A STUDY OF THE REACTDN 0F HlNDERED NH‘RILES WITH SELECTED AROMATIC GRIGNARD REAGENT?) Thesis for $119 Degree of M. S. MICHIGAN STATE UNIVERSITY Burton Perkins Dennis 1958 THESRS (3 \ ? ‘——w LIB R 4.1 I: ‘1, Michigan State University LMWMWHOPWW mmmmmmmmm W Am mmumcompaummmotw Shh Human: of Amman and App)“ at“. 1958 l’ /:.r' .. 1/ L- ‘72" '3 if 1mm: ”mmhmmm ammunr.mn.mram WMWOMMNW mmmmmdm'm flmwmmumm, EH Jun. 192? mmmm mmmnm Add-am.1952-1956 want-um , hummus.» 56-3958 n.a.-amconop.19$6 LS‘NI‘IOFT‘EMG’Z’IGICFPBE mm m3 83141231119 mmmxc @{I’finiflfi ""5611?" 513 53' mm I‘m-kins Dami- mmummummmamm mmmvaammwnmwm umwmmwammmu llama-wot m or screw wan-um AESJ 4.2. M? Wewflmotn'totthio mmmcmmmmm 12mm bed observed thist- nitrileu at that W G R «- (I: :- (Ki 3! “mumumw (Matawmmumbohfirolnod to the acid or m «a meter very rims condition (1.24.3): m. “motion to the mine with 1mm gleam mm m in «or: out ottuvaptod. This MWWeWfimeto m if thmhighhhtndmdnitfllu would mt vita mm magma”. It! nor: am newt one, reaction occurred how these nitriles We in e f f_ _ _ - mama we new. This intimated o difrmo 1n the and. of tho ho whims. It appeared that tho km away of salvation at mam-nu Wflfimumumtdmmuw mmmummmmmeummmm W on: MW mambo. What: of the Origin-m eagle: pounced hatches, hathrmxe: or mm hrhmhlofifim, degenfiing upon the at tho kmmuhzchmmmIv3 ands momma-amt effective six-n.- ammmo,umuamumwmm1y1mmnty1mpoot tho (mm mgmto. In M1, as the army. gum at tho wuxmmmd.fixamuammnnatm Mgm'd comma: mt from ketono to ketimino to 1:0th mamm. kmmeffeotm‘an-mnberuawmwthohmmmlm «mama, mammwmwknmmm wmmmm, W,thomunmct1fityo£om kewumwmmhydrochmummmtmtdmfln Warmestfiesgm. Itappenndtbotthomhflimflmdo mmlmfimmmmwwmmmm thmvhonmbmmtodotathorpommuhinhmoooom mrmemmw, mum‘mtum mwmmothog ecgmsgmotmmmm. Bhrtingnitfllomminmottmmtmofuwflu havingmdpblhydromotm. Matppuredtobeduetoo' mmmmmmammmummmmm mwmmmmmgmamrmm'bymamum mmmmultnponhymm, the mum: at emu-imbue with m1 ond catalylc ummmmmmummmmmwma mu: afimtuun'mm W. W. ' In the mm mm 2-mw1m1-W1pmmm and mitymmmeswomtotmmmmmm We Muppeondtobsnomfion. 11 1. i ate-“.3 mwmm n. 3. mm, Imam-m out. 0011030 ( 1755); h a. L. seem-er m u. a. gem, J. 011.63%” 3,2, 37 (13:11). 2.1;; R. L. Jaceba, 2'1. 8. Theme, “02.1.9211 3 fist-3 Cfie'eé ....:13,-,- 1'1}; Q. I». W m l. L. #1330118, J: Ergo CMO-Zl' #571,535") 31: a) A. 1. 80151913172111, 3. 3. Thesis, E‘icfizigzn State €01.1ch (1955')! 2:) o. 1.. 000mm and 5.. A. Ebleacmh, J. erg. cm... (In m). 1;. a. s. 1&1113‘1. J. Am. Ch“. 303.. E, 1‘73} (35956). 71.1 mm or memes Page memCTIOROCCC.COCCQCUCOOCCQCODOOOO0.0IUOOOU.OOICOO....I.O.CUCOCO 1 mmmooooooooooooooooooooooooooooooooooooooooooooooooooooooooo 3 WC'L'A "“1”? '- ooooooooooooooooooooooooooooooooooooooooooooooooooooooo 16 I Woooooooooooooooooooooooooooooooooooooooooooooooooooo 16 II Fromm O: Emmoooooooooooooooooooooooooooooooo 17 5.: CD It: canon]. Mmum......................................... IV Preparation of Grim W............................ V Motion of. W W with tho Kim-1100......u..." VI Preparation 01’ Mintim...e.......................nu... DIWIEMOCOOIOOIUOOCDOQOOOQOOCOI...OOOOOOCOOOOOOCOOOQOOO00.0.0... wmmSOOOCCIOIOOOOOCOU.0.0.UGO...IOOOOOOOOOOOOOOOOIOOOIO0.0... 