Chapter 12 - Structure Determination: Mass Spectrometry and Infrared Spectroscopy

Chapter Outline 1. Mass Spectrometry (Sections 12.1 - 12.4). A. General features of mass spectrometry (Section 12.1). 1. Purpose of mass spectrometry. a. Mass spectrometry is used to measure the molecular weight of a compound. b. Mass spectrometry can also provide information on the structure of an unknown compound. 2. Technique of mass spectrometry. a. A small amount of sample is vaporized into the ionization source and is bombarded by a stream of high-energy electrons. b. An electron is dislodged, producing a cation radical. c. Most of the cation radicals fragment; the fragments may be positively charged or neutral. d. In the deflector, a strong magnetic field deflects the positively charged fragments, which are separated by m/z ratio. e. A detector records the fragments as peaks. 3. Important terms. a. The mass spectrum is presented as a bar graph, with masses (mlz) on the x axis and intensity on the y axis. b. The base peak is the tallest peak and is assigned an intensity of 100%. c. The parent peak, or molecular ion (M+), corresponds to the unfragmented cation radical. d. In large molecules, the base peak is often not the molecular ion. B. Interpreting mass spectra (Sections 12.2 - 12.4). 1. Molecular weight (Section 12.2). a. Mass spectra can frequently provide the molecular weight of a sample. i. Double-focusing mass spectrometers can provide mass measurements accurate to 0.0005 amu. ii. Some samples fragment so easily that M+ is not seen. b. If you know the molecular weight of the sample, you can often deduce its molecular formula. c. There is often a peak at M + 1 that is due to contributions from I3C and 2H. 2. Fragmentation patterns of hydrocarbons. a. Fragmentation patterns can be used to identify a known compound, because a given compound has a unique fragmentation "fingerprint". b. Fragmentation patterns can also provide structural information. i. Most hydrocarbons fragment into carbocations and radicals. ii. The positive charge remains with the fragment most able to stabilize it. iii. It is often difficult to assign structures to fragments. iv. For hexane, major fragments correspond to the loss of methyl, ethyl, propyl, and butyl radicals. 3. Fragmentation patterns of common functional groups (Section 12.3). a. Alcohols. i. Alcohols can fragment by alpha cleavage, in which a C-C bond next to the -OR group is broken. The products are a cation and a radical. ii. Alcohols can also dehydrate, leaving an alkene cation radical with a mass 18 units less than M+.

Structure Determination:

Mass Spectrometry and Infrared Spectroscopy

267

b. Amines also undergo alpha cleavage, forming a cation and a radical. c. Carbonyl compounds. i. Aldehydes and ketones with a hydrogen 3 carbons from the carbonyl group can undergo the McLafferty rearrangement. The products are a cation radical and a neutral alkene. ii. Aldehydes and ketones also undergo alpha cleavage, which breaks a bond between the carbonyl group and a neighboring carbon. The products are a cation and a radical. C. Mass spectrometry in biological systems: TOF instruments (Section 12.4). 1. Time-of-flight instruments are used to produce charged molecules with little fragmentation. 2. The ionizer can be either ESI or MALDI. a. In an ESI source, the sample is dissolved in a polar solvent and sprayed through a steel capillary tube. i. As the sample exits, it is subjected to a high voltage, which protonates the sample. ii. The solvent is evaporated, yielding protonated sample molecules. b. In a MALDI source, the sample is absorbed onto a matrix compound. i. The matrix compound is ionized by a burst of laser light. ii, The matrix compound transfers energy to the sample, protonating it. 3. The samples are focused into a small packet and given a burst of energy. Each molecule moves at a velocity that depends on the square root of its mass. 4. The analyzer is an electrically grounded tube that detects the molecules by velocity. II. Spectroscopy and the electromagnetic spectrum (Section 12.5). A. The nature of radiant energy. 1. Different types of electromagnetic radiation make up the electromagnetic spectrum. 2. Electromagnetic radiation behaves both as a particle and as a wave. 3. Electromagnetic radiation can be characterized by three variables. a. The wavelength (Ie) measures the distance from one maximum to the next. b. The frequency (v) measures the number of wave maxima that pass a fixed point per unit time. c. The amplitude is the height measured from the midpoint to the maximum. 4. Wavelength times frequency equals the speed of light. 5. Electromagnetic energy is transmitted in discrete energy bundles called quanta. b. Energy varies directly with frequency but inversely with wavelength. c. E = 1.20 x 1O-2kJ/mol -;-}.. (em) for a "mole" of photons. B. Electromagnetic radiation and organic molecules. I. When an organic compound is struck by a beam of electromagnetic radiation, it absorbs radiation of certain wavelengths, and transmits radiation of other wavelengths. 2. If we determine which wavelengths are absorbed and which are transmitted, we can obtain an absorption spectrum of the compound. For an infrared spectrum: i. The horizontal axis records wavelength. ii. The vertical axis records percent transmittance. iii. The baseline runs across the top of the spectrum. iv. Energy absorption is a downward spike. 3. The energy a molecule absorbs is distributed over the molecule. 4. There are many types of spectroscopies that differ in the region of the electromagnetic spectrum that is being used.
a. e

