Rearrangement reactions of some aromatic sulfur compounds

125 Pages·2017·8.33 MB·English

Iowa State University Capstones, Theses and
Retrospective Theses and Dissertations
Dissertations
1945
Rearrangement reactions of some aromatic sulfur
compounds
George Ambrose Martin Jr.
Iowa State College
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Recommended Citation
Martin, George Ambrose Jr., "Rearrangement reactions of some aromatic sulfur compounds " (1945).Retrospective Theses and
Dissertations. 13647.
https://lib.dr.iastate.edu/rtd/13647
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mMmmomsm RmoTioim OF SOME
ARCMATIC BULfm OOMPOUNDS
(3-eorge A. Martin, Jr.
A Thesis Subaltted to the (l-i«aduate B'aoulty
for the Degree of
DOCTOR or PHILOSOPHl
Major Subject J ;._OrgaiilG\. Ghemlsti^
Approved:
Signature was redacted for privacy.
In Cha.%e of Major Work
Signature was redacted for privacy.
/f ^
He^ o'f/MsJor Diparroent
Signature was redacted for privacy.
Dean of Graduate Colfsge
Ioi?a State College
1945
UMI Number: DP12836
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ii
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AGIIOWLEBCaiENT
The author is siriC0re3.j grateful to
Dr. Henrj G-llasJi, whose valuable suggestions
and @Bcourag@feent ha,ve been of f^reat asplet-
ance torlng the course of these studies.
ill
MLE OF' CONfSHfS
Page
INTRODlJCflOS . . . . . . . . . . . . . . . . . . . . . . 1
HISTORICAL . ...... 3
EXPERIMEHTAL , . . . . . . . 33
A. Rearrengeaent Reaction® in Liquid Ammonia ... 33
Potaselua etliylxanthate 33
£-Bro®othiopheiiol . 34
£-Ghl©TOthlop,h©nol 35
^-Bromophenyl methi'l sulfide 35
o-Chloropl:ienyl loethjl sulfide ........ 37
RearreHgeoent anino.tlon of o-bromophenyl
methyl sulflr^e with eodamide in liquid
aisBionla ....... 37
Rearrsngeiaeiit aialni&tloii of o-d'ilorophenjl
nethjl siilfia® '"'1th potassliffii koiae In
liquid araiaonia ............ . 39
^-Brofoophenjl methyl siilfon® 40
Rearrangejaent aralnatlon of o-broraophenyl
sethjl sulfone with eodsBlde in liquid
sffimonla . ..... 41
^-Acetafflinophenjl methyl siilfone . 45
o-Ghlorophenyl raethjl sulfone , , 46
Derivatives of sulflnie acids. u>-PhBnjl--
"beiisenesulfonjlproplophenone 46
^v-Plienyl- oj -( p-toluenesiilfonyD-proplo-
phenoiie 47
(V~pheii,yl- (2-chloro-5-nltrot}enzenesul-
fonyD-proplophenone .......... 48
ir
Page
(aj-Phenyl- E~thlophenoxy-4~iiltrobenzene-
s-alfonyl)-propiopheiione 49
Mag^esii® methylsulflnate . 49
'^-Phenyl- t^'-methanesulfonylproplophenone . . 50
S-Broso-4-methyll)enz0nesulfonlc acid 51
.p-Toluidine salt of 2-brorn.o~4-iaethylbenE6ne-
" sulfonic aold 53
2-Bromo-4-ii.ethylbenzeiieaulfonyl chloride . . , 53
• .Methyl 2-bromo-4-raethjlbeiiz©nesulfonate ... 54
Ethyl 2~bron]0-4-!iethylbenzenesulfonate ... 54
2-Br'0ffl0-4-!Bethylbenz6nesulf0namld8 55
g-Iocl0~4-methylbeiizen,esiilfonio acid 55
p-Toluldine salt ,of 2-iodo-4-methylbenzene-
sulfonio acid .............. 56
S-Iodo«-4-Eaethylben2enesulfonyl chloride ... 57
2-Iodo-4--ffl©thylbenaenesulfonaiSlde ...... 57
An attempted rearrangeraent amlnation of 2-
iodo-4-methylbenzen© sulfonamlde with
sodarold.e in liquid ammonia . ...... 58
An atte»pted rearrengenent aslnatlon of 2-
bromo-4-methylbenzeneBulfiJiaj,tilfle -Kith ao-;"'®-
slde In liquid gmmonla 59
8-Ac©tamlno-4-n!ethylben2eneBulfonlo acid ... 60
p-foluldlne salt of 2-ac©t8ffllno-4-aethyl-
"" benzenesitlfonic acid 61
B. Cleavage Reactions With Sodaiaide 62
.Attenpted cl@a,vag® of dlphenyl sulfone with
sodaiaid® in'liquid ammonia 62
Attempted cleavage of dlphenyl sulfoxide
with sodamide in liquid aron?onla 63
Phenyl aiethyl sulfide 64
¥
'Bimxfl iietiifl n- Ifo ne 06
."c .^f tiiethyl sulfone
tu no^v'TJi e ?ti ii r-r.-irtrdf.. . • . • 66
« o?io-r'--vT''oi^.i.'© QC5
.AI*.orr>tf5r cJitmn'^otMo'! oiio-r)-
In aiponia. 67
of . 69
C* ffiienti:is»«ie .... '?3
73
thl''iithr0ne~n/l*wtetTO:-ia,e , • ?4
'-nltreboiif.eneonl^onlc t-oid . » • ,» • . ?8
'3-Ghlors-5«aJt;Fol5enaeneenlfonfl olil.c>rl<le . • ?6
«'V-l0i'0-5»Bl,trf*^^.)e-}senes-tf'finic EciS . . . • 7?
