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 LIBRARY ProQuest Number: 10666176 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10666176 Published by ProQuest LLC (2017). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 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