PREPARATION OF A CYCLIC DIAZO COMPOUND BY COURTLAND LIVINGSTON BUTLER B.S., Pennsylvania State College, 1920 THE LIBRARY GF THE ray 99 1098 | OV By ih 36 UNIVERSITY OF ILLINOIS THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN CHEMISTRY IN THE GRADUATE SCHOOL OF THE UNIVERSITY OF ILLINOIS, 1923 URBANA, ILLINOIS SS SETAE OP SOE LER TT NSA ONIN wre ay. J a ie, an j ¥ ‘ ‘ ft aN 48 a nlams , Pita PET be Bos LT | i a ACKNOWLEDGEMENT Thanks sre due to Professor #. A. Noyes | for suggesting this problem and to frrofessor W. A. | Noyes and Dr. ©. 5S. Marvel for helpful suggestions | | | | received durine the course of this work. i 4 | {| | | | | a | | | | | ‘| 4 s| be CA w, SAL Ss &49994 I. Il. Til. IV. CONTENTS INTRODUCTION woesssvee cece ane eenwevesecens PROPOSED METHOD OF PREPARATION ...ccesens EXPERIMENTAL .....--00:5 bevver sean mer serene CONCLUSION con esccccencscvesvcevensesescee Page 1 3 7 11 penance RE ST eR TRS A ETT ES STAAL EST TEs | — YAR EA MED SRI MPR SE APIS NN HELA PR LESS EAE EEL EH Digitized by the Internet Archive In 2021 with funding from University of Illinois Urbana-Champaign https ://archive.org/details/preparationofcycOObutl 1. INTRODUCTION Several attempts heave been made to prepnre optically active diazo compounds, with the sim of throwing some licht on the nature of positive and negative valences. CG. &. Marvel with We A ° Noye gh several years aro attempted to prepare various active diazo esters and failed. The only evidence of optical activity they obtained was this:-- on treating certain active amino ester hydrochlorides with nitrous acid, hydroxy acids were obtained which had &@ slight rotation. If the reaction goes thru the diazo stage, this is evidence of anasymmetric diszo molecule. HK. M. Chiles, with WwW. 4, Noyes” two years after the work of Marvel and Noyes, pub- | lished #® paper describing the prepsration of opticrlly active diazo compounds. Pive or eix were prepared in all. They point out the extreme exse with which these compounds racemise, and worked at low 3 temperstures and pressures to prevent this. Levene, in an article desling with hexossminic acids indicated the possibility of opticsll | active diazo compounds. He later reported optical activity* in the ease of diazo succinic ester prepsred from dextro scpartic ester, and in the cxses of the chloro and bromo derivatives prepsred by the S. Marvel with W. A. Noyes, J. A. GO. & 42, 2259 (1920) M. Chiles with W. A. Noyes. J. A. G. S. 44, 1798 (1922) A. Levene, J. Biol. Chem. 36, 89 (1918) A. Levene and L. A. Mikeska, J. Biol. Chem. 45, 593, (1921) " ” J. Biol. Chem. 52, 485, (1922) ange as re i Lei Pm Wie 0 Be eieieeeaamiae - : faa mead : ais we, 44 : ~ | = - +» “ ee Sa se ee grrrRe (vA) ‘yt — = + ie any VAY 1 ) f wtestose: ili a Le aetna a ae “ ru - * ‘ » 5 ‘ . fr ‘ a Ae ees PRR LIe E arate 4 y bea vekee “ate aati | Tee a Hire ong ibe: PANS | tat gil a) BA iS A io ame gee eae Reva ai ‘deen Dw et aonae ee Ho iy wok te it: HL Sy at mit + 16.08 i attain: tf ‘fbb at, ean oh * its ett oh eae fami fee ta on i a ; + ; ote * aT a na 2 rs heab A i ; Mae . 7 Af Uk | a: i 4 : a Li 9 sl Pt ah ed ’ “a ie ca, ; ] nie, . #7 ‘/ ; ea a : ‘ vf 4 { APa I 7a} | ‘ a 5 ' . : ‘ . 