You are on page 1of 8

Chemistry H252 1.

Winter 2000

Exam 3 KEY

February 16, 2000

Predict all the products of the following reactions and show stereochemistry where important (2 points each for a total of 20). Br2 FeBr3
OCH3

+
Br OCH3 Br OCH3 OCH3

NaNH2 NH3
Br NH2

+
NH2 H O O

+
H2 N H H O O

1. Na (0), NH3, t-BuOH 2. O3 3. (CH3)2 S 1. AcCl, AlCl3 2. HNO3, H2 SO4


NO2

NO2 O NO2

Br

NaOCH3 CH3OH 1. Cl2, AlCl3 2. Zn(Hg), HCl

CH3O

Cl O NO2 O O NO2

HNO3 H2SO4
O OH

O2N O

1. CH3Li (2 eq.) 2. H3O+


O

CH3

O O O

1. AlCl3 2. O3 3. (CH3)2 S

O H O

Via

1. I2, HNO3 2. t-BuCl, AlCl3 2


I

Chemistry H252 2.

Winter 2000

Exam 3 KEY

February 16, 2000

Provide a mechanism for the following reaction. Show all intermediates and all resonance forms for any intermediates that can be described by more than one resonance form (5 points). Draw an energy diagram for the reaction (2 points). Will the rate of reaction change if benzene is replaced with hexadeuterobenzene? why? (1 point).
D NO2 HNO 3 H2SO4 + H2O D D hexadeuterobenzene O Mechanism: O N OH + H O O S OH O O O N OH2 + O O S O OH D D D

nitronium ion O

O + H2O O O S OH O

NO2 Rate Determining Step

NO2

H NO2 NO2

NO2

sigma complex

Reaction Energy Diagram: H NO2 HSO 3 The reaction proceeds at the same rate for both benzene and hexadeuterobenezene. C-H bond cleavage is not occuring in the rate determining step.

Energy

HNO3 H2 SO4 Reaction Coordinate

NO2 + H2O + H2SO4

Chemistry H252 3.

Winter 2000

Exam 3 KEY

February 16, 2000

A by-product of the sulfonation of benzene is diphenylsulfone. Propose a mechanism for the formation of diphenylsulfone under the reactions conditions below (5 points). You do not need to show all the possible resonance forms the intermediates.
O SO3 H2SO4 S O OH + O S O diphenylsulfone O S O O H O O OH O S O HO S O H O O S O OH O S O O O OH H O S OH S OH O O OH S + O O O O S OH

O S O H O O S OH O O S O

O S O O S O + H2O + O O S OH O OH2

Chemistry H252 4.

Winter 2000

Exam 3 KEY

February 16, 2000

Devise a synthesis of the following compounds from the indicated starting material and any other reagents you need (5 points each for a total of 10).
O H + H O O H O O H From

O AcCl AlCl3

Na(0), NH3 t-BuOH

1. O3 2. (CH3) 2S Targets

O2N O

From

HNO 3 H2SO4

NO2 1. KMnO4, NaOH, Heat 2. H3O+ O

Target

1. 2eq CH3Li 2. H3O+ HO

NO2

Chemistry H252 5.

Winter 2000

Exam 3 KEY

February 16, 2000

Provide reagents that will accomplish the following transformations (14 points).
O 1. AcCl, AlCl 3 2. Br2, FeBr3 Br 1. Ac 2O, DMSO or PCC, CH2Cl2 2. NBS, hv Br OH 1. H2, Rh, pressure OH OCH3 1. AcCl, AlCl 3 2. HNO3, H2SO4 O O Cl 1. AlCl3 2. NaIO4 OCH3 NO2 O H

OH

2. Na(0), NH3, t-BuOH 3. Zn(Hg), HCl

H 1. NBS, hv 2. 1,3-dithiane, n-BuLi 3. I2, H 2O O

Br 1. Br2, FeBr3 2. HNO 3, H2SO4 O2N

Chemistry H252 6.

Winter 2000

Exam 3 KEY

February 16, 2000

Reaction of acetophenone with Br2 and FeBr3 gives the product indicated below. Does this reaction occur faster or slower than the treatment of benzene under similar conditions? (1 point) Why? (1 point) Using both pictures and words explain, in detail, the regiochemistry observed in the bromination of acetophenone (5 points). In order to get full credit, you need to provide a detailed mechanism showing all resonance forms of all intermediates.
O Br2, FeBr3 O

Acetophenone

Br

The reaction will be slower for acetophenone than for benzene because the acyl group is a deactivating (electron withdrawing) group.
O ortho Br H Especially destabilized (+ charge adjacent to EWG) Br H H Br Br O O O

O O Br2 FeBr3 H meta Br H Br

Br

Br

O H Br H

O H Br

para

Br Especially destabilized (+ charge adjacent to EWG)

Br

The sigma complexes leading to ortho and para products are destabilized relative to the sigma complex leading to the meta product. Therefore, the activation energy leading to the meta product will be less than for the ortho and para products and thus the meta product will predominate.

Chemistry H252 7.

Winter 2000

Exam 3 KEY

February 16, 2000

Chloropyridines undergo nucleophilic substitution reactions with sodium methoxide to provide methoxypyridines. For example, 2-chloropyridine gives 2-methoxypyridine (below). Provide a mechanism for this reaction (2 points).
NaOCH3 N Cl CH3OH N OCH3

Order the following chloropyridine derivatives from high to low in terms of their reactivity towards nucleophilic aromatic substitution. The one that reacts the most quickly should be labeled 1, the slowest 3. Explain your answer (5 points).
Cl Cl N Br N CH3 Cl

Mechanism:
OCH3 N Cl N OCH3 Cl N OCH3

Rate of Reaction:
3 Cl N Br N CH3 Cl 1 2 Cl

For the pyridinium salt, one of the resonance forms of the intermediate bears no charge. This will be a stable, neutral species and the activation energy is, accordingly, low relative to the others. In the case of 3-chloropyridine, the negative charge in the itermediate cannot be localized on the electronegative atom (nitrogen). Therefore, this reaction would be expected to be slower than for 4-chloropyridine where the negative charge can be localized on the nitrogen.
Cl N OCH 3 Cl OCH3 N N Cl OCH3 N Cl OCH3

N Br CH3

Cl

OCH3

OCH 3 Cl stable (netural) CH 3 species CH3O CH 3O Cl N N CH3 Cl

OCH3 Cl CH3O N CH3 Cl

OCH 3 Cl

Cl CH3O N

N negative charge on electronegative atom

Chemistry H252 8.

Winter 2000

Exam 3 KEY

February 16, 2000

Propose a mechanism for the following reaction (4 points).

H2SO4 + O + H2O

O O H O S OH O O O S O OH H O O S OH O O H OH

OH2

OH OH H O O S OH O

Product O O S O OH

H + H2O

You might also like