=hxv

268

Chapter 12

ill. Infrared Spectroscopy (Sections 12.6 - 12.8). A. Infrared radiation (Section 12.6). 1. The infrared (IR) region of the electromagnetic spectrum extends from 7.8 x 10-7 m to 1O-4m. a. Organic chemists use the region from 2.5 x 10--6m to 2.5 x 10-5 m. b. Wavelengths are usually given in urn, and frequencies are expressed in wavenumbers, which are the reciprocal of wavelength. c. The useful range of IR radiation is 4000 cm-I to 400 cm": this corresponds to energies of 48.0 kllmol to 4.80 kl/mol, 2. IR radiation causes bonds to stretch and bend and causes other molecular vibrations. 3. Energy is absorbed at a specific frequency that corresponds to the frequency of the vibrational motion of a bond. 4. If we measure the frequencies at which IR energy is absorbed, we can find out the kinds of bonds a compound contains and identify functional groups. B. Interpreting IR spectra (Sections 12.7 - 12.8). 1. General principles (Section 12.7). a. Most molecules have very complex IR spectra. i. This complexity means that each molecule has a unique fingerprint that allows it to be identified by IR spectroscopy. ii. Complexity also means that not all absorptions can be identified. b. Most functional groups have characteristic IR absorption bands that don't change from one compound to another. c. The significant regions of IR absorptions: i. 4000 cm-I-2500 cm-I corresponds to absorptions by C-H, O-H, and N-H bonds. ii. 2500 cm-I-2000 cm-I corresponds to triple-bond stretches. iii. 2000 cm-1-1500 cm-I corresponds to double bond stretches. iv. The region below 1500 em"! is the fingerprint region, where many complex bond vibrations occur. d. The frequency of absorption of different bonds depends on two factors: i. The strength of the bond. ii. The difference in mass between the two atoms in the bond. 2. IR spectra of some common functional groups (Section 12.8). a. Alkanes. i. C-C absorbs at 800-1300 cm-I. ii C-H absorbs at 2850-2960 cm-I. b. Alkenes. i. =C-H absorbs at 3020-3100 em-I. ii, C=C absorbs at 1650-1670 cm". iii. RCH=CH2 absorbs at 910 and 990 cm-I. iv. R2C=CH2 absorbs at 890 cm-I. c. Alkynes. i. -C=C- absorbs at 2100-2260 cm-I. ii. =C-H absorbs at 3300 cm-I. d. Aromatic compounds. i. =C-H absorbs at 3030 cm". ii. Ring absorptions occur at 1660-2000 cm-t and at 1450-1600 em:'.

Structure Determination:

Mass Spectrometry and Infrared Spectroscopy

269

e. The alcohol O-H bond absorbs at 3400-3650 em-I. f. The N-H bond of amines absorbs at 3300-3500 em-I. g. Carbonyl compounds. i. Saturated aldehydes absorb at 1730 cm'": unsaturated aldehydes absorb at 1705 em-I. ii. Saturated ketones absorb at 1715 cm"; unsaturated ketones absorb at 1690 em-I. iii. Saturated esters absorb at 1735 cm"; unsaturated esters absorb at 1715 em-I. Solutions 12.1 to Problems

If the isotopic masses of the atoms C, H, and had integral values of 12 amu, 1 amu and 16 amu, many molecular formulas would correspond to a molecular weight of 288 amu. Because isotopic masses are not integral, however, only one molecular formula is associated with a molecular ion at 288.2089 amu. To reduce the number of possible formulas, assume that the difference in molecular weight between 288 and 288.2089 is due mainlJ; to hydrogen. Divide 0.2089 by 0.00783, the amount by which the atomic weight of one H atom differs from 1. The answer, 26.67, gives a "ballpark" estimate of the number of hydrogens in testosterone. Then, divide 288 by 12, to determine the maximum number of carbons. Since 288 -;-12 = 24, we know that testosterone can have no more than 22 carbons if it also includes hydrogen and oxygen. Make a list of reasonable molecular formulas containing C, Hand 0 whose mass is 288 and which contain 20-30 hydrogens. Tabulate these, and calculate their exact masses using the values in the text. The only possible formula for testosterone is C19H2802· Molecular formula C2oH32O C19H2802 C18H2403 Isotopic mass Mass Mass of carbons of hydrogens 240.0000 amu 228.0000 216.0000 Mass of oxygens Mass of molecular ion

