.————' _——_’— —_——-—— _—_—— _———— ___._—— ._———— _———— __—_——- ___———- ’—— __————— _—.——— __———-— _———— ACID AND BASE CATALYZED TRANSFORMATIONS OF 2-METHYL-I.2.BUTANEDIOL-3-ONE Thesis for the Degree of M. S. MICHIGAN STATE UNIVERSITY James J. Summary 1960 \ ‘7 "'.".'h . " LIBRARY Michigan State University “'4' L‘ MENTION STATE i!,"='./me OI“ r L‘rhf'UJ'I'“ ‘ .. .. ‘ ,I EAST LANSING, MICHIGAN ACID mu BASE (mums!) mtasmmnms or 2445m1,2»mwsm0L—3m By James J.Sumuy Arm”- Submitted to the 601109. of Science and Arts of Michigan State 8121me In put-Hal fulfill-mt of thu mqulrmts for flu aggro. at 105er OF SCIEICE Dspnrtmt of Matty 1960 A631" 063’ 1.3sz T _ The author wishes to cJ-qareu his gratitude to Dr. John C. Spock, Jr. for assistance and suggestions in thc ucmllshnent of this research work. I extend my thanks to the other members of the Oxamistry Depart- mt for their willing am. To Ihd and June ACID men BASE cummzn msmmnws or mmmm-aummom-ms BY Jam: .1. Smry AN ABSTRACT Shh-ittcd to flu College at Selma cod Arts of Michigan State University in partial mlfillmt at tn. "“1““ for thc dagru at MASTER OF SGIBICE Dtpu'tmt or Minty 1960 W __ ACID AND BASE CATALYZED mmnws or 2-mm1,2-mnamot—3-ms ABSTRACT nu origin-l mun rout. for the synthesis or 2-mtmrl-l,2- butmdiobJ-m utiliud a min of rotation: (m p. 2) which on- tuilod tho ruotion at nthyl isopropoxvl kotono with hypochlm told to m tho intoruodioto chlorolvdrin, with Wt Ivdrolylio to Z-utlwl-lJ-butmdiol-Jm. A m direct rout. in. boon W 2:07 oxidation o: on now: “ml um with ouiu totratido to tho dim new. Acidic. owe, m: 9mm mumum o: sawi-m-mm- dial-6m. and tho distill“. mu running Wm, worn in- mtigotod qualitativoly and wtitotiwly. mo o—dimbowlo promo-d, molly bluntly and “owl propiouvl, vor- dotmniud by pour chron- togrlplv. Tho adieu-bowls nor. am wtitotiwly by comm-t- ing to tho until“ Ind precipitating tin with hide-lou- unlit“. In tho ocidie diotillnto, 70.8 per cont mud as tho oootyl propionyl and 29.2 per mt u blmtyl, while in tho hula «mum. 86.2 pu- cont m bimtyl and 13.8 par cont mtyl propiom'l. In tho glycin- diotillotion only binoctyl as W. Only on: spot W, oor- rowing to bimtyl, m tho «mum m chroutognphod. hob-aim for tho {oration of tho «diurnal-win how aloe bun postulated. mu: OF (IBITENI‘S Page ESITRICALAIIDO'EMCALBAQGROWD............... IITRODIE‘HCUTOMREAGIWSOPWKEWES....... mmm........................... Prooednrea ........................ l. The prepontionofmthvl isopropero'l kotono . . . 2. The much of 2%W1~1,2~MWIOI-Jm . “V’E'PWH 3. Periodete «Motion .1 Z-uWI-lfi- hitmdiol-J-m................. 6 h. Acidic, hula, end glycine distillation; of - 2-wttwl-l,2~hutmdiol~3~m e e e e e e o e e e 7 5. Qulitetive determination or e-dioerbowl W 8 6. mtitetive deter-imam of «:4in CW eoeeeeeeoeeee-eeeeeee Reagente......................... 9 Equixxnent......................... 9 RESILTSANDDISCLBSIQI.....................ll REMCES...........................18. ACID AND BASE ammo mmnms or ‘ 2~mm1,2-3uwmm0L-3m msmmm m amen. ammo In 191.6, J. Colmgc end t. Cunt (1) first momma 2-nethyl-l,2- butenediol-B-one u on intermediate, while seeking e prewetive route for .1191 eubetituted glycerol. which employed reedily mum etert- ing neterielo. Although the well yielde were low, the menienoe or obtaining the initial mount: outweighed this teotor. 