7 7 } fe nm teow eed haat a Sanege A ad tty vy wt) Wendl rh mga swale Pees =f pave b dt ‘ v. : ape pee it) ne ae ea % Cus wy mp es Si ‘thew: ‘nett bee’? au #4 obs tat bso ‘ead, Pad < Sole? Bese nach ebony ; “a moo 8 A Aa dabtsegit oy 2 . | ee O30 ,, eee : Fey plies : Gist} siiivgenoe ne xe “owih.twe ay ‘<¢ ¢ “iy > Fo 9 ans oe “sagan a on + 0) ry: 4 ore cick gM gost @ ey i y rs tw. ‘eaae TOEVOT! OF SOU eee hat Rewer ee ohial lise bialanwezed ar Ma ie bes me o Phe esa. tee a TT 2 ‘Pw oi, f aly LO> 9h PLU LOSS on.o.8) 20 & we Bit ahs ° » - oem Law orvatdent nid Sh Bien inte ae F ee eo ed oe mrt See ee fl oy Faw'svdt ae a | ' iy ,+ ad ia parr r ai a y action of HCl and HBr on the active diazo ester. Levene then attempted to prepsre * erystslline diazo compounat or 2 crystalline derivative of a diazo compound which would have 2 high rotstion. He succeeded in prepsring 2 bromo di-ethyl succinate by the action of HBr on ethyl diazo succinate in ‘ very pure state. This com- pound gave a rotation of about 60°. Levene showed that this high rotation could not come from any impurity and claims this is suffi- cient evidence to show conclusively that the carbon atom of the diazo grouping is asymmetric. All attempts thus far in this field have been carried out in the open chain series of compounds. It wes thought that a cyclic diazo compound mircht possibly be more stable, and that being & heavier molecule would be more apt to be crystalline, and there- fore be more lisble to sive positive results than an open chain diazo compound. It was decided to try to prepare 4 compound of the structure This could be eslled diazo (2) cyclo hexanone dicarboxylic ester Pied} « lp, A. Levene and lL. A. Mikesks, J. Biol. Chem. 55, 795, (1923) ae oe. het hy ae - Ww j f 0 y Au . a we i ni Wi Pee NOs | ie Ones arlene ene eet mes “ee 7 ‘ ‘A ee re nade td ot re0ky L = aad +e , ¢ If. PROPOSED METHODS OF PREPARATION geveral methods of prepsring dizso (2) syclo hexanone mR ie COpH ao oH Hp 5a NE, Ae H» HNHGOC .H,. dicarboxylic exter (1,1) were a vs Sr CN 202C2i5 OoH gs COpH C0 ,C5Hs HNHCOCgHg =- Hy HIHCOC .H. HH» Nog Ae 2 tvis2,6 v Resolution of VI to s pure ad or 1, form OeCoks COoCpus og =N=N &e HKeduction of methyl eslicylute to the hexs hydro compound oxids- tion to the ketone ester, which would contain an active hydrocen atom; subetitution of -c G OR by means of codium ethylate followed by chloresrbonic ester; treatment with hydroxyl smine snd reduction RRNA NS A ELAN INLD NON NE le asear-Sohn, Arbeite Methoden furoreiniseh-chemische Laboratorien, 1907 ed. pp. 362-265. ey A, Noyes, Oreanic Chemistry for the Leboratory (1920) »o. 205. by Js VOn Braun, Ber. 42, 859. (1909) oe oe «DPF: * ey : 7) ) of the oxime to the amino compound; resolution; diazotization. 3. Reduction of anthranilic acid; bromination and preparation of the Grignard compounds; treatment with COg to form the dicarboxy compound; resolution; diszotization. 4. Condensation of delta brom valeryl aldehyde with melonic ester and preparation of the diazo compound from the ketone dicarboxy ester thus formed 2s in (2). 5. Condensation of pimelic ester to hexa2none carboxylic ester and subsequent treatment ss in (2). It was foreseen that the preparation of the compound by method (1) above would be difficult when it came to putting in the second carboxyl group. There is chance that, on trestment of the brominated hexa hydro snthranilic seid with KCN, HBr will eplit out giving an unsaturated compound. There ®re two possibilities ss to which way this reaction would go -+ C oH, oH rs i ¢—cOoOoH (2) O-¢ OH-COOH SHCOOH | si | faa Ras | JN, C-NH, O=NH+HOH C=0+NH,, oh, on, Co This could be checked up as follows:- If the splitting out of HBr occurred as in {1), the carbon stom to which the amino group is attached would still be asymmetric “ni work on the compound could be continued; if it occurred as in (2) an unstable molecule would be formed which in water solution would react as indicated sivine the ketone 2cid. Work on this