Citation
Reactions of aldehydes with amines I;

Material Information

Title:
Reactions of aldehydes with amines I; a new aldehyde reagent
Creator:
Singleton, Frederick Gray, 1914-
Publication Date:
Language:
English
Physical Description:
94 leaves. : ; 28 cm.

Subjects

Subjects / Keywords:
Activating transcription factors ( jstor )
Alcohols ( jstor )
Aldehydes ( jstor )
Betting ( jstor )
Drying ( jstor )
Grana ( jstor )
Internet search systems ( jstor )
Oats ( jstor )
Sows ( jstor )
Toes ( jstor )
Aldehydes -- Reactivity ( lcsh )
Amines -- Reactivity ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.) -- University of Florida, 1940.
Bibliography:
Bibliography: leaf 93.
General Note:
Manuscript copy.
General Note:
Vita.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
This item is presumed in the public domain according to the terms of the Retrospective Dissertation Scanning (RDS) policy, which may be viewed at http://ufdc.ufl.edu/AA00007596/00001. The University of Florida George A. Smathers Libraries respect the intellectual property rights of others and do not claim any copyright interest in this item. Users of this work have responsibility for determining copyright status prior to reusing, publishing or reproducing this item for purposes other than what is allowed by fair use or other copyright exemptions. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder. The Smathers Libraries would like to learn more about this item and invite individuals or organizations to contact the RDS coordinator (ufdissertations@uflib.ufl.edu) with any additional information they can provide.
Resource Identifier:
021714476 ( ALEPH )
13277379 ( OCLC )

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REACTIONS OF ALDEHYDES WITH AMINES I

A NEW ALDEHYDE REAGENT








By

FREDERICK GRAY SINGLETON


A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY









UNIVERSITY OF FLORIDA
August, 1940

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Full Text

PAGE 1

REACTIONS OF ALDEHYDES WITH AMINES I A NEW ALDEHYDE REAGENT By FREDERICK GRAY SINGLETON A Dissertation Presented to the Graduate Council of The University of Florida In Partial Fulfilment of the Requirements for the Degree of Doctor of Philosophy UNIVERSITY OF FLORIDA August, 1940

PAGE 2

TABLE OF C0VTIST8 PH* zmortJCTXov l PASLf X A nsr XIACS?^ for we OETECTZOB op AUilSYnKC !• ri.M«»«iOb «f other t St fk* of 7 8* theory 14 4* .^ehlff Baeee from R»!>Ilbeneyl«e»i^heryleneuicj''i.ne tO (a) Beacylle^ 2t (o) Cli««sylt<*iM3e<>«^!il'eiMsyXeid&^ S3 (d) p«dtb«niyleid]M4mtll])e 23 (f) e«*^*ethoxybenBylldene««a->'!ibefttyXtatln»ph«riylen«'l^elne 38 * 4» V*lwrlbeT)ryl*H**benBoyl<«}«^«nyleRedl«p.l&e 40 k 3* I«3»:;ilMRUqrL*n*»W*«Kil«i«etyl>«»^MPQyl4Naedleadne 41 118365 «

PAGE 3

A* LBp«riM«xtel and Proeadura* (a) 2*S*»Bi*<«aaftaitiiuhHfc»4*«tla«^lbac«7l«iaa» tripbanylBiathaBa 49 (b) 2»t**81a»aaatiMBiBe<^i«4**bt<«K3UM»i^lmiiia*» 2*<*alilara*trttd»aa yl «at^ ^ 46 (0) £*S*«BlSHftoat«BineHk«4*«biaaiUQfl«aiiM>* 4"«4^oro*>tripb«BylaatbaBa 46 (4) 8>2**Sta»a«ataiiitBi»»4»4»«i»ia»^MMfta 50 (a) 8»t*"BtaNifflatMinaw4»4*<»4da«K^lK»«ylaaino» X*«awtbo3qr'<4»rlplMnylMth^ 5t (f) 8*S*<»Bta-aaataaiiMHi4«4*«4>ia*dllMmylaiiiiu^ 4**9f«^rlpiMaylaMtii«aa 54 (g) 8«S*«^aMaoatiuDlaa«4«4*«4>iaMUbaaiiyl(H>iaa» 5^ 4”*awthyl«trtj^M)Qgrlaathana 56 (1) i«t*»81a"apatwdBa»»4»4*«bla«»dibaa»ylaB8lna» 5**«athQ{Ky^*<4<-4.4*«ibla^bai»ylaBiiio» 8*««itro^riphat]yl«athana 66

PAGE 4

EOUUSf (1) '4ttalno»4«4*-ble««;ib«asyltt6iao)«KU aMthsi)« (r) Si»-(t'*BC»tk^ino«-4^l!wm*yl«rdxu>)*dlphtiJsy^ tt*?ropyl-r»«than« (8) B]>9***{ 8 4 •' d H>CBi X y 1 wtiLzto J *» li I P^iB2^X*cii*4ny X* a*th«a« (u) Si*»(t«Baftt»lno«*4^l|j«oeyl«aliM>)<«KUi^^ aftthBiM p«e« 47 49 71 79 7b 77 79 81 88 88 87 90 44i

PAGE 5

ilbll«cn|)iqr n Mkattg»l»4gwwtt« M BlogrMplv M CoMdttM B^p«rt 9e

PAGE 6

xratooocTzoi PrtUaliwry atUmpt* t* oond«&M II«S-dib«&syl«w>ph«njrX«iM» with aroMtio aldahydaa t« fom m^batitutad titniMilnin-tTlphwnyl aattenas «»ra otiaaoaaaBful* tiamrtmr, dortag thaaa attw^a It aaa obaaraad that tha addition of an aldahjrda to on aXooiiolie a
PAGE 7

FAKt I A mm MMAamt rot ms aamtion
PAGE 8

ProbiAily th« Bost g«oor«XXy u««d t««t for ^dohydoa i« that of Sohlff^ lAo Mrrod that f\i^ai& oolutloBa lo«a thalr eclor on traatnont fdth aodlua oulfita or aulfur dloxida «ad that tbo color la raganaratad on additllno>rtrlphoiiyliMthana»aulfoaio aold ahich than adda a aaoockd aolaoula of aulforoua aaid to fom tha oolorlaaa awlnoanlfinla aald , XBaSO^fi ittua an aldahyda la addad to a aolutloo of this oon^Ksund it oondansaa with tha aulf Inlo aold group In auah tho aaaa vay that ald^qrdaa raaot «lth alkali hlaulfitaa*tbiB nav ooapound la nov frao to oondanao anothar of Its amlna groups adth aulfuroua aold and tha naaly fomad aadno»rulflaio aold group aan, in Its tum« add anothar aolaoula of aldrttyda* Tha nmr ooaqpound la unstable and loaae aulfuroua aold« raganoratlng tiaa qulnoiu>ld ^atODu Tha atruotura of tha rlolat dya» t^on aboaa fovMtlon tha taat dapanada* la aa follcarat

PAGE 9

0 OS •• / SB • 8 • a • B •• \ 0 B Xb» Mo^ptaao* of thio thoory nokos It noooootory to dlwMUrd too thooriot h«vo boon fry popular and vdtioh otill find a plaoa s in aoaa of tha latoat and boat bo^a on oreanlo oboBiatry* Tto firat la baaod on the aaauaptloa that tha aulflta raduoaa tha dya to tha louoo baae and that* eubaaqiiantly* tha aldihyda raoKldiaaa It to tha color baaa* Epaotral aba«rptioa atudiaa hava ahofoa that tha naa oolor la sot tha aaao aa that of tha mrlfinal ftiohala and an Isaaatii^tiQa^ in thia laboratory haa tiumn that aldahydoa do cot oxidico tha laooo baaaa of polyaaalno* triphanylaathmaa to tha color baaaa* In aplta of tha ob^otiona to tbia theory* It la tha ooa moat gmarally hold by orgimio ofaamiata today* fi Tha aaoond thoory aaauaoa that tha aulfuroua aold aada to tho onda of tho qulnoaoid ayatea* randariag It oolcrleaa* and ifiat tho addition of aa aldirtqrda o«iaaa tha tranafar of tha aulfuroua aold to tha latter with tha ragmaraiioo of ^lo oolor of the dye* Thla aicplanatloa* although It haa more marit th«s.n tha one deaerlbad obo-ft* la also ahoan to be S invalid by tha aorlc of tioland and Sohauing » Aa aaa lumtlanad above* 8ohiff*a raagant la undoubtedly tha moat aldoly uaed of all tho aldahydo reagonta and It haa baan an in«» valuabla tool in tho atudy of tha aldahydaa and tha augara* ilovovar*

PAGE 10

It im» wUia diaad^tH*** ^ r a aftwt «t«i aada up wrmtl^f «aA «lMa tfA U vwry MnalUvai Imvar* i4i«n aU«Md ta ataad la tka lab* eratary it loaas tbit aanaiUTity rapidly* Tba paeifieliy of tbia raagapt alae laaaaa a fl aatbing ta ba Oaairad* la tha firat ylaoa* it siaaa a paaitiaa taat alaaly with aoataaa^ aatbaaal and atbaaol aa aall aa «itb aartaia otbar aco-aldabyda eaysaaatad aabataaoaa* Oa tba atbar hand, para*aubatltuia4 aronatia aldabydaa auob aa p «a at w o b a nia l dtby da, p*dlaatbylaaiaalmiaaldab]rda, pidiydiaaptMaBaldaby^ aaiaaldai^, aaratria aldabyda, awilUia and pip* aroaal «iaa paar raaoUaoa ar aoaa at all* Bapkalda^da aad aihar bifbar aliphatio aldMaydaa glaa vary poor raaatiana* Baaidaa tba tbraa iaportaat taata daaarlbad abava, thata ara anaral otbara abiob ara vartby of brtaf wUaa in tbia a»aauy* Haa^dt and S* fiachar^ daaariba a taat abiob aafcaa uoa af aaaabasaaaaaulfoBio aaid diacalaad ia aatar acmtaiuiac aodiaa byiraxlda and aadiuB a n o 1d an» Additiaa af an aldabyda aauaaa tfaa i^paava&a# of a rad oolar ia f rcn taa ta taaoty adautaa* Tbia rad aalar U tba aaaa far all aldabydaa* Bansaldabyda aaa ba dataatad ia l/iQOO dilotiata aad it ia ol a i aa o that tba raaotioa ia wosa apaoifio thab tha Scbiff taat, althaui^ aaatona aad aaatoaoatia aatar gtaa paaitiaa taata and abloral doaa set raaat* 3ba aaobnaian af tba raaotioa ia not kaonn*

PAGE 11

«nd brnw ft tft«t f«r ftlot of ?«rt 1 of thlo diooortfttlon lo to doooriho tho proponUoa* proportloo o&d roftotiou of R*B»diboaoyl«*»phoByloBOdiMBiao« Thlo oubotonoo hfto proportUo idiieh« It lo holloood« aoko It ft ooro uooful gooorol roogOBt for oldohydoo thoa oay provloaOIy doriood*

PAGE 12

Tte SysthMl* of »*»»IAboiuty>»»i|>hti»y1oiiii1Uo1no tklt o«apowkd «M prtporod hj obo «m uaoblo to purify it oad roportod it o» * viooooa oU olKLah oxidtM4 iHMdlly in ti>o oir» It wM oloo luroporod *• oa latoratdioto ^ aopor * Co.* la thoir oyothooii of lUlf»iibiaoxX»H*HMHityiH»>plMnylont
PAGE 13

