Chemistry 30B

1.

Exam 2 Practice Problems Solutions

Page 1

(a) In x-ray crystallography x-ray photons are scattered or diffracted by regularly spaced atoms in a
crystal.
(b) In an early but very important application of x-ray crystallography, the Braggs measured (for the
first time) carbon-carbon bond lengths and carbon-carbon-carbon bond angles in a substance called
diamond.
(c) Rosalind Franklin verified that DNA is a helical molecule when she saw an X pattern in photo 51,
one of many DNA diffraction patterns produced by x-ray crystallography.

2.

(a) No X-ray diffraction locates an atom is space, and can give some idea as to whether or not it has a
higher atomic number than other atoms due to the intensity of the scattering, but it cannot reveal
what elements are present.
(b) Yes X-ray diffraction reveals the relative position of atoms in space, so stereochemistry can be
assessed.
(c) Yes X-ray diffraction reveals the relative position of atoms in space, so distance between atoms
anywhere in the molecule can be measured.
(d) Yes X-ray diffraction reveals the relative position of atoms in space, so the relative position of
three (or more) atoms can be evaluated.

3.

(a) Benzene ring planarity: Yes

(b) Nitro group (NO2) resonance: No X-ray diffraction may reveal that the NO2 atoms lie in the same
plane and that the NO bond lengths are equal, but these facts alone are not proof of resonance. Xray diffraction revels the position of atoms, but not of electrons.
(c) Oxygen-nitrogen bond length: Yes
(d) Presence of lone pairs on oxygen in nitro group: No
(e) Electronegativity of oxygen > nitrogen: No
(f) Positive formal charge on nitrogen in nitro group: No
OH

4.

Na2Cr2O7

(a)
OH

(b)

(c)

OH

aq. H2SO4
acetone

CH3CO3H

OH

NaH

O Na

(d)

OH 1. BH
3

OH

2. NaOH, HOOH
OH

Chemistry 30B

Exam 2 Practice Problems Solutions

aq. HI

(e)

HO

HO

PCC

(f)

HO

OH

OH

(g)

Page 2

Ph

HO

OCH3

(h)

CrO3

Ph

aq. H2SO4
acetone

OH

HO

aq. HI

OH + CH3I

HO

I
OH

(i)

OH

OTs

TsCl
OH

pyridine

SCH3

NaSCH3
OH

acetone

The formula of the intermediate indicates it has just one OTs group. TsCl reacts with the less
hindered 1o alcohol instead of the more hindered 3o alcohol.
OH

5.

H2SO4

Acid-catalyzed hydration:

H2O

OH
1. Hg(CH3CO2)2, H2O

Oxymercuration-demercuration:

2. NaBH4

OH
1. BH3

Hydroboration-oxidation:

6.

2. NaOH, HOOH

OH2

I
I

H2O
I

Some variations on this mechanism are acceptable.

H
I

HO

OH2

Chemistry 30B

Exam 2 Practice Problems Solutions

OH

7.

Page 3
OH

HO

OH2

(a)

OH2
HO

HO
H

OH2

(b)

HO

OH2

H2O
H2O

(c)

CH3O

CH3O

8.

OH

H
O

OCH3
O

CH3O

H
CH3 HOCH3

CH3

CH3O

H3C

HOCH3

OCH3

OCH3
CH3

CH3

CH3

OH

OH

The product results from nucleophilic attach at the most highly substituted carbon of the protonated
epoxide because this is where the + charge is largest and the CO bond is weakest.
9.

(a) Alkoxide: CH3O(b) Williamson ether synthesis:

H

(c) Oxonium ion:

CH3

(d) PCC:

N
H

CrO3Cl

CH3CH2I

NaOCH3
CH3OH

CH3CH2OCH3

Chemistry 30B

Exam 2 Practice Problems Solutions

Page 4

10. (a) Retrosynthesis:

I SN2
Ph

Hydroborationoxidation

TsCl
Ph

Ph

OTs

OH

Ph

Forward direction:
1. BH3

TsCl

2. NaOH, H2O2

Ph

Ph

Ph

OH

pyridine

NaI
Ph

OTs

acetone

(b) Retrosynthesis:
CH3O

HO
Williamson
ether synthesis 2x

HO
OCH3 SN2

OCH3

OH

OCH3

OCH3
HO

HO
epoxidation

elimination

Br

Forward direction:
HO

HO

HO
CH3CO3H

KOC(CH3)3
HOC(CH3)3

Br
CH3O

HO
NaOCH3

1. NaH

CH3OH

OH 2. CH3I
OCH3

OCH3

11. (a)

Cl

CH3

Toluenesulfonyl chloride (TsCl)

OCH3

and
N

Pyridine

Chemistry 30B

Exam 2 Practice Problems Solutions

Page 5

(b)

CH3O

CH3

(c) -OTs is a very good leaving group because its departure causes a significant increase in electron
delocalization by resonance.
(d) Reaction:

NaCN

CH3OTs

Mechanism:

CH3CN

CH3CH2OH
C
H3C

OTs

CH3

12. (a) Reaction B An epoxide is an ether in which the oxygen atom is part of a three-membered ring.
(b) Reaction B
H
O

(c)

OH2

OH

OH2

OH
OH

OH

Ph

Ph

HO

OH2

Ph

Ph

(d) This is the faster reaction because Eact for the rate-determining step is lowered by the relief of ring
strain.