'lhroe inter. nedietedimrdrwketmeemeobteinedtorthetiret tineby thin procedure, unholy, E-netlvl-lfi-butmediola 4-0”, 2~nethyl-l,2-pentene- diol-J-one, end 2-etivl-l,2-bntmdiol—3—me. Colonge and Out prepered an um um: in the following m. m... eatureted bet-lie eloohols were eynthoeieed by ellowing the We“ hetone to reeot with inflame, using ethanolio eodiue Maxine u the oetelyet. Fer Danie, 2~netlvlhutenol~>me we: W fro- the motion of . .Wl ethyl hetone with forulcielvde which wee then aerator-ltd, enplmr- ing iodine es the oetelyst for dehydration. Colonge end Cmet obtained vinyl intone: in 63-35 per cent yield: by this procedure. In the enh- eequent stamina-our ecidwu eddodto themtmetedhetonu in e Indium dirvdrogen magnate-chlorim uixture at O“ to 5°C. me chloro- I'Vdrins wore then Wound to the oorreopmding dihydrooq heme by refluxing in e potouim clnrboneto eolution (or two to three home. The W ketonu produced were were proportionally unstable with en inoreue in Ioleouler weight. All were oolorleee at first but -!J_l I ' 's'“ I". 51‘ 1. v 1' Fir—I " “SEX". 2 tuned brown when exposed to the sir. In smry, the following series oi‘ motions wee enslaved for the syntluaie oi‘ dihydroocy ketonest m” mag-oxzmflfi.» : R—c—g-ai; C]. 0 on 2‘93...» R-C-g-GilOH 499:...) xii-fig: In the present work, 2-mtlvl-l,2~butanodiol-3~one was prepared by e procecmre similar to tint described shove. In this methyl isOprOpenyl ketmnwaspreporedbythe lendeusndlrerveethod (2). This eubstenoe as then hydraxylnted directly to the dimldrmqr mm in Mimi-chin“ osnim tetroxide nixtm. Ibis hydrooqylotion or methyl isopropenyl mm was en echptetion (3) of the procothe'e need iv n. o. 1.. Fischer 3;; L' (h) to prove the structure of butane-Lh-diol-Jm by the oxide. tion otnothyl vinyl hotone. me procedm‘e for equems canine tetrmcide- eodiun chlorete oxidation: or organic compomds was introduced by K. A. Horn-n in 3.913 (S). The suggested course of this reaction is sham by the following muons: coo. . R-Oi-Gfi + HOH .......,. mag? . 0:03 0303 + KClO, ----o- K610; e M. 3 0803 '. KCIO: ---—-o KC! “ 3 030‘ By thie prooeduu osnim tetmide cen be used in oetelytio enomts. the purity of the 2-le-lfi-butemdiol-3—om wee minted by «nation with stenderd periodete end detereinetion or the periodete connection. mmuxncn TO THE REAC‘UQIS 01" W KEMES ‘ The reections or 4W ketcnes hewe not been studied «mum however, compounds structm'elly similar to 2-netIvl-l,2-butenediol-3-one have been subject to men investigetion by s. I. Denilow end oo-worhers. in generel, the mum group studied the transformtions or o-hywdrmcy eldolvdes end ketones resulting {rm the eotion of dilute ecids end been. iletellic inrdrcxides heve been used es cetelyste in W ones. For commie, l-lvdroey-i-butmone is isomerised to ecetoin by hosting with equeom lend oxide for ten hours (6). Biecetyl end ecetoin ere toned in 26 end 18 per cent yields respectively by hating n-hy— Wtyreldelvde for 8.5 hours with 2 per cent cums-1o eoid (7). lust-sue other trendoreetions of e sieiler netwe have been