* puriflMtioB «f tbm m» isTMtly alapUfi^d* Xa fatttji it ««t aliMKii laipaMittI* «o purify thu pruduut •btaiatd frou isconplutaly purlflud utartiag aMturiaia* Xa tha aarlaa af raaotigaa uadar omwldaratXoa tha produota baaoaa iaaraaatngly dlffleuXt ta puriiy aa on* paaaaa froa atao to atop and a higb dagraa af purity ia aaaaatial 1 b tha •tartlac natariala* Tha MiitraniXiaa oaad aaa haataaa'a taohaioal grada abloh aaa fraa d froa tarry is^uritiaa by diatiUatioa at • aa« Oadar thaaa aaa&itloaa tliara aaa no iHoBagoaitioa aad tha diatilXata« aftar aolidi« fioation* aaXtai aharpXy at XXS\* aad aaa parfaatXy aatiafaotory for uaa ia tha raaotlM* Xt a«a fouad that diatillatioo aaa faatar* aara aaonoaloal aad gaaa a battar pradoot than axyatallitatlea fiaa aatar or froa dilata ala^uil. Tha banayX ehXorida aaad «aa £aataaa*a baat grada* fha aaalX aaieaBt af hydro(4klorla acid ia thia aaa laaoaad by chakiBg flrat aith 9f> aodioa oaTbonata aolutioa aad thaa with aatar* Tha aoidHPraa praduat aaa driad ovar calaiua ahlorida aad thaa diatillad uadar raduoad praaaura* At XO aa* tha boiliag laaga aaa Tha bancyi ahlorida asiat aot ba diatillad at ordiaaiy proaouro baoaaaa alight daocapoaltioa aaauaa*

PAGE 14

ftm Pfwamttcai of la 4 1 litmr rPu&d«ibottcM*4 flMk w fUmo^A IM grawi (X aol«) of pnrlflad MRltraaUiM* m crmi (t ml««} *f b«c»yl oia»iria4« XM gnM (C a»X««) of powdMTOd OBlqraroai oodlwi 4o«Ut« m 4 X«S fraw of iodiao* 9te fXMk «PM plaeod ia aa oil bath uador • hood oad tho toaporaturo of iba bath raioad oXaoXy («m hour) to XX&*XSO*C» o^iara it aaa walwtalnad for a ataia M w of oovon hours* Duriae this tltao tha tioaoui oil aas siirrad offlcloatl]r alth aa air»jri
PAGE 15

Aa ORMMM of ftloeboX autt bo otod to proiroot tbo Mlutloa froa nw<^ilac tho ooturotion point at a tfs^oraturo abovo tho aoXtSag point of tho oonpeuBd (H^m) It tho pradaot* ohich eooaioto of bright yoUoa loafXoti. nolto at or aboro, a aaootia rooryatamaatlao la tanoooaaary. Altbaugh Daaal raporta tba atltliig point aa alaborai# offerta in thia laboratory hara fOllad to raiaa tba amtiag point abort 72^C* Tba aubatanao aanartlnoa Aoaa diin^rphia proportioa* la tbaaa oaaao It aolta ftrat at 7t*C*« roaoUdlflaa m oootiimod alav baotlsf and aalta again at 7®^* If tbo twparatura la raiaod oioidy froa rooa t«nparattira« oith tha aapillary in tba bath, tba loaar aaltiag point la not obaartad* A Matnanna blotk baa bow rory uaoful la atadylsy tbia naltiag point aad aaroral otbara of a alallar aatora abioh aara aaeovotorod in tba tripbanylaatbant aorlaa* A aaoond batoh of oryatala aaa raeororod froa tha nothar ll
PAGE 16

> Th» of L~lb»dllo»« Za * 2 lltw flaiek «M plM»u 1CX> gr«M of dib«myl<«>«ltmallliio» ndt wm dltoolood ia o adxtoro of too oo« of t6^ oloohol aad fiOO oo« of oowHmtrotod hyiiro* ohlorle «ol4, fondai; on *lao«t oo1;^1om tolutlott (tht iiQrdiroafelorldo io oolorlooo)* To HblB oolution gronuloted fiao «ot oddod Joot foot onough to BOintwis o vlgoroiio ooolution of faydrogoa* About t00»S&0 emui of siao ooo roquirod oad after tbo ocUtltlea of aoot of this qwmtlty f roquoat tooto voro Bodo to dotOMino afaothor tho roduotioo «m cotoploto. Tbit toot to ^boood upon tho foot that tho hydrooblorido of tho altro ooRpouad to abito but is oooily byerolytod^ oa oootoot oltb «ator« to tho yoUoo froo boot* Tboroferof oo long oo oay of tbo nitre ooapeuad roaolas aarodaood, o yoUoo oolor to prodosod vboa o fow dropo of tho roootlea aixturo io pourod into aotor* tbon thio toot vao nofotloo tbo ooXutloa ooo fUtorod to ronovo uarooetod tlno oad pXoood la tbo ioo»t>ox« On otoadlng: oromigbt, tbo hydrooblorido of i«lMLibonsyl««*q^«D^'lox)odioal^ ooporatod out oo o ooUd 0*00 of booutiful ohito eryotolo* tbooo aoro ftltorod ot tho pcoy oad tbo aothor liquor prooood out oo otapXotoly oo poooiblo* Ttw abito ooUd aoo pUood ia o t Utor bookor oad otirrod thoroughly alth 1600 oo, of aotor ia order to liboroto tbo ftoo onlao* Tblo ooporotod ia tbo fom of o bttlky« floooul«ai« abito proapitoto abich aoo flltorod, aoobod ooaorol tinoo with aotor* oad tbon otirrod o|^ia aith 1600 oo* oi aotor ia ordor U

PAGE 17

to r«B 0 V» M wMli 00 poMtblo of tb* roBolalag Itil «ad 2aCl|« Acftia tho aadm «m ooporotoci by fUtrotiott* «mmMio<1 «ltli wotor* *a6 ftoolly •uipondod la X litor of I9( oedioo bydroaldo ooXutloa ond oXlcwod to r — li a ovornlslit la tho vofri(^rot«r la order to roaofo oXX traooo of told ond tiao ohXorldo* nio oiAiotonoe oloo aooiiood a auoh bottor oryotalliao fora oa otaaAlag la this oolutioa* Iho oXightly yollov or;.rot«lo aoro flXtorod off oad aaahod oovoroX tliaoo alth aotor oad thin dried ia a wettua deolooator onror eoXid potaoeiua hydrMide* the yield of orude dry produot fren three •inllar preparatloae aroragod 7« graao or of theory* AeeryataUlsatloa trm ftOO co* of aXeohol ffare 63 graae of the eubatenoo ia ^ fena of aeU*KieflM(i ahlto oryetale ahleb aeXted aharply at lOX^* Af%«r dryiag ia aa ibdorbaXdea apparattto at 80^0* over eulfiario aold at 10 aa*« aitrefoa aaalyeia (X^JeldahX) ihoeed 9»t9% aad •*7t,4| aitregea aaalyaia {vams) aboeed 0«er;^ I* Caloolatadi 9*73:^ I.

PAGE 18

Tim Propwtl— of H^>lrloftl fonmla StrvMtural fonmla Uryotalllao tom md oolor liolooular Moltlag point TloXd inalyoot lltros«a Sol^illtioa T^tor Moohol Aootono Oonsomo Conoontratod OCl “mW. 19ilto oryotala 288.I8 10l«C. 9 (H found Caloulatod 9.76 9«t»7 Inaolublo Slightly oolublo ocdd Seliiblo Solublo Llffioultly aolublo oold

PAGE 19

Theory la tha iatroduotlcm It «a« statad that S«N»dib«nsyl-«f phatqrlaaadia&lae raaots alth aldahydat in tha praeanoa of alaaral aoida tha fonnatlon of latmaa oolora and a oharaotarlstie graan fluoraaoaaoa* Furthar study ohowad that whan tha anlaa and an aiwatie aldahyda wara haatad togathar la nautral aleehol solution tha Schiff baaa saparatad as a yallcar oil Thasa oondansation products do not crystalliso from any of tha solTonts triad, but nay ba obtainad, by rapaatad axtraetion with aloohol, as snor* phous yalloir povdars iriiioh ara pura snough for analysis* Wian thasa oc^pounds ara dissolrad in anhydrous athar and subjaotod to traatnant with dry HCl gas, blood»rad rosins saparata from tha solutions* This aooounts for tha intansa color nantionad abora* If howsrar, tha BSl traatsMnt is oontinuad, tha rad color gradually fadas to light ;^llow* Tha light yallow ocnpounds slowly rstum to tha rad form if laft In tha air* If th^ arc traatad with watar, tha ohanga to rad is followad by a slow loss of oolor and tha appaaraaoa of tha odor of tha aldahyda, indioaiing hydrolysis to the original anina and aldahyda* All of thasa foots indioata that tha Sohiff basas undar oonsidaration fom bright rad nonohydroohloridas and light yallow dil^droohlorldas, tha lattar baing unstabla in tha prasmoa of noistura*

PAGE 20

A •••roh of the litenuturo modo to too if oliBilwr obsorratlcm* hod botti Bade pr .^TiouiAy in regard to analogous cos^ouada 10 •ad it vaa foxmd that Moora and Gale had notload that Sohlff baaea la ahiob one portion of the Boleoule oonatated of an X«H«>dlawthyl-phei^l» enedlaalne reaidue ahoeed the s:\&a pi^pertlea ezaetly as those deaoribed abore* Fron their study they oonoluded that bases of the fonsula font dasdcer Bcno* salts and lighter di» salts than the bases themselves* They stiggested three possible fonailas for tlM red Bonohydro Florida* Tiro of these differed oxdy in the nitrogen seleeted for the addltl
PAGE 21

Xa a MMond Moor* toui^t to *ttid»Uah thi* la«t thoory by pr*p*rlBg th* oorr*^MMidla( »*d|jMthyl«iiao dorlvatlTM^ atitoli oould aot iMMMlbly MSiiao quiacmoid *tru»tttr*i« If th*M tmipomd* did BOt fom highly oolorod aeaoliydroohlorld** th* •vld«ao* vould b* of*nh*Xaingly la favor of th* ^laeooid th**ry» K^or* r*port* that ih**e ooapouBd* MttiaXly do n*t dhov MMrfcod oolor «tuusi^ on tr* a ta * n t vAth B61» no«*v«r« h* *tat** that ao dafialt* a(N(ioltt«iaB* oould b* droan b*o*ua* of tho pbyoiool proportt** of thoo* ba*M« la oont radio tlnotioa to th* *r3rotalli8* proportloa of th* para ocapoaad*« tho a*ta doriratlvo* «or* oMryotalllaabl* rooias* «hi*ria»Bta ia thia laboratory thm ooBdXtiiAvoly that tha m»diamthylaniao dorlvatiwaa, ahaa aubjaat«d to tra a tw aa r t with dry BQl, form highly oolorod monohydroohloridoo aad olmoot oolmrlooo dil^irdroohloridoo ao do tha p*^imathylamino and miKlibanayl* anlao dorivatiaaa* Thia ia uaoaidorad proof th*t th* qttiaonoid theory ia iatalid* Evory axplanatioa offaiad thua tmr for tbaaa color roaotioaa haa aa aoay diaadvantagaa aa advaatagaa* iiamav*r, thara ar* may oalor (ritanomana «liioh do aot land thana*lv*o aaaily to *«pl«iatioa» S«v*ral

