The Sulfonic Acid of D-Camphor and Alpha-Bromo-D-Camphor

62 Pages·04.191 MB·English

by  Long, Frank Wesley

THE SULPOIXO ACIDS Of gM#ABtFH01) AID <*~BH0M0*a*€AMPHOE
W
frank v, os ley Long, Jr«
A ttosola submitted In partial fulfillm ent of the
requirements for the dopree of Doe tor of
Philosophy* in tine Department of
Chemistry in the Graduate
College of the State
University of Iowa
August* 1950
State University of Iowa
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A o n f f i i n w
Ths writer takes this opportmity
to mpmB& M® *&&«*#* fcppjpoelafcicfla and.
mdmiMtiofi to footer laiph I»* Sheinsr* who
soggsstod this prob&wm* for Ms encourage*
sssiit arid: assistance to this research.
Ill
UMtS OF COKfHBSS
p*e»
z, irm o D o ra o K ... .................................... . . . .......................... l
IX. U1STORXCAU.................. 3
III. 8X FK R ia5Sm & ....................................... 10
Dlc@iiSl0f«#.#*##*■*#*•#»#*##♦* *****•*# *#***## ** HO
®*thfi#i$o ©hloidlda#*# ♦ * i t #*####.***#t *####•# HO
teio x ld # a d d itio n HO
SnXfo&afcion of i^awphOT with dlottaxto*
ottlfu# IB
ti*0amphor and dlo*&n#*$tiXfu? trioxMa*##*#* 14
^^Er<m€»^|»aamplior with
tl&oxl&Of#•#**»*»**#**»•*«#+*•*#*»#*»•**«* 14
with sulfur trioxida***** IS
^aXfonfl ohXorl&*«###« 10
<*♦Bi*0m©-#*eamph©r with sM te aulfit##**#** 17
Methyl ©l&oroeuXf mate «*•«••*•*####«•***•*** 17
Methyl cmate*»#*#*»»**»**••# BO
Methyl «w©<tosali©rw3*siilfomitWfe»•*♦*•#♦♦*##♦ 01
°C *B2W©»JL^amph©r and m th.jl ehleresulf©net© 01
d»Cam ph© r«5^snlf«iie a©id moKH&y&rete*#»«*••
J^Oa^hor^S^aulfosii© a© id* anhydrous #«*#»*** SB
dMOisium ©alt of d^aamphoF^S^aul^mfl© a©id#* 23
Aniline ©alt of d^©amptor^i5*@ulf©iJi© acid*#* 23
Oehydretloti of d5» aniline wait of d«*
© &mph02^*&"»eulfonl © ao id # * • *« * « «»*7 ** » * ##«• 23
May© Xohexy lamina wait of .d«t**mp4ie*i<*8*
iiulfoni© Mid***************#*##*.#***##**# 24
sulfa t# of dioyelohexy l&mine#<*«*•«*«*#«**««» 24
Amine salt© ©f J^©amph©i^3^©ttlf0iii© aold*#** 25
Booaldlnw salt of #»©amphor^^®ulf©nio a©Id# 25
©< *ft&pthylf»alne ©alt of d^a©phOF*S*»
aulfoni© aoid*#**#****^*#*#*####**#***#*# 25
fi *$J&pthyl«ine salt of j|^©amph0r*»3**-
eulfonle acid#*####*#.••#*#•*««##«••***«•# 27
<|*©amphor<*$‘*ftulfonyl ©hlorid©*************** 27
pikg»
««*«*«#*«»«#*»*«#«»***
M ^ m p lm ^ S ^ m lfm m ili^ m # * * * ****#**#*«*#•#• #
IfctMYletot absorption spectra of d*camphor*
3*®mifonaml4c and d*eai«phoa^*suTf ©na&l lid# 32
retention trie titration of 4#*o«ph0r<*3»
caif«maniii4c»#♦**##*#*#***##«*«•#*#*»**«** 33
0jcicbc^ylamiTO»*4«cm.mphoF»lO*stilfonatc****** « 34
pxaom aioii m vmiitm*******************.********#* a s
sf?MisAg?«**«*, ** m
d s a u o o iu n r. »• SB
V
m nm m
f P ^ g #
I Helatlirt of &mteo Sulfates
and I^ a w iiiw ^ ^ s u lfm a ta a te 0*2 M