effected (8 _I.b.c.). nominal. Procedures l. The promotion or rottwl-iwpropenyl ketone tron methyl ethyl ketone end pereforneldehyde. Freshly distilled methyl ethyl ketone (350 9., 5 mice) end pere- l‘orneldelvde (30 g.. leole) werenixed ineM-neckedtleskequipa- ped with e stirrer, rei'ltot oomienser, end thermometer. The Claw reeotion mixture was heeted to ILO°C. end 3.5 ml. at 0.5 II potessim hydroxide in ethenol us ended. The solution wee stirred end the tuner- etwre ninteined beta-teen to and 16°C. After the reection sterted, no heating wes necessary, since the motion wes exothereio. Cooling with tepweter wee sometimes necessery to prevent the motion temperetm-e i‘rceexoeeding the euggested temperetune epreed. Intiveto teneinutes the reeotion solution oleered beoeuse of the depobmerieotion of the perelomldel'tyde.‘ The reection wee oomlete in ebowt one hour, es evidenced by e negetive test for fomldstgdo with ‘i'ollen's reegent. Melightucessoi'elkeliwes thenmutreliesdwith lel. ores eoetic ecid in eethyl etrorl ketone. The excess methyl ethyl intone wee renoved by distilletion. The mime, crude R-eetlvl~l-butenoI-)-one, wee treeted with 5 ll. of 85 nor cent phosphoric ecid (1.87 g./al.). 0.5 g. otoopperpowder,end0.5 g.othydroquinone. nueixturewnsheeted to lib-125°C. end distilled in e streen of nitrogen on. lhe eetlvl isopropem'l ketoneendweter leyerswere eeperetedendtheioetonewes dried over nemesius euli‘ete. The eetm'l leopropenyl hetcne wee then S redistilled, end the uteriel distilling et 96-97%... et eteospbcie presume, collected. The yield wee h? 9. or $5 per cent of theory. lbs shove procedure wee repeeted mo siniler results obteined. 2. The caldetion of methyl 1W1 ketons with osnim tots-oxide A solution or 30 g. or oodim chlorete, 0.15 g. or oseiue tetra!- ido (Cautionl Hoar eirtight goggles while wein or blurring of vision will result), end 1.20 :1. or water wore cooled in e W ' flesh mapped with e ncchanicel um.- and mm funnel ooh. tuning 33.6 g. of methyl 1W1 kotone. The intone was added in small portions to the stirred solution over It period at one hour. After each oddition, the nixtore we: stirred until the «garlic 1W dissolved. The tumor-om m miniained betwoon -1 to 4.0a. by cooling the re- ection flash in e salt-toe mixture. At the end of. the addition, the reaction was stirred for 1.5 minutes, while maintaining the tangereture ustetodabwe. ‘Ihe stopperedi'loskmtmnplncod inanioebox 'whore it was ellooed to stand for 12 hours. The eixturo was then re- Iowdfrontheioehmendellowedtodtandforhsms. Ihemixtm‘e wes or e brownish coloration men raved iron the refrigeretor but be- moolorleaswonstnndingetrooetonperetme. Attheendofths tom period there woe little odor of the methyl ioopropenyl lootone. ‘ihe reaction mixture was neutraliood with potassium hydrmtide solution, observing the neutralization process with litms W. lhe solution hem brown dwing the neutrellation end e colorless polyuric enter- iel precipitated. The mixture was ontwoted with potassium chloride, cooled to 0°C., and litter starting for e while, filtered with eoction. 