THE OXIDATION OF ALIPHATIC ALCOHOLS AND ETHERS BY CHROMIC ACID AND ALKALINE POTASSIUM PERMANGANATE

139 Pages·04.743 MB·English

by  RUTLEDGE, THOMAS FRANKLIN

69-7920
RUTLEDGE, Thomas Franklin, 1921-
THE OXIDATION OF ALIPHATIC ALCOHOLS AND
ETHERS BY CHROMIC ACID AND ALKALINE
POTASSIUM PERMANGANATE.
University of Delaware, Ph.D., 1950
Chemistry, organic
University Microfilms, Inc., Ann Arbor, Michigan
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The Oxidation of Aliphatic Alcohols
and Ethers by Chromic Acid and
Alkaline Potassium Permanganate
oy
-
a.**
Thomas F - Rutledge
A dissertation submitted to the Faculty of the
University of Delaware In partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
September, 1950
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Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
AC KNOWLEDGE JffiNT
The author expresses his gratitude to Dr.
William A. Mosher, under whose guidance the present work
was carried out.
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TABLE OF CONTENTS
Summary
Historical Section
I. Chromic Acid Oxidation of Secondary and
Tertiary Alcohols
II. Chromic Acid Oxidation of Aliphatic Ethers
III. Oxidation of Alcohols by Potassium
Permanganate
IV. Oxidation of Ethers by Ozone and Oxygen
V. Velocity of Oxidation of Alcohols and Ethers
by Potassium Permanganate and Chromic Acid
Discussion
I. Oxidation of isopropyl Alcohol and Ethyl
Isopropyl Ether by Chromic Acid
II. Oxidation of Isopropyl Alcohol and Ethyl
Isopropyl Ether by Alkaline Potassium
Permanganate
III. Oxidation of Acetone by Alkaline Potassium
Permanganate
IV. Oxidation of Pinacolyl Alcohol and Ethyl
PInacolyl Ether by Chromic Acid
V. Oxidation of Pinacolyl Alcohol and Ethyl
Pinacolyl Ether by Alkaline Potassium
Permanganate
VI. Oxidation of Methyl Neopentyl Carbinol by
Chromic Acid and Alkaline Potassium Permanga
nate
VII. Oxidation of Heptanol-2 and Heptanone-2 by
Alkaline rotasslum Permanganate
VIIIt Oxidation of t-Butyl Alcohol by Chromic Acid
and Alkaline Permanganate
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Page
Experimental Part
Preparation and Purification of Starting Materials 64
1. Ethyl isopropyl ether 64
Isopropyl alcohol 65
3- Ethyl pinacolyl ether 65
Pinacolyl alcohol 66
5. Heptanol-2 66
6. Ketol of methylisobutyl ketene and heptanol-2 6?
O. Kydrogenolysis of ketol 67
8. T-butyl alcohol 68
9. Isopropyl t—butyl ether 68
10. Acetic acid 69
11. Methyl neopentyl carbinol 69
12. Acetone vo
)x±dation experiments 71
r>eneral procedure 71
1. Ethyl isopropyl ether - C1O3 73
2. lsopropyl alcohol - CrO-j 74
> » Ethjrlisopropylether - KMnO^ 75
4. Ethylisopropyl ether - KMnO^ 77
5. Isopropyl alcohol — KMnO^ 30
6. fT tt _ :t 82
7. t: it ^ tr 33
r» tt ^.
8. n 33
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page
9. Acetone — KMnO^. 84
10. Ethylpinacolyl ether - CrO^ 85
11. Pinacolyl Alcohol - Cr03 88
12. Ethyl pinacolyl ether - KMnO^ * 91
13. Pinacolyl Alcohol - KKnO^ • 94
14- Heptanol-2 -KMnO^ 97
15. » - 100
16. " - " 102
17- Heptanone-2 - " 102
18. T-bntyl alcohol-CrO^ - 104
19. T-butyl alcohol-KKnO^(alkaline) 106
20. T-bntyl alcohol - KMnO/^ (acetic acid) 108
21. T-butyl isopropyl ether - KKnO^ 110
22. Methyl neopentyl carbinol - KMnO^ 111
23. " " " - CrO-j 113
• III. Oxidation Rate Studies (Using CrOj) 116
Technioue hlo
Purification of starting materials 116
Rate Determinations
1. Isopropyl alcohol - benzene sulfonic acid 118
2. Isopropyl alcohol — acetic acid 120
3- Ethyl isopropyl ether — acetic acid 121
4. Isopropyl alcohol — acetic acid — benzene
sulfonic acid 121
5.■ Ethyl isopropyl ether — acetic acid — benzene—
sulfonic acid 122
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page
123
Figure 1
124
Figure 2
125
Table 1
126
Table 2
127
Table 3
128
Table 4
129
Table 5
130
Bibliography-
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SUMMARY
The oxidation of aliphatic secondary and tertiary
alcohols and ethers by aqueous chromic acid and alkaline
potassium permanganate has been compared. Possible
mechanisms have been discussed, and it has been concluded
that the differences observed In the case of these oxidants
are of degree rather than kind of oxidation -
No conclusions have been reached in an attempt
to establish the type of Intermediate complexing formed.
It appears that the function of the oxidant can be explained
by assuming a direct coordination of the metallic atom
with a center of high electron density, such as hydroxyl
oxygen. The function of the oxidant can be explained
equally well by assuming that complexing occurs via an
oxygen atom of the oxidant through transitory hydrogen-
bond formation. In some cases the latter explanation is
most readily applied.
A mechanism for ,the oxidation of ketones and
aldehydes to acids has been discussed. The intermediates
Involved are hydroxy carbonyl compounds, keto-acids, and
hydroxy acids.
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The relative rates of oxidation of isopropyl
alcohol and ethyl isopropyl ether by chromic acid have
been determinedr -The alcohol was found to oxidize forty
times as fast as the ether, and the difference was
explained mechanistically.
The role of hydrogen-ion concentration in the
cleavage of molecules during oxidation has been discussed
It appears that cleavage may be one of two initial
competing reactions.
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