3m WOOCOCCOOCOIOOOCOOIOOOOOOCOICICCOOOOOOOIOOOOIOOOC Eggfiklfi LET OF MES 21133 I W ates-1m Wfitb Selected mam. ”ammo-ooooo-ooooooooooooooooooooooooooooooooooooooo 11 3M “Wooooooooooooooooooooooooooooooooooooooooooo III WM of tho Km 0! HMMW" P330 amml‘moooooooooooooooooooooooooooooooooooooooooo 25 LIST 0'! mm FIGURE Pogo I W 0: mm” Hand in mi, Mooooooooooooooooooo II Rum. Fanning Katmai i5! Whiter!» Acid mick-013:1! at tho Grim 0033113...."u..."nu...uo........u... 19 m xmmxmmmrm'm.mn 51 mm mm and rm WW nuns to non WoooooOQOooooooooooooooooooooooooooooooooocoo-oooooooo 52 Mb) medeWmmhndd Woo-cocooooooooooooootoooooooooooOQOooooooooocoooooooo 53 V m 0: MOMooooooooooooooooooooooooooooooooooooooo 59 mm: mmmmm.mmmauwmmum (hmmtrflo) and hummus-em:- Iflh tho W ad mmummammmunmrm unmammm . 3-6-03 :- mnumwwmumuamwnmpm (1:903). mummm.m.-mmnuumumu me.mdhwuumum. m. mmmmumuummammnummn «man'ummmummmmm medium. mnnmotuummmsommm ”What-13W. mum-acumen“ ummmmumamwma mam. mammummmw mmmmumm. mane-nua- wumwmwmm. nnmmmtmmmusum www.mmumwwmm mmumm. non-mammmumum mmtm'mmwmmm. Mather-1M mammwmmummmwmm mmmmmmwm. menu mwmummwuummm. mmummmwuwmm mmwmmmmmmmm nammmmto. umdew-m “mummwmwmwmtum mmmwmmmm-mmu‘ wumtpommmummmm. KL» .L 9310111. 11. 8. mom (6), “hum ékd.1‘..-'.' ~ mmmmmmawwamwu Immunxm. summon-mum xmmummwmvamw Mummmwuhmmmp,um mm. 8Wfl)u~tdthth189hwmm mmmumummmpnmmmma wmmmaumuumw. mwmwmmuummm mowmwmmahmmuummm mumwflump. m(8)mmm,m.mmwum mmummmamumuxmum ummmmmmmwmuucm mutt-I. mmmthmmmwaomhm ammomwmmmmm momwmwtwmnmm mummy. W(7)an1mwmmmn mmuommmummuutmmn m1.§fll.‘pdfiunadmtomhmmmm um1.3or1.hpomm. Wmmtmuma Mmmm1,5a1,5wuumnmmmtomm mpmldhimowtim. nwmwmmw Wmamummummamdt muuowmummumw. A Mthwmmmu(y)mnmommrw mmuwmwmm mama: mammmmmmmmu humanoid,htfluohongoinmtewhaneomahmmtyrioooflto Mummiemmwlmn. W,thomda menmmammahmw * 'h 3 a 1 “ed“ p o Mommmmmmmotummpmp mmammmammmw. 3 2 1 cemen- on. I mmwmwmammnnmm mumumumonmmmmm. Ibo- www.mm,mmpomumm mmmwmmm .. 33°. c-d—n ' n “Wmuwmowuwnmmom. Ammummmwmmnw W. hwfiowtl)nmthot1tmpoodbhtowdro- 1700th110 «W ca u rpm-2.Wum G «41m 33: 03: ummwmumuumwmm duh-1. m, WWW. OBI-03f?“ ”9‘03 an: OK, mmmuW,mmwowmomucn-. madam-tdthothommtowmo 2-“!- Wm. ewe: WWW (ta-WWW.) on tho m Md, no and]: W. Jacobo (2) W m fiWWu-no DEM-'03:?“ “ WWW: Gig-CHfiB-CW 03- 03. mWWhtb-uuuthmwhm ammouoofl kn- mes. mmuwmmmmotno'mamum WWI-mm. Mama-um Wmammmmhmmmm Wommtmghtomtw-dtbmm. nvm.n.s.m(h)mmomuawmum nudmmtdmotuido. mmmummm wuwwmmuwzmw. 13m mmmmuwmumwnunwss told. nmmmwhmmmuumnun MW. mmmmmammum “MMMQfludmo-M $0de "mamoummwuummmw. “tho manMmmmu-nmmau ~otwil.¢11nptao'olotw1pouponthoolz;taocoo'oonvino-o-ooooppr-lt. mm,ummwmuuuwm mmmuwwmm. 3!!“de msme-ommhmmmag- WWMMWmepamm WMOMWMMWW. Adult-1km!»- mmnotpoumouthontootthohtwwtooflutoh m. “swamwm.mmm Mama). amidtht'hmm mmwmunwwmmuomm mmwmmaomnmmmmmun boflnMdtoot.‘ ”mmpmmwmm mwmmmumtmmuwm in”)... mmmmuwmumm mummnmom H1 9 ara’o‘n no Whathomlmlomsoooflodflmctuu.ltmtnthommuon mummmpnmottm. mmmommmganumummm -Wmmnmu'mmaomum mmmgphlodymmngoooMMJ mm Mommhuzwmtmrwmuunomu mwmmmwmmmmmnmnmom mummmmmumummmmmmpus). ”modem. 0 I / n :1 05.43%“: - - a nmmmmmimymtm-mmutaruw muummmmwamempootWtou Marianna. nomummuotomm ummwuwumwmmm (smuthammwmmgmmmnmrm mummtmmmonmm-qhmmmu “Wflmo mmumorsmwmummu Momm.mmummomomumnmpum mtmuoemmphoommmmmu uni-WWW uptmwlmoitmtodmthoolmmmld muons-mam. mmmu,m1tuupmo mmmwumnmmm. nooflmotmmuwdmmmwm .Waymummmammuamamoau mmmmm-mmumnu. mmmmrmgg.oo)o~uommu mmMmmuwnu-amuamm WW. Wmnuomamm 5043"”quth m. wwwdthomotmxomléd WNWWNHW)¢WMMI1&O uwm3mmtmmmdmmondoothomo mammmgmmmmm mammm~m~wwxmtn>a 1906.