32.2504 amu 15.9949 amu 288.2453 amu 28.2191 24.1879 31.9898 47.9847 288.2089 288.1726

12.2
CH3CH2CH=C

PH3
\

2-Methyl-2-pentene
+ CH2CH=C /
\

CH3

2-Hexene

CH3

mlz = 69 CH3 mlz = 55 Fragmentation occurs to a greater extent at the weakest carbon-carbon bonds, producing a relatively stable cation. Spectrum (a), which has a dominant peak at mlz = 69, corresponds to 2-methyl-2-pentene, and spectrum (b), which has mlz = 55 as its base peak, corresponds to 2-hexene.

270

Chapter 12

12.3

Strategy: In a mass spectrum, the molecular ion is both a cation and a radical. When it fragments, two kinds of cleavage can occur. (1) Cleavage can form a radical and a cation (the species observed in the mass spectrum). Alpha cleavage shows this type of pattern. (2) Cleavage can form a neutral molecule and a different radical cation (the species observed in the mass spectrum). Alcohol dehydration and the McLafferty rearrangement show this cleavage pattern. For each compound, calculate the mass of the molecular ion and identify the functional groups present. Draw the fragmentation products and calculate their masses. Solution: (a)
~ [ I ]

+.

Alpha cleavage mlz = 43

H3C- C-+ CH2CH2CH3

M+= 86

In theory, alpha cleavage can take place on either side of the carbonyl group to produce cations with mlz = 43 and mlz = 71. In practice, cleavage occurs on the more substituted side of the carbonyl group, and the first cation, with m/z = 43, is observed.

mlz = 82 Dehydration of cyclohexanol produces a cation radical with mlz = 82.

CH3 0 +. McLafferty I II [ CH CHCH CCH rearrangement 3 2

H,\ ...... H H3C-C ~ H

M+= 100

/ 'c"" I\
H H

9)~ C

'CH

-CH2CH3

H3C""" 'H

nH2 C

The cation radical fragment resulting from McLafferty rearrangement has mlz = 58.
CH2CH3 H3C+CH2 -N -CH2CH3 M+ = 101
I

(d) [

+.

Alpha c eavage
I

H3C· +

CH2-N-CH2CH3 m/: = 86

Alpha cleavage of triethylamine yields a cation with mlz

= 86.

Structure Determination: Mass Spectrometry and Infrared Spectroscopy

271

12.4

Strategy: Identify the functional groups present in the molecule and recall the kinds of fragmentations those functional groups produce. 2-Methyl-2-pentanol produces fragments that result from both dehydration and from alpha cleavage. Two different alpha cleavage products are possible. Solution:
Dehydration

CH31+· CH3

CH3CH2CH=<

m/:

= 84

cleavage

Alpha

l
12.5

OH CH3CH2CH2C~ CH3 mlz

H3C·

= 87

I l

HO,?"CHS]+ CH3 mlz= 59

Strategy: We know that: (1) energy increases as wavelength decreases, and (2) the wavelength of X-radiation is smaller than the wavelength of infrared radiation. Thus, we estimate that an X ray is of higher energy than an infrared ray. Solution:

e = hv = hclA; h = 6.62 x 10-34 J·s; c = 3.00 x 108 mls

e = (6.62 x 10-34 J·s) (3.00 x 108 mls)

2.0 x 10-19 J

(6.62

10-34 J·s) (3.00 x 108 mls) 3.0 x 10-9 m

6.6 x 10-17 J

Confirming our estimate, the calculation shows that an X ray is of higher energy than infrared radiation. Convert radiation in m to radiation in Hz by the equation:
v = c = 3.00 x 10 mls A 9.0 X 10-6 m
8

3.3 x 1013 Hz

The equation t: = hv shows that the greater the value of v, the greater the energy. Thus, radiation with v = 3.3 x 1013 Hz (A = 9.0 x 10-6 m) is higher in energy than radiation with v = 4.0 X 109 Hz.

272

Chapter 12

12.6
(a)

E = 1.20

10-4 kllmoI = 1.20 x 10-4 kJ/mol A (in m) 5.0 x 10-11 6 kJ/mol for a gamma ray. = 2.4 X 10
X

(b)

E = 4.0

104 kJ/mol for an X ray.

