% ftongla* fr«Q ^lin ForoiveX A ¥ » Satoaitfcfwt to tlso Sotool o f dro&kat* Studies o f Miehlgim St*t* C©XX®$e o f i.pdo^Xtur® *w*d Applied % i«ne« in p«rti*QL fulfiXXasont o f i&® re^oireasaats fo r tiio 4offoo' o f D ocm o r ra o u M o ra r Doportaumt of Chemistry ProQuest Number: 10008405 A ll rights reserved INFORM ATION TO ALL USERS The qua lity o f this reproduction is dependent upon the quality o f the copy subm itted. In the unlikely event that the author did not send a com plete m anuscript and there are m issing pages, these w ill be noted. Also, if m aterial had to be removed, a note w ill indicate the deletion. uest, ProQ uest 10008405 Published by ProQ uest LLC (2016). C opyright of the Dissertation is held by the Author. A ll rights reserved. This work is protected against unauthorized copying under Title 17, United States Code M icroform Edition © ProQ uest LLC. ProQ uest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346 Tim urtter wishes to sjqpres* his appreciation to doctor Robert H. Barbtst f o r Ids counsel and aost helpful suggestion® during th#- sours# of this work, * * ** * * * -# » # ■*> i f ## *#*4* iSv # To nagr H s ia n m m ftariUovfeotaNMMriU* hm& boot* %mm for ymmm (X), * 0 ©»«iJ*F*ti&» of tit* p m p m tim of tlm» wmptmdE# forawl by t&o alkyloitoo «f X~aXJ^X-£^»*lso$«fcriw©Xo* ooggootod ifco* O foo OOdfc-flOM M bAfOOtffc^OO O fO r^ rffh tflfrtOrfc, wm^pTwKSIS'iPw jM UW M fM M AAM 'W kirX-Jift wfefkJ)HL»^| ^Wo ^IJarWEIWlr i$ii^9W 4VKUPd"™ OOiliw@ 4^-4*ewV'W .«gtilfcdtBFlEI# JiaOO •liTllpliiwp""w W# 1fm *WWP Tba proonat iovaoiifsfcion hm mroaXod fcbufc Ite |»rl»elp&X protosfc fra* the *&k^lfcfcXon of • X ^^X ^ioi^totriooX o in a X„l^«li^ «X^X^^i»liiot«tr^oXiiMi *ad *ot • «o bad boon fOm&fttod in #«rli«r studies (1,2). ft&» concluaior* *** *nib~ *fc«*ti»t*d bold* by S3nsthote$,« and dogradotivo prooodiHroft, •yntlsati^ «ppro&®& obomd %h«t tfe# Sim# tti# dXidisylmimiobrgool# mosXiod Opoo aXI^Xofciois of X-«XI^X-^«iiiotati**»oX«# m g»v&lm a of % b# w4«? of jAtrodoetioa of tio aXbfX jjraojs«# m atrwctor# in which Vm *Xfeyl %rmp* oooaplod *Otttvoi««xt position# (FormXsi t ) mm i»dle«t4tftw fis» «l«fradl«tiv« sppmmh ttm eoncluoioTi .^tot fcb# #Xi^X froapa mam% bo in tte X- or ibo ofoiooloo% fc-^oisltioa* m ii v*J5 V. 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W &p^l, botpX, m t^feonyXotbyX gtmpm- m the ww mfoaMktnmt, mud tfe* ba*»yl grotap a* bfea *mm& «iLaALtKLMB.dk: wBm vwiBJwww^ lW mMwpX oblorido to fop* iho ©awmpOf^iog ph»»yX**^ar«a and auXfooyX d^riv^tlv^e. tbo groat m&mmmmfe of tb* li«*&o&by o f tba X ~ teirfweXtnaa m omparod with tins X*^?syX-*5-*«i$imtotr«*oX«# appear* to bo m aooiatod g&tfe %ba $ M im i^ » tT m ^ ltm m W m tw m m& the rm *m m m pO'SOilidXitiOS fltilNMNttNb in tb© fflag't fog* o f X#ii^ii^iJ^X~S*00ot7XlMimtotyaaoXlii8« XM to %im im m tfc im o f Xfh^«Xl^X-^l^t©t#tr«RoXiiso## %. m o cless o f b#t#fooyoXM ses^Ottad#! idw om m id Ip tiro ly ii* of X#b^X^Xi^X^5-mo1yXi«Xmt«tr*^ soXtm# gam tfe* »«Xt of" th e e©3Pfo«i»ondint X fbrtlMir ,1 >1 i»*f^4 ifttvat. ro w a S ls d bb& b lassiilliNads *»** fe ^ iM s X m ia m sr# 9 m m0B flWSjrA JgJS"Wi«^ H8J® ®S* ©w© •HRgfflffeWffw ©a V9Q)lmvBWISIiwW ©*« vffl® babraaoX# moeXaaa * 4 aarloa o f X^aXlgrl^^«X^X«^inot®tra»ol®# mm pvmgtmd by th* iiit#r*&bl' ^ 1 * * M M 4 t ^t ^ M f# *p W «fclo® of X $ %4foXy*l« o f X,lM & tN»i*i^^ ^^ 4 4 #4 9 «4 9 v . **»**»** ACoiaX^oto Of X %&ri&3Wltt of X h w ip w a M m o f X^^b®«iw^^S^im oX7l^mtet3r6«©liji& #tM4V, o f l,l^<31boni«yX~£~ ty)>te# #■#*##. «#* * * « # # * « # * * * # # * « * « « » * * » * • + # ^ ^rdro^sdii and attempted u,# ^ a % 'i^jajfciyiYip?*iti^' 'fey ,?waij* ^ J&tmjpfeffd oootoljitlp o f XyU^b^syl^S^Kiwi^l^triWoXiiws, % ^roi^tlii m d att«H&pt«d *ootol/»la of 5-feo^tyX^d.ti0 t«tr««* so lo ............... ................................... ........................................... . tY , l@nirodMUs mad m *M l& w ia o f 1 ,li«*dlib«ia*^X-^ - M K U OT covxm s - Centliwed Pap PART |Z ...... .,,,,. pi.p|'p..,, jpjp,,.pp,p)............................................ ppirjpjpO ppppippqpjVVO f*Vpp 4pvV~fvpp*O f(JpiBI.V.O ' M O PB 4#* *4# #*'4.4 4 * 4*4 4 * * * 4 4* * * * # 4 *# *#« 4* *4 44** * * # * # # * 4 4* : , V* - 8g* &»7l «l i i m»* »t , « « , |J '« ) l » » f > ^ t l l l M M I , * » . . . . . . . . . . . . .......... h$ fc? Vi VtVfeiAjtflfMtiiillrfteJii'' * * ’» * * * * 44 4 4 4 » » 4 I * * * * * » * ***#*#■*# 4 4 « * 4 4 * f**f gtj^L P Vi '9tSy^b31?fettfc^A&M ^l jfrfart iO lirw W rt 1 fa dfe 4b 1*1liiKiiw/raHgWw# p»oil * # * # »*• # *#-4 • I I I ## wo «•##♦#**» M * t « i * ^ « # I© iiie *a a 4 a a **a *a .a .-4 -.,a {*6 <00 WPBi a^yMI B ff*tt ..mill uuMu^wWUMiiV'M^I4 BV4(P!4t'f4ett&lABfeaB4BaM&Bttlli, 4jtfbj4i4fcjlUib 1ft P’PI 4»* *■* 4 « 4* * 4 * 4 4# **v %J i % d i * i o r t i i d o « . V. l ^4^aa>^.yq*gm iteyii*14iftf» b^#piodlda »*«4« *»««••••» X^/ii^w^^XMyiaaAnetotraaol'®#.**#***#*****#*#♦ *•****##****** *#* lHa*4NtyX*5*n^b|rXoKiaot<*tra«©X# &&K»#**«#«*##*** ^ -8 )........... X -ta^utyl-S-tJ-bntylm inotatfsw l* (M eth o d B ),.,.. . . . . . . . . . . . tm m 5$ 5® SX 58 53 m . or tm W m tu * m a m m m /m » m m . s -’V ts tm w m a u m s s ........................................ s^m a m m m a m 5? X n f e r c iu e t i o x u ... .... .... ..... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . St M fW iM B U X ............................ 58 I&seassion,.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........... m tu n ,, tn w m m m w ........... 6ii 73 75 U M h» Pag* ft- ^it048^a*JHl.B. ■ w i .nfcab.#. ob-$ o % b #.■#b V f n f #•■■♦ o v ♦ o •###♦# * b>## XX Xga«»5»*wiB«4«*i‘a»«>Tlln« %4n >Uw U n 84 XXX ' P4nq4«Mjnur*a &wi«*i&*M X^-^M ^kyl-S -^iw telnrsM lln** *8 gr^ Paw M W l f w y l J>mA wtM .X ^ O l ^ $$o. Cln .->5* I- - *. *?V r ^ ^ It 9 • Ad !’ ' ’ f* n *. |> ■-• • ■;r 2 # T ho X n £ r# ~ r» d $poofc.rf* o f X -'*s X ^ .d « ^ ^ X ty X ^ ± o o t^ 1 i-rs E to X ^ 3 ^ 3* T1v$ I n t r ^ T ' i d o f 3 ^ ^ !^ X ^ * ^ I^ rla f» ij3 o t^ tt* ® s £ o X o fti~,#t^ •, •**?iiy-. ^•»•*>•;- Y j<► ' <*»tf>•*•* <*-t. £*#^j>4*v► -4-t> T he in T r ^ - ^ r ^ tl s p e c tr e i* f X fj^ /^ ^ o c liX o rX j--^s©» i>$ <*«4 * o ^ & >*»■* $ *?-**■■?v' * & ^ '* * ♦ * * ° o '■'* ®' ■ if* <* * ,1* ^ X file pttrp*** o f tfaii etadjr we* to eoiebliah the structure of © erieia d e l a t i o n product* o f hernia©teireecl© * although Thiele end i• XngXe (X ) bed atom th a t alkylation o f S^aBlaotetreeoX© could lead to se v e n ! mono- end diaUgrleied products, the structure* of these com­ pound* resettled to fee established wnefaiv&di&Xsr* More reecsiX j Heitost* R oberts, nodi B ervill (2> haw* studied the elkylotion of o iwwber o f l-elk y l-S -eraln o to tr^o lee. they noted th a t the introduc­ tio n o f * second eltgrl group caused milked change* in physical end chemical properties* xittM gfe stru ctu res were wwdgned to the di~ alkylated products, i t wee recognised th a t fu rth e r work ws* required to elucidate the tru e stru ctu re o f the compounds. When X ««dJ^X ^«^inotetrs 2oXes wm mono alkylated a v ariety of productts can he formed* K i 8 = 8 8 = ( I) 8 (XX) 8 E (XXX) MT If i n Ml — 8 I 8 (I?) * ! K -8 ' <*> Coapemds o f structure (XX) end (XXX) -were expected to predominate flOfig th e re action product#* Xxi Pert X o f th is th e s is the preparation o f a number o f compound* o f the type o f formula (IX), 1 ,X-di®Xk3rl-^<-fe8lix>tetr«*oltn®», 1* 2 dooerlbod mad ovidoooo o f tho oerrootoao* o f tho otruotiayao aoeigood iM davolopad by olrtmo of the method* of «ynth»»is and by dsgradativo jwpocKw®H0paa-d 2n F ort XIf th* preparation o f eoaspotmda of th® typo o f formal* (IH )# l*«llQ ?l^«X kylOBim t«tr ^ o lo o P by srroraX independent pro* oactara* la dooortbod, Thair chemical aod physical proportion are « b w to d tffa ra s tia to bhoaa compounds front predaat* o f typo (II) * Furthermore* I t i« the jmnpoaa of th ia abadty to attempt to da* oolop « baala fo r d iffe re n tia tin g « v ariety o f xmbotltotiozi prodttcte o f $ * « n lo o to trm la by no ossa of in fra-ro d apae iropbotoeiairy. P m 2 3 X jfe S lS 8 B S l8 S yfom ieb srts* end H arvill ( t) allqrXsiad te tre a c le s , dlsX&grlated products w re obtained which exhibited b asis p ro p erties; they formed a d its w ith aeida which were stab le in aqueous so lu tio n , roasted re ad ily id ih reagents seed te charasterlae amines, such as said chlorides and phenyl laotltgssyssiaia, m l roasted with alkylating agents i s form trlaliyX aied compounds* Is ©entreat* l-aliyX -^-sm lJw ^etrasoles formed seyX deriv ativ es only slowly ( 3) and condensed w ith bsm aldehyde te form debtt i bases only slowly on heat** lug in the presence 0 # jd perid ins (3 ), th e hydreet&ertdes o f the l^lyX -5-asinotetrsR oX ee ere said te ho Obtained on eryeialX ia ailon o f the base from concentrated hydrochloric sold hot are not stable in aqueous o r alcoholic solution (|) * Xa addition to these differences in b asis gfcarastsr* the l-alJgrlH S-aaineteiraaolee are re la tiv e ly h i # m alting so lid s while the diaXkyletad products are liq u id s or low m elt­ ing so lid s which oen be d is tille d under reduced pressure, Since the elkylatlcm products had properties normally associated with seoondary aminos, Harbst a t *1.