UNIVERSIDAD DE LA AMAZONIA/ FACULTAD DE CIENCIAS BÁSICAS/ PROGRAMA DE QUÍMICA

ESPECTROSCOPÍA / TALLER DE ESPECTROMETRÍA DE MASAS

1. Propose the fragmentation mechanism of the following compound

2. Propose the fragmentation mechanism of the following compound.

3. Propose the fragmentation mechanism of the following compound

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4. Propose the fragmentation mechanism of the following compound

5. The Compound 1 is a volatile liquid (boiling point 56˚C) that is used as a common organic solvent. The Mass and IR
spectra, are given below. Elemental Analysis: C, 62.04; H, 10.41; O, 27.55

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6. The Compound 3 is a liquid, boiling point 136 ˚C. The Mass and IR spectra, are given below. Elemental Analysis: C,
90.51; H, 9.49.

7. The Compound 4 is a low-boiling hydrocarbon (boiling point 41˚C), that reacts with bromine in CCl4 to yield a 1,2-
dibromide. The Mass and IR spectra, are given below. Elemental Analysis: C, 85.63; H, 14.37.

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8. The Compound 5 is a liquid, boiling point 124˚C. The Mass and IR, are given below. Elemental Analysis: C, 73.63; H,
12.36; O, 14.01.

9. The Compound 6 is a liquid, boiling point 130˚C. The Mass and IR, are given below. Elemental Analysis: C, 64.02; H,
4.48; contains halogen.

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10. The Compound 9 is a high-boiling liquid (boiling point 201˚C), that reacts with alkoxide to yield an ether. The Mass,
and IR, are given below. Elemental Analysis: C, 49.16; H, 4.13; contains halogen.

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11. The Compound 18 is a high-boiling liquid (boiling point 256˚ C) which is slightly soluble in water. The Mass and IR
spectra, are given below. Elemental Analysis: C, 71.03; H, 7.95; O, 21.03.

12. The Compound 21 is a liquid (boiling point 60˚ C) that has Z stereochemistry. The Mass and IR spectra, are given
below. Elemental Analysis: C, 25.04; H, 1.05; contains two moles of a halogen.

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13. The Compound 32 is a high-boiling neutral liquid that contains halogen. The Mass and IR spectra, are given below.
Elemental Analysis: C, 33.17; H, 5.01; O, 17.68; contains halogen.

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14. The Compound 37 is a solid (melting point 77˚ C), that is slightly soluble in water, forming an acidic solution. The
Mass and IR spectra, are given below. The broad band in the IR at 3400 - 2800 cm-1 is characteristic of this
functional group. Elemental Analysis: C, 70.57; H, 5.92; O, 23.50.

15. The Compound 43 is a basic liquid (boiling point 71 ˚C a 10 mm Hg). The Mass and IR, are given below. Elemental
Analysis: C, 78.46; H, 8.47; N, 13.07.

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16. The Compound 44 is a low-melting solid (melting point 36-38 ˚C). The Mass and IR spectra, are given below.
Elemental Analysis: C, 71.98; H, 6.71; O, 21.31.

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 17. The Compound is a neutral, low-melting solid (melting point 50-52 ˚C). The Mass and IR spectra, are given below.
Elemental Analysis: C, 54.90; H, 4.61; N, 9.15; O, 31.34.

14. The Compound 47 is a high-boiling liquid (boiling point 204-205 ˚C), that reacts with Ag+ ion in aqueous ammonia to form
a “silver mirror” (the Tollens test). The Mass and IR, are given below. Elemental Analysis: C,
79.97; H, 6.71; O, 13.32.

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15. The Compound 58 is a low melting solid (melting point 41-44 ˚C), that is soluble in dilute aqueous acid, but precipitates on
neutralization. The Mass and IR, are given below. Elemental Analysis: C, 78.46; H, 8.47; N, 13,07.

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16. There is a sharp peak of medium intensity near 2250 cm-1in the infrared spectrum of this compound.

17.

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18. The infrared spectrum of this unknown shows a sharp peak at 3087 cm-1 and a sharp peak at 1612 cm-1
in addition to other absorptions.

19. Use the mass spectrum and the additional spectral data provided to deduce the structure of each of the following
compounds: C4H7BrO2

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20. Use the mass spectrum and the additional spectral data provided to deduce the structure of each of the following
compounds:
The infrared spectrum contains a single, strong peak at 3280 cm-1.

21. For each structure shown below

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  Identify the site of initial ionization under EI conditions.
 Determine the structure of the ion indicated by the m/z value(s).
 Draw a fragmentation mechanism that accounts for the formation of the fragment ions.

22. Determine the structure of the prominent fragment ions and draw a fragmentation mechanism to explain their formation. 3-
Methyl-3-heptanol

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23. Determine the structure of the prominent fragment ions and draw a fragmentation mechanism to explain their formation.
Dicyclohexylamine

24. While cleaning out old samples from your lab, you come across a vial labeled simply “decanone.” You run an EI GC-MS of
the material in the vial and obtain the mass spectrum shown below. Use the fragmentation pattern to determine which isomer
of decanone is in the vial.

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25. The spectra of 3- and 4-hydroxycyclohexene are very different. Which spectrum goes with which isomer? Give a reason
for your answer.

26. The first significant fragment ion peak observed in the mass spectrum of lysergic acid diethylamide (LSD; structure below)
occurs at m/z 280, corresponding to the loss of 43 u from the M +. Studies have shown that the fragmentation involves the loss
of H2C=N-CH3 by what is formally a retro Diels-Alder fragmentation (Nigam and Holmes, 1969). However, the IE for ionization

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at the tertiary amine group (<8.0 eV) is lower than that for the double bond in the cyclohexene ring (which is conjugated with
the aromatic ring; IE ≈8.4 eV). Assuming that initial ionization occurs at the N atom of the tertiary amine group, write a
mechanism that accounts for this loss.

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