compound would then have to be discon- tinued. ae ne ie YR a >. a ) a \ ; is v <4 ono tie alterna ‘ad ditenes pias: seen toe ta: 62. Max i , f ‘, by ‘ : iy \ Py i 44 ery i piv ire bar Ko Leeper sd, : pit trauddce 26 pie: Another difficulty to be expected is the fact that hexs hydro anthranilic acid is o Pamine acid and is therefore apt to lose NH, very easily. | If work must be discontinued on derivatives of hexa hydro anthrenilic xcid, it is proposed to sttempt to prepare similar -gompounds stertine with m-amino benzoic cid. This compound on reduction should give 2 gamma amino seid, which would be more stable than the beta acid. After substitution of the second carboxyl croup, the diazo | compound might be prepared by the method of Gurtius* or if this failed, by thet of Oppe” since the gamma acid should easily close the ring and form a lactam. From the lactam a nitroso derivative could be prepared which on decomposition with slkali should yield a diazo compound. 00H S00 COOH / COOH a va. Che— CcH;—C | ° ~ ure eee | et iin fe 2 | ooon | | ay | | -— > fa | Pe. ‘ j iH, Hi, CH, oHy » CHy ole | —> te CHy | | | fae | | } aaioncmmnicine ee’ saaee a : —- N— Ns l, _ ste i co H——CHNH, CHg——-CH-NH = Cy —-GH—-I-N=0 OH —Q =N=N In attempting the first step in the prepsration of the compound VII shown on p2ge 3, eatalytic reduction of anthranilic acid was first tried. Platinum oxide wae precipitated as described by Adams and VYorhees” to be used as catalyst. This method eave 1 assar-Cohn, 1907 Hd., Part 2, page 227. e oppe, Bere 46, 1095 (1913) S,dams and Vorhees, J. A. . 3. June, 1922. re i i Sq ‘ es Bao ‘" i : yy i i ia i Fs ; Fe : Bi Pak sta 7 «i= negative results, the reason probably being that the conditions most favorable to catnlytic reduction were not determined. The method will later be studied more fully. Reduction by means of sodium and amyl alcohol was found to be a2 fairly satisfactory method. Ginhorn and Meyenberg* reduced anthranilic 2cid 2nd claimed to have obtained 60% of the theory 2s hexthydro anthrenilic ethyl ester. Carrying out exactly their directions in regard to the reduction but isolating the benzoyl derivative” of the reduced seid instend of the ethyl ester of the free acid resulted in yields of from 8.6% to 9.2% in several runs. If the sodium is added rapidly -- within half en hour for a run of 10 geme. -- instead of over & period of three hours as directed by Hinhorn and Meyenberg, the yield is incressed to from 40% to 50% for 10 gm runs. Subsequent runs using 25 gms. 2nd 50 gms} of anthrenilic acid gave yields of only 30% 2s the benzoyl derivative of the reduced anthranilic scid. : This is as far as the work has been carried starting with | anthranilic acid. A little has been done on catalytic reduction of methyl salicylate. This compound gives = mixture on catelytic reduction. There was not enough reduced material prepared for separation and identification. It is possible thst after reduction water splits off giving 2n unsaturated compound, which in turn is reduced making the end-product methyl ester of hexahydrobenzoic acid. leinhorn and Meyenberg, Bere 27, 2470. fzull and @ernsheim, A. 295, 202. Jphleynnieme aes eres oe Vi ‘\) \) AKAM % =a —— nasciat Micicom! Auta! Sad gan tone 9g Bihed Oey inanaerialit nit ders nd OB Rude oan se benudiey oidytatnn, at began iie>D oven tebteata pd aaa, tee hs or salad = ~] ee ae nei se aie Lodeg tin Tym hes wehbe 59 sila ae ankten tes. nt ee, fedngy oe! A eyo me «hal pou ee date tga eeeiet se | | : Am f oct yn YOR. Bente do awegoue. Bentatea chem #hee pitisesgiar i DED Gare Siew. rg Bont “wien: fetta EST Cre T ornhyAies ae x { ae Abatatnad Bed redtonbes oct! ce biting Ot wd anmteauges a “4 ‘ (ated Peg ty, bas. De han eared Rip a f pas hit mete Be Ser store dciade iaeveruy Bh 2.7 Orgs mewd, be. nifaty. ne Deli NSSE Dink sort: Wey Ant ney Rad atte we er hices Sodbe wba Rios “4a> bya | Swell 4 thhuw es s40a Yo beedhalews soma), Of weve ft Seared Hr Biwi owe ow vive eat Ace .