(2) formulated these compounds as l-*lharl-5«*all^rla»inotetra»ole«. Ihwevar, because of the profound change In the chemical and physical properties observed on going from l-alU yl-5-«sinoteirasolee to the dislkylaied products, some reservation as te the tru e stru ctu re of the d i alkyl expounds was expressed. h Tlw potato o f d o rto o ttw of e e rto ia pair* of diolfcgrl** 5-«nin©totr«*©lo* roportod V Ewtob & | i&i* (It) ©oro rotten* doso* to r I s i t m l tb® hsrdxwblorldoo o f aol&f&O&a nodi attyriotod X H 0 » t^ I^ o d o o ^ tr« * c4 # oterood tte» «s»« dooongsooition potato* Moo tto Molting potato o f tte> pfeonyltMmaroa dortvaMvoo o f b o th O f theOO ©OMJ^ftind® 001*0 tfe® 00M 0* T M s S ^gO O tO di t b o t th ft n o M b e ro o f t h e r o o p o e t l v o p o t a o # t o r i n o t i s a o * , a o tfc y X a to d X ~ o tlty l~ $ N M iX io to tr« » o X o on& o t b j r l s t o d lH M o t% * X « -^» « m iao t« tre« © X « * n o r© id « * sti< * © a* & o©it*ld«?*t&m o f th© vkoto probflbl© prodoot© nl&oh ai«y bo feraod bp* ttei »©arc~dS^X»ti©» o f X^dl^X^$*«aoototroRoXoo vooo&od' tboi in to ta to re h m g o E and It* and o b ta in ' ft mt to M l / I » = H * E«X » -A ---------- 3 » 8 * S I I S = «* *«*• * (I) T im a , a t a r a e t u r a (X ) l a }i n > '® ^ ‘ IW s H W » I I I ll » = * « * * : ---------H (XI) Ml B 1 * 1 H - — MM (XXI) »< f ho#® romiXto indioiat® th a t tbo p rin cip al products formed on the aom&Utylailoii o f i^eXIgrl^S^^ijsotet^^oXigs or® eotusXlj X*h-*il»X}^I*5~fjdmioir®»®XXii«®» th e oi&f ©hhor lik o ly stru ctu re fo r a <&*l3grlftt«dl «*fciotetr*®£>l« in aMoh the %m alkyl g r o ^ occupy ofuXroXeot pooltiona t» ohousi in formula (f)« »= = » i W th e fom oiion of a J’^ iiX l^ a a itto ta tr^ o X e uouM rofuir® m igration of m i&kpX group iron it»® rin g nitrogen to the *»in© nitrogen* Booh a m igration o r appear# to b® unlikely (&)• jMtoXJgrinrino* t®tr«*ol«# have boon 4oMr&®6 (?) mod thoir- proportion oro markedly r iSflBerse* trv m Um pt a p iv tU m o f tfa* «Mp0tu*2* (wcmnI W m w W W t' . " m.Wt * JP ^w B liK H W pW ff^^W IW JiirlW r# • ^w ^HHIfc&ilKis^OO^flO aM N™ kte£ Q ^K^ ^!fe &dkM4H.'04^XAdk^fcdtO t W M wwIw»^«fcwW *W i» w ® ««HpM»lft o f atru o tars (V) toroid bo oagtootod to load to S~«akyliosi*io~ ittr a a a ie s . IkAlJ^iadM ottotracolat h m * booo jjr»|MW*«d by iha radfewtfoo ^fcjrfE djkf.m^i ijb|t JKP_ ^i^OOwu^fO fc-— — - .- .-.O^bMJhiO«b&^AjOl,mJk MSt- » W.OaA^ W e too ooiiMFOdooiwifflf ?*ai|{yx*b©nayi>aotootatirato3»o \0 /f awo jtwo fKpoporb&oa o f th* $«i4l^4M dtetotraoi^*a: or* wwqr diffaw m t f*o* tba M dMattHMifeaaiA kdf P JW sd9t lP W iftuit *1j ^ i . 8000^ ^eeJK^-oi^^taitiM Si^aifcwfc^Mi^KAitoiiE *a yiii4& feboao W ooOA-atoaWodk. IB WSM to pVwjjWwt" twfcW *»w BWTItWTWy^yJBIWirJlflWI waoW I *(00 a*** dWW JHrWWWiw HfMk*# *t^fe ^Mka^AMMfcat-AtJI 4bffc ^ JXJBwwSWCwMrW Of^ dhjat inrOrif MiEii JEJL.-’lif fr** -Seb ■dwBw k-h*Ai IflpwlE^BRttlSw'SX iJk*2 do * ooowad $ha*o o f that* atodio* a aor&ao of l^-d lalk ^ l-* 5 - ioln<»t#ir«tolin«a tn obtoh both a&tjpi, g ra tia m m tho oaoo wao pro* fu&od fo r oowpariaon i&tfc a o tad lar oorftoo o f 1 ^ a liy l^ ^ id ^ io d iio * totroaolao f*r*parad or OaaorXbod Id P art 21* I t m*p ha poiotad o»b imm that the pmpm*ti#s o f th® diss&thyl, , A«tfi ^alssha* 20*1® ( l ) from S*aElaot*tr#8olOB oht&lis&d h r fh la la «n^ ^^sttSjiiototriatol# ms AdanttcaX d ih tfeoae of tha owafa^ oiidlog 1 ^ ^ 4 ^ l^ » ^ A 3 g i^ t« tri» ^ iiia a doaorlhod lo th i» thoalo. fh td lo mH 2nfla aaatgoad tha l-all^l^-alliylam tiiotatrjM B ole atrootora to tto dt»ttlg& and diottyX a»l»ot«tr«iola» oMoh thay ohtala«d$ and oofgaotod -that tho "aXpha* cH,b#issjyl oao^ouad oaa alth ar a X^^^sayl** $«4Mmylottixieto^aaola o r a f*^om yl“5-^«i^ylfi»ln o tati^ola „ th© *©rk dooefitood to th ia thaaia tedloatoo ^feat tha oon^oooda aotnally a obtained I f fH W U aoft XegL* m m , X 9k ireftjieftiteftXjjr# Xt su^r aXee be p&ixstm I «mt th a t Wms^r f&. (^) b v i ra&«»U3r ShitFW ii th a t th e prlftftijMtX predftttb obtained by Use bfHBft’y ifttloiJ triT X eeatkgiH N a^l^^ te * . eWEPF »wTeiW^plWrO ” 1 OwB* w ib ^ ^ A V V W JWFOUW®w 9W MwSWlriwWflt fiw ¥ 0 * JXX e£ Xfh ^ i*lly X « ^ i» t**e te b r^ m prapered in the eosfe* e l title ift^ftM&«yfcets. Ibinfc swsliXy er^teXXiirabXe hsrdro»* ehlftTldftft eMEreaOt 3P8#dlUly idtth ptfttltfX iS9^SW3^to8tiS gmXfesyX ehXertde* fin X bfttSaftilft** are Xwr sm iting aellds e r 3 iftl4 « wl&ftl* may be dtftt&Xled uader redtieed preaanre * 9 % are aeXbl&e is eoXveate gmsh e« ethyl ether* ham m m * chloroform* Aftstoafi) aed the Xsnw yl^fohel f f twitd Xu j^nBMirsl bab&va s^- eeoendary «aiaea* H»* te ry a # le 4 im m & m X& th m baste properties of th© X**t~di~ eligrX^iwiiaetetreeoXe* i« rath er s trik in g . I t has long b@®& m m $ * sifted th a t l^kyl~g~«»iiiat*tra3WJX«a de net ex h ib it t i e ch aracteristic# usually iMweeiftteti e ttb prlssary amtses* Been X ^ k y I» 5*eftto>tetr««eXe0 e f lew ftoXeeftX«3> ewl gtit hivs rich er high eilU jig points baeie p ro p erties are apparent emly *» th e preneme of a %mw* excess o f etroag JwWPspWp O0WBWP 9w e03^(Mr ^w0^3L v31®SJ8f e ^eSB |IICT®^P3LU U LH iy OX teatenerlaai im 4M M $ the aiato» gpmxp m& the nitrogen in the h pnwitixm 9 # g t h # r in g b # P ftftpom ftib X e f O f th # ffte e iiftl^ n ^ tilfN llrA fc fth ^ lb jlW '.ftijftlftlt^ ftfth n fe j^'Mtt&Amrvlffwill1 HAwMV 4 ^TO pftf t i l i y O f th # ^-f% » Ib tfE C h w wwfi* ".JWffnWTO w\m/»*f W'.M dfV 'm-Wftmmmmme ^T #imr#pnr#lPftr^ tfeefc th e eXtr«KrXol#i *p w *r& o f o f th is type do n o t ftepperh the wiem ^tioa o f tm te im t& m of th ie ty p e, They p * * t* r to «m poly-ftoleculer «tgm#iox*ftft {1XEK and IDE) iovolrliig interw olecttXer ^ipo|fiA bonding to ^ the higli asH iisg points o f the## ©on— pcraxv&a {X&)* i w v i r ^ Moh eiruetnre# (?XXX end XX) do not jnFOetJk.*<# Mil Jklk wKQJUUi^ 8S w 06t*«vfltl W l tMtt » i = t in JK^^in-iil — ^— «O■»*-*«■—i«*j* 4M3JMMP#- * JMf » = i * - . . - B ^-H m « \ » - - B- -X «kN.-, X I ( T U I) I «= r » ~ H 1 1 « K*»B - <• MB c jM r n| g M jfc II tint / iu f * = 8 I I ML (IX) - g " ^^*S * MX MX » - II - — » •» 1 i X — H l mop# ftttr#otXre oaqplaii&ttan Mo# to the poaeibls formation o f « M ri« t o f dipolar rmmsmmm fttr®obar#ft, X# #ooit aircelTjre# the primary amino group by formation o f th# iiamcmin® ion mould Xo#o it# a b ility to demit# at p a ir o f electrons to reagent# mith mhieh i t mould aorw illy ho aapeciad to react* The dipolar choree to r of the reftonasce hybrid mould ftlftft oeooftot fo r the high m elting point# of the com­ pound# a# ooXX ft# th# p re fere n tial alk y latien in the h position on the 10 fla g * &1$&oi£en In tfaoi* o f tit* rin g leada te ta Ion vbicb 9&$*wm te Imp irtatlXtood fcgr mmmmom to « greater extent tfeon t&e ettior jpKiif ffl %lfi t f l ff^yK t t l o ti j^i^wiwxts • <♦) 3891 1 998^ ^ fl^ 9t l — M— M l | 938 *** s l9 ^ «) i| | / % I----- 9 9 = 9 ii » = 9 I tlii* o ffera an explanation fo r the formation of 1 £* tfcft iptol ©g itl ami a&taaa iif thd loftlWl— 9K 9 99 th » H * marked taereaae in tfc» b asis j»*e$>©riiee of ih« 5 » im to > to tr a o o llx ^ o as eom parsd o l t h t t a i 1 ~ a lk y l- 5 - a o ln o to tr o o o lo a appear# to to aaeeeiated a ltit tbs etiaage from the taire& el# to the teiraseX lne rin g system, The 1 ^ d ia lk jl-S ^ im in o to tr^ o iir^ stru ctu re to lnoapable o f forming * dipole o f the type postulated fo r the X^illQrl*5*iW^Jaototri»olo» . fWbbermera, the 5- iein o ietreso lln ss u A H lfe O O 'D tS K O O O io l S&ML. ^ k A y fc ^ a fc J lfc .jy. J h .i^ M fc ‘^1 ■&&- fa ig ftt< O L * & J M d W O d J lta mm ill.J * P » E c^ ■^M Pf^cP ^i'lF D M ^J P M hM^k^PiE* .^PPP^R^^^^^DPPP DP■»**-^ h nW iti '^b«^®rooiitorio nAlAlHlikM lL,^ JK &ox« njt „wx«n .