(c) v

10 mls = 5.0 x lO-8m A' v 1015 Hz E = 1.20 X 10-4 kJ/mol = 2.4 x 103 kJ/mol for ultraviolet light 5.0 x 10-8
.£_.

c.

3.0 6.0

X X

(d) (e)
(f)

= 2.8 X

102 kJ/mol for visible light.

E = 6.0 kJ/mol for infrared radiation E

= 4.0 X 10-2 kJ/mol

for microwave radiation.

12.7

(a) A compound with a strong absorption at 1710 cm-I contains a carbonyl group and is either a ketone or aldehyde. (b) A compound with a nitro group has a strong absorption at 1540 cm-I. (c) A compound showing both carbonyl (1720 cm") and -OH (2500-3000 cm-I broad) absorptions is a carboxylic acid.

12.8

Strategy: To use IR spectroscopy to distinguish between isomers, find a strong IR absorption that is present in one isomer but absent in the other. Solution:
(a) CH3CH20H CH30CH3

Strong hydroxyl band at 3400-3640 crrr !

No band in the region 3400-3640 crrr !

= CH2

Alkene bands at 3020-3100 cm-1 and at 1640-1680-1,

No bands in alkene region.

HOCH2CH2CHO

Strong, broad band at 2500-3100 crrr"!

Strong band at 3400-3640 crrr '

Structure Determination: Mass Spectrometry and Infrared Spectroscopy

273

12.9

Based on what we know at this point, we can identify four absorptions in this spectrum. (a) Absorptions in the region 1450 cm-1-1600 cm-1 are due to aromatic ring -C=Cmotions. (b) The absorption at 2100 cm-I is due to a -C=C- stretch. (c) Absorptions in the range 3000 cm-I-3100 cm-1 are due to aromatic ring =C-H stretches. (d) The absorption at 3300 cm-I is due to a =C-H stretch.

12.10 (a) An ester next to a double bond absorbs at 1715 em-I. The alkene double bond absorbs
at 1640-1680 cm ". (b) The aldehyde carbonyl group absorbs at 1730 cm-I. The alkyne C=Cbond absorbs at 2100-2260 cm'", and the alkyne H-C= bond absorbs at 3300 cm-l. (c) The most important absorptions for this compound are due to the alcohol group (a broad, intense band at 3400-3650 cm'") and to the carboxylic acid group, which has a C=O absorption in the range 1710-1760 ern"! and a broad O-H absorption in the range 2500-3100 cm-I. Absorptions due to the aromatic ring [3030 cm-1 (w) and 1450-1600 cm-I (m)] may also be seen.

12.11

o
C

II

'CH3

The compound contains nitrile and ketone groups, as well as a carbon-carbon double bond. The nitrile absorption occurs at 2210-2260 cm-I. The ketone shows an absorption at 1690 cm", a lower value than usual because the ketone is next to the double bond. The double bond absorption occurs at 1640-1680 cm-I.

274

Chapter 12

Visualizing

Chemistry Compound Significant IR Absorption

12.12
Due to: nitro group (1) aldehyde (2) aromatic ring C-H(3) aromatic ring C=C(3)
(a)

O~2 .....
H

CU ?
H
\/

+ ..... 0 N

1540 crrr-' 1730 crrr ! 3030 cm-1 , 1450-1600 crrr-'

°
(b)

111

1735 cm-1 3020-3100 crrr ! 910 crrr ', 990 crrr !

ester (1) vinylic stretch C-H(2) C=CH2 bend(3)

(c)

1715 crrr ! 3400-3650 crrr !

ketone (1) alcohol (2)

12.13 (a) The mass spectrum of this ketone shows fragments resulting from both McLafferty
rearrangement and alpha cleavage. McLafferty rearrangement:

OJ
CH3CH29HgCH2CH3 CH3

+.

McLafferty rearrangement

9.)~ H-C~C
..... H

H H <,\

<,

/\

C ...........CH CH
2

M+= 114

CH3

H ......
H3C_ /.C_ 'C:;; 23 'CH CH
1

mlz

= 86

Structure Determination:

Mass Spectrometry and Infrared Spectroscopy

275

Alpha cleavage:

ICH3CH2?H-g]

CH3 m/z

= 85

mlz

= 57

(b) Two different fragments can arise from alpha cleavage of this amine:

H N-C

\',CH3
\

+"

"

c\
H N-C
\

M+

CH3

Alpha cleavage

CH3" +

lCN-<H
m/z

113

= 98

/CH3
CH3

+"

Alpha cleavage

[ CH2CH2CH2 r
\
/

N-C

/CH3 CH3

CH3

/ M+

H2C

113

mlz

= 113

The second product results from cleavage of a bond in the five-membered ring.