- mmmoma,Wm-dm dthoo Wdummuummmrc odomthomntflhmw. mmm W'Wmtbooomkm. Won-on! ‘ mam-Loam (12) obtainodoSS parent yieldolkatmofmmtho mm o: awwmmmo (effective gag-mm or s) ummmmwmmmmmomwmm- insulthhydmbrmicoom. Brodhngondltmar(33)raportade90par mnmamkamwmcmndommmmhemm hm with 2-W-nsthy1pmtom1trflo in mm for 12 houro and than Wining with W chlorine solution. crammmmmnwmnotmmtmmm ropartod motion bottom WW brando on! www.- mmwuumnggmota). 13:19:8me Mama!) mummtmkmmmmm-mm obtainodoothoMot. mammmmmm. WWMWMmda-mmm. 3311927 mwmw(mmmmmnumkm. xmhmmmummortmmmw int-ha litmmrobommm magenta and nitrfleo. Pan-tot masonrmomuthothmotumoummmw mum-1. ' ' Matthooonitruoohnoolohflolndmguottoohodtofluolm m m... moor and Mott (15) have Miguel tho mm «mumuozmw(mmmm1-7,9mdm,mb1on ondmtothotthooonnrileooanmdergomfimmtmm. A. away-mega: £3... magma may in h. 0 3mg; 3. ,1 12:3 ’3‘! HEP. M1,. “Ova. Ewigx '-—'a"'. Earp-CW M {unrg-umun mg 0 ”mammtimmdomdmtupmthompauda'. Mmthmoboonodthotthoomtormuonbymoofiw amnmwmmmmmww. Pwpimitrflo muummmawunoammmdtm kotono. Tho motion or ,Mhmztunitrflo with lav-whom W(mfim6,hh1onyioldod51poroontotthodinuotm www.mnmomdmmm. Umotthoketmo mm. mummnmmmtmm.mmm mmuuootmbyomt,thommolmm For m,nm2,m1mmmmmmmwim Mammotoghofiparomtdmobotokotmfirflo.36por MOMWMMchondmperemtotmmnfifllo. no motion 9. rhcmaemuno mud on» mumm “mawmtotthommukmondwmcontotthobm Mirna. mmumwmtwmmmmg Ironwooo-tomtonooitflmmmbmo. momma: Win-m with “W bmno (reaction 10, m1- 1) mowwmtmdmmmmombwmof othercondanoodmdnoto. umtodprwioufly,thiomn1h'flo who with fizmcotmitrflo to yield 33 per amt at tho ketono and other products. Ber: (18) ropoo'tod that ho obtajmd 35 per coat of the trim,30poromtotthobotoimmonitrflo, ondeorcantof the nomad. ketcmo in oddition to dighmvl, recovered nitrile and other mats in tho motion of mmflecotcrdtrile with mensflmgzeshm bromide (reaction 8, table I). Tromr and Beck (17) reported only the noun]. totem ond dimonyl for this own motion (rt-notion 7, hblo I). Ho retmmtamdtofimmfimofflfin amounted wmcotmitfiloo vith o-tolylmm we. or “331mm bromide other thin than "ported ohm. igfia 1 mm Egofixfiuvgo 3 £80.39 3 a «A an. 3888. 3. d .936 summon .o 3 an « Joanna...» 3. dd goo gunman 4. a an 83.5. .38 mg. a. nu slag 3. dd 5.5%»... an .e 8 5-8 3.. .13 $.51 533 .m 3 839: .88, 9 ‘3 ma .4. fl «and. 1.35! 38 «:8 33.5.... 6.83.". .4 mm 888.! .18» a. ulna ‘ ma « m g 225...: 3. dd 533.3 agape-moo .n on 3983. .38 fl amuxavmoounuoamoo E a 8 gain g 3.. 1.5%". Seance .« . d. £358 80.836 .3 a a Sagan.» 3. dd 31.6 53.0 A é”? ‘ an? t ‘ : ;§ { r gull... agggggghog Hug 3 {'1‘ 11‘ a 482.5533 4M... WAS..- Ewfliafi... .u «a m 8 m 540% 3. 5 3? 3335.9... .d B m ‘fiogg 3.. .3 so 83339... .8 8 m $8335? 3. 5 3 gaining .2 an a 8 infiaionuxiaodo go Havana-nu .3 a m gang-Kc A... 3.5.51. Ban-cognac .5 8 m 5405...“. 3. 5 8.58 831939 .3 8 m gioluuu.» 3.. 3 goo... axial}? .9" 8 « {gun-ow? game-nae inflow» .5 8 u Ride; 3.. ago... axing. .2 8 « {oozing 3: ago Bionic-nu .fi W Qafioguuuwnomnowfiww «Bog—ounce defiance a a 3.5:. g 38 A 8 go go .fl ma a M“ 83.3 dummy. .3. gaggiu 8-5.”