k x .1 ‘931 : 33.5.: a r ’11» (f . . . , . . . . . . . .. . in? ‘ c . V x L (why... it} 51.3343» .13 .. li..f.1k.. x , .ilfi'll‘. . a. Z N; _. 5‘ . 7.: :r (.3 8.11:”... 35:3? g§§§a§a . (“15515 fly I WW n'iiCE--u.,..-. ST/‘(I’E UN! ERSITY an? .i'.::';-:- u:_'rJ..-. 'T‘JEPAI FAST LANSING, MICH If) (u \ sh‘vii'iiki'i 0F Ci‘IEIWSTRY AN I. . at"!!! ;.-.-m¢ ”5“" 'r ' . ‘ .113 R A P ' hilchlg‘qr' 5-14 -. ."‘ UniV'~ ' THE smgocrmsmx AND KINEHCE 0!" THE CLEAVAGE 0F aémmm Pm ETHER BY mmws HYDROGEN CHLORIDE mania A THESIS £5thth to the School of Advanced Graduate Studio: of Michigan State University of Agriculture and Applied Science in partial muimt of the requirements for the degree of DOCTOR 0F PMOSWHY Department of Chmdotry 1957 C1 13?... {wif— ’i A.) m? 5' [a (P a J. g Ammmm mwtmnmwwmmmmuum 150 Dr. Rat-old Hart. for his mum and emtmtiva within: throughout the own of this work . He also mm. to repress his gratitude to the 393mb Corporation fer amen). assist-Anne in the fan of an immunity. 11 m: STEREOUHEMSTRI mm mmzcs 0? m: GLEAVME OF a-Pmmm Pmm EITHER BY mmzzws macaw CHLORIDE BY Raymond J. Elia All LEW? BMW“ to the 3811001 of Advanced Graduate 5m“ ot maximum at“. University at Agriaulturo and Appl‘lod Selma in mm mummt of the mix-mu far the dew af DOOM OF PHILOSWHY ertmnt of Chantry Year 1957 Approved - -eg~—~Q—L-fl-L9¢§/ Amman m principal mechanisms for the alumnae of other. by Wen halide. how ham prop-coed in me put) thoy commas? mm to the classical 3&1 am“: 5212 WW (1) for dioplocmt mono-I. 1:»: 8.3. haw-61v o a: ---> [Rab-at)" Ht" W N H [héévr JAE... 11" 0 was -- 0 ., h . ._ ., b3? 4s +— gtim' -m-h a; 0 UR' (or {aha I") (a:- way) The particular mochanm adoptm by a particular author :19de. on tho nature of tho 1': groups, tertiary 33. group. favoring the 5H1 m print-y or Wm 32 mp: the! 332 path . Tho Itwmoizemicol communal to bo Wad of than mhaniom, mam tho carbon atom ttt‘oohod to the other owgon is aoymotric , are nomination with om inversions for the 5N1 and clean inversion for the £352. 01‘ partimur intoroot, than, no the reported cleavage of Option]: active e-phaswlothyl phony]. other W hycfirogon chloride with m of configuration in the a-phmlativl chloride praduced (2) . It no tho moo of the present investigation to We this elm in more detail} in particular, a quantitative away of the kinetic. and lturooohomdotmy oi tho roootaon unpaired to ho dooiriblo. lainoo-tho onportmontil port-or'thio thooio an: oonplltoo, tub additional lullvlll 3-0 oloumago lith rotoution of oonfignratton huro'hoon ruportoé (3,h). Both was opening": of Moo in whim tho m involved had a phanyl group-ottoohod. The kinetics of thotooootion of cupboarlothy1.phony1 othor'uith hydrogon ohlortoo in tohnono, diamhy1.kotono, ioohotyl alcohol, and absolute ooh ?flfi ethyl aloohol uoro follouoa or oxtooottng tho phenol proéhood ono analysing oolortootrioally. The hinotioa'uoro‘boot fit‘hy a oooonfl ordor onto oxproooions that in, tho rotation.inl firot orflIr ouch oath roopoct to the othor ooh hyflrogoo onlorido. Tho onto oonotnnto . aura rolattvoxy inooaaittvo to solvent, though thqy‘inoroaood slightmr with increasing solvont polarity: , or“ .1 J o _ -3°¥Vifli- flag}? I 11331. goo. t hfl c. diothyl.kotono 2.h1 isobuhyl alcohol 3'13 ethyl alcohol {oboolnto) 3.fi0 ethyl aloohol (?fl%) 5.53 lottoluonh, tho rota was nine