6 metiltretewes timoonoentretedoneweterhsthstmepressureof the water sapiretor. lt wee necessary to stop the concentration process end remove the precipitated selts. The syrupy residue ma preeipitste salts resulting iron the i’inel evaporation were extracted four tines with 100 nl. portions of boiling absolute etimol. To the ethanol ex- trectwes sddedliOOnl. ofethyl etherend thee-uniting sixterewes snowed to stead overnight. The solvents were reaovedtroa’ this mixture, si‘ter filtering of: the preoipitstod salts. The solvent rel-oval wes osrried out on e 100°C. weter beth, using s water espiretor {or dinin- ished pressure. in. residue, which wes e dork brown m, wes trons- fen-ed in absolute sthenol to s 100-111 flesh, end the ethanol reamed on s. aster-both st the pressure at the voter upiretor. This was done threetinsstore-ovethelssttreossoi’weter. nummthenin e condition comm. roi- “cm distilletion. with the oil-both tmer- sture st 75-80%. end e distillation pressure or 0.03 em, e voter-milk traction distilled st hB-SO°C. The distillate weighed 20 g. which rep- resented s M per cent yield of the amuiyl-lfi-butmdiol-S-ms. 3. Periodste addition of 2-mthyl-l,2-butendio-3-one to detsrnine purity. in milliliters of 0.1019 parapsriodic ecu was pipetted into e supls omtsining 0.01770 g. of the orgenic staple to be oxidised. The mixture wss sllawsd to reset in the din-ii for one hour. The amidstion nixturs was utmted with sodiu- biou'bomtei 5 all. of 0.1315! srsenits all .1. of 5 per cent ”mummified, in the order given. The nature was ellowsd to stend for 15 minutes end titreted to s steroh endpoint with stsndsrd 0.0102)! iodine. 7 Determination of git: 01‘ eagle bx Egiodsts oxigtion and titra- tiono ace cao_0rne. A weighed semis 01' 2-nsuvl-l,2-butmdiol~3-me containing 0.6850 g. was diluted to 500 :1. in s witnetric flask. Mt}! five ailiitsrs of the dilution were pipetted into a 125%. srlenmeyer flash and 150 no. or! soditn sstspsriodats added. me miss were shaken until the per- iodate dissolved. The flasks were covered and allowed to stand in the dark for two hours. Three drops of alcoholic phenolphthelein were added and titrated to a pink color with 0.10300 potsssius hydroxide. h. Acidic, basic, and glycine distillation: of 2-issthyl-l,2-butsnediol- ‘ 3m A sample containing 5.1 g. or the ketone was dissolved in 25 ll. of 1H sulfuric acid and placed in a SO-sl. flask equipped with a three any distillation head and condenser. The flask was heated with s aantls and 15 al. of the distillate collected. Extensive polyuriution todt plans in the flash with the tomtion of s white poly—r. A sample containing 5.1 g. d! the ketons was dissolved in 25 al. of 0.114 pot-assh- Wide and 15 Iii. of the distillate collected. ‘ihs solution in thsrlsskhscasssrsddishhroanwithssull mints: precipitate present. . . A sample containing 5.1g. 01’ the ketone was dissolved in 25 oil. of 0.114 glycine and is al. of the distillate collected. The solution in the flash timed a light pink and a nail mt oi‘ white precipitate its present. 8 S. leitstive detersinetion or c-dicerborvl canpomds in distillstes To the distilletescollected shove were edded l 9. or hydroxyluine hydrochloride end 2.9. 