^S-A-O w .r#gaiiarswio, .M kafe8ifc^fci£Bitm ankJl4iAiS'^M fanlAh ngMSPejynro® tp o l 1 j&HtttMinsylH^^ , Sswewar, ahtn b it teobyl dtrlvt** iiiro m i htafed w ith gt«ol*X mstbXo to ld l,li^btR f.yX «5^^t© tttr«»ollm m i obtained* Vfe«n tin nibros© _jmj»jmijftJiiatSS^ywTO1** eh io rie «&&£ X ,^aib«*iiyXHH^ A nt it bySjmt&ovide m u o b tain ^* ibsb t i t im m a M m ©f t i t .tefefebraRolXat fw » bin Inins t m t l i i s tb s foraa&ion o f on «&$£ da**w«tiiw» followed by tetb o ly s is f stltKf than b y ^ siy tis* XL ^ ista y d rsfe * ©sold b# ssw ssrttif Is tin fertotttratslin© by htnting u tth s e tiie sold m tb tsn g t sen md« to stn ry #»% t i t snaa ro tatio n s ttslng i i m bsstssfX dsi&imitss* iilbfeough bb# bsmoyX d trlr» tiw s s l^d ro ly ttd to l,ii« dibsm yX ^iJ^tnotttrtioX iij© on fe&sbing with *§©son* liyS*<©ehl©rl« sold, i t could m i be ©OHvsrfed t© X w ith m e tis m id * by b attin g IS fl» towi a w iflroitfl rtairtirnt l f o f XJWtlb«»»y:L-5-l»lnot*t*'e- im jaifeiiiiplMw mifch jMlllillfffITT -Ofl&dL. IHm fi&llfflNI Of tfofe tMHEHBfiffit Oftd iMBtiHIBto* flft&fOXtyX ^iBVliVStdl'WS 'ISO W ti& e& t flttOtOlOOfO iHiBllCgtttg ttlitr %h» OOT8IMHP** tjSORI tl80 "KMIlHEFB &£ ■tft* Oli’jdL $?P©0|J* ttwi •^p^ f f t ^ 't -tty Jfegyl«»&» tttlJiiiotOttoiiidJiMi fffliXO tiHtliBW^^flt tte® .^^mmo j^piMiti^iaff o t th i dl.TtOltmyX pmhhmiPmhm pu^<^i fin topw- •ptifcfc ppMvik dwLtpn m jpsHis^yiKiFpPp^^^y^ klpPMApwItiSpk *1 ift ifftH! jt tnHfri# TTihj^^jt^ff midi ft*©** **« gu&d wnlw *1-.*1 h*w*l.»■<£».a^ayli^irl PwNmlSj^&^ I tiililiriflljl mftit mmm mk^-0 *M «£&**& friimftil I luk Btttiftiflttft© XI m r *10® I t pointed mat i&©$ pr©~ m4iiiii>wl 1*1 in mBS^jpSBFJ^^ 3JB ®IWHKl© ^^ .J j« M k !lifc jfc B E > .« M H L ' ^.,m£.^,, m m m m i#B B B k ll'.if, m m jii. ll.ftifc m iiftw tffV if' « u ^, Lw ^Am >k A ^ . ft®* ©*©t l* ftft&t ©<*«**©$ ®)& ftjMtft* (111)« rtF'WW'^ttil ft# ' 1 f(i b$r fl©iSft&J$£ #£©01 ftlm ^M^ydifftff* m jhptat tb i m m m * ifiH f frft^ fey t»nMS)lg tff.ftlfr ©©©lift f ftlH jlS ft fttiiftrill f f t i t o Jteg* 1 -liomiH.tt!!.1it^l^&idiii4mi¥^ vuum_ ^fha $&Mm©t$*© ^ ^^ttt&tu$3i&ii $m 1n^Mi %$s& & n$$- Idtai % $£ t i» Xt In tft a o tt l #l4 ^ il^ ^ l^ ^ lfttfttP 4 W ftlfa ® tiMl y |©#%dUBjg Hm wsflHbSftlft- mlHftftS ftolv^jj't^ * -T3bt ®j*tidss paptelftftti mm %pftftiftd w ltb ft^ftftftftft itLkftH ftfti t i t fwMi tha ©fth|H*ftl w«« ®3s^r»®t«^ idlth ftlter« *» * tfww^elitati \f**n liiftlftftd iM fih «nf©v®^ 1*© b© Idtntdlft&L i« ltl tl» sifttftsdsl Iftttr Id en tified kfttfttfttrfteoXim . 1 ^li^dlbea^d -5 - Fftftftlbl^ m i n i t i o #t!^ litti® n ©X tl® Isd n t p # tM lu w lw i fftHftued b y ' ly^rolyftift ®f tl© fttbyllftdisft le r l^ n tiv e 17 By w**®' R^wWHMr ’W *;»vlU»<»4 IiwWwVWyr|| {BflyBPv *BP Jln&lwRjVty WR3I mwim vO R»il@Qr ItihilS WRlH^fcSB in ilfitSnlILp H M k/ta UI^ nfe #H P tiMtrSyMh^Akrife^llife iAhMhJ^ in #£$f M» tttfto tftp |.3 wMP ?V M kM tifcw flLi* JlK ctH ^f0Jknnkfl^ iA ® S p'^y 3sffH6p3i®' wfelcfe s^NS®1 ttLM ^Jt^0*^B k. »#sSf ^H0yBMr3rV«^9^iw l95tok w •nnm 'fctt fittnhairt <1# -*Am> ttitnibAgtttt % ■% » Titrt'fiHfi Umb ffrHHiytfrii fining 4w l.tt'fesy^NKfcw la g it » wmm&Am #£ re<&tl$i$a Sm m tiM m 1 *li^^3gfl^iR in© t«% r««© ljU ^» 9 RXiMHr wQV 3k8HHBw 8PPv*9pt 3*® *P® #WUff # H§ jNl86lfc|i€HBt Sfflllg^Myt#3^r <0 %jj| Shg- ®jf |$j& 'X#4*» nnuM b# t^ & A . I l l Ife© |||« r is lltr © * f£9n9w«w» lt-ah3ih^lili^n^.M W«SI SJH M dJPt^kA M Ld ftia^UM filiB lm a fe'W itfcJita*<*.;?/ ^Cl,sfiwr® IhM m M rbk©fwml dtfiLijitarifctftfcfliTnils® ^itck^.* i«n AitkJk^j-a*‘jL .^a.-^4,1^1#jjtny«im3JS •A< L tM fc 'IB B lP T »&tHKp«& #©$.$ ®©Xttt&n& ^fev@s gUSSSSMifl® t M SitiSWS tiiM * ill s e n W til © a la lia © . I I g lv a # ^j^giiasdL^i # 1# n iitfn g a s i # «sd In iSLkslSwi © o liilla s I I gjtwS' naa^son 4Si9ridNs# iiiiii$ \ *%* ^d ass©t«®dXi^ ^ fh i# n m b© fnXXnnssi by nr nn©t©ly«dn «f ggngj ^ PapTW ®^e^lvX®%in39i ^**4^ ■^E v*'flPfW f^rvan jf t b i iiiM •w'M 4Hw rpim fP•■^rt^a*p© m d w ls» y mi (CHaCO)^ rk-coch3 Ge% -!iT^ - | C«^OOR C#% ~KIM 50-«H^CH# * C6l?f -S»-C0~CII2 /•Xtbcmgh lb ® © entyXim inn o r s e o ty lia ix io p o rtio n o f the- anXncule In W t S p lit o f f i f i tb s ro e c tlc s s , th e olaT & gt O f tb s ph e n ylim ine p o rtio n don* ia d ld n to th a t gruSMBtitutod in d t* * o f tJxis ty p # sra s u b je c t to soetolysi* rosetlozis* 19 '■ InfolM H ^LS iuttH ^R^R aP^k.R ®0®$ttt®3ti£ll 100® jmjMPflMl fey ittfciuifcijk ^m 8^R^R8wSNmmp tIRRp^w'^R ^P^PJRRP^Rj^ ■«*%S&J*f4fiL m l lm ^pf«0i& " § ^ & m ftasM m pOly i oBX afford o f 31*0 g* Cl ml®) of mtfeylisflim la 2$$ nl« of mfcor mol trootod droj«*t®»f « H lt aM s^iag m i cooling 1® aa Ice-oator b»t!), *l%ti $1 g* (0,5 m l®) o f G$wmpa* broaid® dt#»«lr»d la too «1, of otfeyl sloottodU ffe® addition o f eymo&oi* fenwtid® repaired ®*» Irnar, A oolution o f feydrissole *eid, pr®p«r®d fey adding 150 01* of oo&oosi* tr«b*& feydroot&ori® m id to 110 g* (2 tool®*) o f soditaa nolo® diaoolred l a iOO al* o f m ior* mo eddod f**$dd&y to fcfe® oolailois eontalnlng tfe® oymasid®, $ tfrri» g mo cottHnaod fo r 11 bear®, ife®** th® oolation m o ®v*por®t*d to diya®«»* ftio orod® oryotolMi*® residua g*vs tOJb §» of l-m t^l~ 5~ m d^t® tr6*el® a®, K«p* £2?~228°0, ooXorl&s® aoodloo ofta-r *a* rm rym «llt*& tl® fi from feGO ol« o f o o to r. The prodtmt wto id e n tic a l l a o il respect® aifefe ifcafc obtained fey* Gurfereofet and S&rfesrt (18) , a oolatloa of 100 g , (1,69 aol®> o f n^ropylaaiifc® ia 100 »&, of toopropyl oloobol mm treated dropuis® , *felX® s tirrin g «ad ooollag *All eo*ly*ls m m dom by Biero-Toefe lafeorotorloo, Skokie, XU. 20 4ee«o*nt»r b ath , mibh ^0*0 g* (0 #§S ateX*) of cyanogen broaido iM m dissolved In 200 nl* o l iaopropyl alcohol* bromide The addition of cyanogen X«5 hearo, A m afaM tm o f l$d?e»ole oeid, prepared by adding XJW »3U o f coneenferatad hydrochloric acid to 130 g# ( f nolee) o f «oiSM* m $ M eoeerod d t h 300 a&« o f cold water* eeo added and the re su ltin g so lu tio n s tirre d fo r 2b M i , The eolation mo then evaporated u n til eapstel* began to fbwa and then cooled rap id ly t» an ic*~w»ter both* 2Sn tid e wap # g* o f l^^pn>pyl*S**«isinototriiaol«, needles, «,$.* 15&-153#£ wero obtained (2) , The l^ellgrl^^«® dj^tetro* 0loo which wwr# prepared ere lis te d In M ao 1 * 4% Tinge O v a * ^P t^O O ^^iijO iI* 0 ^ 1 1 J > 'rv were p^opofod bp e x p ia tio n o f a\2&tab le S^ooim tot^eeoloo bp th e Method o f Burbot g | j |* <2)* The appropriate l^ol^l^5^«winotot3fa«ole beipther with the a lk tfL & tU ig agent van heated on an both the en&theivE&c roewtsien vims in itia te d * Beetlng wag o^ tin c e^ fo r botf an hem* to an how a fte r the tggjmrabar® sta rte d to fa ll* The product reati&nad e ith e r 00 a thick* vtgoouo naoo or so lid ifie d on cooling* /Ik y latin g agents smjployud nora e ith e r alkyl heXldee* euXfstee, bem enaulfonetee, o r p^tolueneoulfcmoteo, The 1 fb ^ a X lp l« 5 ,-l» in o tetrao o llm e m m olibraetorisgod se hydrochlorides and ph&ryltliicurea and feenaeneoulfoErl derivatives * 3®oorel ty p ical exawpXee o f the preparation of 1 ^ b -^ ^ k y l-^ in in o te tro io lin e a era deesrfhod below. M lO W V wii*iio crco a H rn » w rw *a i n m m •*mm^|F#'. twniPiijpp nmgrl ma&t JBP^f'FVI^pyf'ifc JlK®QP0^yX fHBtttjd SWMIjf* ^-Pben/Utlisrl t «J?.°C . G rjatalliitrd FjN(B w. an -aze Wntor m m m n n 8L U»7^-Ub0,S Ifoinr fS*M? ■ N v ««A M «m oe Igt-lS J a 6 o -ia Xlt8.5-lfeS».S 187-180 XT«5-a.77 16,2 t. wgtor W$$«r & ^p30tleohol & >kBinoppopjjpi - a*M JtajmpTi *lcobs>X 2 a 2 # f t* ;pt«H in bwrnd m il» nawwmi o f npn»*®&it ^ r m iM «a$&£$«*C n A. f M l A mix* u n «f 8S 4t ff. (0.2 «&«) * f l'^s-fr«pyl-5-*wlBo»t*'fa'«»ol# •ad S tS J i g * (0 ,2 w»X») a f % a*njd a b lo rW * w»* baat«4 m At • b ath taajporateae of feet 53# «£teofeol. eejMKr#ted, three non* 0m a ll b a th . • boMo^nioui w ait aaa 2towa#tfj folloaw i bjr m fcr t l m r t l ' (WMrtriUm, an* tinned at ifcS>% ffer 0,5 t o , m •e lid ifie a tlo a . K»«tt*g wm «Mt» ft* aolld **ei^*i&Xi*ad fitm m & d t* m X r * 4 I in $00 ml, of . $0% im p r & p y l alaoheX to 37 *6 g . of a*p* mttfe deoempoeitloii (fdbi* 33) # 8« ffee* l^enfi/X^fflfaiROtotrossolo A ataetora of S*T5 i« ($*$$ »©i«} of X^fe»n^l^-jM»ii30t«trM of 16>3^C on as nos hooted to forth* A h&a&geaaai aeXi m # fo&mad iftafl the be-tb nan foapt a t bide biai^arabare fo r 0*$ beer* f t* melt maa reeled and tb s emenlt&iRi: ariUd diaeeXred la- a m ister* o f to mi. o f $ B aedlimt i^dl*OiXidO asst SO ®X« of ieopropyl ela obsl * th e re su ltin g aolntioH «ai« extracted m iih three S0 g&# portions o f e tte rj ifea ether meahed mibfc motor and dried ever nodinas eabfoemabe, to tba filte re d eth er so lu tio n mar added 10 ml* of eaaeantrated laydiwfoXerie aetd* A hydro* obXorlde man obtained mfei&fo mao eryatfXl lr#d from Xeopropyl aioebol to giro ?