………………………………………………………………………………………………………………………………………….

416. Identify two peaks that are expected to appear in the mass spectrum of 3-pentanol.
For each peak, identify the fragment associated with the peak.
……………………………………………………………………………………………
417. Identify the expected base peak in the mass spectrum of 2,2,3-trimethylbutane. Draw
the fragment associated with this peak and explain why the base peak results from this
fragment.
…………………………………………………………………………………………….
418. The following are mass spectra for the constitutional isomers ethylcyclohexane and
1,1-dimethylcyclohexane. Based on likely fragmentation patterns, match the compound
with its spectrum.

419. How would you distinguish between each pair of compounds using high-resolution
mass spectrometry?

…………………………………………………………………………………………….
420. How would you distinguish between each pair of compounds in Problem 14.28 using
IR spectroscopy?
…………………………………………………………………………………………….
421. Calculate the degree of unsaturation for each of the following molecular formulas:

…………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

422. Identify which two compounds shown here have the same degree of unsaturation.
C3H8O C3H5ClO2 C3H5NO2 C3H6
………………………………………………………………………………………………………………………………………….

423. Strigol is an important plant hormone that is released by crops such as rice and
sugarcane. Unfortunately for these plants, strigol also activates the germination of any
nearby witchweed seeds, resulting in the destruction of the crops by the parasitic weed.2
Strigol has nineteen carbon atoms. Without counting the hydrogen atoms, determine the
HDI of strigol, as well as its molecular formula.

………………………………………………………………………………………………………………………………………….

424. All of the following compounds absorb IR radiation in the range between 1600 and
1850 cm−1. In each case, identify the specific bond(s) responsible for the absorption(s)
and predict the approximate wavenumber of absorption for each of those bonds.

………………………………………………………………………………………………………………………………………….

425. Rank each of the bonds identified in order of increasing wavenumber.

………………………………………………………………………………………………………………………………………….

426. Identify the signals you would expect in the diagnostic region of the IR spectrum for
each of the following compounds:

………………………………………………………………………………………………………………………………………….

429. Propose a molecular formula for a compound that has one degree of unsaturation
and a mass spectrum that displays a molecular ion signal at m/z = 86.
………………………………………………………………………………………………………………………………………….

430. The mass spectrum of an unknown hydrocarbon exhibits an (M+1)+• peak that is
10% as tall as the molecular ion peak. Identify the number of carbon atoms in the
unknown compound.
………………………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

427. Identify how IR spectroscopy might be used to monitor the progress of each of the
following reactions:

………………………………………………………………………………………………………………………………………….

428. Identify the characteristic signals that you would expect in the diagnostic region of
an IR spectrum of each of the following compounds:

………………………………………………………………………………………………………………………………………….

432. The sex attractant of the codling moth gives an IR spectrum with a broad signal
between 3200 and 3600 cm−1 and two signals between 1600 and 1700 cm−1. In the mass
spectrum of this compound, the molecular ion peak appears at m/z = 196, and the relative
abundances of the molecular ion and the (M+1)+• peak are 27.2% and 3.9%, respectively.
(a) What functional groups are present in this compound?
(b) How many carbon atoms are present in the compound?
(c) Based on the information given, propose a molecular formula for the compound.
………………………………………………………………………………………………………………………………………….

433. Compare the structures of cyclohexane and 2-methyl-2-pentene.

(a) What is the molecular formula of each compound?
(b) What is the HDI of each compound?
(c) Can high-resolution mass spectrometry be used to distinguish between these
compounds? Explain.
(d) How would you differentiate between these two compounds using IR spectroscopy?
………………………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

434. The mass spectrum of 1-ethyl-1-methylcyclohexane shows many fragments, with

two in very large abundance. One appears at m/z = 111 and the other appears at m/z = 97.
Identify the structure of each of these fragments.
………………………………………………………………………………………………………………………………………….

435. The mass spectrum of 2-bromopentane shows many fragments.

(a) A fragment appears at M−15. Would you expect a signal at M−13 that is equal in
height to the M−15 peak? Explain.
(b) One fragment appears at M−29. Would you expect a signal at M−27 that is equal in
height to the M−29 peak? Explain.
(c) One fragment appears at M−79. Would you expect a signal at M−77 that is equal in
height to the M−79 peak? Explain.
………………………………………………………………………………………………………………………………………….

436. When treated with a strong base, 2-bromo-2,3-dimethylbutane will undergo an

elimination reaction to produce two products. The choice of base (ethoxide vs. tert-
butoxide) will determine which of the two products predominates. Draw both products
and determine how you could distinguish between them using IR spectroscopy.
………………………………………………………………………………………………………………………………………….

437. Propose a molecular formula that fits the following data:

(a) A hydrocarbon (CxHy) with a molecular ion peak at m/z = 66.
(b) A compound that absorbs IR radiation at 1720 cm−1 and exhibits a molecular ion
peak at m/z = 70.
………………………………………………………………………………………………………………………………………….

438. The following is a mass spectrum of octane.

(a) Which peak represents the molecular ion?
(b) Which peak is the base peak?
(c) Draw the structure of the fragment that produces the base peak.

………………………………………………………………………………………………………………………………………….

439. Calculate the HDI for each molecular formula.

(a) C4H6 (b) C5H8 (c) C40H78 (d) C72H74 (e) C6H6O2 (f ) C7H9NO2
(g) C8H10N2O (h) C5H7Cl3 ( i ) C6H5Br ( j ) C6H12O6
………………………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

440. Propose two possible structures for a compound with the molecular formula C5H8
that produces an IR signal at 3300 cm−1.
………………………………………………………………………………………………………………………………………….