. .8 ma N M Ban-oi in.» go .a tug? , 4 g _ 113 z 3...! gonad ‘ satin; 1 {33.9 Ewguficmnmouvfiwfiog-u .mn n 8 d S g 33.88 .30 fiioxfiofinfiogo .3 «a .. 23$ 3% 333.5 5 .. go Eaaoxa-ouuumgu .R .3 h gnu-oxiovoqmoomoo 893.". infiovqugé .3 «a S on A; a}. .5 o g”. Baniuvflunga .mn fl 3 pagoaaofiaauuae a3 BAééBu-SE .fl 3 a Reggie goo fidogugoo .nm 3 a g 18.8... . go 523.353.... .«n 8 a panacea-managing “.7 3 go fiumcuflnumoamoo 2R 8 a gage 3a 5 panama signage .R 3 a «donnuulKMu-EJ. gnu-mu... gnaw...” .0.“ «a a luau... on guano... Engage .3 an » gingham-83.3036. go fiafioXJJKéé .3 V «la-«flu a.» . w . «m m ngéofiéoovo o guide..— Bnpmnoxofiovoomno .3 «H . m gauoskam-oxamuguofia nag .. .3 wage anvqovuumno .mu .3 n 4824354033.”. go guxiovofiuo .fi .2 m Joooofiuuxonoso-unu . £333 flagging“. .n« can... , 1 a I 13.... L? I». SEOOHE Lament: flammwmm ', mmuwmuxw «madam dams/5.9mm. III-Wand W» 545° (22 a»). n36 1.5568. wmmmwmmmm. mmmmm. Vandal-lam. wwww. WM¢33IW “513.359.3135. Man-aw $.59” nun-Jug“ 1.5 5.51. (1 1...). ‘12" 1.5539. hmmmm. macaw. WWW. madam. WW.R.I¢¢WW til-tum. noun-mmw. hunch-11mm. “all mum. thmW. Ian-durum wmwmmmmwum 17 II. Premium at W“: baa-twang ma-anommmmmnumw metmnarfln. 20198 g. (1.: manta-mm innz-l.makuaddod269nl.(2.965m)nfmmhufldc. mmuMmmmmamu-m.mhum mmmmmufinumm. mom-omn- mmmn.umummmmmm mummmmmmwmmo. $00an mtimadthnhm-mmcmdapmwu madhmhmmdctbmm. momma“ Wemltmummmmummmmm. thqumuummWWaJwa. commuthWflu-haucn. nae-WW“: “Mumatmum. MmWmeaw mm).:mbonmuna-m°(asu.).ugu.soeo. m ”diam nmmmmmmmawm “mmmg.(9owmnm)um,b.p.m~m° m.5n.).ng'1.soésmnac.(mmmm)ams.p mm°csm).n5' 1.5061. muwmc§.p.otM°(Mm),anfi 1.5070. 18 3.31133de mmummummam W (21:). mm 3. (2.65m)¢m1m«ndh50 3. (2.8.1.1.) um than in: ohm 33% g. (63 par emf: yield) at dour-d Met, b. p. 83-81" (5 am), a;- 1.9.3.. Ila-hailing pom arm-moan :- reputed to be 105.107“ (16-11 an). c.0tharl1trflu mmmmgmn.nmtmm.mp mmummammmmmumu M,orhommzk,umsm. Mam-am martian a: mo :32th or these nth-110a will not be bladed hen-o. numdmhmm,nmmw1uuwdmtm mdiuwmumufled. mamummm Whamtoihroom. m.mIntm-ntim medemmmaothmmm mummmamnmu.mmmdmmpmumamm¢ m.m,nmmu,mmmmumgm. the mmmmmmmnmummmm 4mm. mmummumwmnw pom(o.395mmmuo.2smotumh)mmm «mnemwmnmdumnwu mumtommmmmm. man—mumm- mmpautuu 1.5053 1.5060 um' 1.5081. 1.5080 m (2-) WW aim-13.0 1.1969449?! 1.1.913 m and 1W6W (3) I-vamm 1.5031: 1.5039 mm pd 1.5028 1.5010 W hW-fl-ethyld-uthyl Wan. 15028450142 1. 503? rand 15038-1 50h? 1.501“. 5018 5mm (3) 1.5038-1.5d;0 1.503845%? : .: 4,5“:ZVW‘Q,‘ “u T “w, *mummmum. “1mm in gamut- mm in organic mutations by W described. bycopomd mack (32). mmdnoammmmmmnswmnmm tom. Amumgmtmmmmmedmmmmm mam. Ammmmummmmmwm mmmmmmnrm. numnmmmmm hmwmumwmmw. nap—1mm MWthtmmkm.b-um,or kammwm. mmmmmhmmwomw nbwmmmwwmww mmtm. h“m,bhonolidkabimmohydmoflmwmo “mummmmmmmm. m mmmwwmammmm um;mmtmm,wm¢.mmmmm. Meow-mum. L.:3xh0¢n.celmnckodrith3/16' whammuxmmmmmmmmm mc.asmhvwmoo1m. mmmmmtotbeu mmummmmmm wwwmmmmcmmmm.mu W. mummmmtifladhytubomn'phtm, munwumwsmpmdmwmotm mamgmmmmmmbmmm. mmmm mmmmmor17owm°(sm.). nay-wroughtyallw, W,mmm. mmuwmuotmutmmm m1$mmmwwmumwmm nude. muzonmumnyuommm. hummus» ketmummmmmmthtdmmmmm. flu yieldabnnbmm‘udanthobwinottmmtotmm Burns. . WEWNMWWMWW rem-dwinmdum. w,mmmmmmmmd mdgomaomdimtoobmnthom. mmm kumwmmmmmwmmumm. nmmwmmmmmummMuumumm Sectimnofmltheais. mamflummmmwm www.mtmmmmm. mulb- mma.mmm,mmmumm. fl.mnntiono£m'imm 2.. WWW. T0123 g.