276

Chapter 12

Additional Problems
12.14 Molecular Formula
(a) 132

Degree of Un saturation 5

Possible Structure

co o

(b) 166

(c)

84

12.15

(a) The compound contains no more than 7 carbons. As in Problem 12.1, divide the mass to the right of the decimal point by 0.00783 to arrive at an approximate value for the number of hydrogens (10.7). Since the compound has an even mass (and an even number of hydrogens), it contains an even number of nitrogens, or no nitrogens. The two most likely formulas are C~lOO (W = 98.0732) and C5HlON2 (W = 98.0844). The latter formula agrees precisely with the given molecular ion.
(b) The compound contains no more than 9 carbons, and 4.1 hydrogens. The number of hydrogens must be odd, since M+ is odd. Assume the molecule has 5 hydrogens, and adjust the numbers of nitrogens and oxygens until you arrive at the correct value for W. The formula is C~5N02'

12.16 Reasonable molecular formulas for camphor are CjQH160, C9H1202, CSHS03. The actual formula, ClOH160 (M+ = 152.1201), corresponds to three degrees of unsaturation. The ketone functional group accounts for one of these. Since camphor is a saturated compound, the other two degrees of unsaturation are due to two rings.

Camphor

Structure

Determination:

Mass Spectrometry

and Infrared

Spectroscopy

277

12.1 7 Carbon is tetravalent, and nitrogen is trivalent. If a C-H unit (formula weight 13) is replaced by an N atom (formula weight 14), the molecular weight of the resulting compound increases by one. Since all neutral hydrocarbons have even-numbered molecular weights (CnH2n+2, CnH2n, and so forth) the resulting nitrogen-containing compounds have odd-numbered molecular weights. If two C-H units are replaced by two N atoms, the molecular weight of the resulting compound increases by two and remains an even number. 12.18 Because W is an odd number, pyridine contains an odd number of nitrogen atoms. If pyridine contained one nitrogen atom (atomic weight 14) the remaining atoms would have a formula weight of 65, corresponding to -CsHs. CsHsN is, in fact, the molecular formula of pyridine. Subtract the isotopic mass of the two nitrogens from the value of M+, and divide the quantity to the right of the decimal point by 0.00783 to find the approximate number of hydrogens in nicotine. The molecular formula of nicotine is CIOH14N2. o find the T equivalent hydrocarbon formula, subtract the number of nitrogens from the number of hydrogens. The equivalent hydrocarbon formula of nicotine, ClOH12,indicates five degrees of unsaturation - two of them due to the two rings and the other three due to three double bonds.

12.19

Nicotine

12.20

Use the technique described in Problem 12.1 to find the molecular formula of cortisone. Cortisone contains approximately 25 hydrogens. Make a table of possible molecular formulas for cortisone that have around 25 hydrogens and calculate the exact molecular weights corresponding to these formulas. Isotopic mass Molecular formula C27H20O C2sH2S02 C24H2403 C21H2S0S Mass of carbons 324.0000 amu 300.0000 288.0000 252.0000 Mass of hydrogens Mass of oxygens Mass of molecular ion 360.1514 amu 360.2089 360.1725 360.1937

20.1565 amu 15.9949 amu 28.2191 24.1878 28.2191 31.9898 47.9847 79.9746

The molecular weight of C21H2S0Scorresponds to the observed molecular weight of cortisone. (Note that only the last formula has the correct degree of unsaturation, 8).

278

Chapter 12

12.21 In order to simplify this problem, neglect the 13e and 2H isotopes in determining the molecular ions of these compounds. (a) The formula weight of -CH3 is 15, and the atomic masses of the two bromine isotopes are 79 and 81. The two molecular ions of bromoethane occur at M+ = 94 (50.7%) and M+ = 96 (49.3%). (b) The formula weight of -C6Hl3 is 85, and the atomic masses of the two chlorine isotopes are 35 and 37. The two molecular ions of l-chlorohexane occur at M+ = 120 (75.8%) and M+ = 122 (24.2%). 12.22 Each carbon atom has a 1.10% probability of being l3e and a 98.90% probability of being 12C. The ratio of the height of the l3e peak: to the height of the 12Cpeak: for a one-carbon compound is (1.10/98.9) x 100% = 1.11 %. For a six-carbon compound, the contribution to (M+l)+ from l3e is 6 x (1.10/98.9) x 100% = 6.66%. For benzene, the relative height of (M+1)+is 6.66% of the height of W. A similar line of reasoning can be used to calculate the contribution to (M+ It from 2H. The natural abundance of 2H is 0.015%, so the ratio of a 2H peak to a IH peak for a onehydrogen com£ound is 0.015%. For a six-hydrogen compound, the contribution to (M+l)+ from His 6 x 0.015% = 0.09%. For benzene, (M+ It is 6.75% of W. Notice that 2H contributes very little to the size of (M+l)+. 12.23 (a) The molecular formula of the ketone is e5HlOO, and the fragments correspond to the products of alpha cleavage (McLafferty rearrangement fragments have even-numbered values of mlz). Draw all possible ketone structures, show the charged products of alpha cleavage, and note which fragments correspond to those listed.