*3 § * o f fin e mt&be aeedXea, ^ t t a f {t& & M n> * X5$~X35%, mibb deeempo* £ wteteam * f 7 M $* (0*05 m%m) « f in i f # (£M$ mol#) of «& « H a S iMttiflhifl w»' dUBt’ wJS3t|» JpV^lw mm ta»tal on m%% mm tm m & kKb Um M B1F%££ iwSWHr* W®B|$V sE m *& IS8°c ***d the b tih n » jBd nfJEW A9 «W8fcS4B % 1I. JwwW *tP^Mittittflhwdil vibfifc ^.fWf W Hh JE W B il c o o lly , vaa diaoolimd in a abator# o f JO 1&* of 5 I ooditsft fc^roa&i* aad 20*flU o f ioaprop^l iltataS . ta t bta t a l t a t a o x tr ta ta n ith m%h»r« f t a n tta r ta& rnei n « dspiad oir#r ta & a t carboaato, f l l t o t a t , t a t 10 *&. m t f&m m M wfctal* f t a s&xto© wan i& lo ta to o*a$tata ta i tta rotating taLid «m a oi^balX ita ftm* «n isojjrafyi i&otaXMSib«F iBtabari*. In bb&» map $ M g., m t pmm b g d rta ta ^ i* * n *p * fOI^-Ofa*© * nibfe daooi^sitX ois, mm t a t t a * I *® whit® o ta ta r* fta 1 by applics-tio** o f t t a pm m ^sm m Jta* t a t a i t a t ar* H * M in tM m XX to ^ tb # r * lttt t a i y t l t a i m l d ata, P$MfMM2$mm 8M!ttAt2V£$ JCUk o f t t a tctataa&ittMi % M rnm » fm ^ tm ®hmm%m$MM% m p im w l** dtatvativoa by ta ta ta m i of. t t a tarn * w ith jfataL itaM aoyiaabo* fta $ra^&s*«biom of t t a jim ^ tte tw ro a doHY&tlvoo of n il! *«ws an m ttm %mm mm i t t a r t a d tv m hydrootilorldflr id ih $ i m dlum fa&$mxid® m l e x tr a c ts udth « tta r . th * °. o. Si ND NES & if, s *1 3 lAVtWVt CM * $ i g s «aW * n W W n •o > i m b 3 * * f t a wtAfcvo *o *»«$*&*» %nv% n '* n *s *; *•! n <4 m m v t M * ®. n n *•>•&. y\ n n n ^ H n n kat n * i n n H ^ i^ H s * t #t« k n *»■ n tS *9 8*4 ft ft ft 3 *i o I *I I ft JO ♦

tttetoi, V ttg^r vioeoiiwi oil no* Obiain&d* thin ttoWft id th 50# Os cooling, * vaobsd *iih potpoloaw ethor9 ' oloofcol, tin phen^libiourfta doriY«ti*« Hfeteh osnofctoiacd Ijy tl&* tvojrtttoafc mm ©tfyataXlioiw* tvm $$$ ioopropyl •loohol, #uj»„ li^4® A s# . ^ H jf £in$X*« Apjnrniiaatoly fet&f * grfi«ft of l^o*i«7X 4i*^t^l-^iM m totra«olin» >$rdroa*iloride «odi iiilf o isillilitar of tMmstn^ouHonyl ol&ooid* woiro ploood in 10 wk* Of 10# ocKtion m& th®jaistwo sklOii, 1 00114 no* fomod on cooCUUtg Hhloh^oftor cryofcaXlia etion £rm 90$ loo~ propyl alcohol, g m « par® Wn«om»ulfon^X derivative, >a0p , 82-S^°C * u in n m 1 »•* » .r.° c 9#wul# e 1#iiMit.s fwwEQrJl BtwaayX 12H 8S Beirayt in -i2 fe StfyX HobteyX a|i»L JBwHIBjrS 117*118 BumtydL fflfcjfl. n t* a i8 w »W iwSi H *W tiltw S IM SD Oy*. 13it*135 ' O^hN^rS. tt*Butyl 111" 1 ir " 1 ir ,m CS le'd Pound Found as .9 25.8 25.7 e*A *W * ati.s *0f,<;2) 83,9 23,9 ai*.o 23.8 23,8 m » w n it-u s dwnsyi u^SuiyX n> m ^pbwsyXotlQrl B***#yl 125-126 82.9 20.3 a iM a i C*9%4M 33.8 33.6 33.7 ( a a jw ) 12.9 13 «b 13.2 30 «& 30*6 30.5 (Sulfur) 11,6 11.7 11.9 ®WW»«8 (Sulfur) 87.6 27.2 27.0 10.5 10.5 10,7 Cm Bm ^.8 25.3 25.6 25.6 (Sulfur) 9.6 G ««W (Sulfur) 21 .0 m«&. 95-96 8lwliP|ffllFffl^ g S illU S b g k K flN M itfftMk AV ^ ■ • ■ '^ ilJrl > .S ^ .-i^ fc ... •* ^ a ^ ifa « a fc io iM o jg K_ .: F'^dth M u g Q a A .^ lA > 00 ogtal^rot # fho jg. M ^ ■ » * - JREJpQHPmP Ww vJBBHflpAw» ^mjt^S^Mk^H^MMk .^ J S S \*hl&H*mMmaJ% ilk A gelation o f f*5J g« (G,®1 i«&«} o f ilvt fc^rooKLorMo of »*jjr©f>yX»oai , f%o tbsoi'otiteal mount o f hyiwoy « u dmoAad '1a f I m n , fh* © atidjnt nog t$X1mva& o ff # n&g&Kt n tth hat im p a n e l alcohol, m l t t m f i l t r a t e m i imMLngg sad# fcaaio n tth godtm oaafconatg* ft* «&1»~ t l m * m then oosggitiraiod, d*o*lo*"i*«6 nltts H orito, tlltm r t- , cam cooled, & tJalg wagr 1*1 §* (if# fUStf) o f X ^ » ^ w ^ 5 -» « im t« tp « o lg wta obtainad, *«$» %$l*l$&*®* M tm pl* of & mMmm m tU m point with m m thm tie M tam S * was m t 4©pre«g«&* Itytirogenolyaia o f Ite fcydroohlorido of hm fX atod X m « p r« ^X ^ a»inot«tr«goXtt m d m italX m ma&±M .m& gang l-^ ^ ro p y l^ o a in o to ta ra ^ m l* in «^n*lly good ylold 8»»d n itli M ^ntioal phynioal pro|5®rtiog* 25 f J IM I f □h M O M im « It H JP*%, Hetfejrl i« m y l ae-su Utrmjt ^ _T frifc .,-Tf ^W W *W W l|^Rp6 82-8U »6wyt;® ' eo-a* 21.3 Biwweyl 67-66 B m ifl 67-68 /^honyU tfeyi »#»*?! 98-99 &»I!*yl 4 -Ptamylfttbyl 97-98 Methyl llethyX O u fc A fe * e«B»x*e of co lo rless noodle# , ».p* IDS-lOd^C* AmI.. CaleM fer Oi^lf^XS^i G# 6T.fcf H* 5 3 * S* 21.1. Found# S t d t.T i 1 , 5 J l ** * M * B* By the interaction of the iminetetreeolixe and nitrous sold. One gram o f 1 >h‘-4ihen»yl-*5-i»inotetra8oline hydrochloride wee placed in 10 01* of voter end 10 sal* o f 5 U sodium n itr ite added* th e mixture wee warned end voter added u n til e eXesr solution formed* When tM s solution wee cooled, the n itr ite separated as needles, a,j»* XOsPc., with dsconpoeiiiOB (1 ), a fte r one c ry sta llisa tio n from e th e r, The n itr ite was dissolved In g leets! acetic sold* 0 ^fcter was added to the solution u n til turb id sad, on c e d in g , the B itw n derivative m i obtained, m+p. 10^ C . with deeenpedtloa (X ) * The nitro ao derivative w i dissolved in 3 d . of g la c ia l m o tto a d d end fatitod on & o to m bath t o t 10 dx&tes* The aolutton t m d fre» a y iU w o d o r to o d o rle s s , b a tin g vs# oomtixmeti. to r O S hour o tto * which 20 » ! . o f wstsy e®d 20 *&, o f laopropyl alcohol war* added. Wbwa tM o n h itlm i was co d e d , a white so lid separated which a i i ’n** c ry sta llise d I m eyde&axaae to give l,b diben*yl~$~ke to ta ira so lin e , «*p. XObdOdftj. TM« product showed no depression in m elting point tm o tim ix tn ro o t the eewpound obtained by tre a tin g iM notetreaollna w ith m ootto anhydride as described above, bftnzyl~5~k«tot*!trc*oli*m we* also ebSdosd by hooting a g lacial acetic ao lf so lu tio n o f the n itr ite dedvettv© fo r 0«5 hour. Preparation o f 1 ,l^ ^ b ® m ^ l^ iic o t^ liM n o to tri« K > llm "arenokrdrate*^ fh iw *ta ffiir« 4 th o o f a mole ( 0 * 0 3 g«> o f 1 te b rfts d lm hydrochloride m i converted to tho fre e boon by adding th e h^rootCLortdm to 0 s i* o f w ater which contained h &, (0 .1 s o le ) o f so d iw Igdrextde end ex tra ctin g the mixbare w ith e th e r, eth er so lu tio n oontelBing the fre e base wee added o f seet ie anhydride. b ath* To the g # (0 .0 J so lo ) f t m eth er s c ia tic a woo evaporated os a steam th e residue m i covered w ith 20 s i . o f water and s o lid oodles carbonate added is a s a ll portions u n til the evolution o f carbon dioxide cessed* 1 w hite s o lid was obtained when the reactio n aixtw re was cooled in an ice-w ster b ath . The s o lid was reerysbaU lsed fro s 0 )1 Isopropyl alcohol to y ie ld 7*1 g . o f colorless c ry s ta llin e s o lid . 31 » #p * 62~62#C* tli# prodiw t gev# t l i i« H P 9 ti Analysis fo r l^Jt-dlbw rnjl** ^ ^ sn sb jd rsi# 1** Anal. 8*de*d fo r Found# C, 62.8, <5* H, $*?i » , tl* S Jf# M , 5 A »* t i J , a i j i too graae o f the acetyllmlno t# tr aftoliite was yoflnxed with g la d s ! acetic aeid fo r 0.5 boor. Watsr was added to the to t solution u n til tu rb id ity developed, a fte r which the mixture wmi cooled In en io«*» water both* C eleries# c ry s ta ls , m0p . 9T**102%# separated end core reetysbaiX iasd from cvel©hexane. tb » pore m aterial melted #t X05-J£ 6°C* end o o l^ ed 1.5 g. and gar# no depression in m elting point on admixture of' s saaple o f 1 ,b4&3M«»gyl~$4sBto^ proptrod by tto above methods. About on# gram o f the acetyliM noleiresollne was added to 10 ml. o f concentrated hydrochloric acid and the mixture hosted under reflu x fo r tee o r three ninute## A eery floeuleut whit# m ateriel p recip itated ■* frost tii# bet solution* The white so lid wee collected on a f i l t e r and washed with ieopropyl alcohol. ttm so lid B elted a t 2X3~aih0C. and the B elting point was not depressed on edoXxtwre of s sample of 1 ^ -4 1 b© m yl-5-iai»otetr«5ollne hydrochloride . Htodroganolysis of 1 A 4db«im yl^5*sc#tyli»inototrasoliiis ^Bonohrdrcte*. fwc*hundredtfe» o f a so ls (6*11* g .) of 1 jh-dibenasyl-S'-ace tylim inoto trsso lin e *m©uohy^#ia* was added to a mixture of O .l g. of palladium n oxide and 150 nl* o f M l « l i th e mixture was a t roan tanperaiure in a Burge»a~Ferr hydrogenation apparatus u#log itt i n i ti a l pressure o f $0 p*e.l* a fte r 3*5 heart the reaction s&xfcure vas f ilte re d end th e residue sashed s ith 20 ml* of hot v oter, ^hen the vaeli vo ter vee cooled a co lo rless eolid separated. This m aterial vaa reerystalX tead frsai voter end gave 1.6? g. o f colorlee* p la te s, »«P* 2&30O w ith decomposition, vfclcb shoved no depression in sa ltin g point upon admixture o f m authentic stap le o f 5^*»etyX«alnot£ir«~ sole (1 3 ). frw » rt,% i» B a t lJ w d lH ta l.