•-'••! tro--2-*sill,.* > 3 ' , 7 8
S«l#lti'«t!.lrntlif©fit »»•»•.. 78
.'•''-•""•AffjS.! *0«1'Ar'Ulii "J*®!!® »*•»••»••*••• 79
SO
f). I>11>en2ofurrn Gtmpmsi&B 82
i>"Fliioi?©&il36fiEOfttroa 85
2«Fl;aeTOdl1:5efizo?»i»s.fi 84
2,3~'&3,aolac>s311jsn.sofmi»ai'i 8S
S. • In©!l it© cmpmmAs , • 86
4f~ 88
••4iiiiioltee»4-esi%fi:s^lo sqM 87
•' •»*'Jii3,l'o.=ylnol1'uv4-<'5 rbo-'ylls acM . » • . • 87
vi
Page
8-'Hy'droxyq«inollne-4-o.fii''boxyliG acid ..... 87
Methjl 8-h.ydroxyqKinolln©-4-earboxylate ... 88
4-Chloi'Ooer'boiiyl-8~aulnolinesulfonyl chloride 89
Qitirioline«4-08.rboxaiii4e-8-swlfonsilde .... 90
Methyl 4'-oa]rt:5oraethoxF-8-quinollri0Sulfonate , . 90
The stsnnio ohlorlrie complex of S-mercapto-
q«inoIi3fie--4~oa,rbo3?:jllc acid ....... 91
8-»Methylmercapt©quliioline-4-earboxyllc add. . 92
M.ethjl 8-Eiethyliiereaptoqtalnollne-4-carbo.xy]^e. 93
Bis-(4-cai%e3cy-8-q«iaol3rl)dlaiilflde . . . . . 9 4
Bls-C4-ear1^oiiethoxjr-8-q'aliiolyl)diaulflde ... 95
6-Metfeoxy-S-phsnyloMinoline-4-carboxyllc acid. 96
6-Metlioxy-«-2-pheyiylc}iiiRollne ....... . . 96
MitratioB of ,6-ia©thoxy-2--ph8iiylc}uinollne.
Prepi^retion of dlRltro~6-.nietlioxy-2-
phenylculnoline and mononltro-6-iaethoxy-
S-'Phenylraiiioline ............. 97
6-Methoxy-S-( m*-nitrophenyl)q iainoline-4-car-
'fe'OxyX ic HO id ... 99
Decgtrboxylatlon of 6-raethoxy-S-(m-iilti»o-
phenyl)qylnoline-4-carl30xylic aoid ... 99
nitration of 6'*iiethoxy-g-phenylnulnolln0-4-
08,rl>02:ylic acid. Preparation of nitro-
e-raeth.oxy-.S-phenyla uinol in e-4-oarl30xylio.
aeid and, dinitro-6~methoxy-2-phenyl-
qiiliioline-4-carboxylic acid ....... 100
2-IJltro-4-afflliioani0ol® 102
Be.n2al-3-iiitro-4-i!3etlioxysiilllne ^ ..... . 103
Attempted preparation of nitro-6-raethoxy-2-
plj@iiylQtilnollne-4~C!arboxyllo acid fro®
!senzsl~3-iiitro-4-iietlioxy64iiiliiie. Preoara-
!iltro-4-i3etliioxyphenyl)anil ...... . 104