Table Of ContentPURDUE UNIVERSITY
THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION
Daniel Grafsteln
BY___________
Synthesis of Some Halogenated Sulfides
ENTITLED
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
- T
Phofessor in Charge of Thesis
Head of School or Department
August 14»________x-951
TO THE LIBRARIAN
THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.
FHOFBSSOB XV CHABGB
GRAD. SCHOOL FORM 9
SYNTHESIS
OF SOME HALOGENATED SULFIDES
A Thesis
Submitted to the Faculty
of
Purdue University
by
Daniel Graf stein
In Partial Fulfillment of the
Requirements for the Degree
of
Doctor of Philosophy
August, 1951
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ACKNOWLEDGMENT
The author wishes to express his sincere appreciation to Professor
Earl T• McBee, the director of this research, for his guidance and en
couragement throughout the course of this investigation*
Appreciation is also expressed to Dr. Z. D. Welch for his many
helpful suggestions and to the Atomic Energy Commission and to the
Westinghouse Electric Corporation, for the financial assistance which
made this work possible.
Table of Content3
Page
Abstract ............... 1
Introduction. ................. 1
Discussion... 3
Part I. Addition of T richloromethanesulfenyl chloride to
olefins. ....................... 3
Part II. Fluorination of 2-Chlore-1-trichloromethylthio
alkanes. ........... 8
Part III. The triehlorosethy 1 carbonium Ion. Some Reactions
of Trichloromethanesulfenyl chloride........... 11
Part Hf. Miscellaneous Reactions........................... 15
Reduction of 2-Chloro-l-trichloromethylthie
alkanes ....................... 15
Organometallic Compounds and trichloroaethane-
sulfenyl chloride... ....................... 17
Synthesis of 2,3-bis (3-trifluoromethyIphenyl) -
dioxane.. .......................... 18
B^erimental.. ♦ ................. 22
Part I. Addition of Trichloroaiethanesulfenyl chloride to
olefins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Triehloromethane sulfenyl chloride.............. 22
Cyelopentene.. ............. 22
2-Ch lor o-l-t r i ch loromethy It hi o-cy clopent ane.... 23
2-8hloro-3-trichloromethylthio-n-butane........ 23
2-Pentene. ................. 24
2-Pentene and Trichloromethanesulf«iyl chloride 24
Cyclohexene .............. 25
2-Chloro-l-trichloromethylthio-cyc lohexane ..... 25
2-Chlor©-l-trichl©romethylthio-2-methylpropane « 26
Sulfone of 2-Chloro-l-«trichloromethylthi©-2-
methylpropane. ........... 27
Dehydrochlorination of the Sulfone of 2-Chloro-
1-trichloromethylthio-2-methylpropane. . . . . . 28
Page
3-Tri chloromethylthio-dihydropyran, ......... 29
Styrene and Trichloromethanesulf enyl chloride. •• 30
Trimethylethylene and T richloromet hane sulfenyl
chloride...... ............. 31
Hexafluorocyclotntene. .................. 31
Hexafluorocyclobutene and Trichloromethane
sulf enyl chloride. ............... 32
2-Ghloro-l-trichloromethylthio-propane.......... 32
2-Chloro-1-t richloromet hylthi o -ethane ................. 35
Allyl bromide and Trichloromethanesulf enyl
chloride.... ................. 37
1,1-D ic h lor oet hy lene and Triehloromethane sulfenyl
chloride...... ................... . . . . . . . . . . . . 38
Oetafluoro-1,Z-dichlorocyelohemene and Trichloro
methanesulf enyl chloride..................... 39
Hexafluoro-1,2-dichlorocyelopentehe and Trieh-
loromethane sulfenyl, chloride ........... 39
Aerylonitrile and Trichloromethanesulf enyl chlor
ide....................................... 39
Dichloroethylene and Trichloromethanesulfenyl
ch lo rid e................ . . . . . . . . . . . . . . . . . . . 40
Part II* Fluorination fo 2-Ghloro-l-trichloromethylthio-
alkanes............................................. 41
Fluorination of 2-Ghloro-l-tri ch loromethy Ithio-
cye lohexane. .......... 41
Fluorination of 3-Chloro-l-triehloromethylthio-
n-butane.... ......... 44
Fluorination tif 2-Ghloro-l-tri chloromethylthio-
2-methylpropane ........... 45
Fluorination of 2-Chlor o-l-t rich loromethy Ithi o-
cyclopentane. ................ 46
Part III. Some Reactions of Trichloromethanesulf enyl chloride.
