Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G.

Zagorski First Exam, January 28, 2011

Please answer the following questions in the spaces provided and use the extra sheets in the back for scrap paper. Besides a calculator, you are not allowed to use any other material during the exam. You have 50 minutes to complete the exam (9:30-10:20 am). NAME 1.

ANSWER KEY

Briefly define the following with either a small figure, chemical structure(s), or less than 10 words: (1) ESI, (2) CI, (3) base peak, and (4) a McLafferty rearrangement of acetone (20 points total).

ESI Electrospray Ionication (5 points) CI Chemical Ionization (5 points) Base Peak Peak representing the most abundant ion in the spectrum (5 points) Will not undergo a McLafferty rearrangement - (5 points)

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

2.

Briefly describe FIVE features about the MALDI and ESI techniques as applied to proteins (i.e., sensitivity range (such as mmol or pmol), accuracy range, simple spectrum (yes or no), etc.) (15 points)

3.

Assign an elemental formula for the following EI-MS data in the high mass region and label the M+, M+1, and M+2 peaks (15 points). m/e 130 131 132 133 134 135 Relative Abundance 1.0 2.0 100 10 0.65 0.03

M+ is 132, M+1 is 133, and M+2 is 134 (2 points each) C9H8O (9) points

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

4.

Write the structure for the molecular ion for the following three compounds showing the location of the radical cation (15 points).

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

5.

Shown below are MS spectral data for two unknown organic compounds (A and B). Determine the chemical structures for both compounds (7.5 points each), plus for compound A show the structure for the peaks at m/e 105 and 123, while for compound B show the structures for the peaks at m/e 222, 220, and 43 (35 points).

Compound A

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

Compound B

m/z

relative abundance

CH3CH2CH2+

CH3(CH2)9CH2Br79 CH3(CH2)9CH2Br81

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

Relative Isotope Abundances of Common Elements Relative Relative Relative Elements Isotope Abundance Isotope Abundance Isotope Abundance 12 13 Carbon C 100 C 1.11 1 2 Hydrogen H 100 H 0.016 14 15 Nitrogen N 100 N 0.38 16 17 18 Oxygen O 100 O 0.04 O 0.20 19 Fluorine F 100 28 29 30 Silicon Si 100 Si 5.10 Si 3.35 31 Phosphorus P 100 32 33 34 Sulfur S 100 S 0.78 S 4.40 35 37 Chlorine Cl 100 Cl 32.5 79 81 Bromine Br 100 Br 98.0 127 Iodine I 100 M M+1 M+2

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

Chem 325/425, Physical Methods of Organic Structure Determination, Prof. Michael G. Zagorski First Exam, January 28, 2011

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