w fcw S olution* **««»•#• **»*«##*•***«**#•* f f
I I ie ltte g Point# of ^*£y«pf*or su ifo n ie
m -M D e r iv a tiv e s #*«*•##* *«««* ***««*»#**«» o t
III f&kom i*€«pbor Porimtives and their
I 4 t ® w w fiefarenaaa*»##»*###*««#****•#$ 4§
IV Ce&poian&8 Prepared for this Reamiwh* *•***# Ml
v i
tmrn of urnwm
§ m p k P&B®
I Fotmtlmvtvlo. titratio n of
®muMmmtlM® « * * **«*#««**»*• »«*#*«## 4$
II; Ulteaviolat hbmrption ********* 44
III tlttvaviolAt A ^© rpti« Si^ets*** »**»*•*** 40
X
I
IWfROOttOTlOH
Tim us* ©f un addition confound of dloMne and
sulfur brioxide as si aulfating and sulfon&tlxig agent was
fir at announced fey a*. M* sutey (1)* The primary aim of
this worte was to identify the products obtained by the
reaction of ^camphor* d l^ amphor and ^bromo*d*oamphor
with dioxana^sulfur trloxlde mm$mt# It was hoped that
a much mere convenient method of isolation of the sul~
fonie acids formed and higher yields could bo obtained In
the sulf ©nation of camphor# This is to fee desired because
present methods of sulfonatlon of JL^e&mph r or o(#bi*«o*^
camphor result in either low yields or time consuming
methods of isolation or both*
Methods for the satisfactory preparation of &*
oamph0rwS*anlfonio said* Its methyl eater* sulfsnyl
chloride* sulfonamide* and sulfenanllide wore considered#
Frere Jaoqua (2) reported, that ^^amphor*3*sulfonai»ldtt Is
dextrorotatory while d»oamphor^5^Buifonanilide is levora*
tatory* An attempt has been mad# to determine the cause
of this unusual behavior#
B
ft» purpose of this investigation was to contrl*
huts to the ehralstf? of eaiapher sulfonic molds and their
derivative®, in order to help &dwmo# their use m rnmlt**
ing agent® for optioallf active has®® and asiuo a®Ida*
fhr®e sulfonic aold# of j|*^&nphor are known.*
f s
«%
< . f w ,
0^^ ■ '■ '■ d —I— d*0 G%------0 ---------CO c%- 0 — 0*0
•
o y L v j u a i c%»c«c%
1% ■OH- *c% 0 % Oil 0% c% CH----CBS%H
i 3 m
jJ»® am pher*l$* d^aaqpfoop* TT* ifo a n phor^w
sulfonlo &el$ su lfo n ic acid aulfottle aeid
3
XX
IX $f0iX «&
f'tew BuMmi® acid® of j|*oa»phor tmm hmm, r®«*
ported* lipping and Fop# (a) reported Oho firs t «aoee«*fttl
ftuXfmatlon of J^amphor In 1893* tlm®® mmUwa Identified
J|*oamphor« Tt^eulfonlo aoid m the product of oulfeoatloKk of
jNswnphor with either 8QJS fwtog aulfurlo aeid or ohloro*
sulfonic acid,
cH,
|% I
{®g--------G—— C*0 CHg-------0-------C*0
4*0% | CHg4«CHg4fi OgH
®%
<JBg CH CBg C % ------SI!-----GHg
lS
CHg-------<3-------C-0
w ho3s| — cj’ig-e.ciijj
0%-----Cl----GHg
ftmf also obtained ~r"»0ulfenie acid from
<<»br«€^*oamptor * the le t tor nirn was ueed to denote the
now position m different fro® «<or | positions* and refer*
to carbon atom 8 or 9* Th® choice of *f ir n mm &m to the
fact that identification mm made hj ttpyroly8i»H of the