PAGE 22

•aoMdlM imf9 bMB inoauiKt«r«d ia th» ;pr»Mol limMitlcRtloii* r«r «ttnpX«f it MMHM dimoolt to ooooottt for tho triglit rod color of diaothylH»«ltra»illao la rioor of tho foot that pwa ioooor lo polo yolloor la color* Aloo dlb«as 7 l««a*«ltrozilllaOf liiiOh thoerotloolly ihould bo dorkor thia tho dlaothyl«o»iodtr«allizio* lo bright yolloo* Boaco^ tho foroatloa of tho aoeohydrodhloridoo of Iho £>ohlff baooo offoro o foaoiblo oxplonotioa of tho oolor roocUono* Homotot* oiaoo thooo coo^euado aro aot floorooo4mt« this lattor (^larootoriotlo of tho toot aaot bo OMoontod for by a ooooadary roaotlon* Although ropootod offorto to looloto oaothor puro ooapouad havo follod^ ^oro lo Uttlo doubt i^out tho origia of tho fluoroecwioo* Xt will bo rimarfiml thot thlo toot oao dlooooorod dnrlag on apparoatly oaia att«ipt to opUt out oator froa too aoloeuloo of tho »-dloalao ood oao aoloonlo of oXdohydo to fora oubotltutod tottoooiao^trlphoaylaothaaoo Iho appoaronoo of tho fluorooooaeo ooa bo oooountod for by ooouaiiif that thlo rosoUca dooo toko pXaoo to a oortoia oxtont tad that o— onto oplltt out to fom the ouhotltutod dlhydroaorldlao

PAGE 23

E Md 'ttwt this OBldltM ^p«nt«aM»ous]^ t» tlM nuormwMtt AcwidiM d«rinttiv« (1) 8«w of thooo doriootlvoo nor# propurod fron ttio aootylotod ro«
PAGE 24

•orldiiMia* Co^pouBdit aMM»lu>l«ci*dlitttUM0 •Bd l•ltiNU»thyl•«H»ph«^ ««r» fottad to flTt roBoUactB •laAlftr to thoM glTOB by tiM dlbwuyl dorimutiio* I 3 of»o«or« la tho«o ooooo tbo flttoroMotMO «M suoh voakor «a 4 oat tloaor la apptarli«* (8) Zt «a«Md ttxaaet at flrtt tbat maoaU ooald b« aplit out of ih 9 triphtnyZatilumo dorloatlTtt at rooa ttaporaturof hoarvar* attti^a to doaeotylato oflapouadt tuoh at t*S*«>eliaeot«iilao^»4*«bit* dlbontyltaloo-trl phony l»ttha*it Xod dlrootly to tiM aoridino dorloatlvat^ iadioaUtc that tho fraa totmaalao^tilphtiiylaothtaot art aoro oatlly qr«Xl*o<2 than it atual in thit toritt* Iho btaoy dibeasyltEiao i^roupt art uadotljtodly rotpontiblt for thit*

PAGE 25

Sohiff B*Mit rrM SIMM ocMipouDda wn pr«p«r«d Igr MSdlac alcMljr to oquiToloat Mwunto ot Um •bUo dlMolMd In boiling olobhol* la aoot ooMt ooatiauotioa ot tbo hMilag rooultod la tho Mpoiatioa of tho product «• o soil cor or ligiit ortogo oil within ton aizMtoo, HoMoor* tho preduoto froa o n looldohydo and o^oMiboKybeMoldohyao BOporotod only on eooliag* Kepootod offorto to roaryotallito UtoM Mbotaneoo «oro unoueoooKfol* Thogjr oopomioc; olw^ «» oils whicdh boooiBO oaerphoue roolno ttXtor otonding in tho rofrigomtor* ShOM sonworyotolliiio oQwpounio« hoMvor* woro pnpvmd in fom puro Mough for oaolyoio by ropootod oxtrootioa irith hoi oloohol follMod by oopnroiioa twam n nixturo of oqool port* of oloohel and dioaaiu faoy war* poardorad am than drtad aaurafully cnrmr aullWla aoia in a aaauuc. daaiaaoter ot 10 m» AU of o thoM oaimMNinda tool tad oaar adda rangaa baloa 100 C* Xhoy fora intasMly oelorad neaohydroohluriciaa and olaoai e^orlaoa dil^droahioriiaa*

PAGE 26

Iwaiylldwat aUxagylawiiwni lia» ^iriotl i^naal* htni»tar«l t'orail* • '<3 CjryatAlUa* f^m and ool
PAGE 27

te^rloal fonuU ®tT^» Struoturtd f omnia CryatalllM fam mod aolor ^olaeular mi^ht {^altiag paiat Yiald Aoalyaaa Kitroeack fialublUilaa tmur Aloohol Aaatcina iitla»r Banaana Jiogtaa Lieht oran^a aaMarphoua aoiid 39i*8l Immi stl Found Galcwlatad Inaolubla siiglttljr aalul»la hot Vary aoiy>la Solubla Sel«d^a Salubla

PAGE 28

CiiwayU/ Ha t a AlhtniyUwlaiewBiXiao ?iKpiri—l fonsoU Struct'jurml fonsul* CryvfeelUm tnrn «od oolor Uel4Mtt]ar lc«ltlQ5 point noU An&lyMf Ritrofoa Solabilltloc Voter iloohoJl teetme hth9T h0oMmt» uioatm LXgitIt €tna£m amwptoua mlid 4QS.1P UMOt Found Cadooleted $07rfi ••tT5i lBaoltd»Xt aoXvbla liot Very eeluble Soluble Soluble Selubk

PAGE 29

pMa>lor
»r.'Bylld cin ««tw> l lbmylinAtto a BiUa* iiq»irlo*X foiwia* 87 S8 t &truoturftl ^nnul* Cry«t*Ula« fom mA eelor Kelto\ l«r Might litltiag point ruu Anolyao* 81t««c«a mtrnt Aloobol AeotonO Bonsono Ethor Lif^ ylXme «aw>rpheu« Mild 410*6« fkmo TemA Calottiatod 6*68^ d«8^. Xn«olt8»l« Slightly «(diiblo boi fioiubio ^l^lo Solvblo OiOMU Soivbio

PAGE 30

iiiplrloiUL fomiilt VmV st r wo t iawfcl fMwtlft Cxy«t«lllwi f«ni Mtd oolor V^«cal«r Koltine potst n«l<3 sitroe«Q SolubilltlM JJLoobol Ao«tan» Ethwr BMecsui Monn Pttln jfHlUow MMKI^OU* Mli4 406*18 lhM« ffnMBiV Pwoid c«l(xil«t«a 6»7T^ 6«9C^ laaolubl* Saluki* hot Vory oftliAilo tolublo £oliri»Xo £olii>I«

PAGE 31

•^iwtlioiqfbwuQrlidamavBwilbmByJjBd^ itm>iriQ«l tonulrn, Sirmtxuptd fomil* CryatalliiM tom «na Aolor Kilting polzxt n«la AuftijrMia Ultrt^aa SolubUitl 9 » iloobttl kxurtovm &tt«r Bvnsnat LdoSMt Cggi^gO P«l« yvlloar «w»«^hou» MUd 40 ««SS )MMi 9 rotoka 0 *i 4 ral«t «4 «« 8 (^ Xiwolubl* &olul>l« b«t Vm 7 tolttblft 8 olvi>JL«

PAGE 32

:««trii>tloa of tiio Tott for Aldoh^doo fb» otofik oolutlon oonoiott of o Ijl oolutioa of »»phoqrl
PAGE 33

(1) g»tur»t»4 »XlptJitU »Id»hydM» 7b»M fAddii^t glv* a U|^t rad initial oolor ioilottad vittdn tan nlxmtae hj a brigbt graan fliioraaeaasa afaiob bac and no flnoraoaanoa* (2) qnaatnmtad alinhatU aldabydaa* UMiibara of thia data fiiva, in £anaral« a dar^r rad initial color than tha aaturated ootawMnda* Tha rittoraacanoa appaara la a fair ninotaa aa la tha oaaa of the aauiratad aluohyciae^ hut laataad of batag brif^ groan it ia a dull broanlab* groan color* Klaod aldahycNMi auch aa al p ha » a>NaBylo 1iwi ana l dahyda balaaig in thia olaaa* SxuapilosuM Qanadiana*«*d«al and aiwanaldahy<:a ^hov uanaually dark rau initial oolora^ tout gioa no oobowiuant fluoroooonoo* (9) Arawatio aldohydoo* Honbora of thlt olaaa giro initial oolcura ohich tary fron brigiit yallow to dark rod* iho ohiorino aton and tha nltro group daoroaao tha color uhon adbatitotod in tha ring* vhilo tho hy'iroay* awtiiony and dimothylaadno groupa iaoraaca tha color* Tha flucrosoonaa* ohiali la bright groan lilca that of tho aaturatod alipiiatiai* appoara auoh nora alearly and uaoally tux toe detoot4»d only aftor too hours or noro in tho diffuMai light of tho laboratory* Uttoptionst iitro^dafaydoa do not giro tho fluoroooonoa* but uooally prooipitato tho Schiff baooo aftor otanding for tooloo houro or noro*

PAGE 34

Furfunddffhyd* omi diatlaeulalMi! from til otii«r aldirttyd^a •ip> » It sl'vaa a brlglit rad ooXor vhloli ahaagat aloidy ta dartc j^raan ao ataadlag* Tba ohaaga la oeapXata at tha and of ana bour aad tha oolor la eo daap that ahaarvatlon la facdlltatad by dilating atroog^y atth alcohol* Tha praaaaoa of alMiydaa aa laporltiaa in aolarata aa^ ba dataotad by adding ft ad« ct tha raagant aolutloa to 10 »!• of tha aal» rant* Zn no aaaa did tha raagant fail to ahaa tha praaasoa of 0*01^ of tha aldahyda in taat aolxitlona* AliphnUo aldahydaa aay ba dataotad la aaneoatratiotta aa loo aa 0*001^ baoaaaa of tha anra latanaa fliioraaoaoaa ahlah thay glaa la tha taat* at ocaaaatratloaa of 1^ and 0*lj( tha oolor appaara hnaadlatalyi hoaaaar* at 0»0U aad 1 :«ar It U aaoaaaary to aalt aaaaral houra or prafarahly aaamlght bafora ooaiparliig alth tbm blaoric* It la probabla that tha araaitlvl^ of tha taat oouXd ba laaraaaad a^raolably by tha aaa of altroTiolat lli^ aad ty obaarviag tha ooltttloaa la graatar tfaickaaoBaa* anall awHsta of alcMiydaa a»y ba dataralaad qnaatltatlaaly by oaaparlaon alth atandarda praparad by addlx^ ^ raagaat to portlona of tho oolarat oeotalalog kaon qamtltloa of aldohydo* Frolialaary oxporlaaata haaa ahowi that thla toat aay ba oaad to adaantago for tho dotootloa of aootald^da la othor* Malliaokrodt^ haa riiom that tha taata la uaa at tha praaaat for thla purpoaa ara unaatlafaatory*

PAGE 35

Tb» la asirmaly apaaino baoauaa tha color am flttoroaoa&co ara duo to dafialto eontwonda fornad alth tlMi al«CHiCH«GOQa Ihla la praaipltatad in tha fam af a hrlcht yallov povdar tram a rad a^utloa* lha aolor la doa to tha aanjagata agrataai of dovbla boada« 10 floeraaom&a la aba^rtad In ^a oaaa* Cyalehaaaiioaa'a aaoltly pealUva raaation «aa aooountad far by Ita apllttiag la aumllght to fom oaall MKuzita of tha aldahyda OB^ I GB(CB^)^,C80 Ofepurlflad dlosan and dliaopropyl athar both oontaia aufflolaat aldahydaa to flat a poaitlaa toot* latanaa do not raaot vl^ tha raacant undar ordinary aondltlona* Chloral vaa tha only aldahyda aa wnc thoaa laaaatii^tad nhloh faUad to giro a poalUao taat with tha raagont* Ihla la baaaus# It