rolativoly inooooittvo to tonporatoro, tho mm: activation mow (mm 20" to «3%) being only 3 .2 huh/m1... . the entropy of activation .32 .5 o .u . The Itorooohumiotty of the oloovogo woo axonfinod.1n the first three ooivonto liotod dbovo. Artor ouitSblo corrections were made for rooouiootion of the amphanylothyl ohlorido during'tho work-op ”comm, and rue-mm h 3 tho oolvoh'h, and w the pimp]. and: Wm omorldo mt .3. gm flung-o, it as am flint that cal-mm motion 1W1: gamma: with 919053 mom of m- flgmaflm 11’: mt: Wm. . 3 it to W tht tho Wino: om hoot ho Woo who follow 333 $33.3 m or the mos-3mm: 3...... 33., H ., Deal: / \ 73“?“ . ‘ . i. (.3333 1.... 3;- a ' O 3 *3 31 * 3O amwmwmumammmmnummwm (1} W, 33. 1..., 3:3,, chow. R3333. &. £25 (19%). (2} M. ii. m am, 1:. 50., 3. My am. mo 12' 13?? (Wk? {3) W, E. 31.. ow. Anti-ray, 33. .33., .3. Am. chm. Son. fl, 17-2333 (1955). (is) 3mm, .3. 3:... 3-. m. £33m.5oo.1§_, 433.1 (19533,). ME (IF comma Page mmomanQoo-ooooooooooooooooooooooo-ooooooooooo-oooooooooooooooco mmmfii‘!iQI-OIOOICOOOQIOQOOCO'30....0300OCO‘CII‘QififliiifiloithI Aw Proparatian and Purification os'hhtaoiolo................... ,1. OptiOIl y AGtiVQ Edphanylathy1.AlGOhfiloooooooooooooooo 2. Optically Active o-Phonylethyl Chloride...oo.......... 3o acPhonylothyl Phenyl Ether..............o........¢.... ho Purification 0f SOIVQRtCooooooooooo-oooooooooooooootoo So Anhydrous Hydrogan.Ghlflridaooooooooooooooooooooooooooo B . Kinetic Mmmnto on the 01mg of «doom-um PM hy'Anhydrouo Hydrogon Chloride....a....o..........o......... 1. Apparntusooooooooioooooooooooaotooooooooooooooaooooooo 2. Exp3r1m3fltil.Praeedflraooooooooooooooootooooooocooooooo a) Rate Determination aploying 3 Largo keen. o: Imogen ChloridaoooooooooOM-oooooooooooooooiooo 13) Rate Bowman Using Cormorablo Amounts of Hydrogfln Chlorida ODd Ether................ooo.. 3 . mutical Methods Imoatigatod for the Rate Hamm- manta...................o...o.................oconoo-o a) Titration of Hydroaan Chlflridflocoooooooooooooooo b) Bromination.Procedure..........o................ C) COIOTiMfitriG MBthod for Analylil a: Ph‘flOIQooooo lo The GanarflluPrboednreoooooooooo'coo-coaloo 2o Reagenta.........o......................oo 3. Preparation of tho Calibration (Mn-nu... h. amoral Prooechu-o Hood. for tho Rota Datafminfltianfloooooooooooooooooooooooocoo- S . Determination of the Solubility of wow-- gun Chloride in Talnflneooooooooooooooooooo 6. Tho Rfitfi Data.................o........... C. cleavage of Optically Active c-Phwlotm'l E’homl Ethic: by Anhydrfiufl HYdrogan ChlorideoooooooooooocooooooooooooooooooOQ 1. Genorcl.Procedure....................oe...........-... v11 1 10 10 M38235 Sh 5h fihflbfi-GF CGHTENES urcontinucd Page 2. fittest of tho Ioolotion.Prooodurohoa.tho.Rotntion.of ofhenyletlvl ChlorideoooocuooooooooooooooooooooooOoo 3. Extent of'Raconination.of’aAPhonylothy1.Ghlortdo‘uy thlooItoooooooocaoo'OOooo-oooooIcoolfioooooooocoo-OOIO l4 . Stereochmutry of tho Cleavage of Optically Anti” o-Phemrloflzyl Pth WI” in Several Solventlu..u. RESULTS AND BISCUSSIOH........................................... A. The Kinetics, of the Olmego...u...u.u.................. B. Tho smoochmtry of tho Cleavage......u.u...nun...” C. Moohnnim..n...............................