441. Limonene is a hydrocarbon found in the peels of lemons and contributes significantly
to the smell of lemons. Limonene has a molecular ion peak at m/z = 136 in its mass
spectrum, and it has two double bonds and one ring in its structure. What is the molecular
formula of limonene?
………………………………………………………………………………………………………………………………………….

442. A compound with the molecular formula shown below exhibits a 1HNMR spectrum
with only one signal. Deduce the structure in each case.
(a) C5H10 (b) C5H8Cl4 (c) C12H18
………………………………………………………………………………………………………………………………………….

443. A compound with the molecular formula C12H24 exhibits a 1HNMR spectrum with
only one signal and a 13CNMR spectrum with two signals. Deduce the structure of this
compound.
………………………………………………………………………………………………………………………………………….

444. A compound with the molecular formula C17H36 exhibits a 1HNMR spectrum with
only one signal. How many signals would you expect in the 13CNMR spectrum of this
compound?
………………………………………………………………………………………………………………………………………….

445. How many signals would you expect in the 1HNMR spectrum of each of the
following compounds:

………………………………………………………………………………………………………………………………………….

13
446. How many signals would you expect in the CNMR spectrum of each of the
compounds in Problem 15.35?
………………………………………………………………………………………………………………………………………….

13
447. How would you distinguish between the following compounds using CNMR
spectroscopy?

………………………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

448. Predict the multiplicity of each signal in the 1HNMR spectrum of the following
compound:

………………………………………………………………………………………………………………………………………….

449. For each pair of compounds, identify how you would distinguish them using either
1
HNMR spectroscopy or 13CNMR spectroscopy:

450. A compound with the molecular formula C8H18 exhibits a 1HNMR spectrum with
only one signal. How many signals would you expect in the 13CNMR spectrum of this
compound?
………………………………………………………………………………………………………………………………………….

454. A compound with the molecular formula C9H18 exhibits a 1HNMR spectrum with
only one signal and a 13CNMR spectrum with two signals. Deduce the structure of this
compound.
………………………………………………………………………………………………………………………………………….

455. How many signals do you expect in the 1HNMR spectrum of each of the following
compounds:

………………………………………………………………………………………………………………………………………….

456. Identify the structure of a compound with the molecular formula C9H20 that exhibits
four CH2 groups, all of which are chemically equivalent. How many total signals would
you expect in the 1HNMR spectrum of this compound?
………………………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

451. For each of the following compounds, compare the two indicated protons and
determine wheter they are enantiotopic, homotopic, or diastereotopic:

452. Draw the expected 1HNMR spectrum of the following compound:

………………………………………………………………………………………………………………………………………….

453. Consider the following compound:

(a) How many signals do you expect in the 1HNMR spectrum of this compound?
(b) Rank the protons in terms of increasing chemical shift.
(c) How many signals do you expect in the 13CNMR spectrum?
(d) Rank the carbon atoms in terms of increasing chemical shift.
………………………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

431. Match each compound with the appropriate spectrum.

………………………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

457. When 1-methylcyclohexene is treated with HCl, a Markovnikov addition is

observed. How would you use 1HNMR spectroscopy to determine that the major product
is indeed the Markovnikov product?
………………………………………………………………………………………………………………………………………….

458. How many signals are expected in the 1HNMR spectrum of each of the following
compounds?

………………………………………………………………………………………………………………………………………….

459. Compare the structures of ethylene, acetylene, and benzene. Each of these
compounds produces only one signal in its 1HNMR spectrum. Arrange these signals in
order of increasing chemical shift.

………………………………………………………………………………………………………………………………………….

460. Assuming a 300-MHz instrument is used, calculate the difference between the
frequency of absorption (in hertz) of TMS and the frequency of absorption of a proton
with a δ value of 1.2 ppm.
………………………………………………………………………………………………………………………………………….

461. A compound with the molecular formula C13H28 exhibits a 1HNMR spectrum with
two signals: a septet with an integration of 1 and a doublet with an integration of 6.
Deduce the structure of this compound.
………………………………………………………………………………………………………………………………………….

462. A compound with the molecular formula C8H10 produces three signals in its 13CNMR
spectrum and only two signals in its 1HNMR spectrum. Deduce the structure of the
compound.
………………………………………………………………………………………………………………………………………….

463. A compound with the molecular formula C3H8O produces a broad signal between
3200 and 3600 cm−1 in its IR spectrum and produces two signals in its 13CNMR spectrum.
Deduce the structure of the compound.
………………………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………………………….

464. A compound with the molecular formula C4H6O4 produces a broad signal between
2500 and 3600 cm−1 in its IR spectrum and produces two signals in its 1HNMR spectrum
(a singlet at 12.1 ppm with a relative integration of 1 and a singlet at 2.4 ppm with a
relative integration of 2). Deduce the structure of the compound.
………………………………………………………………………………………………………………………………………….

465. Propose the structure of a compound that exhibits the following 1HNMR data:

………………………………………………………………………………………………………………………………………….

466. Deduce the structure of a compound with the molecular formula C9H12 that produces
the following 1HNMR spectrum:

………………………………………………………………………………………………………………………………………….
415. Although 2,2-dimethylhexane has a molecular weight of 114, no peak is observed at
m/z = 114. The base peak in the mass spectrum occurs at M−57.
(a) Draw the fragmentation responsible for formation of the M−57 ion.
(b) Explain why this cation is the most abundant ion to pass through the spectrometer.
(c) Explain why no molecular ions survive long enough to be detected.
(d) Can you offer an explanation as to why the M−15 peak is not the base peak?
………………………………………………………………………………………………………………………………………….