-(O.Smlo)ofmwiun1na500al.tbreo-mckedm oqlippad with I. “1mm, 1mm“. tube for dry nitrogen and a; droning Wmfimemmtacmflbhmlcmmdrymgm maddednsalntionofé z. of bmmmmmmMfl. dmmw ether. When the reacticm began, the etirrer was started ml an Addiflmnl 72.5 g. at 121qu (a total of 0.5 3013) in 160 111. of unharm- ethermmdmmeofbdroppdngmnmapododofom-Im bmzr. mafimcomwmmsimmcmwtartowmtfim mmmmm. hummus-W10: mmwmwmmmmnmmmumombm and than titmtad. madmanmmm wrwmmafimmnmdummwu tmfiWfianthtmtmmmmm. nu- mmfimmhmmfiQWhuMguflJaAMhfi. mmmmammm, mmtinnmmh‘onodw mmnmmmwpotmmmmmmwpu mmmmm. AWofBSég. (0.530100: 22 mummuwruu-Muumuna not any-aim. wmmmawmmmu mmuummgmuutwmm. album-mm mommlmmwtormibflnmbma (26)“1nthopromt1mofmmm bromide. motonmdng Wimmhomtod. mmtmammummgtmpuaby unmitionotomnmlm grammmmmm gmflohootmgmootmhbb. mmwbommmomml. Ibmfmndnmmrytoflnoomnmotthobrmidoinm mammemumurwamummmmtm mansions ugcmnyvithomrp was red. WWI-auction had been initiatodondbndprooeodod tabletofi nimtoo,tbocontenta of the meomoddodbothomtimfloflc. Imam!) g. (0.5m1o) otbrmeoitylmoinmnl.otcthumnddodton.2 g. (0.53010) W. {die addition” ample“, WMmbaatod with mmanmodmtmmdcnoedfltosmm required). mmammmwummnm m reaction of two-mun. with WW breadth wmwmmmmm1pmmmmmm «mammumtormmmummmum Origmrdraogemto. ammumgmm(n) 23 and m‘mrt-Lucu and Salmn-Lemgmr (3.2) was used as a. node]. {or this Wianflm. W in boluone for bitten hours with can‘t-imam summatmwpumwmumumummg at90°£orthom1m¢tho£tmowm1uommat time. 1110 mm 71mm; motion conditions, with alight uodflicatinl, 'meusedtbmmhmttho Manon. ThoracticnboMmo—tolyla mum; brawn: and 2-Wuat’vflmmitfilo doacrflaed below 1.8 a typical martian. After the preparation of the o-tolz'lmgzoaium bromide, the stirrer ‘ was tumed off to allow settling of the nag-1351113 particles. The 110' of nitrogan no increased to insure an amap'mm of dry nitrogen ms. Two 2 m1. alimots of the: Orig-ward. reagent were moved from the flask by means of volumtric pipettes and m placed in bro 100 ml. beaker! (2?). Appratctmbaly 5 m1. of distilled water no added to ouch baker to hymw the mm reagent tenured by mm at. of 0.1078 x. mm- chloric acid (a known was). The bakers were heated on o than both until the basic mmainm oxide was dissolved. Tit-stitch to t rhino- ;htalain end point mired 11.0? ml. of 0.1153 R 006ml W Mon. mmummdnmmmlmdmmm Whoflutoninhinonflootlfimhlotmmmmt bomonolnofutflloiaufonmn fatal Wham of acid 0 112.07 x 0.1078 l - 14.535 Total meantime or bone - 11.07 x 0.1163 1! '- L221 Want. at acid/2 ml. mm mgmt 3.21.8 WM.¢Wm-JM0L6& mmuw.mmmumummo.m mmoaswdnam- rfifl'fig- m mwmmmmmmmmm mmmmmwmmnommozso dam-NM. hWWtdmI‘I-tln mmmumsoomwmwwmu www.zsan.mmmm.mmm m. boa-WWW (50.5 3., 0.8 non) in manhotmtohmuoddodbymdomnnnm amaze-nu“. Mama-mummy... MWuMMWMmpfl-flmomm. mummmmmumm. mound-Iowan mommummmwmmmmum mmmmmmham-mm. Atthoo‘niottho www.mmm‘ummmmsum m.vmmmMmMmm-Lam MhMfl.o¢mquid. WWII m.hmoMonmehyuu-m nun; mum-um. momma-now mu,ummmummmm~m woman-unmoumumnuam. floata- muuonond. mmmmmmwmn ”ummnmuuhg.