:~: [ H3C-rC-rCH2CH2CH3
I I

] +, Alpha
C

~]

+ +

M+=86

eavage

..

H3C-C

m/z
+,

= 43
0

[ H3C~C+CHCH3 J
I

o
II

CH3

Alpha
C

M+= 86

eavage

...

[ C-CHCH 3

II

CH

I3

]+

mlz =43

m/z

= 71

Alpha cleavage

CH CH -C
3 2

0]
II

m/: = 57

Either of the first two compounds shows the observed fragments in its mass spectrum.

Structure

Determination:

Mass Spectrometry and Infrared Spectroscopy

279

(b)CsH120 is the formula of an alcohol with W = 88. The fragment at m/z = 70 is due to the product of dehydration of W. The other two fragments are a result of alpha cleavage. Draw the possible Cs alcohol isomers, and draw their products of alpha cleavage. The tertiary alcohol shown fits the data.
OH

l
[

CH3CH2-TC-tCH3
I

1
1

+.

AJpha 1 .. C eavage

M+= 88

CH3

OH CH3CH2 -

yI
CH3

+.
_

CH3

Dehydration
___;__-

.....

M+= 88

12.24

H3

CH3CH2CH2CHCH3

2.Methylpentane

k-

CH] [ CH3CH2CH2bH~H3

+.

+e

~
+ CH3CH2CH2CHCH3 + 1 CH2CHCH3 CH3

+1

CH3 CHCH3

m/: = 71

m/z

= 57

+ CH3CH2

m/z = 43

m/z

= 29

The molecular ion, at mlz = 86, is present in very low abundance. The base peak, at mlz = 43, represents a stable secondary carbocation.

12.25 Before doing the hydrogenation, familiarize yourself with the mass spectra of cycIohexene
and cyclohexane. Note that W is different for each compound. After the reaction is underway, inject a sample from the reaction mixture into the mass spectrometer. If the reaction is finished, the mass spectrum of the reaction mixture should be superimposable with the mass spectrum of cyclohexane.

280

Chapter 12

12.26 (a) This ketone shows mass spectrum fragments that are due to alpha cleavage and to the McLafferty rearrangement. The molecular ion occurs at W = 148, and major fragments have mlz = 120, 105, and 71. (Note that only charged species are shown.)

(jC~
0

II

Alpha cleavage

(YC [t/"r
0

II

C1OH120 M+

= 148

mlz
H
~~

= 105

mlz

= 71
+"

l,0
II C

u
]
+"

McLafferty rearrangement

-o
= 110

H,

H2C

~CU I
~

I °

mlz

= 120

(b)The fragments in the mass spectrum of this alcohol (CgH160) result from dehydration and alpha cleavage. Major fragments have m/z values of 128 (the same value as the molecular ion), 110, and 99.

I l

U
OH

Dehydration mlz

M+ = 128

mlz = 99

m/z

128

(c) Amines fragment by alpha cleavage. In this problem, cleavage occurs in the ring, producing a fragment with the same value of m/; as the molecular ion (99).
H
+"

Alpha cleavage

~N""'CH3

m/z = 99

Structure Determination: Mass Spectrometry and Infrared Spectroscopy

281

12.27 CH3CH2C;;;CH shows absorptions at 2100-2260 cm-i (C;;;C) and at 3300 cm-i (C;;;C-H)
that are due to the terminal alkyne bond. H2C=CHCH=CH2 has absorptions in the regions 1640-1680 cm-1 and 3020-3100 that are due to the double bonds. It also shows absorptions at 910 ern"! and 990 cm-1 that are due to monosubstituted alkene bonds. No absorptions occur in the alkyne region. CH3C;;;CCH3' For reasons we won't discuss, symmetrically substituted alkynes such as 2-butyne do not show a C=C bond absorption in the IR. This alkyne is distinguished from the other isomers in that it shows no absorptions in either the alkyne or alkene regions.