PAGE 36

^ 4e«« not rMdily fom ocOMOthlaoi* fbm p«nM»nl>ftltttt«d nrontu •Idofagrdoof odiioh do not (loo tho Sohlff toot» rooot ttonodly ntth tSio diMiao* Aldohydoi uood in tho dovolqpoMnt of thio toot wntoi U) 8ot«r»^ oUpbotto* Fomaldiribydo, nootoldofeydon prppio»> oldohydo* butgrroldohydo, oolomldobydo^ honldi^ydOf hoptoldofaydo* ootoldofaydOf SHitliylhosnldohydo^ pb«oyliMotol(Miydo« hydro* einn— 1 dohydo» «nd oitroMllal* (I) Ihmturohod oliphotlo* ioroloia^ erotoenldohydo* h«iciaol*2|i t*TinyX*orotonojldohydO|i £«othyl«8*propyl**oroloia« Imndloao* 2«4Hd» eijBuneoldMtiydo^ ol{dMM»HMylcian«a^ ood oltrol* (8) Arwaotlot 9on«a« (UmI {Ncltro* b«ncol
PAGE 37

PnpMPKtlMi «r «h» »*o«nid ttd net haoo a good atoltlag polat* It no) tod olowlp with dooor>poidtloo at tonporaturoa abowa IM^C* tad furthor atton^ta at porlfloatloa fallod ta litprofoa tho woltlag polat* 32

PAGE 38

Pro7«ftl«fl of »»Dl»w»ylawtno«ni Udi of itelolo Mid ^^irlool foianlft Struoturol f onwAft OaCHioE.eaca uryotelliao fom oui oelor Molooolor tpoicbt Moltlni point noU Amlpooo Wltro(on SolobiUtioo fiotor dXoohoI BODMM Dioaon YOllov «ryotelUao poador S8e*f0 IH d« m Found OoIoiilAtod um ram laoeloblo Slightly oolttblo hot 60I1A1I0 hot EolOblo hot 88

PAGE 39

PART II REACTIOHS OF ALOEHTDES WITH I.I-DIBmTL-l*-ACSTYL-«»PH£mEH£DIAMlHS Introduotloa The purpoee of this part of the dissertation originally aas to prepare a series of 5«6<-bis<-dibensylaBixto-eioridines of fonnula in order to study the effect of the heaey hensyl groups on the equilibrium between the orthequinonoid and paraquinonoid struetures* The existence of suoh en equilibrium has been shown by RaBart»Luoas« IS Grtaoes and Hartjuioff in speotral absorption studies of acridine yellow, aoridine orange, benzof la-vine and tetraoethylflaireosine* An examination of the means of preparing -bhese oceipounds rerealed that the method most likely to sueoeed consisted of oondezising H*V«^ibenzyl<-m>phenylenedlsBiine with different aldehydes to form ei-ther diphonylnethsne or triphenylsiethaae derieati-ves, depending upon the nature of the aldehyde used, and the subsequent oycllzation of these deri-vatiees to dlhydroaoridlnes irtiich, on oxidation, would yield the aorl dines (see pages 17 and 18} •

PAGE 40

Bow*v*r* th« ilpbtBiyl* «d trlphMylMthMM d«rlir«tt&vM •WL®h ••r* pr^wrvd IntanaikUAt** uliawvd s>ropet of a «<^p«rat« lafMtleaticm* SflM of tho ooridinoo bovo boon proiwrod ond thooo odLU bo dooorlbod la o lotor pttbUootloa* j[4«oiMMilott Olid Koviov of tUo Utoraturo Mdotqrdoo do not roaot with bonaoao undor ordinary emditionit boooTor« if OB or«lto*|iaro dlrootlag oabBtltuont« oaoh ao a hydroayl crot 9 or a diiaottqrlanlao groan, la lowaaot in tbo rtng, tho hydrogan atOM ortho and |wra to tho aubatltooikt ara aotlaatod* Too nolocoloa of a phanol or on aaOna oan than oondanoo with atm nolaottio of an aldahydo, oith ^ 1 >aa of aatar, to fom iObotltatod dtfdiaK^l* or trlphosylaothanoo* condantiar. aganta aaiat oftan uaod ara aulfurlo aeid, Iqrdrochlorlo ooid, aahydroua alao
PAGE 41

«nd that th» hmaylUmm ertHip rMurraot»a« takiac tlia plaoa
PAGE 42

th# oth«r Mr* wuofe mr* mctlf thftn tarn*!* tin** groap* dir*«t t* th«M Tb*T«fer«» th« two ligrdrogta Muted A la Ite »> 5 teBQrl«MdiMdM Mteottl* Mr* Mrjp r**oU**« Th* ttydros«a Atei at B it «1*« aotitnitad tei aot t* th* **M MtUnt* Ite r*MK» for thl* 1* **td«Bt la *i*» of th* foot that croopa which dir*et ortho «ad para «B»rt aoot of teotr iafluMM* toward th* par* poMttoa* 09bXw^^ p«apar*d t«4«B%4*«t*tr*aaiao*ft»»*»diM»h*ayl«oodiaHdM* ar* tt**d« th* mi3>» •tltutioa tak*a plao* para to th* aubatltutaa ooIm group* ihia la Ulu*trat*d by th* pr^aratloa by BiahriBeor^^ of 3«S**dlaaiaa«4*4** bla»dia*thylialap«>dlph«ByXa»th*n* froa th* dloothyl uaapOMkS ate foTMtldriiyd** Th*r* ar* pataat* on •aaaval oth*r alokllar raaotlesaa* Slzto* that* dialhylHpr*f^MDyl«B*dUaia** raaot aaoothly with aldabyda* to giT* avd^staBo** which ar* hoaologoua to th* dOairad oaopetaida* no sarieua difflcultia* w*r« Mxritioaad in pti^rmtim of th*** dMriaaUw** by oLnilar aoaaa fraoi K«IC*Niib*Bayl-phMyl«na» diaaiaa* Aoaordingly* thia ocapouad waa pr^arad by th* aathod

PAGE 43

DM»rib«d la Part !• iiewmr^ tha pyaduota obtaiaad tvm tba raaotiont of thlo ooiflpouiid with aldoh^ v>oo vraro not ^Jam doolrod diphoogrl* and trlphongrlaMtliittMo* Oa roactlooo gavo pxlaarily tha iiaMff basaa and tba aaaXl aaounta of daalrad ooaipoua^^ fontod «ara oyolltad lanadiataly to tha oonraapondiag aarldlnaa* Ilia falluro of thaao yoaotiona aaoaad to ba duo to tha raaetivi^ of tha priaavy aalzM group* ‘Jharafora* tha aoatyl daritatiaa of tha aaiaa aaa praparad and aubotltutad for tha froa aaina 1 b tba roaotloaa* Uadar tbaaa ooudltlcoa tha diaeatylatad dariaatltaa af tha (ia^rad predueta aara iaoXatad in yialda raaglag froai S4^ ta S6r>* Tha baosoyl dariaatira aiao vaa praparad and warn found to raaot oisilarly* hlpha^ batai>unoaturatad aidot^doo did net raaot nonsally and thia roaatlon trill ha tha objaot af a aaparata inaaatigation* Praliniaaiy aiqrariawata baaa ahcam that tha diaoatylatad dariaalitaa land thoisaalaoa raadily ta oyol Italian to tba acridinoo*

PAGE 44

fh» PrwpMmtim of a A Udt Mopomd pt«par»d bf mkI liy 8«y«r «as co« • M» Mq^rla«n.t«l pr«««dur« «m Iqr •ithttr* Qm liimdrvd mU rorty»four bam (|f m 1«} of H^B^jlboniylo at-pbonylonodlMBiM OM ploood la a iOO rauad«4>oit«ao ParttMr cvyattolllsotieM foilod to rolso tho aoltiiic polat* Mtrocws aaalyols abowod 8«4!;;( f* Coloolofeodi 8*4h% I*

PAGE 45

PwpAmtIoo of Thl« ««c9«aad «a« pr«p«r«d Iqr irite gaef no •sp^rlMaatal prooodun* FofurtMD and tour-tmxtiit erm§ (l/K> mU) of «»li»dib«nsyl» ppfaMxsrloDOdlMiat «M oooiwnd*! 1 b tOO oo. of ICfC nodim l^drooddo •elution wad 18 gnmt (i/i nolo) bontogrl ohlortdo «m nddod* Tho nisturo voa ihakan for half an hour and then all^nod to ranain at ro«ai tanporaturo for aoaoral houra* Tho floooolont aiiita oryatala noro fUtorod off and aaahad aoaaral tinea with aator aai than taloa nith aloohol* RaoryotalllaaUon froa aloohol gaoo lT*fi grnaa (909i of tiaaory) of a oory pure produat naltlaR at 171*^* l^aaai ra^ortod 171»17I*^C* iaalyaia aboaod V« cnloulatodi 7«U|f V*

PAGE 46

Bixt—n *Bd fiv*«t«aths terms (0*06 w»l«} of I*lii>diboiityl»K*««c 30 <^l««» jriMDyloaodiOBlao, C»E gramo (0«l0 »oXo} of (HU^Urcwui oodluo ooctoto fta4 lOS grmB U»0 aolo) of oootio oshydrldo ooro nfloid togothor for fit» boon* Aw roootioga nlxturo ooo pottrod ovor erockoa loo oad oUoood to otond idtb ocOMlQool oUrritig uoUl oU tho ojcoooo Motio wibydrido vmo doooapoood oad tho dioootyi oaBpouBc oopoxmtod out *• o uhi^ fXooouloat preolpitoto* ffcio uoc filtorod off oad Muhod flrot with wotor oad thos with oloohol oad fiaaaiy woo rooryotolUood trcm MjS oXoohol* Tte oryotolo, whlofa wore in ttio fern of wy oboU nooiloo« wwro 4rUd in an Abdorhoidon opporotua ot 100^* orwr •olforie ooid at 10 wa^ proooturo* 3ho ylold wno l4*t grano or 0Ofi of tho thoorotlool« Sltroeon anolyolo iritowod R» ColouXotodt 7«890( B* Jho noltlag point of tho pur* oubotoi\oo 41

PAGE 47

Th» Proprtlti of tepirloal fonulft 8 tru 0 tund foiwil* CHjCO^I 1 <°*«o Crystallino fom *nd oolor IQilto noodlM lN»X«oiil«r ««lgbt S7t«U M«ltlag point ISI^C. Tiold 80J{ Aaaiysoa Found ColeulAtod Utrogos 7.81^ SolubilitiM Wfttor Inaolttblo Aloohol SolubXo hot ootono Solttblo OiOXUMI Solublo Aoetio Mid Soloiblo 42

