3-alkyl-[delta](2)-cyclohexenones and m-dialkylbenzenes

149 Pages·011.069 MB·English

by  Plapinger, Robert Edwin

3w ajan>A. m b m rum jm jm m m B
By
Robert Bdmtn Flapinger
Thesis submitted to the Faculty of ih® Uradu&ie School
of the University of SSaryland in partial
fttlfilliaexit of the requirement® for the
degree of Soot or of Philosophy
1951
UMI Number: DP70525
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ACOQ^DGSENT
The author wishes to express his sinsare gratitude te Br*
0* Forrest Veods for his counsel and guidance throughout ih#
sours# of this invest igat ion *
The author also wishes to thank Mra* Mary Aldridge and
Hr* Byron Baer for the misSremlyai* of the various sompounda
feaoountsred in this invest Igsi ion*
TABLE OS* GOJITBPTP
IIITB OBL'CT XCUi • • * » * * * ♦ * • * • * * • * * • * # • * * * *
HISTORICAL.......................... t . * » i t « t * . 3
Synthesis Lith 3~Othoxy-A?~cyol©h©xo»©n® « * * 3
Preparation of ^~hlkyl~£S?~oyolohexenense * • « 10
* * * * * *
Method© of Measuring fypereonjuget ion * * * * * if
Conversion of 2 ^ 2H3y cXohsxenones To Phenol© * 29
* * * * * * *
The Preparation of j^DIalkylhensenas * * • « • * * * * * « 34
11 ,U*C LfOiSr ltd*' * * * * * * * * * * * * * * * * * * * * * * * * * * * 47
Preparation of £^~Oyelohexen©ne and 3«*AIkyl«<Z^~
oyeXotiejsenon#® * * * * * * * * * ■ * * # * # • # * * » * * ♦ 40
liyperso»xn^j onrraation Studies § Ultraviolet Absorption Speotra of
3*A‘lfcyln^**,oyelo&e3tsnoaos 6i
« « • * * * * * • * # * • # • •
Prep&r&t ion of sfDialicylb ensenes * • « « * • * • • • * • * 73
Off
ut r'-X: i,; j\L # » « # « • # * * • • • * # * • * • * * * * • * * • flJ
Prepn.rat3.011 of DiJtydrerosorclxiol • • • • » * * * . * • » • • %
Fr operation of the Silver Pali of Lihydror os orciaol 96
* * * *
Frspanrt ion of ih® &ono "Sibyl Siher of Bihydroreaorc inol
Preparation of 3~Alkyl~/\^~cnrcloheatenens * * * * * * * • 97
IT operation of 3-B‘et clohoxenon® * * * • • • * • fS
Preparation of»3~IaonrQrvI«/\2'»cyclohexenoHe * * 99
Preparation of 3«*ss»»Bai vl-/\ &*eyoishoxenoao * * * # * •* * . 100
Attempted Preparation of i-Bufcyllitfciusi « * * * « # * < * * * 101
H©setion of 3-Bthoxy»^2-*eyclohe3cen©ne Pith Lithium. Aluminum
Hydride (Preparation of ^ 2~Cy olehexenone) * * * * * * * * * 102
^reparation of 3-Phenyl-A ^cvclohox^none * . * • • « • • • * 102
Purification ©f 3-»A2JtyX-A.2**©y©X©li#x»iBim©« f«r Ultraviolet
Absorption % $etra dttoraim t ions « * » » « • * « » ♦ « * * * 103
U ltraviolet Aboorpfcioa Spectra o f/\ %-Oyolola©3fc©**&ao and
3*-fclkyl-^^'»eyeXoh^x©nones « * * • * * » • • » • • * * * * « 104-116
Frop&r&tion ©f X-£1i©»yl~3^©thyl©3r©i©k©x&di©ii8~l § 3 * * # 4 * 117
Preparation of 1* 3*Dfe#thylojolofe.@j![mdi©B©**i^ 3 * * • * * * * 117
f¥©parait©n of 1, 3*91et>wleycXoh«xa<ll«iiO"»lt 3 * * * * * * * 118
Preparation of l~3Efr*Bttfcyl"3~©tJiyley©lohe3u&£i®2S©-'l* 3 * # « * * 118
Proparation of X# 3**&f*a**»^yXoyoXoA#«adieBO^i| 3 • * * « # ♦ *-J1it * •1£* O^
i’roparo.t ion of l-i~But yl-3**o-but^X©yclohesKadistto-X * 3 * * # * XXf
&ttempted Pr operation. of I~ii*Stifcyl~3Ht~fcufcyX©y©l©h©xadi#&©~
i 'i *. - *. « * ^ Ilf
Preparation of Qhlosrcmll * * * * # 121
•r;*•, .rat tor. of 3 hylfcIphony1 » * • • • • • * » « -• * * * * 121
Frepar&t ion of 3-aengrlearboxgrlic Acid * * * « • « • » » * * * 121
Attempt a To Befcy or ogemt © X9 ^^T^Xkyioyoloheaatlione^ls 3 * 122
Fropfcraiioa ©f ra~Xyl&m « « • » » » • » # » # * * » * * * % * 123
Preparation of 2> 4* €~trinitrc^m-nyXone * * * * * * ♦ * * <* 124
Preparation of loophtbalie Acid from m*>xyl®m • • • * * ■* *- * 125
Preparation ©f ar&i«t fcylbosiftoao * * * * * * * * * * * « © •' 125
Preparation of ia**Ei byl~n~b«fcyXbens ©ix© * • « • * # * * ♦ # # « 126
Fropar&tXon of X-2fcJ*yl~3~*i~bwtyX©yolo&©xa»© * * * * * * * * * 127
f*#pamii©» ©f ia»Bi»!>4&ufcyXb©ns©n* * * * * * * * * *' * # # * 12?
Preparation ©f la^a^Butyl-t-butyXboogon© * * * * * * * ♦ ♦ # * 125
Froparatieti of »»t~&tftyXbeiUBele Held * * * * * * * • * # * <* 130
U ltraviolet iboorptioa Spectra, of m-Dia Xfcy Ibon**nea * * # * m X3X-H9
U^.VTUTO: CTTtB # * * * * . * * • * » • * .................. 140
XU-'SCHC kI-UT IGh
Sarlior workers 3» *» ^ in this laboratory Irnvo shown
that the jsobo ethyl mml otlier of aihydroresoreinol can be utilised as
A
a synthetic agent for preparing 3-aryl- ^-cyclohsxenones and a*
diaryIhonzones by the following reactions
Pd-C
>
'00
II If'
where ii^ and B represent aryl substituents*
Ik order to demonstrate the v@rsat ility of this enol ether
as a starting m aterial for the synthesis of different types of compounds*
it beea&e necessary to establish that the above reaction series could
be used a© a general method of synthesis regardless of whether R^ and.
S were aryl or alkyl substituents#
Therefore this thesis concerns itse lf with the preparation of
A 2 ~eyelohexenott*» 3-alkyl-A . ^»cyolahexemm©s 9 X, 3~d ialkylcy clohemdiene©**
l f 3» and the ra-dialkylbon«©ne8# A general method is also put forth for
the preparation of the rn^alkylpheaols• In the case of the ketones of
formula. (II) * the eubsrfc ftuoni m e varied from methyl* to etltyl and
through the propyl and butyl radicals* :<vith the diaJJcyley olohexadieiies
(III) and di&Xkylbensene* (!V)f aid were chosen in such a manner
so as to represent as nary diverse types of hydrocarbon® a© was
ey nfc hot ically feasible#
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