CHM 424L Organic Laboratory, Dr. Laurie S. Starkey Introduction to Mass Spectrometry

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1 CM 424L rganic Laboratory, Dr. Laurie S. Starkey Introduction to Mass Spectrometry Mass spectrometry is used to determine a sample's molecular mass and molecular formula. Some structural information can also be determined by mass spec. This technique is especially valuable when used in conjuction with gas chromatography (called GC-MS); the GC separates the components of a mixture and then the mass spec analyzes each component. To obtain a mass spectrum, a sample is vaporized and then bombarded with a high energy beam of electrons (this technique is called electron-impact ionization, or EI). This ionizes the sample by knocking an electron out of the structure. A nonbonded or bonded electron is removed, resulting in radical cation species. Although it is now missing an electron, the intact molecule still has the same molecular mass and is known as the molecular ion (M ), or the parent ion. In addition, this high-energy environment causes the molecular ion to and the various pieces can be analyzed to learn something about the original structure. All charged species are separated by mass as they are passed through a magnetic field and a detector records how many pieces of each mass have been formed. Note that because this technique does not involve the absorption or emission of energy, it is not called spectroscopy. sample of a neutral molecule is vaporized blast with electron beam to ionize e - e - e - loss of an electron results in a radical cation (no change in mass) ation occurs mixture of charged and uncharged particles magnetic deflection separates charged particles by mass-to-charge ratio, m/z (charge is usually 1) detector records the frequency of each mass; the taller the peak, the more abundant the lower mass higher mass (M ) base peak (most abundant) defined as 100% to set scale molecular ion, M (~highest m/z) gives molecular mass (in amu) Spectral Analysis In this spectrum, the sample has a molecular mass (M) of 100 amu. The most abundant, called the base peak, has a m/z of 43 amu, or (M 57). This was formed when a 57 amu segment of the molecule broke off. Many other s were formed; not all will be analyzed. spectra have been reproduced from the NIST Chemistry WebBook note that a small peak is observed at (M1)

2 What is the mass of a single molecule? C 4 Mass = C 4() = but ~1.1% of carbon atoms exist as 13 C isotope! 13 C 4 Mass = 13 C 4() = What ratio is expected for the molecular ion peaks of C 2 6? the number of carbon atoms affects the relative height of the M1 peak ther isotopes of high abundance Cl (35.45 amu) atoms are 76% 35 Cl and 24% 37 Cl Br (79.90 amu) atoms are 51% 79 Br and 49% 81 Br s containing Cl or Br have significant M2 peaks What ratios are expected for the molecular ion peaks of C 2 Br 2? possible masses? C 2 Br Br total amu mass spec of chloroethane (M 64) mass spec of bromobutane (M 137) mass spec of dibromomethane (M 172) Determining molecular formula from high-resolution mass spectrometry (high-res mass spec) exact masses of various elements: C N amu amu 12 these molecules all C amu C amu have a molecular C 14 N amu mass of 98 g/mol 5 10 N amu C amu amu C amu the molecular formula can be determined from precise molecular mass

3 Mass Spec Features of Various Functional Groups Fragmentation of the molecular ion Which is more stable, a carbocation C or a radical R? C vs. C ation is more likely if it gives more stable carbocations and radicals Alkanes C 3 C 2 C 2 C 2 C 2 hexane C 3 remove 1 e - C 3 C 2 C 2 C 2 C 2 C 3 a radical cation (M ) m/z 86 C 3 C 2 C 2 C 2 C 2 C 3 break a bond to give two s: one cation and one radical C 3 C 2 C 2 C 2 C 2 C 3 C 3 C 2 C 2 C 2 C 2 C 3 m/z 57 (M-29) C 3 C 2 C 2 C 2 C 2 C 3 m/z 29 (M 57) C 3 C 2 C 2 C 2 C 2 C 3 m/z 43 (M 43) C 3 C 2 C 2 C 2 C 2 C 3 C 3 C 2 C 2 C 2 C 2 m/z 71 (M-15) C 3 note: hexane has peaks at m/z 15, 29, 43, 57, 71, 86 C 3 C 2 C 2 C 2 C 2 Branched Alkanes C 3 m/z 15 (M 71) Explain why the base peak of 2-methylhexane is at m/z 43 (M-57). C 3 C 3 C 2 C 2 C 2 C C 3 Why are the peaks at m/z 15 and 71 so small?