PAGE 48

IXPEBIVOITAL TABUS AID FKOCtDOIBI ?Y«p«ratioa of •thmt* fitm grmu (0«01S aolo) of l*lMib«EUi3rl*B**«ootyl«oH>plMMayl«D^ dlMlao «ot dlMOlirod ia 60 id* of hot oloohol onl 9 e>«M (0*0079 «olo) of Milfttrle 0014 «x^ 0«9 groBui (0«00?8 miIo) of boaooldoitydo mum oddod* This solution on* hontod undor roflux on tho *t**n both* Aftor About f 1ft non ttinuto* 1^ *olutioo bnoosMi light groon in ool won hour* ond thoa about half of tho alcohol ms 4iatillo4 off and tho flMk naa plnood in tho rofrlgmmtor and alltorod to ronain oromight* Ihoro ona furthor arjratalUaAtlaa dnriag iho night* Dio eryotolo noro flltorod off and muifaod odlli alcohol in «hioh they aro inaolid^la in tho eold and only oory slightly aolAble at tha boiling poixet* Ihoaa orsrttalo ohan d»y nolghod only 1.1 eroaia* iadlaatiag tha poaaibllity that thaxo aaa an appraclabla quantity rojaalnlTig in tho nothor liquor* thia aaa pourod ooor ohippad lea and aftor tho ioo had aaltod tboro ronalnad a yolloa rooinout aaoo idiioh idumod a dooidad tondonoy to turn groon on ataoding la tha air* This aiMrj^^a natarUl oaa haatod idtb 60 *a* of 96j£ aloohol and aoat of it diaoolrod laarlnr a roaidua af uhita w^atala ahich aora ihcan by a aijcad aaltlag point to bo Idontioal with tho ooapowid loOlatod aboro* Ihoao too portions aora ooodiinod* Mtraotod alth bot alcohol nod

PAGE 49

r*ory«tiaU»«d trm dUtite dlwnou Th« yUlA «m 8.T g^mm or 48^ of tbo tluiorotlo«l« llko OMuplo «m drio4 la o ro
PAGE 50

*«W4«» B^plriwa ^MRualft 6truotur«l foreul* CryttftlliiM t«m «nd Mlor «Hi«o povdor K«l«cul»r vtigbt 74ft*4t MlUnc point £S0*C» Tiold «e< Aaalyioa Foond Oolottlotod Mtrogon 7A3si r«4a^ Sol«jbilitloo f^Btor IaMlv3>lo AlodM>l &U|^tly Mlu(blo hot Aootcgoo Bolhblo hot 1 AOOtlO ooid Belhblo hot DlOOMOl Solublo hot

PAGE 51

t» Py^pumtlon of » ^ a i-a 4 nff •• 1 1 1 * ~M t ^ flltiwiiyl —l lu'iwf trlplMoylaothMeMift avo groM (0»0U m»U) of l•S^boll•yl•R••«ootyl•«|l.ph«]yXon^ dianlM ooa ditsolTol is 50 bX« of hoi oloohol mud 1 gnaui (0*0075 aolo) of £1^ otiXfuylo oold ood 1«05 grwMi (0*0075 aolo) of o t nhl irrfdT *M*i voro oddod ohoroupoa tho oeluUon boootao oUshtly yolloir* StibooqiMiit roflttidng on tho atoon both yloldod o groon oolutlon oftor ^ hour oad o toady oHito prtoipitoto oftor throo houra* ibout half of tho aloohol oot dlatillod off oftor too BM»ro houra of hootli^f md tho floA inm olloood to ranala la tho rofrlgarotor ovomight* Ihoro ooa oary Xittlo If any furthor proo^itotien tad tho oryatoXa oaro flXtarod off* la ordar to rooovar any of tho aohatanoo ahich raoaiaod dloooXaod tho Mthor Xiquer ooa pourod lato o Xorgo iioonUty af ootar oad olXoaod to atoad for aa hour oftor ohioh it vao fiXtorod oad haotod oith tO ol* of ooatio oatydrido for thirty aiautaa la orior to rooootyXot# any of tho ooag>oaad ahloh adght hooo boon hydroXysod darlne tho rooctloa* la oaooaa of oloohol ooa thaa oddod and tha aolutloB ooa ballad to doocogieaa tho oeatle aniydrldo* fha fXoak ooa oXXaood to nan In la tha lco«ibaK ooamlght aad aa additional qoaatl^ of oryatola aammtiag to 1*S grooa ooa fiXtarod off* lha total ylold ooa 5*0 grana or of tho tiioorotlaol* la ordor to purify tha aotpla for aaoXyaia it ooa flrat oxtrootod olth bolllag oloohol* than foeryatolXlaod froai ooatio aoid* ooahad oith oXoahoX aad finally raoryatolllaod froai dilttto dloaaa* It ooa driod la o rootan daalaootor orar aolid lOB* Vltrogaa oaalyola ahoood 7*0»;S ». Coloulotodi 7*145; I* tha oaltiag point of para aubatanoo ooa £41^0* 40

PAGE 52

ai9lrl«il fcnroNLU StruAtumO. HnaAm V«T**V* CsyttalUiM tom tml oolcr BoWoalwr Mltlac point TUld An*l]TM« XltrogAo nkt«r Aleehol AMton* Aooti* Mid idiitA powdnr m»M t4t^C* Found Coloiilntnd r«0l9^ iMOllAlO Vory ooltdslo liot 8ol«d»l« hot Solublo hot Oionn Solfftlo hot

PAGE 53

PnpwUm «r t•^*«4>l•HM•t«idlio^•4••4>l•iKSib«na7l«dnOii4*•obl«ro» trtptupyl— th4nt> Six «xd tix^twith* iwm» (0.08 m 1«) «f •-phMylOTMdiaxliM XU dluolud ia 880 xl. «f tO^ xloxhol md 4.8 grww (0.08 mold) of p^ohloirxlMRuixldtlKyd* nut I §jrm (0.01 xoU} of ooxMatrxtu •nlfurix Mid MIX xddxd. Thm tslutlM ut rxfluxxd f4r four hourt am th« oUom bxth. A lifiit gUM MlorxtioB appMud olmoot inudUtaly tad •ftar fort|«-nM xUrntu itoiM •lyatxlt bafu to praaipitxta. Aftar tha and of tta ftour hoara of rafluxiag. tlia flxak mo ploaad In tha ram« fOMtor and allMOd to rax a iia oaaniigM. tte idiita praoipitata mo filtarad off. aaahad xltli aloahol. aoEtnaotad aith hot olaofaol «id rom aryatallisad txiaa frcn dlliito dicotax. Aftor dr]rill^( in a aaouna daaio* ut«r amr aolid KQn tu yiald ua 4.8 gnm our 69^ of ito tfaoaaotioal. Analyai* for nitrofon ohMod 7m09^ V. OalatilaUdi 7.10 I. 8ba Halting point au 848^«

PAGE 54

I ^*^*^^^ **'*"**'*'**"" * — i*-fihl f>ro»trlphiiiiy1ait1nM# ta^iwioml fonmU stiMOturtl fonwla '^C^Ki CryvtaUia* font mad o»lar Mol*eolwr Mtclit M4»Uiag point \i«14 Amlptos lltroclo VOI7 ilichtly oolubXo hot Solublo hot ftoloblo hot Sol^blo hot

PAGE 55

4« m^wirntion oi , 4 *_ iijMthoaqr»tnph«3y]|Mthaii9« ?H*i gnM (0*080 Mol*} of V»!l*villNMS)^K*44UMtyl««pph«i^ dlnim «M dlatolvtd la 100 al. of hot oloohol oad ais gnaa (0*015 aola} of 25il aiilfbrlo oold tmA 5*5 fnao (0*015 w>lo) of oorotrto oldahydo waro oddodi* Tho oolorlota aolutloa ooa roflaaod oa tho otoaa both oad ot tho oad of tawaty aisutoa It waa doifc groan* Aftor to\» aad ono«4aolf houro toady irtiito oryatola ooro prooipitotod and tho wao ooDtimiod for on odditloool too honra oftor ohloh tho floah ooa ploeod la tho rofrigoimtor aad olloood to roBoia ovornight* Tho oryatolo ooro fUtorod off adth auotloa and oaro fovad to ooigh flao and aiao« toatho groaa* Tho fUtrato ooa troatod la tho oold olth flftooa grant Hi oootto aidiydrldo la erdor to roaootylato any of tho ooagNnmd ohioh aii^t hora boon hydrolyaod durit^ tha rooctioa* Thla aolatlan ooa pourod ooar aroahad loo aad tha roaultlng rool&oua naaa ooa rocryatalllaod tho foUoolac day ttm dloma oad yloldod 0*7 gran of ohlto ocyotola ohlch ooro ahoon by nlsad aoltlng point to bo Idoetiool with tho aobatanoo laolotod abooo* Tho total yiold ooa 5*6 grant or 51^ of tha thoary* Tho two yioldi ooro ooablnod oad rooryatal Iliad tadoo froa diloto diotaa follonod by oxtrootloa olth boUiag oleohoX* Tho aobatanoo oao drlod la oa Abdorhaldaa drlor ooar ooaeontrotod oolfbrio oold and nitrogaa ****^y*^* hoood 5*58^ I* Colaulotodi 5*88)C V* Tha naltli^ point of tho piuro ottbotaaoo ooo SS1*C*

PAGE 56

4 « phumgdMthMM* aipiriMa foiwlA etiMctiaria fomtl* ®».w« Ct7«teUlM f«m mA color UOlocuXor ooli^t Moltiac pola* Tiold Anoljrolo M^rogoa Wdto loofloto 0QS«4t S81^C» roaai Ckikloiilatod «*es9( e«f99i( Solobllitioo Khtar Aloohol Aootoao Aootlo ooid Inoolublo Vrry ollghtly oolublo h«% Soltdilo hot Solublo hot DioMoa Solublo hot

PAGE 57

•• PinparfttlMi of s»thoacj*»irtyhoivl»tho»0* Te« groM (0*080 nolo) of K*S«41boaiyl«s*woootyl«Mwph«ny ditBiiio* tf E^pm» (O*0U aelo) of W ottlfurlo Mid ood C.84 giwt (0*018 aolo) of o*gMitliooyb«ig«ld^qro aaa hoatod for too »oro tiouro aad thon «oa allovod to cool oad ooo epoaod aad tbo oiyotala flltorod off* Thaoo ooro aiyatailUod toioo froa dlluto dioiaa aad thoa oatraetod idtb boiltag al4M0iol» flltorod* «ad drUid la «a Abdorbaldoa drlor* Ibo ylold «aa ?.8 gim or «7lS of tho thoorotlohl* Aaaljoia ahoood T*ll?C K* waloalatodt 7*80^ f* ma aaltlog polat of tbo paro oiAatoBOo «aa 844^6*