@ ronesn fa ii # P | . “: ,ikev. ef! Sraitee pou P ee Hone SR et mV 8e eed water edd we wh: On at DS Eee sh itea.'s EIt 7 a a - tee a SC Mbrecivew extysctob wo ecop ee eee éfoard Wohi arr fst4e co etwhedes « Bands hate Sats uae é ‘wate Sea RLU yay, Hg a ho taiknonl FARA OE beoctor sla take ROM name Hiteh hie tes eae sod pe Feaa La In mey oe. 92 | sae Tam Dip bea wo | 2 SOT abd tata ie isco ine Ra hem: iad aaaie tte aaa ixhiteet hip ties witwr eee ee oe eee eee ee eee re + omen rmtnamean i sD wis yt hs | | ; ': — : ee. ee ee er rs iL. - * iy a ee a — =" +> i . oy s f rinpseestietcniee etsy see cireeon cease te oe q , {4 : | 7 "7¥ Ries a eee ji , it) ® ian oi Lape (uy) Aw eee thi ue Oh te Ae AR ey! be f a -7~ Itl. EXPERIMENTAL I Preparstion of anthranilic acid hydrochloride and attempt to reduce this compound eatalyticslly in water and in alcoholic solutions. Anthraniliec seid from stock room 100 ems. Alcohol 400 Ge Gs This solution was digested with animal charcoal and filtered. The ae solution was then poured into 2 liters of cold weter and the an- thranilic scid thus precipiteted out. ‘The precipitate was filtered | and dried. | Recovered enthraniliec acid 83 ems. The stock room anthrenilic ecid is thus sbout 83% pure. To make the hydrochloride, purified anthranilic acid wos dissolved in ether and precipitated out with dried HCl gas. In the attempted reduction, the following rune were mede. the time for 211 runs wis twenty-four hours. (1) Anthranilie acid hydrochloride, 0.1 mole = 17.3 Gms. Water 100 Ge Ge Catalyst 0.20 ems. A% room temperature, with hydrogen at 25 pounds, no change in the resding of the pressure gauge was observed, hence there was no absorption of hydrogen. (2). Anthranilie acid hydrochloride, 0.1 mole = 17.3 gms. Water 100 Gs. Ge Catalyst 0.30 gms.e No absorption of hydrozen could be detected. Epael Rete EW. eee rah, we ti !( i iy ee Dy. oa LAER. am ao. oa a Tate ' =~" —— er ee, * Le ~ io ‘ yr €52 Foce a2. Ba, ee oii ah aKiae una Yoo ‘ ; i ' {?; i Pr) rary Pp ‘tTolve py ae oe OF Us: * . ; b oi fin t7o botor ta toony.o8 tooth 10 seri ’ - a) see? 2 ; wu : , maw t ' ie HELIO? add ,wekrpubex berqueee ee, ae Ree : y Seed Wel (laget, OPH AOS. Th, Set. one | Ce a es Ma £D shitsb Tay hk Sige eas tatsiaah (Lae bined Nb ac oo == ‘ sieidy ih jes eee srvikeitaile Pern Shiaiio wh, whet OF s doy basen 3 te wna ose 4 mori Gee — eS RL Leia a i « >= - ‘ ae ee ee ee oy A — Me le bs ceyorrtnt % wetoiteon od, Ot RO, ae B TAP @' sey. Le! i ol ters d ‘Y (Ob hyo Stems see lor ested GO Wad renee sauew pil Ay. etHaRerm, odd te atthe ade: ax... oa itt ae * es $a - eel » oir 4 4 ip ran : +) i y f a a > ' ree i» se y | 6 i A i P| y, | oy A ¥ at a ee . i ay ae : 7 yeh ° iy es re bay ’ a} ; e (3) Anthranilic scid hydrochloride, 0.1 mole = 17.3 ems. Aleohol -- 95% 100 co. «a. Catalyst 0.25 gms. No reduction. Il Prep2ration of methyl anthranilate hydrochloride and attempted reduction in water solution. fhe hydrochloride was mede 2s for anthranilic acid by precipitation from ether solution with HCl eas. Runs corresponding to those made on anthranilic acid hydro-j chloride were made, 411 sivine nesative results. Lilt Preparetion of Benzoyl derivetive of hexehydro snthranilic seid The materials