01' sodium ecetote lmirete. lhcse reaction mix- tin-eswensllcwedtostmdstroostempersttrstroativetotmhms to ensure the cowlete (oration or the dioaiiaies. The mixtures were saturated with sodim chloride end extrscted five tines with SO .1. por- tions of ethyl ether. The octrscts were comm end dried with segues- iue mm... ‘ihedher use removed by distillstion, with the lest 25 .’ per cent of the distillstion under disinished pressure to svoid over- heeting the residue. The residue wee equilihretsd with i ll. of wetsr by tuning the mixture sliditly. l'he sixturss were filtered, end the spots of the filtrste applied to mist-en Ho. 1 filterpsper for chron- stogrsphic espsntion. The paper wee pieced in weter seturstsd l-hep- tenol, end the solvent sllowed to rise by ssoeading chroutogrsplv. 'ihe filter psper wee dried before en electric ten, without hest, end sprayed with e 3 per cent solution of nickelous enlists to which wee eddsdo.lsl.or2Bpsrosntmonispsr lOOel. 6. Quintitetive detersinstion or c-dicefiotvl cospoeeide The wtitstiwe procedure was mutated as follows: A weighed suple (epprmiieetely S g.) 01' 2-.tivl-l,2-hutmdiol- J-ons wee dissolved in 0.1!! potsssius hydroxide or ill sulfuric ecid or 0.13! glycine end distilled. ‘ihs distillate (15 IL) was collected in sgredutsd tube. lhsoodicsrbavls i‘ornedwere oonvsrtedtothe di- 'mineshyeddinglg.lvdrowlsninelvdrodiloridomd29.otsodim sostste hydrste. The dioxins were precipitsted es the nickelous 9 comlexoe end filtered, using e eintercd glass crucible. lhe precipi- tste wee dried st lie—120°C" weighed, end bested in concentreted nitric scid to oxidize the organic portion of the molecule. The scidic solu- tion was evaporeted to near dryness on e hot plate, diluted with weter. end the nickel precipitated with s l per ocnt elcoholic disethyl gly- axim. 'lhe insoluble nickeloue complex of dinethyl glycerin wee {liter- ed, dried st 110°C" end maimed. lhe per cent of the glyominee in the originel mixture can he rm by calculation. The detereinetion of the nickel ei‘ter oxidation with concentrsted nitric scid wee es follows (9): The residue was diluted with 10 ml. of weter and amine roidroocide eddcd dropwise until slightly slimline. It s precipitate forced, eman- iun chloride was added to clear the solution, followed by mime try- druids to mutt-slim the scid. The solution should remain clear ei'tor this treatment, otherwise the amnion chloride modded until u.- seupls would remain clesr. The sample wee heated to boiling and the slcoholio solution of the diesthylglyoxine mono untilths reegent wee epprooiisetely seven tines the weight of the nickel present. Anemia: hydroxide wee now edded until s distinct odor wee present. The six- ture containing the precipitate wee heated for 15 to 20 nix-sites before filtering. The precipitste wee dried end weighed. Monte All reegente used in experimental procedures were of c. P. greds. W A high vecuue ”Como" m wee used for the vecuin dietilletion. A distillstion heed designed by tr. J. C. Speck, Jr. wee used in in the dietillstion procedure 10 RESUL‘iS A‘n’D 1315055169! The preparetion oi‘ 2-nthyl-l,2-butmdioi-3~one by the oxidation of ntlvl isopropeuvl hetons has been carried out in 112 per cent yields. The product prepsred by the uthod outlined m is or high purity, in the order of 98 per cent. ‘me purity was determined by ooiidation with stsnderd periodete end titrstion of the concede with iodine. The results are tabulated in m1. 