PAGE 58

ft • S «ft * «4 ' abi •»dib«acyl«Bia
PAGE 59

•• Pr*p«i«ti(m of £»t*«^iOHioot«odno>4»4*«4>lo«dlb«iayl«iiiMH4*'*M (0*016 nolo) of i*M*4iboiu^lH^*Hioo^l««i>>ph«aylono» dlMlao* 8 STMO (OvOOfB nolo) 8^ oolfttria odd oad 1«S7 laroM (0*019 nolo) of oa&Mddohgrdo ooro diaoolood in 00 lOL* of oloobel ond rofluMd for firo tooro on tho ot oi both* iMrlac thio tino Iho oolotloo booaao intrplo* lo proolpitoto «oo fononi on otondtog ovomifi^ in tho ioooboz 00 tho oolution noo trootod with ton groni of oootie oahydrldo in tho oold for thro# houro ood than noo pourod ovor orocdcod ioo* Tbi groy oryotolo ohioh rooultod oftor otondinr for boontyafour hoivo ooro naotohlo in tho oir and tornod porplo rapidly* la ott«H)iiac to ostroot tha i-yoritioa froo thooo oryotola with hot olodwl o pooulior {AMnoBOttoo ana cbaorvod* Oo prlaoiy ooatoot tho hot oloohol tha acftotonoo ml tad to o doHc oil and than auddaaly eryatdliaad in tha fom of o whita poodar ohich noo vary iaaolvhla la tho oloohol* Tha aoluUoa cbofva ^ oryotola ahooad oary atrong gva«n fluoraaoanoo* iadiooUag ayoliaotiflci to tha oaridim dariaotiro of on op^dobla port of tha triphoeqrliBotliOaa dorlaotiao* Sta oryotola nara filtarad off and oftor drying aara found to voij^ 2*8 grona ohich ri^roaanta 00^ of tha thaaratiool yiald* Aftar rooryatolllaing flrat from ocatia aoid and than trm dlluta diaaoKi and axtrnotlnt vrith boiling olodiol anolyaio ahovMOd 7*ll;ii V* Oalaolatadi 8* Tha naltlng point of tho puro canpouBd ««ui 824 *^ 0 *

PAGE 60

aapiri««l roiwil* ^82So^4^8 $truetuaral fontul* Grjrstallixw tom omA color Molocolor ooight MoltiBg polst Tiold inilto oryotalllno powdor 778.44 224*C. 40f, Aaolyoia flltrogott Soliibilltioo Found Coloulatod 7 . 11 ^ 7 . 20 ^ Votor loehol Aootono Aootio ooid laooluiblo Vary allehtly aolublo hot Slightly tolidilo hot Soliulo hot Soluble hot

PAGE 61

7* Pr«|>*r«ticm of t*2*<>blo^otaBdZM>Hl*4*«idibot»ylaBiziOii«**«Mtli^ trlphoaylBoth«&o« Ton ^r«M ( 0 *^ a»ol«) of pha«yloM4ltodxMrf 1«9 iboIo) of »*toilooldot)y(!o ottd 0 i^rtam (0*01S Molo) of £$/« mlfurio oold woro tHooolvod in IQO mXm of oloobol owl rofluxod for o toioH of «lx beuro on tho stooa botli* tho ooluttoa bocoM £,rooa olatooi innodlotoly ond oftor thro* oad orMN*bojLf houro tiioro ooo pmolpltatien of ohlto oryotolo# Thoto ooro flltorod off aod driod* Tho yiold «M «*e ,;roMi or ^ of tlM» thowry* Xn mo oooo no ottoi^t ooo Mdo to roeo^or i*oythinc tho fUtroto. Aitor porli i.ooUoo by oxtroaiioii with hot oluohol oori rocryotolllsotiun front dlXuto follovod by rooryotolUsatioo froa ^loclol oootlo oold tna o oooood oloohoX oxtrotitiau* tho aoltiuf polat «»• fouod to to &3o^u» Tho onolyticol sonplo voo ^riod la on Atdorh«X
PAGE 62

7« t*2*<4t«MiP«t«aliio«>4«4**4>l»i>dlb«Duiiiyl«Kixio»S*«Mtli]il*trlph*iiy2B«thwa«* B^>lrlo«l foraala ®68^S0*4®f Struetnral foranla CryctalUa* tom wd oolor Holtottlar weight Melting point Tield Anelyeia litrogen Solubilitlei Meter Aleohol Aoetone oetie eeid Dioxea Send^ ehite oryetele 782*40 216*C. aojt Found Ceiculeted 7*509^ 7.S89C Ineoiuble Very iQightly eolvible hot Slightly soluble hoi Soluble hot Soluble hot

PAGE 63

•• PiwpMf»U«n of triplMngrlMfthMMi* fW (SrOM (0«090 Mil*) »f 8«fMllMmC3rl)^*M«4rf^lM^ dlMtMf cr«M (0«Cft» Mlt) of pwliolMldoi^fM Olid • iproM (0«t)li m1«) of uni oidforio Mid «M0 dloMlood ia loo •!« of hot oAmMI oM rofloMd m tbo MOM flio ooltttiM taiood dMk grton olMot tiMUdiofly Md ftftor OM hanr and fort^ioo almitoo thoro «m proolpit*ti«i of whito cryotolo* Soflwiae Mo ooBtiiuMM for lootMr Mur oM o Mlf o»d thM ttMi flMk MO oUoHod %o rMbiB iM tM tiOrifmmtw oMraigbt* 3M •ryotolo Mro ftltorod off and dHod om Mlghod* tbo yiold mo 7«f giMO or Cfti of tho thooty* Tho oruiit foodoot mo furinod If oMtooUm with hoiUaig aloohol foll^Md h^' Mo rooryotomMtioMi tnoi dilott OIomo* nm par# oMotoaoo mo drlod la m ihdofMldM opporotM oftor oHloii aitrogoo Molyolo otoood nM9i X* i*loiil«to4« 9* Mltlag potot dotovftlMUoo OB Mo IMiMiKoo hlook (Oioaod tho doMlo ooIUm point pMmmboiu If tho oryotolo oro piMod o» Mo tloM vbM tM t«M porotoro io bolow tU^O* ttiof oolt OMrplir ot iS6*«« Hooovor* if Mqr oro pot M tho hloofe Mm tho thoMoooWr fMdo botoooo Md ttll*C* thoy aolt tolMly and than ilMly rMryoMUUo an tho olook* If tho toaporntato U Vbm nllooad to riM oioaly tho aMotaoM aolto aharply ot m*6*» tho origiMl Mltiag points if Mo to a gaw rotwo of tho hloofc io dhoao Moo tho oahotanoo it appl&ad^ noltlagc a acw a r a iaaatdiololy ant

PAGE 64

tlMT* !• n0 mAiMqMot Mlidlflaiitlan* «!mb tU« awltliig point «m Uk«n bp th« aonvwtloiwl onplllArp tub* Mthod* tb» iwlti^ point «»• found to bo tSS^C* ftftor oddltion of tbo ot«o oorrootioa* Booooor^ tho dovblo nol* tlof point uno obaorvod Juot oo in tbo eooo uboro tho blo
PAGE 65

Saplricml foiwultt straotuna fbnsula Ci7«t«llii» tom oad ftoior Mol«o«d«r UtltiOK poiat lUU imXjmo XltrofM SolvIbllitiM AloolioX Aoatea* Aoatio Mid iiBiit* •«ytt«Illa» povdar 7B8.40 BX8*G, m fmmd C«Xottl«t«d r*ti^ f«iS^ lUMluibl* V«iy BLiid&tly •oltibl* h«t SUfiitly hot BoluhXo hot Dloana Soloblo hot

PAGE 66

0« ?r«pftniti4(l of aMl>li«RqM”«4qriroaqr«itrl{^^ ThirtMo MBd two*»i«ith« gr«M (0*04 smI*) of •HwOUMHuyl** phny l tW Kl l fi ao ^ 0*1 gnm (0*06 «ol«) of vooilUa oad t«0 gift {0^ n»l«) of ooBo«Ktroiod iolfurto ooi4 mrm dLotolvod 1& COO «!• of olec^tol ood hooWd uador rofluat for four liooro m tho stoon both* Oaiiiig ^o tino tho oolutien boowto doop rod la ooleor bvt no proolpitoto dm fomod* Reworor, on itwadlng In tho rofrlf;orotor for ooottrftl doyo • prootpitoto of gray oryotnlo tlovly fomod in tho bottoi of tho fliule* ihio not filtorod off at tho pa^p* aaohod «ith aloohol and driod* tho ylold aaa 7»f grmo or 4fl9( of ^oory* Dwrlag drying tho oon^oimd booono parplo mry ro^ldiy and all attoopto at porifioatlon fallod to yiold a oolorlooo produot* Tho orodo •ohotonoo aao rooryotalliood taioo trm alo^l, in abioh it it mach oro aolahlo than tho othor noohora of this oorioa (iafluonoo of tho tqrdronyl g’nitxp), and driod la oaouo oror aolid potaaolaa hydronido aftor ahi
PAGE 67

i* t *»81— o^ tw i l tl o w I >4»<«M»>dib»niyli«Ano««y * * <4ylo hot Aootono Solvfelo hot Aootio Mid eolt^lo

PAGE 68

10* PmiAimtloa of MtthyUsiodlegq^trlphmj^bMt^^^ HXm Mftd »i»*t«aitlui grMM (0*02 ml«) of f»SMtlb«U 3 rl«>S*» oo*tylH»»plMnyX«Mdi4MaiMi« 1*9 grmm (0*01 m 1»} «f ylporoaawl oati t sTMMi (0*006 mX«) «r mllWio atid ««r» dtaaoli^ 1» Mvanty ala of hot oloohol and rofltan^d on tho ttan bath# Tho oolutioa tumod TOiy dark alBoat iaaodiatoly tad aftor tao aad oMNbalf hours of haatiac a flaaly dtaldad ablta praoipitata «as dapoaikad* SafXvatixic; aaa o{ t* Iho aoltiag poiat of tho puro oubotonoo aao 2t6*C«

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10 • 2*2' «Bi 8>«oe tamino^ • 4 * *bl s-dibanxy iMDlno-S" •4" -methylanadios^* triphsnylae than* • Bapirioal fomula Struotural formula °82®48*4®4 Crystalline form foid oolor Moleoular welglxt Uelting point Yield Analyses Hitrogen Solubilities bater aloohol Acetone Aoetlo acid Uloxan ifihite leailets 792.42 226 ®C. 44 ^ Found Caloulated b.92^ 7,07% Insoluble Very slightly soluble hot Slightly soluble hot Soluble hot Soluble hot

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11* Pr*p«r«tloo of t«S'»bloi-soot«Biino«»4«4*<^to«dib«n«yl«ftlno<*€”*Bltrotyl«o»i']^nyl4m^ dlanlno* 9«t gnnto (0«O22 s«lo) of o-oltrobonsoldirt^o oad o ixrmtm (0«016 noXo) of 86^ oull'urlo oold voro d&ooolvod la 150 of oloi^l ond bootod la o coolod tttbo ot 100*^» fof throo houro* M tho oad of tiitio tiao thoro hod booa no proolpltotloa oo tho oontoato of tho tuho noro pouiod ovor erooiMd loo oad olloood to otaod la tho rofrleorotor for 2« hour#* Hio o«ol«>roolnouo oolid woo flltorod off ond oxinaotod with hot oleohol* whloh loit o yollow oryotolllao rooiduo* Ihlo woo rocryotolU»o& froa dlloto dloxoB ond oftor drylnjit tho ylold woo found to bo 0«4 {crowo or thoory* At thio point o aoltine point woo toJMa ond tho portlolly purlflod Mbotonoo ssoltod ot Aftor rooryotollloias ogola froa o Biioturo oi oquol poa^o of alonon ond oluohol tho ooI^Iuk point woo Abothor rowryotolliootlon froa tho oom oolvoat fair follod to roloo tho oaltia^ p lat* Aftor drying in on Abdorhaldoa opporotuo nltro^M onolyoia idtowod 5*70;^ iAluulotodi d«h2Nii h*

PAGE 71

ia^lrloftl foiwlA Stmotuiwl tormlM 'ttV.®. CiyvtaaUa* fora ond color YoUlo AooUo 0014 8olui»lo :.loMi SolOblo

PAGE 72

1B« Pr«pftrttion t*S<«4)i»NMMrtaidJioHU4*«^l*ipdlWsyla«lao<>8*ataaoa aaa foaad to ba Ill^C.