*rg o g ta M w ^ Tuonty grcms (O.UU nolo) of 1 ,i4^iet% X-5-dadnotetr«K oline, ofetained from the hydrochloride by adding base, extracting v ith ether , and d is tillin g (b*p* 121^122°C at 20 bbi» p ressu re), see added to ho g. o f acetic anhydride and the resu lting eolation d is tille d i Fraction S.f / c a t 2 »*« a 9 k -n h FS e 9 $ -8 t «§® tfelgbt iM m i 3 A g* 1.U896 112 « . -X M fO 5*7 g* Fraction (h) wee re d is tille d and the following fractio n s vere obtained* 8.P.°C a t 2 an. a |S w»igi* 9W 5 1.1*901 2.1 g. U 95 1.1*90? 2.3 g. Hi 95 lU»5ao 3.8 g. i* C, W .0| It, ?.X | * , 38,2 round# C, kSS $ Mf ? ,2 | ** 3$#1 F ifteen grm m o f tbe orad# aeetyl derivative m i heated under re ­ fill* f« r bm b w f nitfe 20 nX# o f gXsolaX acetic acid , ofto r which the solution us# d is tille d coder reduced p ressure, th e following fractio n s wens obtains#! B ,P ,°C . « t 2 on. 2$ «0 Woight • $5-60 1,1*511* 1».3 S» b 60-61 1,1*586 5 .2 « . « 62 1.1*606 2.b 8 . <1 62-61* 1.1*631* 1.? 8 . Fraotloo F raction $&) so lid ifie d a t noon ten p erstare* f in so lid m i re ery atallin e d fro» im prep/X idLsolioX#|oXobsn«ms alattors and was id en tified as eeetm ide, »*p, $M®%* f be m elting point was not depressed on gd~ adjciure o f on authentic 4M*P&# o f so stm id s, th » othar fra ctio n s wars combined and adds# to cvclobftxane to p re c ip ita te angr aeetamide th a t m s present* / « n U amount of seetm ide which p recip itated m s collected on a f i l t e r end tb s f iltr a te again d is tille d . Tbs following fractio n s wore obtained* 3k a t 12 m W mofoim. 11 HI 1* $h Mi j& V. PW S F jM h tte ( t ) m e heated w ith 16 m l, o f 1 1 eedium hydroxide fo r 0 few «*m i*e in order to tgte»l#ee m r emiaaaide th a t might etiXX he p ro m t, A fter aooling, the solution me. extracted with e th e r, The o tte r o c te tte ! m » dried m m r w d im carbonate end d is tille d , Is thle m y on o i l , fc,p, Jflft*, a t I f m , p m w m m 0 gj® X,faS30 # woe sbtat& sd. te ly e le o f fra c tio n ( i l l ) indicated th a t the m aterial earn l #h-*dietiigrX* teel* C«te*d fo r OftH ^ 4Oi Cf fct#«j X, T ,l| M, 3 9 .h . fo w l* A m ly m # 0 , t t j # h f,2 | t , T ,f, ? ,6 j X# 38,1, 38,0 o f tee eth er e la ilo r p re ja ^ tle n e gem acceptable carbon- m luee hot low nitrogen mtaaw, Tide could he due to a trace of aeetas&de in the preparation o r to en Idiosyncrasy- of the ossspomid, greet o f me heated under re flu x fa r tme hear* with 5 m l, o f o e m a ite te t bydrachlorie aetd. The reeultlag eelutioxi me then added to 15 «1« of aoefcoae end ether added m il l pmmmmt tu rb id ity resulted, $a©rt colorless modlee mere formed m cooling, » ,p , 22?*$28®C, with d@o«e^oaltioa, no depression in m l tin g point on. edtetetnre of an- antbesitle senate o f 1 ,h~di©tbyi~&" isd n o tetreeolin e %drae J te rld e , *b«rt raa *rra o f 1 ,U -d ib ra*yl~5-i»lratatr**olliw i tydraefalarlda was puLaood la SO *1. of 101 radlu* ttydroxida rad 1 «1, of banMyl ehlaridn waa addad, ffc* aixtura vm ahaluro for a f«v ainutaa sad than ooelad la ra iea-vatar bath, Ths banaoyi derivative vtdah foraad was reerjrstaXXised fro* lsepropyl alcoh ol, «*g»* 85-86°C Anal. C ala'd fmr farad* C , 71.5 j H, 5 .2 | » . 19.0 C , U M «* $.3) I , 18.8 M tattaw pfd acatrlrala of 1 .U-diOaMyl-S-Oaa«orllataoAbout mm grim o f wo* added to % »X* o f conoentreted hydrochloric oold mid the mixture fcootod to aapA OOO'tJLO OOi.4 Wt-tX 0 OXOOT OOXutlOIl WIUK Ot* tidiod* fho solution s is booiosl under refXox fo r 0 *5 hour mot thffl cooled mul diXuted eiifa 20 ox* of motor* A flooulant iM t« p reeip iisfeo not obtained .1M 0I1 melted *b 2X3~2Xl4°C. end shooed m depression Xu point oo odotxtufo of en authentic ssmpX®of X^MlS.boetxyX^ S^imlnototrj&aXXne i^droehlorid® . About o m gr«m o f X,t^b*m yl^5^aiw o/X X aiiJiot«itrm s^liiio van bested under reflu x fo r 0*5 hour o iih aootie told* %oo the mixture ooo cooled, o b its needle* m m obtained, »*p, 85~$&°0*# which showed no depression in m elting point whom mixed with X,iiKiibera*yX~$~ben*oyl~ im inotetresollne # About one gras o f 1 #ii^ibon*^^5^»n«olyi»lm tetr«»oX iue mss bested under reflu x fo r *0*5 hour with seetie enhydrlde, th e sta rtin g m aterial we* again rueomered unchanged* > $rm# of 1 ,i*^b«ri*yl-5 ^«na*n0 «ulfoi^liffli»©tetraa0 lina oao «**«l ho to ml. of 3, f bydroehlori® told m I iho n&xturw loaded oador w fltt* for obo hour* Tho hot solution wo doooahod from m oil* Ob ooollug* tho o il solid ified «ad oso rooiyoti&llted from iaopropyl alcohol to yiold tho starting MtoylaX a* detarwittod by melting point oitd nitftoro ooliing point, fhto jrooadurs ooo roposhod notag in plaoo of tho 3 8 hydrochloric mM 6 8 and 12 8. t^roohloric oeid* glacial anotio ooid* m& 1®$ mymmm p0t®aoi«» hydroxide, hot only starting BSomlTXwAi wW #,w®WwwPBMBfc* AMiwaiM .hmHWjwMi i t 1 About M with % m l* m t e*®« £ fc w t« & ilhA M jiiif'fra 'fb w m rt * £ *flk lL tffc M * fcm jA im M am ktim A kk jfe iM fc 4 h % lM fc wn vm luJEVwrR l* «® W wi W oFyllw* im vW a at*** fc*th. ifffcwr th» *«*&#»• ww* .MriMt with wwtwr and driad l a m w m 9 * w & a tX m * m U M m *p* &®2~20k*c#$ m tiw pem m lm w aiting p o lat or* iM M m with m asa&hadli *«$&« «£ S 9 l t (1 9 )* in F>«r l l *a f t m m * h a m Sm tm ? t t t l m t t t » p r i a c i p s l p r o d u c t f o x m d h r t ! » a o n o H a ^ o tlo a o f * i^ ^ ^ a a ! d a ^ t« ir « R ® X « io ia o te tr a * o lin « » «oo * 1 S i m * i t m m p m v tw & fy t h o u g h t t h a t th o * * ( 1 , 2 ) , i t m m 4& * tio a p r o d iio ts w m e o ira to S * t o p r o p e r # « m ti.9 9 o f o rd o r te i a '' e o « ^ i» m t h » i r p r o p o r t i e o o t t h tfe o t o t r a f t o l l j i © # «**$ « lo o t o iftM r' feey w ad * « h « 4 o ir o f « d o u b t t h a t t t i o # lfc y X a tio * s p r o d a e t i s m % * ffeft oyathftoift o f l^filtyl^5^^^ftffii453»t«tTrft«olft» «nd X~ih^X*$*' ar^l«Ki»fttfttri««ilft ftftfi b# ftoftftiiflijiliftd fey several methods* S tolU (SO) prepared h r ttm ifst«r#etio» o f diphsnylthiouraa midi' sodium soldo in ^ r l o l k solution la tfc® pm m m m o f lo«a ©add© or lo o t o«i4ra«*o» fooeh and 8 « « r ( t l ) proper#** the ombo compound fey trootixig B ^Gainoguftsidiise o ith n itro aa aeld* Tfeta lo tto r reaction 1# «n*&o$9M& to the ono oaod h r th io l• (a t) oho preperod 5*«»ti»&i«traft©Xo fey tho oetion of nitrons «eid on caiim-* g««iidine0 Koro t« M M y , Finnegan f t j l * (83) fereo ao«# su b stitu ted jMlnaguiasidlnea to prepare « naafeor of or imiaotfttrftftoloo. D o procedure o»pley»4 fey $toll& (3,19,80) fo r the preparation o f su b stitu ted anlg&tfttrftaoloa iaoolrod the tro atao at of su itab ly » atfbatltoitod t U m a i o itli la sal m M m o r eaTboiurfco l a th* pr«M89« o f aodlwt osId# in o om%on dloaddo otatoapfeftra,. Mtboogh ibo fo ra rtle o l ' W O^o j k j f l f ' I SfO kIK ^V M & Stiftdfctffr otfJ0f0P®fO SO OfK ^M dpISf& fcvB U kr1^fefeMI 010^ si^Oo fM ^® nfH oV r3f(tpd*!fto ow^U H io1'B ■M oO aO tW H Sla^’feO piS^ooO illll^O^tiO ioftP'fe^ ^aw graotor iaoolubilifcy o f load eesfeooefca and load osdUloa* ^ itM rn fi^^iMw»^iii author ragawrfcod «o c& fftoultioa, a itU * bfeo bo* o f rook a s&xturo o f re*g*i£ta In n o t p « ^ im a ir3 ^ «%0r«o%ivo0 IOi ffem atioa o f a *ab~ ffottqcfoMf. iip.■ihhiMmgh U s g&iioii o f load offld# o r ewctoon&i# 00' th» Ohlswos Oio^iroOloo mo auggootod aa Sba l i p f t atop In H o ro** 1 wM m -mtmmBrnt toXto&mI by oMUOoo of liydroaole nold to tbo #«yboOi« IxolOo^ oo$ oyolSsstdto,fii to fosw iba ir t f f l HHl S*NoOoolNH#iHMde#» 'fttHiJ 0oo0Po0W fclW .^l“iy 001f «opHlw IO^aO^^^OW jOO O aO O OtM OOnitah^w ttO ^H e‘ ttlS* aOfy OQdC,O S tfM IM t iniV a^t^OO to^V Ow #4 O tkfiW a^t -jflW 'OtfM K dkpW t'fM e.W fi*1 eA^*^ -•W fW llk wppffl' aw W *^*to'O M H oO niO \oi*« i3O W W W ViO pf'OoiH Oi< O ^H V H ’tlo o fpo ioolatdjOiBi of a viB*ioty of d ia l teylo-to^oOidtiold®# In jward form idiellaa.tlilaaraM and wwwario acid s.’ This off«r«d tto p o srtb U tty »f Mp«r«Un« Mi* a«cg*a e t 8 W U f'« syBtbMla ■ attd jBNXldSOf bbO woo o f ooOloo soldo iii it® .pm m m m of boory wotdl ©xldoa o r oooboxiotoos & ardor to w sdtitar tfco p o o o ib ilitio # o f tit* prooodwre war* i r t * M 3 y # tb* |a«^«rotioo o f & p o t o f H^ •«*&^ l^ c srb o d lla id o # w«* wwdo?b«&mf m &m *&» «o**»ral ptoooiteo dovolopod by Scistidt o t jil, ( 2ii#25 , 26 ) . Siooo o i l of tlm diO l^leiatodilssidoo wood la ib» prooosit work b«fo booa dooorlbod la tbo litorabwpo* tboy « n not pwrlfiod b u t roiJaor wood d lro e tly la ooloUoa fo r tbo ooemd otop iM ob im lr o d the M dltloa of i^draooio «oid, Bfotb atop*, fomiafeioa o f tbs ew bodi- |» |4 o * m ad d ltlm o f Isydroaoio ooid, ooro fowad to prooood rsp id ly 0 f i» w n iaaXtttod and pari* J3M a# vodi o r fcgr n*«ar o f tb o ir i$iri&i£Uttp£M. Tfeo § ~ m im % Q trm h l* m r tr m tr n t- praparad h r llil« procedure tlo ta d in fife&o fX. m th e ir 1etenttty, m wt o f tin X-i&lg&H** *a&yXi»t*M>t*trjwoi«» &ut*d in fa&io adaptation m i tb * «* t l m m hr m nothod m i Fisangioi g t «i» (2$ ), m m p m ® w m d -irm tM m m m «&ao p m p n m d the appropriate I ^*«HfttriUty&’* in aororal atop#, nhieh ItsroXrad it m t , th e to m m tim n m i ih# ®n®atfc(pt ioottiaWKoooinia oaXi® ty tls® in teractio n m i ttoo tM oorea d»* *&railt»® *itfc v m th tfi iodide,. mad m m m d* th e tm m tm n t o f tfc® ion #eiito ifiiij to fcano ilsn aci&otitdiod of^y^Bffienidiiioo» F in a lly , th e -«ftioo^imidiiia» m m treated nitfe nitron® acid to e o n w i tte m in to goai^anldo* mad th e la tte r m m tmmhrnd o ith h em to inm sm th e ir ooag&ot* o y clitatio n to m tm te trm m X m * Ho attempt wm mmd& to irn H e m tin w m a p le m im *, d m to tin nano trlifc M b they n i o M eyollaatlon* b-* b - § « *** 5Sd a ^ s J ^ w i «#»»« ,HS s-*-9-« b « k HJMIH, S ^ t **-?«*b»s 8* B-«* IBLJlttLJtt *•& > * JMSX Nl I t H *= E fin X^I«yX*5^oX^X*»i**ot«tr«®oX«# o h t& im d in ifci® nay m m id e n tic a l idifa th e a io ila rly o M tito to d product* tew m d h r in teractio n of the oaifbodiinidaa and hydraaoto acid. : , toiaam Idst& lssl dielkylsteti tstrssels* wwre sbtsi&sd by two H&!qrl*$H^ |ti4 been bawd la Wbteb tbs two *lky? issesfNif wwps wot the rlag sad which was m tb» »dissftitm®?m* to avoid tteu d ifficu lty owXy sla ilsr ly ift^wtltb tsd tliisujpsae ey walaofiosiildtitss maw used, IfctdNfri* tb sss n^iMfyff t t ofts ysgt H IH ff o f tb s o f ydtot sloso®11® M M 44 ^ N/ '•* » . the preparation of l-elk ?i or eryl-g-elkyl-or »*yi-*ila»t*tr«»<»X«» tram the IM m rm by **y *6 the csrteodiioidee {wwghed *) 1* melt me** eeamttteitt that by « r *f ■the a d it ptenidlmw (mttod 8 ), Starting «ith K,8 t-dieotoetltuted Mdoweae ubteh iw «**Ueble acoswroiUlly or « « be readily prepared (27,28), only tw operation* wr* bbeae conpownde into antoatltuted totraaolee by Method A, where** Method B require* three rtep* l&veMUtg fire *#p«r*t* operation* and i* moh aare tins ooamMing. Melthar netted require* jmrifleatlaB of intem ediste*. h i IM R M 4 IN 4 I M L H-S-C-g-S •% , H-B 8 . i u *s 8 .* i m r t . i "' ; | no, iw ra ^ -B iw ' c s »x r i * & •. & m 4 *c s . S-CR, ****b pM p® r*& i n f la t m n k k y b e o lo i« U d * « /X th o u g h tfea^ r i » | l l i s m t h i s iw r k « r« o x y o tttlH z ia a m o x io o o iv e X jr 4 » - undo** «#«eN % ti££LV a salg ritro ii* c c m d it Io tjs j ? th u o # s s l t B ooogNSNWWt i t t te m m m im juocm o w^ni&tt* 1% h m w o t h * m jw >m 63& » o r b im to i^ a u if o ia r X g o H v fttd w o * t r m % » tr« i« & o o # I t * # y b « r o o o llM p h m tfl* %hm t t i e t im efe d o r lv w tt v o o o f ih ® « l l ^ l ^ & a i S 9 t » t r 8 » o I i i a « j i im e m A v a r y « a # i l y ( P o r i X ) . T lia ®b»®»©« o f t y p i c a l a w im o f c a r o e t o r i o t l o * i n tfe o o t e p l y c ilf f » y * » ti® t® « % 1m m v tm p o m & n tm m s a lin o f t* fk m b a n i t i e h » r* a i® 3 r o f tfew s jf to & r a t o fe# a m m itiw fo w $ m m m & m tb® 1 t y l m & n o t o t r as* & « * l to I W o f X ~© X Jl$y#ie*>l end efeeaXeel pr^wrtloa eeggeei th#h natth & ferni feekee a dXsMffletSLr IttM f to ‘the reaonenee hrv** brld than to the eeee of tin X~i&iq^5«NWBiiw^ » =■ * n — n (-)* * U a $tae# the peiwd&iXiiy of fom lng dipolar m tm m m # etM etane* doe# oadei, on® waald aaqpoet th at the m im group eenXd Iona a m i of it# a b ility to donato * p a ir o f ©leetrona to a proto® o r eth er © leetrophyile group* Bowmar, tb i* loan ehmxM net be a* greet a# i® the eeee of X^^X^5^*Bdnototr#aoX©# elnoe the additional alk$i group on the oxoHoitrogen eheuld ineegee the eXeebrem danelby. Severel etrmftftire# a an bo w itto » fo r the #&Lta o f X~*l I^l~!r*aXS$rX~ enljieteienaeele * , t a t i t m m m th a t the moot lik e ly structure oeuld i®~ i o t a the addition o f o proton to the b position on the rin g elite* tvum till* „ Wwft X*#04^MEdttO4 w v »-» 8<») I I 1 = 8 J* 8 -8 I 8 = 8-41 84^ | — I 8 8-H l — 8 = 8 M t ■ | (•) 8 -8 I 8 = 8 %3>pa Mletat 8* «8pwrK*i to vttottto* 8te» (tt0.**, tbsy aw attlX mfejmt ’%• •M&tttH&INI €■» tw»ia^ia;afe ^ W ip p tW ^ m ^ W W S fto ▼ W w U jjf '**■^rtp H 'W W W# ■ » # • flP 8 * y ifM W F 8 !ir p p n P f8 p p p 'w P m p N N N W P 0 , at ^ l <8afofflMj P " W 3 * T W J I|l# ^ W I, iW ** IP 'Mgr to tow effwtstiNj to toto tnst,*ne« tom to to* ew* «f l,b- S-toto*t*to*»ltw*a be«a«s» e f to* ftoterej flr* t, to* 4tp»tor *to<«to** tvm totah to* gttmtoto* tgp* toa to tototeiA am 8fctoto-«M tfltoto by w*«nmo*, * 8 MMnd, tb» gnantototaa ton took* agamtototl AtotrlbaUon of atoafettamfc grasp* to to* totometo ring. (♦) (* ) (*> ouM-a*. lAffll ^mm- M^JLJfil if O * * ' NIMt JMi^C''8 (.) 8 * 8 %8 1 t I I *— * I J VLM-& 8-8^ ^ 8 II «— I I US «*t * ,* ,~^-B»btttya*U.our«* mm 9b**ta»& , tr m fifearplw QtamiMl*, $lNS)lxr£4l&^^ 3m . *J » * tjpam, JSawteaii with m i K,s»-di«i**~ &©. fiio otlM r %Mow&oww O jOW tiMMb ’0%WBttifcjM kOOW IttfcB )lMiMP Wmm JJwWi^PplwPSw JlOttB fP mkiI* 'MP' i^w I'S k^m O t^HHtoW fcMfeW I^HHMMt W flWy*JipW jpw W ^i9l ~m# m die*aft&& ( t? ) f «3P , .dh.O .Ow KiW MAfiqS O^taOO PBwLIWr Wtw Kfc. P FMW I■ l»teriM iil»n o f tha qpgwraprlftto isothtoo;jr«n*t« mitts tit* ajyproprlsti* ■twisaw (i$ ) * m s U,8*« dibwm^thlm«r«w'won* pr*p«red bp ib® firw t swrtbod md ttfK*«dt«ietig&<» thiQ urs* bp the Xait*?% fiftg r gr«s* o f m (0*85 is©X«) w » . Sow of $b» toXaea* east m m rnm rna nlP*iF%ftn /M m r**-dj&flfrteiiiiirfW ff l* W P IW P P IF ia< W O f llp W O a 'I* l P H W f'W W P ip W * ■ ® w * e w w ^ ^ m m m t p fiftd OB cooliufi iSsbO 1?N®»sSj$1b tb» wtiM «tpl«y*d) «T o n dbtsiasd {29}. g. (91*.5# «f the tboorrfcioel yi*ld a .p . 71-W0C ., * M ita M M t f SO f « (0 .2 3 M U ) « f bw ayX m im U ta M mm t u M In *5 0 * 1 . • * In an t oe m rtw feafcb a * to | , (0Jt6 malm) at *mptxm MmtiMtim #d • 5 2 ^ 3 ° C #, (8 g $ y t* M fc*##d on t l » la o tliio o y tftta t# ) o f *f,H*~di8WtML- 1M#w»# #«# obtaioad (t9 f|l ) * S«IS3£MMS M * f to S-««thjrl** ,K • XDDIDM AltgrliM thlauPentoig lodidM w n yrapjamd by tte awttoit of Bram matt SmMMIX (3*1, fbs proparotlon « t S^wthgpXII ^ •^ •« > p t^ y U j|o th l< n u ^ 8 lv a > Sad& te ,«B»hnU 00 oooopX# o f Us# nmtitmd ###4* lMUtharX-BJ»»^^w roE rU aottetottm iiw i todld# A oolutlon a t 20 g, (O.XtS im»X«) at S.S^lwv-propj^UhiooroB tnd X8 g. (0.X2S nolo) of mrtlyl iodide In 100 »1, of ioopropyl alaohol w kr to*tad and** rafltuc fa r 0,?$ te w . Tte eolation m ttan avn>©r*tod atoeat te Aryan*, « m M in in te*"W*ter t e h , and ether added to penuaaai torb td lty. A atoeaaa a il aaparetod and so lid ified a* atandtog antor atfcpi'M wtute. *Ma eaUd am id to roe*7* ta lliie d tmm impmpgA a la a to l-a ttel am tote ntotore. Tte S-*»tojrl«8,8*-di>«^popylimtfcloarenluM Iodide waited at 61.$»&}*€. Tte n ite r toagwanaa prepared in th is mgr are liste d in T«a»le V '■" sw ep t fa r ite d i-n -to ty l smpmad, 8-«*tfeiyl*4r^l»- a te a tiv n a i ( II) , were jnrefHBvwft oy ^pb ^ to a te ,J I w V a iin te a n W h O k ^ ^ W lta k ^ S o* a P ^ to a a e A J t1 a a h ans ■ a B U te V d H a a L » spxwi the pmm&sm emd te r t&» pwparetteii o f # ,8 * * *** 4M&e0g0e8t&it80 WtH 40OFOO 441 10® IMftllBJpSt#* f© * «©lttil©» o f 30at g* (0*X *«©X®) of em&* g ^ th y l* # ,8* betylim tidem ^m dwi iodide la 100 ml* o f l4w$*^grl *X©oh©l woo *0dta4 fa*t$ g. (0*lt5 nolo) o f 95$ hyd^aBlsie* The roaoXtlwg eoluiioB ws* heatod tasSar reflux oa a oles® hath for 1*5 hourg then *Xlow«i to m p * ©reto a te a t to tsador r*s&um& pm wm e* On cooling and wool** lug tiaa re#t.BBJI -**«* fa. % Jt-> *** aarf’Vsa sawftfca 91 1 0 .2 9 .0 9 .7 1 1 .7 1 2 .0 1 2 .0 0 ^ -4 3 9ti 9 .3 8 .7 8 .7 1 0 .6 1 1 .0 1 1 .1 1 2 2 -1 2 3 98 9 .3 9a 9 .2 1 0 .6 1 0 .7 1 0 .6 1 1 9 . 