Table Of ContentPURDUE UNIVERSITY
THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION
Henry Rakoff
by_______________________
gggggffP Derivatives ofLILaxachloronynlnpentadlene
COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES
AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS
FOR THE DEGREE OF
Doctor of Philosophy
TO THE LIBRARIAN:----
THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.
PROVES SOB m CHARGE
GRAD. SCHOOL FORM e—3-49—IM
DERIVATIVES OF HEXAOHLOROCYCLOPENTADIENE
A Thesis
Submitted, to the Faculty
of
Purdue University
by
Henry Rakoff
In Partial Fulfillment of the
Requirements for the Degree
of
Doctor of Philosophy
June, 1950
ProQuest Number: 27714152
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ACKNOWLEDGEMENT
The author is deeply grateful to Dr. E. T. McBee
who was in direct charge of this investigation. Acknowledge
ment is made to Mr. J. Sconce and to Dr.'s H. C. Brown, 0. R.
Pierce, and Z. D. Welch for helpful advice. For valuable
suggestions and criticisms, thanks are due to R. K. Meyers,
to E. Rapkin, and to all the research fellows with whom the
author has been associated.
This investigation was financed by a grant from the
Hooker Electrochemical Company administered by the Purdue
Research Foundation.
TABLE OF CONTENTS
Page
ABSTRACT
Part 1# The Preparation of ^-(Dichloromethyl-
ene)-l,?,4,4,5,5-hexachlorocyclo-
pentene ........... 1
Part 2. Diene Reactions of Hexachlorocydo
pent adiene with Halogenated Olefins .. ix
Part 3# Attempted Preparation of 5»5“Difluoro-
tetrachlorocyclopentadiene .......... xviii
PREFACE ......................................... 1
PART I. THE PREPARATION AND PROOF OF STRUCTURE OF
3-(DICHLOROMETHYLENE)-l,2,4,4,5,5-HEXÀCHL0R0-
CYCLOPENTENE
INTRODUCTION .................................... 3
DISCUSSION ...................................... 4
EXPERIMENTAL .................................... 12
Preparation of 3-(dichloromethylene)-!,2,4,4,5,5-
hexachlorocyclopentene by the reaction of hexa-
chloropropene with hexachlorocyclopentadiene:
With continuous removal of tetrachloro-
ethylene .......................... 12
By repeated filtration of the solid
product .......................... 13
In a sealed tube ....... 13
In a sealed tube in the presence of
diphenylamine .................... 14
At the reflux temperature at atmospheric
pressure .............. «.......... Im
préparation of 5-(dichloromethylene)-2,3-
dichloro-2-cyclopentene-l,4-dione .......... 15
Action of potassium hydroxide solution on 5“
(dichloromethylene)-2,3-dichloro-2-cyclo-
pentene-1,4-dione ................... 15
Page
Preparation of hexachlorobenzene by prolonged
heating of a mixture of hexachloropropene
and hexachlorocyclopentadiene ......... 16
Reaction between hexachloropropene, hexachloro
cyclopentadiene , and tetralin ..... 17
Reaction between hexachlorocyclopentadiene and
tetralin ............................. 17
Reaction between hexachloropropene and tetralin .. 17
PART II. DIENE REACTIONS OF HEXACHLOROCYCLOPENTA
DIENE WITH HALOGENATED OLEFINS
INTRODUCTION .................................... 19
DISCUSSION ...................................... 21
EXPERIMENTAL .... 2?
Preparation of 1,2,3,4,5,6,7>7-octachloro-
bicyclo(2.2.1.)-2-heptene ....... 27
Preparation of 5 >6-dibromo-1,2,3>^>7>l^hexa.^
chlorobicyclo(2.2.1. )-2-heptene ....... 27
Preparation of 5-methyl-l,2,3,4,6,7,7-hepta-
chlorobicyclo(2.2.1.)-2-heptene ...... 2&
Preparation of 5-chloromethyl-l,2,3,4,7,7-
hexachlorobicyclo(2.2.1.)-2-heptene ...... 29
Preparation of 5-Ghloromethyl-l,2,3,4,6,7,7-
heptachlorobicyclo(2.2.1.)-2-heptene ........ 29
Attempted diene reactions of hexachlorocyclo
pentadiene with:
Vinylidene chloride ..................... 30
Trichloroethylene ....................... 31
Tetrachloroethylene ................... 31
Tetrafluoroethylene ............. 31
asym-Dichlorodifluoroethylene ......... J2
1.1-Dichloropropene ..... 32
1.2-Dxchloropropene ........................ 33
2.3-Dichloropropene .......... 33
Page
1.1.2-Trichloropropene ..... 33
l*2,3,3-Tetrachloropropene ........... 3^
1.1.2.3.3-Pentachloropropene ............. 3^
1.1.2-Trichloro-3,3,3-trifluoropropene ..... 3^-
1.1.2.3-Tetrachloro-3>3”d-ifluoroPr°Pene •••• 35
2.3-Dichlorohexafluoro-2-butene ...... 35
PART III. ATTEMPTED PREPARATION OF 5,5-DIFLUORO-
TETRAOHLOROCYOLOPENTADIENE
INTRODUCTION .................................... 36
discussion ......................................... 37
EXPERIMENTAL .................................... 42
FluorinatIon of hexachlorocyclopentadiene with:
Antimony trifluoride at atmospheric pressure ••. 42
Antimony trifluoride in an autoclave .......... 42
Hydrogen fluoride at 0°C. ............. 43
Hydrogen fluoride at SO°C* ............. 43
Hydrogen fluoride and mercuric chloride ..... 44
Potassium fluoride ......................... 44
Antimony trifluoride and catalytic amounts of
antimony pentachloride ................... 45
Antimony trifluoride and antimony penta
chloride .......... 46
Hydrogen fluoride and antimony pentachloride ••• 46
SUMMARY .................................... 49
BIBLIOGRAPHY .... 50
VITA ...........................................
LIST OF TABLES
Table Page
1. Diene Reactions of Hexachlorocyclopenta
diene with Halogenated Olefins ♦•••••••••• 22
2# Action of Various Fluorinating Agents on
Hexachlorocyclopentadiene ........... 38