12.28 Two enantiomers have identical physical properties (other than the sign of specific
rotation). Thus, their IR spectra are also identical. spectra are also different. structures:

12.29 Since diastereomers have different physical properties and chemical behavior, their IR 12.30 (a) Absorptions at 3300 ern"! and 2150 cm-i are due to a terminal triple bond. Possible

(b) An IR absorption at 3400 cm-i is due to a hydroxyl group. Since no double bond

absorption is present, the compound must be a cyclic alcohol.

[>(
OH

CH3

OH

(c) An absorption at 1715 cm-1 is due to a ketone. The only possible structure is CH3CH2COCH3. (d) Absorptions at 1600 cm-l and 1500 cm" are due to an aromatic ring. Possible structures:

CH3

282

Chapter 12

12.31

(a) HC=CCH2NH2 Alkyne absorptions at 3300 cm-I, 2100-2260 cm' Amine absorption at 3300-3500 cm-1 (b) CH3COCH3 Strong ketone absorption at 1715 cm-1

CH3CH2C=N Nitrile absorption at 2210-2260 cm-1

CH3CH2CHO Strong aldeh1de absorption at 1730 cm-

12.32 Spectrum (b) differs from spectrum (a) in several respects. Note in particular the absorptions at 715 cm-l (strong), 1140 cm-l (strong), 1650 cm-l (medium), and 3000 cm ' (medium) in spectrum (b). The absorptions at 1650 em"! (C=C stretch) and 3000 cm-I (=C-H stretch) can be found in Table 12.1. They allow us to assign spectrum (b) to cyclohexene and spectrum (a) to cyclohexane. 12.33 Only absorptions with medium to strong intensity are listed. (a)
0:-.. .... H O C

6
-9'::::::-..

--.;:
3030 cmcarboxylic acid 1710-1760 carboxylic acid 2500-3100
I

aromatic ring C=C 1450-1600 cm-I aromatic ring C-H C=O

(b)

O~

crrr l

O-H crrr !
(d)

...... OCH3

aromatic ring C=C 1450-1600 cm-1 aromatic ring C-H 3030 crrr' aromatic ester 1715 cm-I

(c)

III
C

aromatic ring C=C 1450-1600 em"! aromatic ring C-H 3030 cm-I alcoholO-H 3400-3650 crrr ! nitrile C=N 2210-2260 cm-I ester 1735 crrr+

alleene C=C 1640-1680 crrr ! alkene =C-H 3020-3100 crrr'! ketone 1715 cm-I

OH (e)

ketone 1715 cm-l

12.34

(a) CH3C=CCH3exhibits no terminal =C-H stretching vibration at 3300 cm", as CH3CH2C=CH does. (b) CH3COCH=CHCH3, a ketone next to a double bond, shows a strong ketone absorption at 1690 cm-I; CH3COCH2CH=CH2 shows a ketone absorption at 1715 cm-I and monosubstituted alkene absorptions at 910 cm'" and 990 cm". (c) CH3CH2CHO exhibits an aldehyde band at 1730 cm"; H2C=CHOCH3 shows characteristic monosubstituted alkene absorptions at 910 cm-I and 990 cm-I.

Structure

Determination:

Mass Spectrometry

and Infrared

Spectroscopy

283

12.35 Compound
(a)

Distingu ishing Absorption

Due to:

1715 crrr+
(b)

C = 0 (ketone)

2100-2260 cm-1 3300 cm-1

C-C C-C-H

910 crrr ! 990 crrr , 1640-1680 cm-i 3020-3100 cm-i

RCH=CH2 C=C =C-H

(d)

CH3CH2CH2COCH3
(e)

II

1735 cm-l 1690 crrr !

C=o

(ester)

Q-gCH
0
HOvC,-? ~

1450-1600 crrr 3030 cm-1

ketone next to aromatic ring aromatic ring aromatic ring aldehyde next to aromatic ring alcohol aromatic ring aromatic ring

(f)

o
II

1710 crrr

3400-3650 cm-i 1450-1600 cm-1 3030 crrr !

12.36

1-Methy Icyclohexanol

1-Methylcyclohexene

The infrared spectrum of the starting alcohol shows a broad absorption at 3400-3640 cm-l due to an O-H stretch. The alkene product exhibits medium intensity absorbances at 1645-1670 cm" and at 3000-3100 cm". Monitoring the disappearance of the alcohol absorption makes it possible to decide when reaction is complete. It is also possible to monitor the appearance of the alkene absorptions.