4 Alkenes C 3 C 2 C 2 C C C 3 remove 1 e - C 3 C 2 C 2 C C C 3 allylic cleavage gives stable carbocation C 3 C 2 C 2 C C C 3 C 2 C C C 3 C 3 C 2 C 2 C C C 3 high-energy pi electron is most likely removed C 3 C 2 allylic carbocation is resonance-stabilized Aromatic C 3 C 2 C 2 Alcohols tropylium cation m/z 91 C 3 C 2 C 2 C 2 C 3 C 2 C 2 high-energy nonbonded electron is most likely removed also, loss of 2 (M 18) may be observed (multistep mechanism first involves an intramolecular proton transfer) Note: loss of molecular piece results in retention of EVEN mass number C 3 C C 2

5 Ethers C 2 C 2 C 2 R' R C 2 C 2 C 2 C 2 R' R C 2 C 2 C 2 also, loss of R may be observed C 2 C 2 R -R cleavage C 3 C 2 C 2 m/z (M R) Amines C 3 C 2 C 2 N 2 Nitrogen Rule: M is odd if there are an odd number of nitrogens! odd molecular mass indicates one nitrogen (or 3 or 5 or 7 nitrogens...) even molecular mass indicates zero nitrogens (or 2 or 4 or 6 nitrogens...) Note: seemingly illogical ations are common in mass spectrometry. Most amines have a peak at m/z 30 from the very stable cation shown. N?! C 2 N 2 Aldehydes & Ketones R C R' R C R' acylium ion is resonance-stabilized m/z (M R) loss of larger group more likely (more stable R ) McLafferty rearrangement is a common ation for molecules containing pi bonds (e.g., C=) Note: loss of molecular piece results in retention of EVEN mass number CR' McLafferty rearrangement C R' R C C 2 C 2 favorable 6-membered ring in transition state R C C 2 C 2 molecular ion cleaves between α and β carbons (note transfer of for calc.) Esters esters can undergo, McLafferty rearrangement, or loss of R R C R'

6 Mass Spectrometry Discussion Questions For the given molecule (M=57), do you expect the more abundant peak to be m/z 15 or m/z 43? Explain. C 3 C 2 C 2 C 3 For the given molecule (M=74), which peak do you expect to be most abundant: m/z 31, m/z 45 or m/z 59? Explain. C 2 C 2 C 2 C 3 Explain why the mass spectra of methyl ketones typically have a peak at m/z 43. Provide the structure of this. In the mass spectrum of the given molecule (M=88), account for the peaks at m/z 45 and m/z 57. C 3 C 2 C 2 C 2 C 3 ow could you use mass spectrometry to distinguish between the following two compounds (M=73)? Provide structures (and m/z values) for the significant s expected. C 3 C 2 C 2 C 2 N 2 and C 3 C 2 C 2 N C 3 What would be the m/z ratio for the resulting from a McLafferty Rearrangement for the following molecule (M=114)? What accounts for its base peak at m/z 57? C 3 C C 2 C C 2 C 3 C 3 Mass spec problems (Wade 7th or 8th ed.) Chapter 12: 8-11, 18, 20.

7 Mass Spectrometry Problems 1. Explain the indicated MS peaks for methyl butyrate - provide structures (and m/z values) of the s and show how they were formed. C 3 C 2 C 2 C 3 M 102 m/z = 43 m/z = 59 m/z = 71 m/z = ow could you use mass spectrometry to distinguish between the following pairs of isomers? Provide structures (and m/z values) for the significant s expected. 3. (PBtext) From the mass spec and NMR data given, determine the number of Cl and/or Br atoms present, the chemical formula, the degrees of unsaturation (DU) and the number of rings in the structure. 1 NMR shows 14 atoms 13 C NMR shows 3 π bonds m/z abundance M % M % M % M %