PAGE 73

fia^rloal fonml* etrtt«tur«l fonmlft ««Vi«4 CwptkAlim tom tod eol«r ItoltMlar «ti|^ K«ltijic point tioU Aeolyaoi ntrogon 8oli4>iUUoo motor AlodOol Aootoao Dioana Aootlo oe&d ToUoo loofXoto 7M.48 SU®C, $ 0 $ fvmA Coioolotod 8«71l( Inoolublo Tory aielttly oolulblo hot Sllchtly oolt^lo hat 8ol«l>lo hot Solublo hot

PAGE 74

tl« Prtp«s«tloB of a«g*«bi ooot—i triphoojrloothoao* FliPO sroM (0«01S nolo) of !i»ll"^tooPtyl»?1««NMoty l »n»' } 3 h o iy dioaino« I*t» grnoo (0*011. nolo) of p«nitr(tft)«oMldidqftUi ond 8 gnmo (0*00T6 iM^o) of WBl^ ittlfttrlc ««14 «oro diaoolnid in 80 nl* of 88^ ftloohol oKid hootod in ft ooftlo i ttibo ftt 100*0« for tiuroo ftod ncMM^iftlf hours* OuriQK this tiso ttioro «ftt proolpitfttioii of ft yolloir oryttft] liai poardor* Tho ooatonto of tho tub# nor# trofttod with ton of oootlo •ahjrdrldo in «rdor to roftoo^oto nagr of tho oniao oiiieh hod hoon hjr* drol|!>od diiriac roftotlon* Aftor hoftting to hoillBg in ordM* to dooonpooo tho oaoooo ftootie anhydrldo tho solution nos pourod oosr orsckod loo snd ftUoood to rs s oin in tho roftigorotor ovoraifht* Upon filtrstion ft yolloo solid «»s ahtftinod idii«h osanol aomrrdiotts and otilob DOS dlffioult to fro# trcm onooss ufttor* So«o«or« saEtrootion vith iMtt ftloohol loft ft fiaoly oryotslliao rssiduo tddch nos forthor purifiod hy roorystollisfttioB frost dionsn* Aftsr drying tho yiold nos found to bo 4*0 grsno or TOJC of tho thoorotioi^* Ibo oaolyticftl oonplo u»o rooryotallisod ftgoin fron dioasn* wtrootod nitb hot olooh^ oad driod in on ibdorholdon oppwmtao* Ritrogon onolyolo ihowod h^90}^ I* Coloolfttodi 8«6I8( >• ^0 aoltlag point of tho puro product nss foood to bo E81^«

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IS • 2.2* -Bis-ao«t«Blno-4«4* -bls*dlb«atylnalno^"-nltro«^rli^eiiyl»BthAne • Ea^lrloal fomula Structural fomula °6XW4 Crystal lino fom sad color Ifolooular weight Uoltixig point Yield Analyses Hitrogen Solubilities llater Alcohol Aoetone Aoetio sold Yellow leaflets 795.4S 261®C* 70 ?{ Found Calculated 8 . 80 ^ 8 . 83 ^ Insoluble Very slightly soluble hot Slightly soluble hot Soluble hot Dloxan Soluble hot

PAGE 76

14» Prvpftxmtioo of 8#l*o»4'*«»ohl»ro«> 6*««d%ro«itriphmyl»ottuM Six oad oiawtiotho groxo (0*0t wolo) of M«S«di)>«ns]rl«S** oeo^l<»*ph«i 9 l«iodioaiai» 4*4 gnai (0*(9 mlo} of t*iOhlcMro«4««itro» bootoldolqrSo oad I gnw (0»0i aolo) of ooocwstroiMKi ioifurio ooid «oro dlotoiood in S40 xl« of 98^ oloohol and rofltaod for six houro m ^ otoaa both* Utriag thio tino tho ooXor of tho oolutlcai ohongod froa polo yoUoa to brlgtit yoUow but m oryotolo ooro dopooltod* Aftor oooliagf tho oaetooto of tlM floilc voro trootod ulth If gna* of ^dotio aEri^jrdrldo la ordor to rooootyloto oay of tho oubotoooo ublob hod boaa hydroXyaod during tho roootloa* Tho ooluUoa uoo ollcaod to r o woln la tho rofrigarotor oo»mi|^ oad tho yolloo prooipitoto obioh ooporotod out doriag tho night uoo f Utorod off* Aftor dryii^ thio uoo found to uoigh i*S graoo uhich roprooonto 60 of tho thoorotiool ylold* Iho oaq;>lo for onolyulo uoo oxtrootod ulth olo^ol aod thoa rooryotolUood taieo froa diluto dioxan* It uoo ^od In o uoouva dooloooter ovor aolld XOB# Annlyoio for nitrogon ohoood 8*8i;i g« OoloOlotoda 8*4f!* V* o_ Tho aolting point of tho pur« ad>atonoo uoo 140

PAGE 77

X4* t*t*<^tt^e4rtmiooHi«4*«i41»«41)>«8syl«niao«4*«ohloroi4*«nltro* a^pirietl fomtla 9X 40 B m Stmotural tonmltk Kolvottlftr wilglit CiyttfdliiM font m4 2or lC*ltlne poiat n«ld AnalyMt fitrosan SoltiblliUM fmtmr Aleobol Aoatoat iKMtla Mid Dl«xaa 8S7*88 Y^lonr i40*C. 64 ^ Pound Caloolfttud 8*8^ ••489( laaoltibl* Slifbtly telufel* hot Slightly oolublo hot Solttblo hot Soloiblo hot

PAGE 78

U* Pr«pMmtian bU»( f 1iin » 4 » d tb t hM Mi» Tim ud ala»-t«Btht gr«M (0*01 w>l«) of »-phMiyl«aaodio«lao dlMolood la o aixturo of 900 of votor and 10 00 * of ooe— atrmtod hydroiAlorio ooid« Solutloo lo offootod aoro oaolly by hMtluK to « 0 ®C. Tho oolutioa ooo ooolod to 0*C« Tturoo oad oovtn
PAGE 79

U* gl«»(2« Hwlnp » 4 iwdtb«MylMdxi»)<»dlph«nyla»tiuai»« a^plriPiCl fonula ®U®40*4 Struotuzml fonml* eryviAlllm fom «iid color Mhlto ooady oryotolo Koloeolor ifolght 688.S6 Molting point 198^C« TU14 TOjt Analyooo Found Coloolotod lltragoa 9«4T^ 9«8a;( Solvbilltioo Tsotor Inoolublo Aloehol Solublo hot Aootono Solublo hot AOOtlO Mid Solid) lo Diona Soluhlo

PAGE 80

Id* ?nqp*r«tian bl»»( i— o» tMn1 l no » »4* ; UxanyXMKino )-dlphwnyl— tfaajaii# two iod srmm (0*0078 w»U) of l*»*dlb«aigri*V** 1*6 fmm (0«0080 nolo) of 28^ oulfurlo ooid and 10 Hi* (a lars* wimm) of oiKtroHiaHtoly 40$( fonwldol^ oolttUon wort dloool'vod in SO al* of W5S aleohol «ad hootod to o OMlod tab# «fe 100®c* f«r throo hotm* v;orl»£ tblo ttno thofo hm olcar prooipitotion of irtiito oryotoio trm tk* oolorlooo aolution* Aftor ooollac la tho rof rledrator* tho tObo vno opoisod and tha oiyotaa mtarad off, vMhad with aloohel tad dicaatad with 80 «1* of boiUac *lufitiol* After drying tha cryotala aaii^d 1*8 srHao wbloh ropraaonta 78^ of tho thaoratiaal yiald* !!ha aaalytioal OMpl* raearyatalUaad fren dioana aod drlad In a Toouna daaiooater owar aolid lOE* Analyaia for aitrogm aheiMd 8*U^ X* Calottlatadi 8*S3^ X, tha laalHag polat of tha puro oanpouad waa 141^0* thia ooBpmiBd WHO alaa pra^rad by taatylatlng bia*(2«aeiiao» i^ib«iuylattino)
PAGE 81

16* Bl»»( I— wo w 4 » d ibetu>yliMlao)«tthMi»« S«»lrlMl f«rwiU «p w # I 8tru«tuiml tonoiLm CiyttAUliM team •nd o«lor nhlto powdor Vol««ttlAr iwight 67t«W v«ltljnK point Ul%» TUU JUHtljrMia Fouad Colooloted ntrofOB BMi SolublUtioa nrtMir sUil^Uir •olttbl* hot AOOtoM Sll^ly oolvblo hot Aooti* Mid Soldblo hot dOMIB Soldblo hot

PAGE 82

Vf» Pr^pMmtieo «f bl— (f iitlM I llb«i»yli»tm)«»dlpamyl* Six *xd g fx xt (0*0t aol«) of S»Bi»dlb«a«yl«8*« xootyl w >» ph o ny lonodiiKla>, t*e gr«M (tho oquioolont of 0*06 a«lo of oootoldol^o} of povoldolqr^o* ocid i*0 srao (0*01 nolo) of ooaoontrotod onlfurlo oeid ooro diooolood Ui UO »1« of Ml^ olo<^l ODd hootod lx o ioolod tobo o% TI^G* for four houro* Aftor oooUag, tho «o« ^OBOd oxd tho oOBtonto, ohloh oonolotod of » polo rod oolutloBf «oro pourod ovor oroekod ioo« Aftor oooorol hoaro tho roaoltiof rooinrnio yollov xooo ooo flltorod off ood ostrootoa with oloehel« ohloh loft tho prodoet biAlad oo ohito eryttolo* Tho ylold «o« gnaw or 79( of tho thoorotlool* Iho ooo^lo for onoXyoio wot roeryotollitod toioo tram dioxoa wd aitrogoo oatlyoif « oftor drylag ix o -voouax dooloooter ofor tolld XQ8« (riHwod S*0a^ t« udottlotodi a«lT|i X* Tho aoltlxf polxt 0 of tho port oObttaxoo «ot ITt C*

PAGE 83

ikpmaa f.»ta V4i*4®» Struotoml fonmlft PtaCH CryttftXllM tom aafl •oler FMto poviter KolMolw wilcht dM*4i Mltliic point m®c. Tiold AatlyMi Foand C«Ia«lotod Bitrat^ni 8*08^ 8«m Solobilltioo nttmr Zoooli^io Alemol slightly oolt8>lo hot oOtOM Solotlo iMt AOOtiO (Mid 8«l«rt>l« hot rlOHtt S^ohlo hot

PAGE 84

Pr^[Mw«tl«a of bi»»(t*4"iilb• Caloulatodi S»00^ I* Iho aolUac point of tte part oid>otano« was 190^*

PAGE 85

16* Bl*»(t^o«t«Bi]io«4«lo hot

PAGE 86

I0« Pr«pM«tloo of niylMdoftMlphwByU Six «sd «i3»i>t«nth« grMMi ( 0*06 of X»BMiib«i 03 rW*« 4 M»o 1 yX«> »*pboaylon » t ^iw ii no , t«t gram (0«0S »ol«) of butgrvoldohydo OBd 1«0 ffrm ( 0*01 BoXo) of c^ of tho thoorotiool* Ttm oaslytiool sooq^lo oao oatrootod with hot aloohol sad lator oos rooryotollicod toloo trm dlosaa* iaftor dryiag in an AbdoohoXdoa opoorotua^ aitrogoa oaalyoio ohcswl 7«8S!i 8* COlouUtodi 7*8^ 8* mo point of tho puro oubotoaoo oao t48^* A1