284

Chapter 12

12.37
CH3 CH3CH2C,CH2CH3 Br

KOH
CH3CH20H

yH3
CH3CH2C=CHCH3

or

RH2
CH3CH2CCH2CH3

3-Bromo-3-methylpentane

3-Methyl-2-pentene

2-Ethyl-l-butene

The IR spectra of both products show the characteristic absorptions of alkenes in the regions 3020-3100 cm-1 and 1650 em-I. However, in the region 700-1000 cm'", 2ethyl-l-butene shows a strong absorption at 890 cm-1 that is typical of 2,2-disubstituted RzC=CHz alkenes. The presence or absence of this peak should help to identify the product. (3-Methyl-2-pentene is the major product of the dehydrobromination reaction.) 12.38 The following expressions are needed:

e = hv = hcl): = hev, where v is the wavenumber. The last expression shows that, asv increases, the energy needed to cause IR absorption increases, indicating greater bond strength. Thus an ester C=O bond (\' = 1735 crrr+) is stronger than a ketone C=O bond (V = 1715 crrr+).
12.39 Possible molecular formulas containing carbon, hydrogen, and oxygen and having M+ = 150 are CIOH140, C9HlOOZ, and CgH603. The first formula has four degrees of unsaturation, the second has five degrees of unsaturation, and the third has six degrees of unsaturation. Since carvone has three double bonds (including the ketone) and one ring, ClOH140is the correct molecular formula for carvone.

Carvone

12.40 The intense absorption at 1690 ern"! is due to a ketone next to a double bond. 12.41 The peak of maximum intensity (base peak) in the mass spectrum occurs at m/z = 67. This peak does not represent the molecular ion, however, because M+ of a hydrocarbon must be an even number. Careful inspection reveals the molecular ion peak at mlz = 68. M+ = 68 corresponds to a hydrocarbon of molecular formula CsHg with a degree of unsaturation of two. Fairly intense peaks in the mass spectrum occur at mlz = 67,53,40,39, and 27. The peak at m/z = 67 corresponds to loss of one hydrogen atom, and the peak at mlz = 53 represents loss of a methyl group. The unknown hydrocarbon thus contains a methyl group. Significant IR absorptions occur at 2130 cm-1 (-C=C- stretch) and at 3320 cm-i (=C-H stretch). These bands indicate that the unknown hydrocarbon is a terminal alkyne. Possible structures for CsHg are CH3CH2CH2C=CH and (CH3)zCHC=CH. [1-Pentyne is correct.]

Structure

Determination:

Mass Spectrometry

and Infrared

Spectroscopy

285

12.42

The molecular ion, M+ = 70, corresponds to the molecular formula CSHIO. This compound has one double bond or ring. The base peak in the mass spectrum occurs at mlz = 55. This peak represents loss of a methyl group from the molecular ion and indicates the presence of a methyl group in the unknown hydrocarbon. All other peaks occur with low intensity. In the IR spectrum, it is possible to distinguish absorptions at 1660 cm " and at 3000 cm-l due to a double bond. (The 2960 ern"! absorption is rather hard to detect because it occurs as a shoulder on the alkane C-H stretch at 2850-2960 em-I.) Since no absorptions occur in the region 890 cm-I-990 cm", we can exclude terminal alkenes as possible structures. The remaining possibilities for CSHlO are CH3CH2CH=CHCH3 and (CH3hC=CHCH3. [2-Methyl-2-butene is correct.] (b)

12.43

12.44

The simplest way to distinguish between the two isomers is by taking their IR spectra. The aldehyde carbonyl group absorbs at 1730 cm", and the ketone carbonyl group absorbs at 1715 em-I. The mass spectra of the two isomers also differ. Like ketones, aldehydes also undergo alpha cleavage and McLafferty rearrangements. McLafferty rearrangement:

[~F-[ H2:)'c+·[~H F-[H2::tH J r

= 58

m/z

= 44

The fragments from the McLafferty rearrangements differ in values of m/z:

[~r~[)J
mlz

Alpha cleavage:

= 85

F [tJ
m/z

= 43

m/z = 29

The fragments resulting from alpha cleavage also differ in values of m/z.

286

Chapter 12

12.45

The absorption at 3400 em" is due to a hydroxyl group.

12.46
OH CH3CH2CHCH3

M+=74

12.47
3 .heat

H 0+

o
CH3CH2COH

II

M+=74

The absorption at 1710 cm " is due to the carbonyl group of a carboxylic acid, and the absorption at 2500-3100 em -1 is due to the -OR group of the carboxylic acid.