5 - 1 2 0 .5 98 7 .0 7 .2 7 a m & l 75- 7 6 : ; «*4 t a i f g r l : ' 8a 8 J 8 .S ?h*» eoapmA** v«r» «»**alttMA fro* i*opw»pyl eloohoi or loopwpyl •leotol-Hrttgri- «MMk* B r tu n , * » te U « * i » j w s p y l a lc o h o l a n t hM * . ( o ,e k w » ia ) « r t e m y i s i t e i p t e s*te*. f te wmwIWLii* M taU se « u tested «n * steal bsth f* r « tew ■Haute*, te ste * , «te a tte r tedsd te psrasasnt tu rb id ity . tte terns*!, te r tr s tir s o f ^ r to d ld . whiob temwd m te r tte r #o«»llijg o®aM te 'te a tH ilU te i tvm sib y lm &l9V3im ^$ » t p ,t ^ M 9ts. ■' te a t. C ale'd. te r 0»»H„K*I » K, Uj.Oj I , » .5 fw w at » , H i,o, i , 31.1 '-snlrioguMiliiJjw lontriodidc giiMil,d£#a$i u rn pt*&p&x*Gd sis&e iN^r ®# daaertbod fo r tbo 4gfe» ttfL eowjscraad, i s ft% t f jiM in Urn ws# Qh&r*ct»rl*od «tt t&e betas*! b^drlodide bjr addtiag bett*«M«%ds to *n iA&gmgpX aloohd! solution of tfc* isy&Ptodidto asd beatltsg fe r « f«* n&avitee, TM§ beams! derivative o w M be r#ory»taili««d Ifcan a o ia W ’e . eXeohol, a„p* 59 HuH. Otto** fo r tam a&i V, U M X, 36.7 •*, 16 . 2 j X, 36.6 W» « N * t^rlw aW w o f tl» tmmmad %gr • m thod analogous to bhs ono in tH M m obtslnad fa 83* yl*M fo r W» d ib u ty l ooopoatid. 6 piorsto «m yoaparod by dloadvlRg a «n«H n a n t of tha la l aopropyl 4 w lwt m& addin* an aquooiia aolutlen of #Uvio aeld. S,**-r;i-ff-prcpyl»** '-aolaogaantdiiM p io rrta «as raeryataU iasd fra* o rto r, ».j», Jjl^-lO ^e. Aaai. C«J**d fo r 9# ii».bl S, SJi| *> 2S.3. Foowii 0 , iO .S| H, $.6j K, 8S.5. i«^SlCXIi»5"/il3StifiOJIOT8rfiA20JiS8 J 1 ; iH fe u ^ A a 'O .. ib i'm i'b b A i ft iH t jh J o ' W P ® C P B 9 W B © W mw o*£%ot2£Spl4o« T£t&» asot&wl H d iifM M B ttf-lir ti A o itffe jflj*tf J M h a a b 'Q * ’W fflfSwG l ( H I o m HWf .o fc t a f c * » o f c O M o . J t mi*+ ^ © 0 » ^ W ^ jW r llS S U S j ^ , tip pmpm&Mm of tfeo osrbodiiiatsio % tb® of $aM M j j jgjo 8*$ tsbffirsottoi* of th» 4. " : oasMUiaaMo wttfe l*^#*oio *&± m&mm ism&md %im moo of m ottor^ooter oolwmi (l$etft&4 *~l) «z&d tt» ettsor iw»Xv«4 tb» ooo of « tip pr«p$reti<>« of X**s*»btstyX~5"*^ «Mg&* o f both procedure. adUstwo (M«th©4 A«*2). «f£ord« *& *£» SL A m m m m o f J M s . (#«f * o l* ) o f 300 stt*. o f o if c s r, sod 1*00 *&* o f 0 0 $*? ws# rig o r o u s ly o tim K i w h ilo 5^ g* (0J&5 *©1*) of joXXowiwoarXo o poattod of %m Mm%m+ foot os it*oo«&M» mm &M*d la ontol1 portions ovor ?l» m m m Ss w «w»rOBtrio **&£*» 30© i&* of bonion*, 2M «&• of m l IS §* o f cafoitaa fm m i t m « f l» MLmlfe n w i e va# feaataf ^ d « r rofXttx nm cw&laotad m * f i l t e r o ifh 00* o ff mt mrfcto® m l vnU id * ith .$© a&« o f tea* o^toofoxw . $$# m M n tH if lltr a te a m o p& *m i in * $ 0 0 *& • m n i ^ o i l m s ffa a k m l $0 i(0L# o f m % y l*m sofattim a o s liis liii § g* (0JL? stala) of Ja$,0*m»i0 ao&ft: m o loNifcoii tisd^y so flm tw 1*$ r m o afOot!* Tlwi W8&&iQMPQ #0*T*#A iMeflAl IkttlONItt 1^9 H l’yiB^ *tom% 100 s&, o f ttoXmtton mm l o f t , ffeo w©liitl 0% *p, n»i ©v#% l2 C* J9N * * V%\fS 56 *% m tn ^ n jm m «©-4 £5 n J m m m 1 I 3 ^f fst g|| || H| I SI a a i if *t fj# 4 o ** m *jJ5 SJ <4 *4 « t A* % m t t I m « n* 2 i o t> o 4 e«trfc eould w rlintftijr «Xfe^iat«4 $~afcii>ft£fttrftft*l9ft. ******* w ili*' && i i**w st^ Ottbsiltttftni vftTfifift PP ^W W fp BijftftlilcHa rVWWW HW IW W rw ^ w pW |P *W wW |fW W“““*WW * ^pImeoftftd tw ^^P^TW ^W ^W *"** W sta in i^ r# 1 «#$sklfn!gftgi$ft ft** ilm S*«»te®t«%r»35oIft m tslm a, i t mm f f tit t M ftpftftitifit *b»arptioa tontft muftmifttml uitfc ©fe«riiftti«dftt*ft *%im&bvr*X £a&1m,rm m&$& tm iw ^ w i.. ft mmpirnmbOL A Ktaar doablw Im»«m «uto**tle reeording *p»ctropbot0 *ot»r «ADk w m m »4 liquid M ilt of 0.5 m b. tU sin m «r> w ith q s I I b ■ hKJm 4 jW fcudiLO M K^k.H e.« — •■*If A lfel3 ki® ek F#$iB1r6fiBB6 tlL AIdd lfIc « 4d kM *^«K 3i 4*$$^J€ftl» H HsuUfM P*.w™P#-i— w|W K w EM pM w «S lo ft ojw* tboootrastttrs&lai) of ifas mmp&wv& in 10# t>y ©Kiorafom ms upproxi- o il pasts* oona ^and, fctn w&M eoaaon* trails** m » aftjiiotod to §iw in opa$s# t$ M $mt% ita« oonsiatsiscsy of ©old ©ro«a &*! a strong i&oorpi&e® Osnd in ifc* 6 iv&wm xogtan Tfe* opaotrs mm $m f%%mm X4** sod in T&hX» TEEC mm liotsd ite pfiaslpal m m rpm m - bmrfm i M sssh of ooB^xmi^ stodisd. mU $m mm&*Uw& for flggKPII 1* X* T strm olo 2* m h ^S' "W B lTH jp vKl* f^** k, Sm $^»% ^X m iilm % »% t*m 0t^ 6# ?* X ^t^X ^S ^^a^notatrm olo 8* X^fegrX>*5^«»iao%atr«*o3L» i l l tlui wsifte^ra nttsm slsdydUaid ntfftrtHr a HttJoX m ill o f %im Figure- I* n y~\ iP f ___ -L- --------- 1 V- __ ^ r - v - ~ M L I f f- ' ■■"- A / ’" V I* 1 2 r \ ar V r'VV ' ----------- / — 3 /r y \T ^ - f Y 7 - 1 A — -A ' r t / - - ( / - H u uTTflfi i_ f f mk r_ 7 \ y -------- V- '~\y-- - TV ~ 1L II ___ ■- — 1 V ~ ~ K l T f / f / K SJs / * - I i f - 1 7 f — . KJ 1 v - T M A / Hr V f ^ 7 ) ---------- V 7 t W\t- ~\r~\ / M/ W-------- H F - *V\ ^ 7 t*. AXX %%m 5»p«ctr« *»*» <&ij$j»ft6 uaiag « solution o f fcfe© impcmad, «pps»o3dy8®:t®X^ X©$ fey lUu 60 60 4u 20 6u 40 40 20 So 4u 20 4 lu 12 f>am 3L* Z* t^d rm M X m ±4 ^ %» h ^ r m h la r lM 2t* 5* l(p dm «$ lm l^ ^tf»mi*lml«il# 5* h3^3^l^l«>rl4e ?* X ^M m ^X ^^m yX m im -tm fa ^m Q X ® h^m ®$&&TXd& % «trife l r Z 9 w & J ®b%#Xm& wsdtatg hr w&’mi't, Sjp&rtr# i # 5, 6* md f mm obtRtaed ww&&% m $bj©3l jm ll M l 1 iW ' Mtttg efeXoretfow $« 4N&vwt, %#otrm u , 5* ®e& -6 m m m*ing m ItijtiX mtiXl of its® Mflgwtttid * F ig u re 4. 100 80 60 40 20 80 60 40 20 80 60 oP40 'am2Q s"l „ :,o c £— -2 , E/J ^80 — ^ ■ 60 -O 40 20 80 60 40 20 80 60 40 60 0 63 w k rm o m & m m im c m m s m tm w m M sm t m m x u t m ¥(?) a ) * ' * ' * (k) i i u— n t|^ o of Compound l« o loogth (KUrom)^ i | tii nij 3.06 307 3.26 6.04 7 .6-6.0 13.57 K -O lnlkyltw inotatrm alw 3.76 600 7.09 9.66 13.65 lw4)gl-5-*»in®ttakylanii»t*tr*K >le hyd*wrf&»rl<3«i 3.09 308 £.o— it.it 5.95 7.31 9.5-9.7 10 ,> lo .5 1 ^ .^ * l!^ l-5 -l* 6 * K ^ tr «*oll»» h/drochlorldoa 3.22 5.96 6.66 703 9 .5 6 it i&»©«pt etaure la d le feted th© m m lis te d correspond to tb® p o in t o f isaxiMHH #t>»orpticm £ 0 / ) £ m icro n s . & M in a p o e tio n o f t l i t i r o t o i & i d ' i t a t to tr # * © ! ® * hmm o o r ti& s * bond* in «31 X d k a if io e , o o o ii o f t t » group* e ih o r f ^ii^i^iM dU ioiotrm H ^o^ hydro* o h lo rid **, *ad h3>dj^fclGri<^ «ho««d band* oluriofetiriaft&e of th® iroop* fo r laabanco* 5-#Xlcyl«RiBoi«tr**®X®« «io to® dtotiagaliib®® ftam toy th® nod&ni etoaorption bond 4# f «f fb® *towr *b~ oorpbion in bh&® rogion ifsm so bto® $**cfc|.a&byl#niwt*b$*6®ol»s do so t. The J^i41^«siltKsbot.r«ioXeo ©I®© giro ri®« to absorption «to afeotsb 3*0 miMmm, as i® *ta*» oittio r by • bond or ® airong mtmXd»rf but ito* gw tj «&W*! *«t ®h*ir BO diOtiOOto *0S®®y»bi©II $B tM® rOISiOf*. f f on TtteL* T O «* mtfUL ®& bto® apoetr® {Fipo-oo 1*4) «m eon «*®*?t«£» tofc* band® wMolt dlirtdtapxiaii ®»® p o i of totreooXo# fr®» «*©ifc®r, iltfeougb M M w m m m «®» bo foand* i t i« m d i i r spp*r«»fc th a t th® apaotra o f ®XJ0&®t®d or® oisdlor in many r*ip®®to, on* o tto ^ to to M tm ign opoeifi® aboofptlon feaodUi to «$*«ei£I® jppsmp® in thooo ooo^HBondo j> mm i t oonfrosxtoeti « lth tbo oooibor o f tm trn * norio form® otsiob thooo eompound*? nay poo®®*®* fo r inotonoo^ tfc® fOUonlxig «tra«totar®» #«si to© orittno for ft M l' " * I * = I * f 8 -*K v ®-8 i t * = cn) * w im t^trasroloo * JM f'' P I H II 841----- 8 (in) m K* i» afetltian , «m m u M m m t h r t t h n * vmpnmSm mgr a t d n to w , tl» nmhtr «f iwMtt»nitl«« <♦> <♦) P J M f N » (* ) I I -— k || i*n t iwi E^Si {-} — I < » > * -------- 9 * — * * P j u r ' -' 9 (trx) | -*— ' in m^« i ii (-> * — » (t o ) Sam w rk no tha irafira-nni apeetar* e f ‘fcrtrraol*# hm been roported (3Jj *35) «ad «*>W a atraotw rea heva 1>a«» aaoaeiatad a ltb ohareotartatlc dhWMWftd&tt f» t oaaationadQ wdjwi tiitBft tlta&e eawinijasMS* Idobar ap« (j&J a itrd ta ttd tfco atroag bead la tl» 6 aleron region t« &h$ aaiiie ftwup proiw&t Isa 5~«s»if3o~a»d * S a t, im tb© #M» papar tissu&e ®s*i!ser» dtite&feutirii tin# atrong bawl #£ tba g&arddims at stadiod a f«v ba 6*#fc ^iieawma to an $Mm gmxp* Th@y eiao m m •ab etltttted 5~wdmt gnelamleaP1lo^*0|ge$t h-anist 0— H f t in i. . w * * i * s 0 —«&*&♦ *&* Sv it*lK I 8 = 0 = 8 I i w r » —0 * 0 i 0 *«*I- * 'fcn*' 8 = 8 8— 8 f t I t 0 8 * 8 .«, - Jf^Lt IMt .0 - 8 t ^*k P -0 —8-8* Wf 8 -0 — ** M i* 1 I I 8 they s ta te %h*& H ite s&otnni m m m «do• su it# *ru« bat i t fa il* to WNwM* * wtttafiwtwfy aag&aaai&ra to r tho r«rt«HoM In bMlo I t mow. Jwfc m Uto»Iy ohwootor « f ■UoAatodi tb et « rwMHMHHW itm ebia* lttvalrlag a w jw attM i o f abar** eaaU •m anat f«r band* la. tto» l«fr*~rad wrrMpandiag to both tb# $al»a» •ad ■Itoitoewwr** aaob * dtpa&ar rtraatur*, *a petafcad •a t la ta r t I md t« r t XX, aartaa m ftl to «*pX*in tba proparti** # f eX.kvlOfeed •^pr jgpv‘ »»^p'W VWIVflrVW. M et ' 0. "vi * — * (EC) Jlifcoogls Morphy Wool* Jioiro aofldgood the bond at ti&oot 6.0 xoiomfi* to «n oaRMtttao i t m m m m m roaoon&bl* la vtour o f th® oboorvofciono o f K M or « t j&* (Jfc) and otisora <36*3?