
What is the coupling constant, and what units does it have?
Why are coupling constants independent of the magnetic field in the spectrometer?  
How do cis, trans and geminal coupling constants compare?
Why are high field nmr spectra often more simple to interpret than low field spectra?
Why don’t OH or NH protons show splitting?
Why is there only one peak in the spectrum for all the OH and NH protons?
How does the exchange rate of an OH proton affect the shape of the nmr peak?
What are second-order spectra, and when are they observed?
Why do alkanes often show second order spectra?
Why do alkenes and aromatic rings generally exhibit second order spectra?
What are diastereotopic protons, and what is the significane of this in nmr spectra?  
What is the nuclear Overhauser effect?

Carbon-13 Spectra:
What percentage of carbon atoms are ¹³C?
How does the magnetogyric ratio of ¹³C compare with that of ¹H, and what are the consequences of this?
Why do carbon-13 spectra require so many scans?
How do carbon-proton coupling constants compare with proton-proton coupling constants?
What is proton decoupling, and why is it used in ¹³C nmr?
Why are the chemical shifts so much larger in ¹³C nmr than in proton nmr?
Why aren’t the number of peaks in the nmr always the same as the number of carbon atoms in the molecule?
Why don’t carbon peaks overlap with each other as is seen in proton nmr?
Why isn’t integration reliable in ¹³C nmr?
Why are methyl peaks generally largest, and quaternary carbons generally smallest?
Why is the CDCl₃ signal a “triplet?”
You should be able to calculate expected chemical shifts using the tables in Chapter 5.

Infrared Spectroscopy
What are wavenumbers and how do you calculate them?
What range of wavenumbers does a typical IR spectrum cover?
What is the order of X-Ray, UV/Vis, IR, microwave, and radiofrequency in terms of increasing wavelength?
What type of bonds absorb energy in the IR region?
What information does IR give you?
What are typical absorption values for common functional groups?
What are fundamental absorptions?
What are overtones?
How do you calculate theoretical absorption frequencies?
What is the difference between a dispersive IR spectrophotometer and a FT-IR spectrophotometer?
What are the different ways to run IR samples?

Gas Chromatography-Mass Spectrometry
What is a mass spectrum?
What is GC-MS?
What is a quadrupole MS?
What is a base peak?
What is a molecular ion peak?
Describe the process by which a sample enters and exits the GC-MS.
How long does a radical cation need to exist to reach the detector?
What are the relative abundances of the Cl and Br isotopes?
What are meta stable ions?
What is the nitrogen rule?
How do different functional groups fragment?
What are commonly observed molecular fragments?
What is the McLafferty Rearrangement and how does it work?

Advanced NMR
How is a DEPT experiment done?
What are the results of a DEPT experiment?
What is a HETCOR experiment and what does it tell you?
What is a COSY experiment and what does it tell you?
What is a TOCSY experiment and what does it tell you?
What is a NOESY experiment and what does it tell you?
What is a COLOC experiment and what does it tell you?
What is an INADEQUATE experiment and what does it tell you?