(uapm}am mm. Ww.umm.3.mu1.6zh mmuwmmmummwo.m mmoasnuaumu- Egg-55,5515»- 231 mmmmmmmmmmm mummmwmmngmmuaso n.9moodmm. mmmummm “Whomsoon.wmwuuu magmasommmmm.wum om. mama-1.1.50.2; p, 0.25th 100:1.otwydrmntdmmfidodbymdomm-1m annual-mun. memorandum-mu. mmummmmwmamm. mummnumhsmmumm. mound-Inn! Mun-«mgmumwurmmmum mmmrumwmm. Lttbuldtho www.mWMumumxto-sum m.mmmMmmmaoo-Lam mummuwww. MW” m.uwmumnuwmwoynm m minty-0mm. ammonium dfioth..dfilmuhtbmmumw num.auhmmmmuunw. hm mono“. mmmmmmwm. mummodequfiawandutt-ho W. WM.«wm-s.wu.m Immanutw‘mwummwo.m mwoasmuum- digs?“- 231 mMummmmmmmn-Am mummmwmmnommuso flummmmo mWMJWMII “Mandamus-wwwwmwuuu mum-.2son.mmmm.mum W. nut-MWGMS ¢.,o.!5 nun-)1. mn.ummmmwmanm:m1m .motzomu. mnmnummxs-mau. mmauwmmumwmomm. mnmwmmhsmtoum. WM*~ um.ommmmmwmmmm.um mmmmfimwm. Atthluottho www.mwmuamummsum m.utcwohthom'mmdmmn.¢m mammocmmmmumm. Inn-WI- W.ho1wlomnd.onwmwwmm m botany-Imam. magnum-um man-.uammummmmum nuns-ruuhmmummw. ”w unwound. WWWMMMWWC mummaw«u¢¢.(uamm)umu mm. mmmmmmwmnmm tho Mmmwnmwwmmwn ommmwmu MWntmm mammmammm. homo- an: m nmmmn 01‘ mm 0? H mmnfia-W‘Wm 1 50-90 3.95 1.5051 2 90-120 1.30 1.511» 3 120-150 .15 1.5233 In no-m .65 1.5217 5 182-187 2.73 1.51.56 5 167-193 3.35 1.5552 1 man: 9.35 1.556: a 191-193 8-30 use 9 ”3-199 3.15 1.5568 (won) 10 199-220 1.85 mmmmmpwumm. mun-Vulno mutter-am... mswymmuu mm. ”Whfifimwowdfinfi. uwmammkmwmu 63pm. mwwmpmmwu Mmumkm,uwmmmu. 26 mmammmmmmmm Wharton-um. autumn-unloa- wuuomammumwwh mamomumamwtwmm. nmm,mmmmmmmuumm mmuummmmumzzm. mada- mummbywmmummmnowmm. Arbor rep-om «equalization the and.” o! HwW)-2~W~ mm. c.n.c(o.a.xc.u.)c(o-cn.c.n.)-aoa, mm a 131-1325." mammal-0.13.»: 3.13.53. M 1.1.4.1. knottupttomthakom,omtmlg.dtho mwmmrummunnm audfipormtotbonol. mmmumuuum mtbohtmmdbymmmwootmhth. Ami-lam ammwmnmmwnmmm sumo-n. muralmwuusou.mmu awn-mammal... mmhmmmnmn. mmhmnmgmmum. awn-mm m. Amdmwmummnm nuwmmammmkmmm-m ammmmwmmm. tummy-am Watsasmmmdmmaésmmmmu mun-madam. L.mo£mmm mmmm (0.6 1.010) m MM to rant nth 0.375 mdmxmmww. mutt-snowma- mmummmmmm, 01de mdwawmmnmmmmmmm. column are 28 g. «mmmotm.S-151°(Sn.). bourbon. lolidifled 1111110 being distilled and upon ”room Win-1.1m from W nth-ml mm ut 56°. WWI. OLGflGfiMOCJ” uWw-muflflsé). and... wagon-M mummuuannmm, mulwm°mmmp Wucnfimmm mmuwumtum" (36). gm * mm. W" armory-tom mamnmbzmm W m 3: 1. 15-56 ‘ 3.6 1.14328 2. 56-79 - 2.2 ' 1.52m 30 M 5.9 ‘ 1&78 , 1:. 91.131 2.3 1.5211 5. ' W 0.8 1.5510 6-11. 336—182 19.3 1.569 1.5751 12. 132.235 3.5 mm 3.1: 28 Wlmiwmhm’bhm. WM mmmwmzummmmedng- Lsmwmtmmummmummmmmm. nmmbmmeMMomumm°m m)(&).m£udmmoumom,thomm mummtmmmmmww. unintu- mnmammwmmmmmam mmpnhwumwmmucmmmmumw Wommuommmmotwmhtho mamotatoédom. FactionJoon'umd-toouwmt Wummwm. thdumtdamm hwmumbaumm. Wémnwammmmm an. mwmummwmmmumms..m.6w Myzfldethokotmo. mmummmotmmuw mun-1m, cwcgmou-cwa.» an Mr. And. mm. for OuHuOI c,85.57;tt.1.19. m 0. 85.853L743. mmmmmwmommmwm hour-roan. Amwmmmmtmmmumn mltodht128°. Amman-a. .tcr W. 3.5.35. rm I, 6.05. mmmummcmémaumw. nun WW4t173~l98°Gm.),fimthobonmgm www.mmrmmmu. mausoleum -Wumwmmmmmmm mehn-unnflnhmp. W. mmmmormmtmmm thontuhyormoopntodmdutnctoduthtohm. Dmmntim otflnoraniclmrthrmwoohmafioldodthotonwmmcma ‘ P ° - m 1‘3: 1. 1.3.5-59 5.1 1.1.91.1 2. 53-68 5.7 1.1993 3. M 1.2 1.5011 1;. 814-93 9.9 1.5137 5. 93-169 0-7 1.5367 6. 169-182 16.1 1.5357 7. 111-186 12$ 1.5860 8. 