Chem 201 Van Vranken

Problem Set 4 - Key

Due October 25, 2016
1. Suggest a plausible arrow-pushing mechanism for the following reactions.
a.1
O
cat. HCl O
O
CH3OH HO OCH3
65 °C, 21 h 85%
b.
O
10 mol % Et 3N O
O
CH3OH HO OCH3
20 °C, 1 h 100%

Answer:
-A:
H A + A-
O: OH H
OH
O+
O O O
..
HOCH 3

H : A-
H A : OH +
OH O
O .. O H CH 3
O O O
+
OH

- O :O -
O: O
B: H OMe O O

O O
CH 3 CH 3
O O
O: H B+ OH
-

b. Using the pKas below, estimate the relative ratios of HCl/protonated lactone/protonated methanol at the
beginning of the reaction.
Chem 201 Van Vranken
OH+ H
H Cl +
OEt O
H
pKa -7 -6.5 -2.2

approximate ratios 1 1 10 4-5

■ Since MeOH is the solvent and present at around 20 moles/L,

it will have about 20 times more of the protons than we estimate here
■ The important point is that most of the protons reside on MeOH 2+, not
HCl. However, since HCl is 10 5 more acidic, you can't predict which
species is acting as the acid catalyst. Use H-A to symbolize the acid
catalyst in your arrow-pushing mechanism.

2. Suggest a plausible arrow-pushing mechanism for the following reaction.2

BF 3•OEt 2 O N
OTs 91%
O MeCN
0 °C TsO
Answer:
Me
Et
BF 3 - BF 3 C
+ O BF 3 .. - ..
- O +O F 3B O N
Et +
N C Me TsO
..

TsO TsO

3. Suggest a plausible arrow-pushing mechanism for the following reaction.3

OH
O 80%
NaOH O
OH
O
O O t-BuOH O OH
reflux, 24 h
OH

Answer:
Payne
: B- rearrangement OH
OH OH OH
O H O O O
.. O = O
O O O
O O - O
O O
-O - O:
..
O O
O - O the desired O OH
O O
cyclization
O O OH was not O
OH OH observed: OH

4. Suggest a plausible arrow-pushing mechanism for the following transformation.4

Chem 201 Van Vranken

cat. O
Et Et OEt CF 3SO 3H Et
Et 74%
O
CH2Cl2
H - 78 - 23 °C
2h OH

Answer:
Cl H Cl H H
Cl E2
Cl Cl
CH 3O: H 3CO H 3CO
- O :O H
H - O H
: B-
H H
H 3CO -
H 3CO2C ..
O
:OHCH3 H OCH3
B
-

5. Suggest a plausible arrow-pushing mechanism for the following transformation.56

Cl H excess H
Cl CH 3ONa
H 3CO2C 70%
65 °C
O H OCH3

Answer:
Cl H Cl H H
Cl
Cl Cl
CH 3O: H 3CO H 3CO
- O :O H
H - O H
: B-
H H
H 3CO -
H 3CO2C ..
O
:OHCH3 H OCH3
B
-

6. Suggest a plausible arrow-pushing mechanism for the following transformation.7

O Ph O
NaOH
O HO 87%
Ph
H 2O Ph ONa
Ph 100 °C, 6 h
Answer: This is called the benzilic rearrangement
Chem 201 Van Vranken

O Ph Ph Ph Ph
O Ph -O
.. Ph HO Ph HO Ph
HO: HO Ph H
- O Ph O O -O O Na-O O
:O ..
-
Na+
7. Suggest a plausible arrow-pushing mechanism for the following transformation.8
i) NaOH, Cl2
O H 2O, 80 °C, 30 min
O2N O2N NH 2
NH 2 80%
ii) aq. NaHSO 4
(workup)

Answer:
O : B- O Cl O
Cl
O2N H O2N ..- O2N Cl
N N: N
H H H
: B-

- - O HO O -B: H
O: O O
HO:
O2N Cl C
N
O2N
N O2N N: H B
= - O2N NH

any order

-O ..
-O
O O
workup +
O2N NH
.. O2N N H O2N NH 2
O C O
H H
A

Additional Problems

8. Suggest a plausible arrow-pushing mechanism for the following transformation.9

OAr Me 3O+ BF 4- OAr

NH 2 NH 2+ 76%
9:1 CH 2Cl 2/Et2O BF 4-
O 23 °C, 6 h OEt

Answer:
Chem 201 Van Vranken

CH3CH 2 CH3 CH3CH 2 CH3

O: O+ O O OAr
CH3CH 2 H 3C CH3 CH3CH 2 + CH3 CH3
poorly soluble major oxonium NH 2+
ion in soln
OCH3
OAr OAr OAr Surprisingly,
..
NH 2 CH3CH 2 NH 2 NH 2+ only 4% of the
O+ methyl product
O: CH3CH 2 CH3 + OCH 2CH3 OCH 2CH3 was obtained.

9. Suggest a plausible arrow pushing mechanism for the following reaction.10

BrCN NCN
S K 2CO3 S
N O
CHCl3
Ph 62 °C, 24 h Ph
OH

Answer:
N NCN
C :N –
S S S N S
Br C Br
+ + C
N: N N OH
H ..
+
Ph Ph Ph Ph
OH OH OH

10. Suggest a plausible arrow-pushing mechanism for the following transformation.11

CH 3CO 3H O
O Br BF 3•OEt2
O 70%
Cl 3CCH 3 Br
50 °C, 10 d

Answer:
- +
F 3B OEt2 BF 3 + Et 2O -
F 3B - +
- O+ F 3B O
BF 3
+O
O O
O :O +
BF 3 O H Br HO :O - O
O: HO
..
R R
OH
O

O
-A : H O+ O O
-
O O
I can't rule out an .. O
F 3B O
R Br R
alternative mechanism via...
Chem 201 Van Vranken

The full text version of Advanced Organic Chemistry. Part A: Structure and
Mechanisms, 5th Ed. Francis A. Carey and Richard J. Sundberg is available on
line at: [Link]

I recommend that you also work these additional problems in Carey and
Sundberg, 5th Ed.
Chapter 4 (Substitution) 4.2, 4.3, 4.13, 4.17

References
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40.
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Letters 1970, 11, 1071-1074.
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Chem. Educ. 1999, 76 (12), p 1717.
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Res. Dev. 2009, 13, 415–419
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Bremner, J. B.; Brown, E. J.; Chohan, V.; Yates, B. F. Aust. J. Chem. 1984, 37, 1043.
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Helvetica Chimica Acta 1983, 66, 2512–2518,