ond proportions used were those of Binhorn and Meyenbere. Anthranilic seid 10 ems. amyl aleohol 400 Ge Gs Sodium 52 2MSs the anthranilic cid wee dissolved in amyl alcohol in a one-liter round bottom flask, connected with » reflux condenser, the solution heated to boiling #nd the sodium sdded as fast as the resction permitted. The mixture was refluxed until 411 the sodium was digested, the time required being about one and one-half hours. The amyl 2lcohol solution wes then extracted with weter to remove the sodium sslts of hexs hydro benzoic, pimelic, and hexs hydro anthranilic scids. The alkexline aqueous solution was extracted with ether to remove amyl alcohol, and the lsst of the TT peat ae baer, ap A amet 87 he ‘whe tt: akan! ry nha * | ee eo, ; : ae ’ , ‘= i . * . i 7 n as led . “i ne = - . . Betgesied Bae wtpiaidoediew aval iessdsae sh side +6 settee ae ‘ sity: : ela si ot OF Hiek ell sadsistys. 16} ge ehie we ahises¢ oor f une . Vea ; si Be: AP ee ge ltatom ito me o% ooieht ME QeP YS: DAR hd! hoesdlpyie: Oo oheln onode 6S Ge angeEseg BARRE ; a 4 ot fae i _—: t < 7 . ad ; ; PLP bape 4 ¢ i; 3 Panty 4 t* é “ 7 I y at 4 oad ott “aie eae Lt a > ‘ F é iy: M A y f ‘ » re J S x 3 4 } 2 dn é aes wet | r 7 * : “ 7 {e Dre é 2.9 rs , *; 2 3 + 4 ts j ao Shr, : fy 6 es re 2 ’ mie SN ; 2s F a , Pe ckle as 4 : A sia Oh er , . a Ps at _) ! 4 Kes 4 7 » urs sa ¥ ait. ie ] ive : aa ap? Ms & va Cae A : i i ; q 42 Wee } hy or fi ee ee te BOA | ‘fedonn: ; ie , sitees St . baat futhpe ae : 7 & a; ease ee me] “yionr IS. 4 rw ° At Qa ont thor fis wai ie eof pat ; “pitex : ae im per neguus seers wood bales soth ONE ee hebhe ‘elke ade tee: pied bied wa Pot ett avltofeail ae aes 2 Ai x ef ae “4 § y - hare ey rn doay a7 ioe 4 bogtinite nd ' ee D4 e tees hy ; eee tS tit.gny hae soto Prove whos ford sick’ oat aseugtl ‘ ey na , , * os eh ) a in. « tetee Atte £asnestes rieitd aed fetta toe. Sosamt kad’ eee i o | F AAs Sores ; F ae La ed : bia: th 7 Goede SO pekeat vited mend $e aston ht dy — i pete fon Beeanee ang hax re ie. {abd as) puah beer, nd eon Hedoare Dye apie ot aE o ¥ a i ey Jf ‘ ‘fi Ba [eee as ¥ iis Tor a a Vite ~~ : . jae a ‘a 4 ni - “ —_ * —_e 7 = ry : oe ny if Gia) "9 ee ie A Wry. i, a Cee i 7 | ti ye a vy. , ether removed from the solution on the steam cone. The solution was then scidified, precipitating the hexshydro benzoic, and pimelic acids, whichwere extracted with ether. The &queous solution was made alkaline and treated with benzoyl chloride, in an smount corresponding to 60% yield of hexa hydro anthranilic acid (Schotten- a4 Bauman Keaction After completion of the reaction, the solution was filtered and acidified, precipitating out the benzoyl derivatives of hexs hydro xnthranilic scid and of unchenzed anthranilic seid, and benzoic cid. The solution was then filtered sand sucked as dry as possible on a Buehner funnel. The mixture of acids was next placed in =: beaker end just enouch boiling dilute slecohol (alcohol three volumes, water two volumes) was added to dissolve it. on eooling, the pure benzoyl derivative of hexs hydro anthrenilic acid (li. P. 220-222°) crystallized out in needles, leaving the other materials in solution. Subsequent fractions did not show any benzoyl derivative of hexa hydro enthranilic acid. Following “inhorn and Meyenberg'’s directions and adding the sodium to the amyl @lcohol solution of anthranilic scid, slowly over # period of three hours gave the following results: Run 1. Anthranilic s¢id (stock room) 15 ems. Benzoyl derivative of hexshydro snthranilic acid 2 oMSe Theoreties!] yield % yield Correeted for purity of orizinal snthranilic scid luassar-Cohn, Ed, 1907, Part 2, 34. 