1 below: ' TABLE- I W" ‘°" mm... 1.333;... . 13“.; SW“ “h % MW :11. :1. n1. 9' 1 10.00 5.00 _ 25352 0.01770 A 100.80 2 10.00 5.00 25.15 0.01770 100.00 3 10.00 5.00 2h.85 0.01770 91ml. Aver-9o "9??? __ fi— W W A second esthod for determination oi‘ pin-ity was stteeptsd, using sodium estsperiodete es the oeident. The ecetic scid formed wee titrated with standard sodiue ivdroniide. lhs procedure mire high results, indicating greeter than 100 per cent pititar of the semis. heed on the first detcrninetion, the results were 12.7 per cent too high. Table 11 indicates the results. It is quite possible that the formaldehyde present in the couple mdcrwent the cemimro reaction and was subsequently titrated. 12 man ---.-.-- 4—.— Samle Sodium Time in Std. Acetic lo Hillimolee Fates Hrs. Base Acidle 2 X Purity ' perigggte Ml. Hillimles 1 0.2910 150 2 6.30 0.321. 111.6 2 0.2910 150 2 6.20 0.320 ' 110.0 3 0.2910 150 2 6.30 0.327 112.1. Avenue 111.3 ._v iv Acetyl prepionyl end 111le uere detected in the ecidie end he“: dietilletee by urtreetim with ether, dietilletian at the ether tree the ample, end the deter-ninetim of the e-diarhenyle by citrate- grephy, ueing water eetureted l-heptenol for development. The bieeetyl gave a pink spot with at value of 0.91 end the eeetyl propionyl gave edeepyellae epotvithfltnlm «0.85, m the cure-eugenics wed with 3 per cent nielneieus eultete. ‘ihe 'quentitetive dens-nineties: of the bimetyi md wetyl prepieqyl in the distillate employed the retention of ineoluble nickel-9W1. mime. In gems-e1, m bieeetyl then m1 propionyl w W in the heel: distilletim, while more e0etyl propimvl than biecetyl an produced in the ecidie «humus». 111. 9131.11: distillation gm only bieeetyl, einoe enly one spot, corresponding to hieeetyl, acme-red when the distillate m clmtographed. The results of the determine. tim appear in 'ihble III. 13 TABLE III 5! Diet '11. Ht. 9. g. ' ethyl glyoxine Hi complex 11 eagle: Acidic 5.127 0.0171 0.0160 3.97.71: 10“. 1.62 x 10“ 70.8 29.2 ‘5 sum 5.0869 0.0151 0.0119 1.12 x 10“ ““1 '1 1° 1” 56.2 Glyeine 5.057 0.0025 - ~.-‘ - -- 100 Method of Calculation: let A - termle weight or nieheloue eethyl ethyl alumnae. bet 8 - female weight at nickeloue dinetlvl .glyatine. let H‘ '- eolee of nickel” nethyl etlvl om. Let 33'- mice 01‘ nichelewe dieetlorl glycine. Let [5 '- mlee or nidueleue «ii-ethyl glyaeiee, in the eeeond precipitete (U3) ’A‘ O 338 O U. 0 NAB 9 .33 '3' ‘ 3&8 131:3) - iii-w, Simple Cllculetlau w 4 - "A . i i . 00ml! . Gem! . 3.92 x 10 5 -s m _ EL” .0160 - 3.921110 A . " 5051‘ X 10.3 " 3.92 x 10-.5 ‘ 1e62 X 10" x 31mm ”W1 cum 913mm gig": x 100 - 70.8 1 z Bickeloue 111.com glyouine fig; 12 100 . 29.2 x The admire tor the {oration of the e-dioermwl made from 2-mou1yl-l,2-butmediol-3m bee not been studied. Below ere given some uohenim which my be poetuleted (e) Eerie distilletion with the {creation of bieoetyl. 11. 0. 