PAGE 87

foswil* ®4t^*4®| £tro>tui«l fomil* CiystaXIlM f«n «ad ooXor ViAtm pOMd«r KoX«
PAGE 88

20* mpurtUon of hi»rn{Z<^o0tmtlUao»*<^th9OMylmKaM)^^ w»Haxm» Flw gnoM (0*01> moim) of I.B*Kil•«ntyl«»K»-oo»tylH»^li«Vl««^ diudat* 8.0 gr«M (O«00T8 «oU) of £«^ milfttrio Md 1*0 gfw (0.01 flioU) of bowddolqrd* w» dloodlTod ia &0 *1. of »8?t oloohol 0 •sd hootod la a toalod t«d>« at 100 0. far four hour*, aarlag tbia tiaa tha aolutloa baaaao dartc rad la o
PAGE 89

20a hapirisBl foimila ^ 5 oS 4 ^ 4^2 Struetural foraeola CxystAlXixM Tom «eui oolor lfol«oalar wi^t livltlng poiat Ti«ld AsAlyMt ]Htrog«a Solubilltle* Vmfr Aloohol AMtOM Ae«tlo Mid Diwan Walt* p«vd«r 742.47 201®C. £4?( Found GAloulotod 7a44^ 7.46X lasolublo Vory •lightly tolubl* hot Slightly aol^lo hot Soliibl* hot Soluhlo hot

PAGE 90

tl« Pr«p«f*tlott of blo»(8»*oot>w1ii0»»4«dibon«ylwitao)"»dlphooyl* bonsylaOMthuM* FIto grmm (0«0]16 awlo) of S«BMiboBoyl^4;*«oootyl««0>pteagrloiio» diooiBO* 10 al« (o lorgo otsoooo) 9t 60K |Ai«iyloootol
PAGE 91

81 • Bl»*( yl«aa9)«^phmgrl«b«BiQrl«wttMO«* forattla Struoiurftl fonnlft OUJh. 2 CH^IIi CrytttaiiM t9m mi oolmt Khltw powder Hol«cttlAr wiicM m*4 Mlttac point 840®c. Ti^d AaalyMt PoMOd Calottlotod SitrofOB T.lt^ y*9«ii SoltO>lUtUi imt«r XaieliAtlo ilooliol Slicbtly ooli^lo hot AoBtom Solv8>lo hot Ao«ti« Mid Solvfclo hot OiMtUX Soluhlo hot

PAGE 92

St* Rr«pM«tien of Ub*n»yIwiAa»)«»dl^>>iyI» aMctt^,>h«BgrX«UiylHMthiRM* Six «ad grmtt (0«0t awl*} of ff*l»dlb«Dayl«8*««o«tarl* M>p)MiiQrl«wdiaBla»f 4«0 ctmw (0*0t aolo) of hydroolaBOowl. didiydOt tad 1*0 s>^ (0*01 Mlo) of ooooontrotod aulf«ario Mid «»r* diooolood la 280 ai* of 90^ oloehol oad hootod imdor roflus oo tlM otooa both for four hour** Thor* mo oo proolpltoto oftor thio tisw oo tta* flook «m ploood la tho rofricwrotop ood olloood to rowoln oror o portod of flrt doyo dorinr ohloh Um ohito oiyotolo proeipltotod voiy olovdy froa tho oolotioa* Ibo eryotalo ooro oofarotod froa th* aethor liquor# ohloh OPM rod oad ahowod otrea£ gr*o& fluorooooaeo# by flltrotloa oad oor* MOhod oooorol thiwo «ith olcK^wl* Aftor drjrlac ^ yiold aoo 4«t groM or of tho thoory* Tbo ooaplo for oaolyolo «oo oryotollUod froa diluto dioxac oad *coln froa a oiacturo oonoiotiag of oqool port* of bonooBO and hoptoM* It aoo driod la ooooo onr oalihrlo Mid oad altrogoa onolyolr ihoaod r«ll^ l« coloolotodt 7*21:^ 8* The puro oobotonoo ihoaod o teuhlo aoltlof polst* Xf hootod oloaly oo tho yoquooDO block or la o oopUlory tObe la o both# tho soapouad aoltod damply ot 184^* !loaoo*r# if eryotolo aor* droppod oa tbo blo
PAGE 93

MdLUas Afftia At 184*C* uiyitAld iippliA«vt MltAd laBAtUAtAly tad tiMur* «*• ao MibMquaat •olidifiMtloa* 1hl0 phann a anna it att oauMNi tgr tht iott of «olT«nt of eryttollitotiaa iiao* tht Mat atltiai^ poiatt «trt ohttrttd at aattor itMt ooivtat aat uotd for rtofyitalUtatloo*

PAGE 94

St« £**o» twin> » 4 »i d lb#niyl«wlDo)«KiiphtByl"Cw» g »»t^iwayl
PAGE 95

SOaCART X* bat b««a pr«par»d ia pur* oryttallln* term and It* ua* a* an aldafayd* raafant has baas iin«atigat*d and *^**®*^^^*»(r»dib4atyl«aNpb*i^laa*« dlaa l aa baaa baaa praparad and daaerlbadi (1) 8*H*£&baaayl«*If**ll*«Kliaoa1yl««&«phanylaaiadlaaiBa (8) Tb* "dlbaatyla a l no a nl lldo of aalalo aold BO

PAGE 96

V« Thm following now dipliraylatothoDO dorli«tlio hoo boon proporod frcai dlbontyl«a>phon9rl«Bodl«BLiio oad fonwld^qrdoi (1) 81o*(2«onlao^«»dibonftyliKlno)<^lpbOQylaothaiM TX* Tbo follovtlng now dlidMoarl* taoA trlphonylnothMM dorlontiwoa hOTO boon pn^porod by tioodonoing 8*S-diboacyl»8*<«ootyl«opt«i^aiiylono* dlanino with dlffoowit oldohydooi (1) S«S*»&10iNMOtaBlno^*4*«>bio*diblowdibonsylonizwHl''*ohloro^riphonybMthano (4) 8»8**B10Hioo ti Wi ln o» 4 »4*<»bio*dtbon»ylo n1no «»8*»4*«>dinotb03qr» triphonylnotboao (8) 8«S*«4iOMkootonlnoi>4»4*«biowdibonsyl«»iBO»E''>aotbooy<>triphonylMtbaao (6) 8>2*«^l o »o o otonloo»4»4*«^>lt»dlbTOtylai n l no «»4 * «>no (7) 8*2**31»Hioot«BittoM«4*<*blo^b«nsyla«iBO^*«aothyl*«triphonylBoth*iio (8) 8«8*»Bia^ootOBlno«4»4*«bio«dib«ntyl«ttlnoHl''««Botfayl*»tilph«Dyl»othoao (8) S«t**BiOMicMVbaRlnOi»4«4*<^3io^iboa«yl«niao««8”*«BOthaa(yi4''<4iydrony» triphMylaottiono (10) S « g**Blo» H i ffl o tM i loo » 4 «4 *«bl o»diboncyloadBO«*8'' •4*'«aotbylaiMidi<»]f*» trlphonyXaiothano ( 11} {•8**Bio-OQOtomino^«4*>bis*>dibonsylonlno*S''«i«itro»trl|duNiylaothflno (It) t*t*«>BiOH&ootoalnoo4«4*«bla»dib«asyl«Bino«8*'onitro<^rl{dMRiyl»otb8ao 91

PAGE 97

(18) 8»8*HBl«<»»o» t > min o» 4 »4**bl»»dibohl4^b«usylwiiJM}«Kiiphi«flylHW (17) Bl»»( 8*»o» t>a i ao « 4 » A ibeacylawino) "Kilphaayl«»thyl«i»ttbM» (18) Bli«»(8«HK n itiBi tn i Q «i (l >» d ibnyl«< a i» pr o py l« (IB) Bl»»( 8»»g» t 4w liw> «» 4« d lb#o»yl— iBo)«»diphapyli. «u ia ^^y (80) Bi*-(8*«o«t«Bdiio<>4i^lb«iiqrl*«wib«]M (81) Bl>»(8
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BIOUOGBAPnr !• ridilffg Cwpt« r«iid« ^ 182 (1887) | Amu 144^ 48 (1687) 2* 6i«l«i^ And SohmiBCt B*r« 8<|^ £827 (1981) 8* FidMT« iiiQMriMmtt ia Organia Chinistry (Saath)* paga 88 4« £laglato& aad Pallard^ Unpubliahad amk §• 18iitBora« (M>pu:ila Chaaiatfy (Van Itoatmid Co** Ino#)^ paga 849 6« Paasoldt and B« Fiaohar* 8«r« ^ 887 (1888) 7. dagali^ Qaaa. ofain* ital* 2^ 17 (1892) t Rtalai« Ibid*, ^ 84 (1901) 8* Daaaif J» Indian ijImbi* S>oo« ^ 46^ (1928) 9* Bayar 8 Ca.« 0«R«?« 81»874| FVdl* 4^ 204 10* Uoara and Gala» an. Chaau Soo* ^ 894 (1908) n. raortf 4m in.Chcm* Soo* ^ 882 (1910) 18* iialUnokrodt, J* m. Uhan. Soa* 2888 (1927) 18* ItaBart«*Luoaa* Orunac and liaiiynoff* Uoitpt* rand* 207* 1108 (1988) 14* Dllaiaim* Jm pr* Chan*« 8^ 248 (1887) 18* Fiaohar* Bar* 899 (1880) 18* oahlar* irdl* ^ 104 17* Bitfiringar* 4m pr* Chan* ^ 242 18* D*B«F* 87*609* 70*938* 133*709* 141*297

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ACaORLEOGHBITS Ih* author wlohoo to oxprooe hlo olaooro apnroclotioa to Ifew* Poollao KaMrt»LuoM^ la vhoM laboratory this ooric bogim* •nd to Or* G« 8« Pollardt Cholman of tho Author*a St^arviaoiy uooBlttoo UDdor «hoM dlrootloa tho vovic hoo boon ooatlmiod* E>r« PollordU friondohip and hla guldanoo* both in tho Xaboratoxy oad in tho propomtlon of this diooortatloB^ haro boon tho aouroo of auoh holp ind inoplratioo* Ibo author also oiahoa to axtond hlo thwika to Prof* 8* J« Otto« uurator of tho D opar tnaa t of ChaioiaUy^ for hlo ao«oporatloa at all tlMo* and to Dr* J* B* dmdclna idio offorod rnnay oaluablo aug* foaUona durlag tho proparation of tho aaauaoript. Jqiproolatioii la aloo oq;>roaaod to tho Social'' doa Aalo do I'Qni-foraito do Parla tndor lAoao auaplooa tho author «aa Hoeoaroh Fallow at tho Soitomaa during 1988
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Bxomm FvvdMrIok dneltton bon oa Koroh 16« 19H4 ot I'ort tMMido^ flcrl<3a* Hla imdorsnduoto ««x%; vm done oit tho UnlTorelty of Florida* fron i«hl^ ixuitltutloo bo roeolrod tho doi^roo of Ba
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CCMRittM R«f>Ort This di«s«rtfttlon «ft« pr»p*r«d uad«r ih« dlrwotloa of tte Chalnan of tho e«Bdldat«*o Suponrloory Camtlttoo* and has boon appnrred by all MNBbara of tba C<«Bltta«* Zt ms aidiaittad to ths Oraduata Counell and aaa mppror^d as partial fulfilaant of tha raquirssssnts for tba lagraa of Dootor of Fbiloaophy* Cuparrisory ConRdttaat