> to assign tfeo bead * t 6 .0 ail©r©n» to IX and the bond «t 6 .£8 idora«i to stim ctoro fXSf rttljo r than to « pwW m &BP g m ^ la tb®#» struot«r@B0 ^ t h e r tha gmvft a tsto o f tS m m w & m to m char®® oaporoUoii o r aibfc* im rolwa a «troot«m * ith b ^m g m bonding, i t e i i l l io io^oooibXo to ©©nig** ib® absorption a t 6.0 m l® m m to the ®xo~iain® group* 1 ^ # *N*«®N&oi« of iM ifc atwotar© is aoad to iNsprocwmt the ground ototo* * ***on»bing syataa io hm d m ism S k m & p m m m fo istg on the mm ©ado- C«H liakog® eoajugetod vdth ea erndo- MS llokogo and on 68 ®ttier ^ Itofeipu tot#** c m linkage eoa^ttgatod eitfe %to end#- t*K i t tto jntieii o f # tt# c bind «t 6*56 B&oreaa. ; to e m r* i t mgr to pointed e s i t t o t to tre e e le -&* 11 saedoratoly strong ##46, ito grouseI s to le o f wMeli »«y lim»lv© e proton m$. ito toir®*#!# anion* Tto Sottas' present# * etoeed resenaitof systow mslogpm to that pmmmfo in, t e o o , Tto utofc fdjeerpiion a t 6.56 s&orons exhibited by 6 .? | astorene o r b i t e d by t« ® » e (3ft1 * On ito m m m $W m to s t toeei^iton to tto 6.0 a l o m region to too to ststtetsjpoe iewssSetfaeg end to too 6*f® w & m m n m & m gnesp (H ) end th u t fgNMKSptlen i# 0 m to i t o t t o t f im to to g 0 conjugated esato* cm linkage (n iX )# tto spectrum of 5-«»toots»triatol« (Figure 1) rev eals t t o t utoeotofoa tsm to to v to th toe sees* cm and ito undo- cm gmss* meat be eensidersd nine® *stoH^I4*m occur® both a t 6.0 saioron® and € M microns* On th e e lto r bond i t eiSS be Obeerfed th a t S^dli&Isyl* m ine* end $~&%k&lmsdmfa%rm®%®® giro ris e to absorption a t 6.0 end 6*1 e to e n s , «ednototra»oloo tid e **er to totoa to indicate I to t 5-aHqrl^ m i 5^i& J^X m inotoir*m el## «3&et noro to tbs •go* Cm stru ctu ra ito n doe# 5~m im toir#so£#. ftone conclusions are In accord e itb ito diffearenee# in ito ohmic «l and physical ps^opertlee 69 mMMtm by 5-aaiaotetreeole on the on* &«&£ and the $-&lkylaninotetareeelee or 5^i&kyla*ii»b*trao*l*e on the other (?*©> * ft* o f an *xo~ 0«H etru etero by ©barge s u r e t i e s veald lead to * tetanege in the apparent aeid atrengtli o f thee* M tpew le* A daereeee in acdd strength in going fxam- ^«a&mteiras©l® to $h&!qp&» ante©* o r S ^ a ll^ X ^ n o ifc tra so le a hsa actu ally boon observed (? #B) *. TS»»* the ©poetr* and bh® properbi©® of t tm m ©an be corre­ la te d , ®a© © ill «&©© ©Imm*** th a t l^ e i!^ ^ i* i$ * te tre e o te e give ria e to fibeorption in both the 6*0 atsdt 6»S® uteron regions, indicating th a t stru ctu re f i l l end etm etm e IX both e^etrlbnte to the ground stab© of these fro * the m M & baei© ©herimbcr of these ©oeposisd®# tfci® *©i&& be expected, m pointed out in Fort Xt the leek of p rim a ry mfLna ohereoter nan be a&tribnied to the formation of * dipolar e t m e fo m tt m I «im « th is etow itare ineeivee «n e^-iss&m grenp the bend, a t 6 # i t e m atooM and done appear in the spectra of the eoninoonde* I t ie in te re stin g th a t l-alkri-5^® iH yi»i^tetre® olce ©ho* 00 absorption e t 6*0 nionma b et 0© give ris e to ** strong absorption bead a t 6*27 nterenau fM # Indicates th at s tru c tu re involving an ©Jso-Jjaino 0 map mm -timm& ©rat tocat mm mm pm wm t t© tb* *mm ©seUfti tbit ttoiy «** in %t* *to*r ©toitot,, it «b«a jgy^^ p ^ toto& t # r eoaidtfar^bXjf $eM3j*«atod k e ham m pm tefc 1 trtr«n«l£si» «a$&fe£t* « n te n g a&aorpfclim feotid i t 6*0 n&crtraa «*S %ha mm m v f t e -wflpwatii * nh»*&te « t t e » t 6*3 «teon»* Ji&iMgKt tfenln&Xoviaft mmmmam te n * m y %& w crltte t e X*Ji 4i*»thyl« ttht ttnfrtttlWa* twtfHftltW ***** JtalM| TSW ■ 1fe^^k 43 ttn^.^n^ttttnA ik^to4 ilhW iA- JU^**4jLt|i'1< WWW* wtf '6fe Vw ^*8wwBW HO * r ogr I 8 = 8 txr) %. <♦> 8 O & jK 8*0% CBb-»^ *-c% I I ’ • *— ► ' t I 1 = 8 8 = s= S (m ) ( m i) Ml padatad v at ia f a r t X, th is is ta bs «***Btsd slneo the X>» <^(CllQ4V$>lminBt«trM«ltB»a ara Saw m ating solida or U Salds. This tha apeotrs and tha jangparfeiss em again bo eorralatad. f t* Ivdroatdarldoo o f I »lj^ia!^I-^I* iaot« rtr» *o llfl« » wars atudiod in tb lo labor ahoiy and f t waa found th a t tbay givo ris e to a strong absorption bond a t 6.0 nterona b at l i t t l e i f aaar absorption a t 6.88 nicrone, tn d io stiag th a t atm atu re W ill contributes noot to the ground s ta te of the** o b its . j N JMT i 1= W«E I « { x ra x ) n Iks the 3L0 micron yogim 0 although eaMfcited b / »*a?' *# ib» 5~«ateietr«s0X ee obadied, t e * met Xml X ttelf t» etreetiu?* in terp retatio n * i l m mdmm m I im te e both afeeerfe in fsidUv region mad 1tim efoaQrptlone overlap 0 ^ ,3 7 )itte z itie n ahernld fee o*XXe4 to ttm aide strong abaorptiea M ateeet b«0 microns e*fci&ii#& b / *11 X*alkyX»5~«Xigr2^ efcXedUte. fM # fe©«d i t a «t fe^ire- erne to dieting!*!®!* e«*lXy b # tm m thee* emapound# m i ilm X»b iw&rwshXm&dm wldefe « t e w & y % ellgfeb ebsorption in b&ai region* <£%shsy&d, *&$ s^lis^Lssdi iAM& i&4&ttx^ tint ojiooIhp# o f tii9 ^iadi*©** or m t t a ^ 0«» tjp® * f etamMtamt* bfet# a m net meisn th a t ih» eanpetmde eadei erolsmdwXy in -am t e or iim ether, i t tM e time* a » 9 m ei&y eoneider ilis&r *$©ebre te in&leate * sh ift one *ay or the ether te m higher e r 't e a r aemeem tetieft * f *fc» ea&~i»ine or *roSe~ 041 tm m in tha ever-eXX raeemegiee p ictu re. T3 X* A i p f o f nas pr«p*r«d fey the la te r* fef hydraaaio eeld w & the eorrsepordiog sXkyioyi&iealde* t* A awrtaa o f mm prepared fey i& Jyietion o f X-fe«m34^^i«Biwjt®tr*9fc0le «ad fey hom yX tfoion o f the # tM fr mm characterised m h y d r o o p l w i ^ l t M 0 «raMi* and team m ate!' 003ft dortvatete*. flid Id e n tity o f #£si$X*r$y ^i»iiiiot«fer»«elli30# prepared fey the %m pm oodwm o #*i«feXl»bad tt» otruetera# 0# the*® compound*, otndi** ®t®d tftfflffji' ^^WHiTfoftyftm e 3* & m m im o f X ^^«&SyX>*S»l»to nitfe tb® 00m . alkyl %ewp# in the two poattlc«* n«* p ^ iw s l fo r c^porlton i&th * $*wp of * &, The aeeteXyoi* o f 1 ^solino# ha* boosa 9 ] m te giro X Tfe# foateteteiwliB*# co& etitete * non Ola** o f ta te m g rtll* m apm m M * S* £ «*x»i#9 o f ««• prepared fey th© in te r­ action o f hydnwcoXe m id m d WPM* ^ l^ lk y lo m to d lim ld m , th i# i s m rntmo3&m% a silttd f a r tba ppopm ®$Lm o f ttm m f e fe o ttli derivative#, «aad eaastiiftte* & B$ir n etted of 6# <&*«rl** o f o f IMm type of om pom d* o## pmpmemd fey tte ic te r t e iia a o f nitrera# sold and the oorrsependltig M 1*4i#Xigrl -$*f- 8a»inopi«mldii!so* * ffeo hydrochlorides of nor® prepared fey the itti®raati©n o f dry hydrogen oHXorid* Mid tha oorroflponding X«^ligrX^5^fiXKyisBd.«K>t#tr^ol© In m h y d rm * solvent#. Tb® 1nfre^r^d m m rption apoetre o f t M i>sr of aoiio* and diel^jrlatod 5**««1*»tr*t r amtilm ab®arp‘t la n band® w ith tb& h«a boon attempted „ obtelnod and a correlation o f cortcln i properties o f tb® cosspouxids 75 jjpnat/ymtB C3PTS30 1 . 4 . th le l* ut& 8 , In g le, ab b ., J 8 J , 233 (1895). 8* 8 . Bertwrt, C. Jtofcerte, end S. B e rv ill, 4 . Or*. C tan., 16, 139 3 . 8 . S to llS , 4 . jvekfc. S ta n .. 13b. 888 (1932). k. I. B irtoT er, B o r., ‘jfffi. Is«9 (1 9 l2 ). 5 , 8 , K. 8 n t« t M S , 9 . P arcivol, 4 , 0*g» e lm ., 1*39 (195b). 6 , V. It. Swbroefat Mtd &. 8 . Jforbefc, 4 . Or*. Ohm ., J g , 1269 (1953). 7 , W. 1>, Oartereotat end 8 . 8 , Bertaet, 4 . Or*. Qfcau, J8 , 1S03 (1953). 8, W, 1 . M m M end 8 , M. Iferhet, 4 . Or*. C tm ,, 1§, 1028 (1953). 9 , 8 . A, »® ry, W. 0 , m£ t* tim es*, #*. in , 01m , $©$** Jg* 10* Be S* Mmphp r n 4* P* P£®m# J* Or** Clm*, jg, 1807 0.9% )* H « B, iX3syl«t»(t %kmaM$m&9 fb a ir *ad M, a* ?&«*&*f. MtoMgm $i*&* c©xx*g©# 1952. la* Stedtii ml <1, m* ctm, seo*f x i XI* ft, H* Bst%#t ml v# X, iiilmo&fe* X&, E, M* 0s*, 0fcm*# 12, 1283 (1953) * 1>, ?* X, SuWfct#, B, Hsroi^lfort, «*se£ 9 , I , %m Mttfe, # , M 0 Clm , &**„ X$* f , X, &**!# met i , ft* Ikm niiM # *• m* elm * $**?,, JggU 2112 0 » l> . XT* M tem ife, t e * , $ , 1X&1 {1875) * IS* w. X* Omjrw&M m l 1* Mo Saxfcrt, 19* s* s to ix i, a*n * j£* xub (w ). <*g* , »# * ., J J , 105? (1900). S3. J . T k U h , Aim., 870. 1 3|« v. a. TTroMsnt* a. a. ', 3 . &■». Chm»„ 18, 179 ( l“ f "***# f-* »« ww* «*# 87. J , 5 , <588 (1®78) 20'# IS* 12&33 t to* 2?* *MUt, *i 3^ * 0#r ■$'* 31 , w«fto# j# m , u rn )* to# =M tor*i*.#Jj^ £* I&M&, il# C$m* $©©## 63, 32# C* S* '* *** 33# t# V* (# 3 * ^4PW #< *1*• 1**■ # 0* *8 Jjft* ♦9 4Sw* 3lu *< 35# 8 . 0* * ** ’ 30* X, 0* .* |t * EaasialX, # #wwwwp ***^ «— 9teti0%mv 8« i„to|9(W ,” 1607 (19SU) w .# -«wt o#«t ot o ^ t# H B ia « ii© n © f m&totmA 0©*9 If# t* *