1.. Fischer, 9; g. (1.) prepared 1,2-mma1o1-Jm by us. following prooedmn fiim). mag-C320" * 911° é=5= msggf'law I! we enu- the medulla in e genenl hue-«tweed eldol condem- tioe, we w postulete e eieiier neon-hire toe the eetieo ad 0110111 on . z-uthyl-i, 2-Welc3-oae. ‘ihe {oration e! the eoetoin mice is initieted by e retrograde eldoi ooedeoeetioo. 2 15 (h) 04,-3.ng * 1/2 0‘ —-----p Diva-84113 ‘ Hzo In step three, the eoetoin oerbenion reects with water to m we- toih, which ie oxidised to bieoetyl by the oxygen in the eir. (b) Basie dietilietioa with formation of eoetyl propiowl. (1) (lb-Brgalzw e (11" -_-_'-__—--7 dis-$1011 e HOH 9 3p 9 a ,. (2) 013%., 2"“ deny (3.3%; t OH {I (3) CH: .. 3w 0‘3 1013 Initieny, there is e mieophilie etted: w the Wide in. Realt- inginthetonetioooteeepatide. A _ etrone withtheni i done i woe-e eeetl ' i i. m. leewn e of the , f i r be 1111th water. A theral cleavage is eleo possible. An eltermte petiom my involve e melanin sinner to the pimeol-pimcolone wt. (1;) Midi-o dietilletion with the rotation on: bieoetyl. ‘H m .2 ., 0.1%,. 1:, W121... # (2) 61:.5. (JR-Ema! <--—’ card gaze“ 16 m “LEM 1.; mafia... .12.... a... . H+ (1;) W32" 3% mafia-Q13 ° 9 (5) 013-5 - (TH-CH, + 1/2 0, --——--«> dis-c - 0.013 + 3,0 OH . ‘ihe eddition of e proton to the cerbonyl oxygen, with the subsequent {oration at resonance hybrids es in step two, is the generelly poetu— . leted secheniezs for the production of the initiel reacting cerbonius 1m in en ecid-cetslyeed eldol condensation. The eoetoin enol tewto-er is produced in step three by the loss of e protoneted formidehorde. Aoetoin is then oxidiud to himtyl by the oxygen in the sit. (a) 11.21416 distilletion with 11.- formation or ecetyl propiowl. In the trmsfornetion of 1,2 glycols to the corresponding csrboro'l W, it hes been sham (10) thst mil snomte of eponides my be toe-nod by the eotion of strong ecide. In dilute equeous solutions, they ere subsequtly hydrolysed. Epoxide internedietes ere poetulated below for the (emotion of ecetyl propiorxyl: 4. O OH (1) 013-5 . £311,011 . 11* ===—b 0-13-13 . £311,011 O . 011 (2) 013—3: - £31,011 4—-—----o my?!- £51,011 (3) (11,- gi’ijéxon -----—-6 013-2“. €131,011 H «I» (L) 011,-?» $311,011 16., cuf- gig/31331, - ”SH, .49.... .3/ 1-?! 9 01,-0 - g-a-lpx, 4—? ca,-c - 8,411,011, + 11* 17 (1) (2) (3) (h) (S) (6) (7) 12mm J. Colonge end 1.. Onset, Bull. soc. chin. Frence 838 (19117) E. ’0 W.“ 1nd Be Po 1w. Je Org. Chas 2:2." 1‘22 (19h7)e J. C. Speck, Jr.w, Umblished work. H. O. l... Fischer, 3. Beer, H. Pollack, and H. Nideoher, H.1Ve Chilh Mus E, 1217 (1937). 11. A. Harmon, Ber. 9.6.: 1661(1913). S. l. mnilow and ll. 5. Tilmonirowe-Sidorowe, Zhur. Guhoei Khie. 23, 1.58 (1951). E. D. Vems-Denilowe end V. F. Kseinirove, Zhur. Obshcei Khin. 3Q, 2099 (19116). (a) (.1) s. 11. 0mm end a. nuns-mum, Ber. .6112, 21. (1931.). (9) ( 10) (b) S. I. Denilow end I. S. Tikhooirove-Sidorovo, Zhur. Cbshchei 11.1.. g, 153 (1951.. (c) S. H. Milov and E. Vows-Milan, Ber. 92}, 2765 (1930). U. E. Scott, Steward Methods of Chemical Analysis, Vol. I, 5th .de 90 620, be m 308m Co" u" YMe C. U. Porter, Koleoulsr Reorrsngemente, The Chenioel Ontolog 00., How York, (1928), p. 90. References given. (.1ILI‘r-HGAI. STATE UNIVERSH Y LIBRAR‘EE, ' 1 “g: 1' ,. i l i f ' t 3| ' l I 3 129 3 031461910 ’1 l l