1 Lae aise re » ye EAP ] ea ae ne ar ul . ry wen ae 7 = f Tau ae AS Ti aes A ae a. ; as | aa) Mi ab ik : a ae ] ap wy mm) fh) - 5 4 — aw ‘s ‘ , ae ’ wii. CS se by) e sa ft va “hae So donned punrink er aaa pie paitf Sie ee Wn 8 a uaghlh Wet ypttenstah ee Me patentee i yee iio ee ideo igeadod &ti8 Dud ness nae wedioste i H,bes maw. Loa. B0eN and Re omid + Cron aceite ened ie ~iontin pony (FOP bao Bae Preis. | f\ Rvp #. abi taoeina athe sl vast | iw Achiotee adh ge esenaeee Tenet veertodt 6 tm: onctanng ‘eal oat See: m4, our Taree apne tie: vie qed rr: ots 7a Sonya eae As ae wile Pr at chy 6498 sy, oF z nna wrnent 5a ito hindes Dodende: Puen! oil ei me nvbi nave weyedy 10 kolveg ws 4 goere 1 Afee elgheds sd chalice det he ESA NYS OF Sires ) byaay, inpas pth phen ae ret iimitan Chbieie “be ye eeee ‘Hed pete rece ee ee ee ne serine sever tah hy at ae coe 4% ‘spel ey a sf a Lie SELLS LEE ENTS See ee os i i’ Tae Sony" ie Life atte Anthranilic acid (store room) 10. gms. Benzoyl derivative of hexahydro anthranilic acid 1.4 em. Theoretical yield 18 gms. Per cent yield 7.7 Gorrected 9.2% Anthranilic ecid (store room) 50 ems. Benzoyl derivative hexahydro anthranilic acid 7.0 gome. Theoretical yield 90 gme. Per cent yield 7.7 Corrected 9.2% . Addition of sodium 3s rapidly ss the violence of the reaction would permit eave the following results; 1. Anthranilic scid (stock room) 10 ems. | Benzoyl derivative of hexahydro anthranilic acid 7.5 gms Theoretical yield 18 ems. % yield corrected 50.6% Anthranilic scid 10 ams. | Senzoyl derivative hexshydro anthranilic acid Theoretiesl] yield 18 ems. % yield corrected 43.3% Anthranilic seid 25 ems. 5O ems. Benzoyl derivetive of hexa hydro anthranilic acid 1 om. 23 gms. | Theoretiosl yield 45 2mse 90 ems. % yield corrected 30% 30% - ai) oe amt ane spire a cae aa lad sheers we is iy Kite Ni edey! tinct fw , n ; fl % Pay WER to an pbs sina” i Lak ontenlt one Oe vA eas a i | tu) | Aon Fra ah An vometee us . (geos vrate) abet, eth pave J * i ’ eu Rab hihi cutee wat wilomed. ae lary mab 1 panseal % a fh oF t eg htargon? ‘i. hah di oky, +a ee wrare ‘ hot ro ee beet & ote > ae oat BIB ined Oa. eagrw “Os TE a i } . ‘ F . $ § t bY Saget tua sat ive rifercat ait oT ai relies Yentey Saae og CRN a: 7 ts PL : eet te aw hierivet tinh nt bteke Lewtke oneal ap poteawven $2028 Lie ieee aby vuhhan. etteteced \ | p1eh Tyoatel a :' Or i fed frrtoor ends boatowitee b1 0% dé Wel Peary? hina titer a weir. SO. ovis etre jonni riae Qikbiwdece: wang poke! Lenteveget te cin tren, BFa he at lm, 2 pe qn — - } : fe fiat ah ol ry , y, ‘ : ‘ \ : , is fF rl De b 7 7 1, as i = 7 Wr ; Ya i AST Wh are Cths |) eb Tae a ‘anes f io Lit Ac : i © IV. SONCUUSTON ls Uneneceseful attempte to reduce anthrenilie acid ond methyl anthranilste esatalytically with hydrosen ueing platinum “s estelyet have been mide. Be In attempting to reduce methyl es lieyisate to hexs hydro methyl exlicylate eatulytically, it wae found thet a mixture resulted. Thie wae not separated. Be The benzoyl derivetive of hexs hydro snthrenilic acid was prepared in yields varying from 30% to 60% depending on the amount of miterie] need. fhe method used modifiee thet of Sinhorn ond Meyenberg in the matter of time consumed in the #d4ition of sodium to the amyl “lcoholic solution of snthranilio seid, snd the end product isolated. Diesen jos SEE Sheep reh g Act he meh Am rm eee amen retereteewtatis Feiner errnenaney ; : ' y! e) ” oe Se) Pisce : ‘ , i a il ¥ ras Far ai) 5: als? ia eee ae ay To er ] mere pec tec ain ee sasha bisa ATA Tah Re ‘ ; { . \) i | i