13. (a)

(b) Reaction E

(c)

(d) Reaction F is less efficient because NaOH will cause E2 elimination in competition with the
desired intramolecular Williamson ether synthesis reaction.
Reaction G is less efficient because it requires an SN2 displacement of a leaving group at a 3o
carbon. A 3o carbon is too sterically hindered for backside attack required in the SN2 mechanism.

Chemistry 30B

Exam 2 Practice Problems Solutions

H

14. (a)

OH2

Page 6

OH2

HO
H
H
H

HO

OH2

OH2

H2O
H2O

HO

OH2

OH2
HO

H
OH

OH

Product H is not major because the first step gives the more stable 2o carbocation. Because we
cannot easily predict whether the capture of water or rearrangement step is faster, we cannot predict
whether product I or product J is formed in a greater amount. You may find it useful to review the
carbocation tutorial at the course web site.

(b)

15. (a) Hydroboration-oxidation. Addition of BH3 to the pi bond to form an organoborane is hydroboration. Conversion of the organoborane into an alcohol with HO- and H2O2 is the oxidation part.
(b) Product H The net product of hydroboration-oxidation is anti-Markovnikov addition of water
across the pi bond.
H
BH2

BH2

(c)

(d) Anti-Markovnikov
16. (a) Oxymercuration-demercuration. Addition of Hg and water to the pi bond to form an organomercurial is the oxymercuration. Reduction of the CHg bond to a CH bond is the demercuration part.
(b) Product I The net product of oxymercuration-demercuration is Markovnikov addition of water
across the pi bond. A carbocation is not involved, so carbocation rearrangements cannot occur,
and product J cannot be formed.
Hg(OAc)2

HgOAc + OAc
HgOAc

(c)

OAc
HO

HO
HgOAc

OH2

HgOAc

HgOAc

Water attacks the more substituted carbon of the mercurinium ion for the same reason a
nucleophile attacks the more substituted carbon of a protonated epoxide.

Chemistry 30B

Exam 2 Practice Problems Solutions

Page 7

(d) Markovnikov
(e) The reaction does not involve a carbocation, so carbocation rearrangements are not possible.
17. (a) Oxonium ion: A molecule having exactly three covalent bonds to an oxygen atom which bears a
formal positive charge. Your example can feature three carbon-oxygen single bonds, or one carbonoxygen single bond and one carbon-oxygen double bond. One example of each is shown here.
H
O

O
H

An oxonium ion with three

single bonds to oxygen.

An oxonium ion with one single

bond and one double bond to oxygen.

(b) Not all oxonium ion fates are possible for all oxonium ions.

Be deprotonated:

O
H

OH2

Ionization of carbon-oxygen bond:

OH

Elimination:

H2C

CH2 +
HO

H2O

H
I

Displacement by a nucleophile:

+
HO

18. (a) In each case, the reagent converts the alcohols OH group (a poor leaving group) into a better
leaving group:

OH

PBr3

OPBr2

OH

SOCl2
R

S
O

OH

H3O+

OH2

Cl

(b) PBr3 (phosophorus tribromide) and SOCl2 (thionyl chloride) react with methyl, 1o, and 2o alcohols
to give alkyl bromides and alkyl chlorides, respectively, each with inversion of stereochemistry.
Due to the SN2 nature of these reactions, 3o alcohols or alcohols in which the OH group is attached
to an sp2 or sp carbon are not converted to the corresponding alkyl halides.
PBr3

SOCl2
OH

Cl

SOCl2 gives alkyl chlorides

OH

Br

PBr3 gives alkyl bromides

Chemistry 30B

Exam 2 Practice Problems Solutions

o

Page 8

The reaction of aqueous HCl, aqueous HBr, or aqueous HI with a methyl, 1 , or 2 alcohol gives the
corresponding alkyl halide by an SN2 mechanism. Inversion occurs.
aq. HCl
OH

Cl

When the alcohol is 3o, an SN1 mechanism occurs, and a mixture of inversion (major) and retention
(minor) products results.
Ph
HO

CH3

Ph

aq. HCl

Ph
+

H3C

Cl

Inversion
Major product

Cl

CH3

Retention
Minor product

19. (a) Alkoxides are good nucleophiles because they have a negative formal charge.
(b) Epoxides are more reactive than other ethers due to relief of ring strain when an epoxide CO bond
is broken.