186-209 1.1 1.5M: Roam. h.8 AWdWWWmMMGdW lmdflflththobomngpointor66°(22n.)wash'ldoflaf muwuuomwmmmwmm mommawumwwm» mtmnmdummummnmwmmw meuththototommplomtfim. mummuumnmmmummm Man. ammummmmumum. WGM'IWWbohothokm. MW “28.53.0ro11oudk55mont. mxmmmod ummmmu. m- ommmwmmwnmmbyzzm nan. m udn a: 1thw1mm-m, ca.cn(c.na)0[2.h,5 (cm),c.H.J-ma, mm no 139.5". Ana. anew. tor Currant): I, 5.21.. round: 1.5.33. 30 rho motto of 1wm-emmm-m m». mmcgnam (2.x..6(cna).c.n.l-uaomc.n.(m3),, mm at 1&489.S°. Ann. mm. for CW‘QI I; 11.66. W. X. 11.35. 3.3mcfimd2m1buumtrflo AIQWWWWfiIWVdZ-W mmmuummmmwummmuubom mxwwmumfianm. nan-mm Mummdfmmlysmofmfin. hthotiwtmufi www.msmotuanmmmmsomnaofi mama-mum. mmmummm uwmmmuummw-emmmu thootnrtotthuuom. W. momma... WW «mommmmmm B. . 6. m. M E: 1. 174.6 .5 1.14766 2.. 50-379 1.) 1.1.932 3. 85451 3.8 1.5260 1.. 1014.03 16.0 1.5251. 5. 103-125 1.5 1.51.80 6. 118-159 1.9 1.5615 7. mm 28.0 1.5109 8. 160-13105 23.5 1.5711 new. 9.5 Mmlwsammwhlmtm. 31 The boiling point of fraction 1. compared thumb}: with tho bailing pcfin‘a 99-103." (s m.) of 2-meavlmtmzmitz‘ila. no W W of this 11mm mdfibited the damctérisfic absorybim of tho cyano mpat 1.me mafidibimma amnesto the infrared-been» tics: mm c}: o. Imam 33:11:21.3 or zfimmmum 1n the region of. 2 to 6 Meme. chticm 1. remomted o 22 per cent recovery of 11.th may... Era-Latina (a, 7 and 8 solidified mm taking rafmtm indict—:5 and after two mmmmtim iron aqueous ethanol malted .. 93. Eflurhinstmbemoin, cggcmcsnswmaga, is reported to next. at 58° (35). Second reaction. the organic loam-m Wm through colmml wndmnntm mm smut-bow.» WWW was obtained. The lower functions option-ad to ho um: balm. mo mm (2.3 3., 1.7 per 963% m) Wot 118.120" (ah-:5 n.) W W1: am. the b. p. at 122.1213 (1.6 m.) upon-ho by Cm and 11.11am (23) m- eommmmunmm. Itm Mixer oun- flmodutbonitzflobyits infrared mm. m madman, a total «33.1. 3., 56 Wm 71-14. dist-filing ot 170-182“ (Em-13 m.) ammo: um cooling and upon mm mm m aqueous otbnnol mm .1: 55". m _mimm'mndbytho othmomfldim mmwzs hours reflux and upon ”out“ Wuumtm tron moons ebb-ml melted at 129430". m m u upon-cad to am a Jaw-130%”). mm. mummwwmmumshg. (miwomfidd)attbokmhydmb1m. We: thomtophouthnmghoolmAmuatoWW 1. 2. Jo h. S. 6. 7. 8. 9. homo Wlmlomdtohmtdm. g: zal‘fil 1% ad 25-36 25 25-33 33-71. 719-113 113-111 127 127-11.! ”ti-178 m 15.6 5.1 1.2 1.0 3.7 1.9 18.8 3.2 .1 10. i 1.1.918 1.14920 1437?! 1.156% 1w 1.5!." 1.5053 1.5110 1.533 Man-éurmdmtobuuymmmbyu mammmmmmmm mawmuamtawmunm manual-Ammo... Wém'lw uoanmmummm. ' Itummummmmmmm nmwmdmdmuumummmm mono-mm. mm MW33WW. mum mumwwmmumaumswwmmm «momma-Woo. mwmuwm 001ml. 33 ummmmtim,mdumummum maul-am. mmmtrm,auunmu mes-111° (n m). .3- 1.soss. man-am .. (13.5 W «as many). mwummmmmxmww mmummwwwmmumam nun. mumms$wmmummu14cm)- emu-1m. cmc.n.)c(o-ca,c.n.)-m, um. sultan! a 127- na.s°wmw mama-«mum. Am. mm. for can“: I, 5.52, ma. 3, 5.53. Mummwmmmmmuussg. (115mm Math-WW. mmm,uumu wmcmmmummmm.m mum-cum. mmaumwmmumw mwmmumm. any.numm mmummwmmm. a. mum at mama-cmm-m him, 0.8503(8511.” manhud-u mum»... u- m m- ou- muon- m..- ‘WumunxaM-m". m.enwa.mc..x..x.o,a I, 11.33. M I, 11.1.5. 0 mmoIW-Eutbfihwmitrflo dem (0.251.010) m pondttodto mot moafiwumwmm. humanism uawmmhmsmnmem mamamsmz mm- Wmmw. mum mumuwmmumtomhag.(mmmw)oém WW. mummmw. mummmmmumflfu n3'1.55h6-1.560h. mmmnh ¢.