The Triehloromethyl carbonium Ion,................. 47
Trichlorofluoromethane from T richloromethane-
sulfenyl chloride..................... , 47
Tolrnic acid from Toluene ............... 48
Anisic acid from Anisole .................. 49
Preparation of p-Ghlorobenzenesulfenyl chloride. 50
p-Chlorobenzenesulfenyl chloride and Antimony-
(III) fluoride.............................................. 51
Preparation of Ghloromethanesulfenyl chloride... 51
Part IV. Miscellaneous Reactions. ............. 53
Organometa llic Compounds and Trichloromethanesul-
fenyl chloride. ............... 53
m-Bromot rif luoromethylben zene ................. 53
Grignard of m-Bromot rif luoromethylben zene and
Triehloromethane sulfenyl chloride......... 54
Grignard of a-emyl bromide and Trichloro
methanesulf enyl chloride.................. 56
Page
n-Propyl Cadmium chloride and T rich loro-
met hane sulfeny 1 chloride.................. 57
Di-n-Propyl Cadmium and Trichloromethane-
sulfenyl chloride* ........... 58
Phenyl mercuric acetate and Trichloromethane
sulf enyl chloride .......... 59
Reduction of 2-Chloro-l-trichloromethylthio-
alkanes. .......... 60
Trans-2-Hydroxyeyelohexanethiol diacetate... 60
GyclWiexme chlordhydrin.................... 62
Cyclohexene oxide. ......... 63
Thioacetic a c id ............................ .. .... 64
Preparation of Trans-2-Hydroxycyclohexane
thiol diacetate. .......... 64
Reduction of 2-Ghloro-l-t richloromethylthio-
2-methyIpropane, . . . . . . . . . . . . . . . . . . . . . . . 65
Synthesis of 2,3-Bis-( 3-trif luoromethy Iphenyl) -
dioxane#..... .............. . . . . . . . . . . . . . . 66
Summaxy ................. 68
Bibliography. .......... 69
List of Tables
Table Page
1. Triehloromethane sulfenyl Chloride Addition Products.*...* 19
2. Analyses and Physical Constants of Chlorinated Sulfides••
and Derivatives........................... 20
1
(Contribution from the Department of Chemistry and the Purdue Research
Foundation, Purude University, Lafayette, Ind.)
Synthesis of Some Halogenated Sulfides^
by Earl T. McBee and Daniel Graf stein?
ABSTRACT
1* From the Ph.D. thesis of Daniel Graf stein, Purdue University
2. Present address: Westinghouse Electric Corporation, Bast
Pittsburgh, Penna.
A series of chlorine-oontaiming sulfides have been prepared by the
addition of trichloromethanesulf enyl chloride to olefins. The addition
occurs with simple olefins including ethylene and the addition follows
Markownikoff1 s rule. Negatively substituted olefins failed to react
under the conditions investigated. Several of the addition products
were converted to the corresponding fluorine-containing sulfides by
reaction with antimony (I II) fluoride. T richloromethan e sulfenyl chloride
reacts with either antimony(III) fluoride or zinc fluoride to produce
triehleroflueroaethane in good yield. If certain aromatic solvents
are present during the fluorination of trichloromethanesulf enyl
chloride, aromatic acids are isolated on hydrolysis. A carbonium ion
mechanism is proposed for these reactions • 2-Ghloro-l-triehloromethyl-
thio-cyclohexane was converted to trans-2-hydroxycyclohexanethio 1
diacetate by the action of ginc and glacial acetic acid.
An .extensive study of the reactions of aromatic sulfenyl halides