(16.hy1dd)uo _mwumm. mthm-dum mnmmmwmghmmmumm wwoMH-Wt an and-- at hum-emm-lm. cwtcfixcmmm.» mmumwmmmmmmkmm- mummumwmmmmmm mm m. m.wa. for 0.3.1.). a. 81.313 x, 8.5331, m. m. a. 81.313 x. 5.53: I, 5.71.. W. MWUWhMfl wmuwm. W. ”WM-“www- Wmammufiumamcmmtm WI . . m. m 3: 1. 31-38 2.0 H.681 a. 38-1.!) 10.8 1.1.976 3. her-ha 5.9 1.1053 1.. 1.2-80 1.5 1.1055 5. MI l..o 1.51.19 6. 91-95 2.9 1.5115 7- 95-410 3.1. 1.5155 8. 110-126 1.5 1.5101. 9. 126-131 1.6 1.500 10. 137-200 3.1 - 1.5270 11. 200-210 15.8 1.5531 12. 206-212 16.8 1.5563 1.3. mm 18.0 1.551.: It. 215-213 ma 1.5506 15 0 M2 3 09 1.53463 m. 6.5 35 mmzmhsmmmummuunmm «manta-emu}... AmuwmmuMW-am msmvmmmpfimuzzs‘G-uduqum deWW(h)th-Wm momma—n... MWmMW. mnmummmmmw. thou Numismnawoteswm. mutt-mum.» mwmwmmmummauunmm «mm. mmuaxmqu-nm, wanna.» DA.acn.).c.n.m-mc.n.(m.). ... m a... 36 tho mm and melted at 138.3595". um. 0.1004. for 02%! I; 10.18. pm. " 10023. D. inaction of 2vW1~3~mtm1pmbm1brfle EMonmbmmtrflo (0.25 no.1.) s... purified to moot with 0.375.010 crouch 0:th mm Hogan“. W mymmnmmrmm m “mewmtntmumhmépfi7wcm MMMWWWW. Wflhmm wmcmmrmmm W m 39: 1. 20-110 1.3 1.5130 2 o 13.0 ' ( Us 1 051109 new 3 0. “8’35 1‘ .1 (now) ’0- W 2 .5 1.9.23 (-0114 a: mu) 5. new. 5.0 1.5310 6 121.9173 2.9 1 .5366 7 113-005 (”3.3 and): w 1.5 mmmwmmm Ludhiymm “mm-muster. mamas) mammufimummmmuuuw mommuummnmmm. 37 Ahmedmommwolbhooohmfithflmomgmtnbmtt unmatabobiphm. mum1.5m6.mdthofnmutmthoobwoumum .mWNWWQcflmmOhflnhW (353.)mm1nbon1ngp0mm26tol550(5m.). mama mm.mumnwmumm. ' numermkmmmmmmumduw mmmmumhodwwwmmmumam roam. w.m.mmmmmmuam wmmnnmm. m min at 1.2-01m1-WW 1am, 0.0503(039 08(0.H.)c(c.n.)-m-m6.na(m.).. - punt-ad m 0.. mm:- hadro- mmmmmmmwmmmmmmm “150-1515". m. 0.1.0.1. «20.0..an I, 11.66. m l, 11.18. mmdmmtdbymhIflmtomflldflyu-m)“ «limo. www.mmumwmmm new... mmm.m-m°csu.)m.5u.soaoam ammuumbmmgmmmfismamngusm era-MWp-mmm.’ .mwmm dwmmmmmmrmmorfim W “mwummmgnmm. Mum-noun... Wham-11W. 38 mpmflmadditimmsimmrmtharem @2150 6mm“ 0.. mum; absorption spam... .2 0.. lW-3WWW hood in this reaction. mmamkmmmmmaommmomww awmmmawtu mmmnmzz bmronflnx. touch-.mmnmmwmmmm. An attempt m nod. to prepare tho ‘mcrato of 1~(o-toly1%2-phezv1- 3mm'1'033 131m. 9.3563673.)Cfitcafla)C(O-Cfia°.fi.)-fl-mcofia (00,)” A (turnaround formed nanny, mutual-um}. nonma- nuuou rm- omoouo mum: mm at 253-455" an o .110»; point blank. ma. 0.10.0. m canary.” I, 11.33. m I; 22.93. _ This Wmmmmmufiunmm 22.67 par out 01mm. abhor pier-too or 1:00:10 an! (18.3 put out nit-om) an mom-d by tho high um also”. Heaifilmeoomm biggie. Hydrolysi- mo two hm. Distillation otthoorpniephouthroughoohmc path-tonaingmcumt I. 73°C. {g 3.] m i 1. 39-02 5.7 1.0893 2. 004.1: 13.0 1.0902 3 0 162.51 13.0 1.1957 5- 51-109 . 2.7 1.5092 5. 109-321 3.5 1.5121 6. 121429 1.2 1.5216 7 . 129410 1.2. 1.522.: 8. 110-187 2 .9 1.5362 9. 186-193 22.6 1.5601 30. 188-193 18.6 1.5631 11. 193-201 33.2 1.5638 12. 201-250 I»! 1.5652 Realm. 5-9 Fraction- 1 Wzgh 3 were untitled u meitylene u ascribed m 0'1”” ‘ C mm«5,mohcomsmdltom8.5 prowl-coma! uni-acted nitrno. we identified 13 before. Emotion: B through 11 were named to be the Rename. Tm WhU-hs.orcy1ddot6hpercant. fienfimcmldnatba Wbytho Iflmnal-pflmmmthodflthflmnfln. 11:. plants or 1w1m-2-phm-3mtmv1m-1m’1ndm. cafiamwmmmccfisk £2.h.6(°H.)aC.H.1-m'mcofla