-.....u.w...” D. Suggested Future Exparimonto.....o.o................o...... SUIMRX..............................mu...""unnuuunuu RWMCEBooooooooooooooooqoooooOOUQooooooooaooootcooooooooooo‘ooo Sh 56 56 63 63 7O 77 79 81 83 11213101360le MWiocmmfitthWIotthomby thick othoro ore. clawed with ccidic meats. It will to well, than-- m, in thin Motion to briefly mica m of the portiont ”*1“ m6. tho comma and somatic” concerning the mom of cm. process Mob have boon cxaoflncd in tho put. Tho chmotmcthcroclwambondmmotmmd by national in 1661 (1) who found that caWauc acid reacted with concentrated mm momma acid at now. am" to fora lactic cold no ethyl iodide. m yum um, :31: Itcdont cm: (2) reported that mam ammo hydrioéio acid: olmod We acid ummummmlimccmumummfi mum up this work, Grubs in 1866 reported that «mutt-stud mow chlorlc acid effected. the cm reaction under the one common- (3) , with My]. chloride being fanned in this once . Grccbo was the flat to War that Woolc acid had a. greater reactivity than hydro- emnc mid, mm hydriodic acid and mimic in a. sealed tube at 135° mo phone]. and mthyl iodide, but no cleavage of missile as Med with Wehlorlc cold. ‘ Among the problem connected with Manama the W” of 0th» cleavage are: a) the direction of clccvcgo of magneto-lea]. m, to) tho foetal-o which inflame tho kinetics of the reaction and o) the smoochcmie’a-y of the cleavage. The cleavage of In muawaeWrmmmmmmwMommm 131906.th that We Wm maids 91% mm wwamwmmwmmmm. mmummwmmummezmmum Wmmbyn-mrmless (Shmrm mtthomwlom of mutual, m rapidly cleaved by awn hydriodic acid within fifteen minutes at rem WW6. The only kinetic Studies! in whiah halogen acids were mloyed III the clearing 33m“ in the shame of 3 W116 solvent m made by Mauro, 33g. (6). Kinetic data were obtained for (111th (0.5 M) 001m- fim of Wm brands in «has? and far roughly aqnfimlar solutions or other and war-03m bromide in ckzlovobwme, toluene, and ohloroferm at m twat-am. Ethyl ether was the only om studied. In a largo excess of ether, or in chlorobenzane, the rate ammonia: “ducaflahol / dt " kfl'firla [(Cafifi)flol Thou-national mtumumm, Mastomolmfiunbytho nuke). Weed. With high almhel WWW the at. lu hulls "d[(cafla)a‘°] /dt." mm: 1 autism} {0.1150111 The W mggasufl that a. bimols—cular molaophilic WW .- mam batman (0%)3O-fmr and rm. The Wm: W 0th" fwd Wmmdom «mod tobounimiaodbytho 1mm, (caught)? Br“, mid 1m to the same: We. In chloroform, the rate expression was 3/ “(WE-WV at - Hwemm ’ [mam which was 13th as Matting mum batman (3%)30-833' and Br“. m Imam—em concentration m named pram-um u an mare root as Realism: {rm-3. Althangh the kinetic. m attuned, mu (7) mm that the We of Br“ mm.» m o: (cashew, magnumimpairmdboatlaastuutmmlwmmmm complmc. Varimm mechanim for ether change have been advanced, but in wt was tam propoanla are too 3mm]. and aver-simplifiad. In 1932, M Ind Fulani (8) pregnant! that the mmmnmm ion, 3.0142 WMmWIwIMmimmchmwufl: MCI? (or We 1m) to term the ”com mole of gradual}. This flow In W by the taunting deem order of rate of elm: W cm 3-» momentary ether: 2» n-alk'yl ether: 2» methyl ether] but then am my diam-mien in this order and, as pointed out by W m. the third inequality is mar-root and the mom in W. W!» and Roi-ts proposed that the reaction a: the diqu 1m with the. “tax- (111 the me of cleavaga by aqueous Lucian) was 613333131312 as 3. 1313501qu mxclaophilie displae'ammt (SHE) (9) . HOE + 3303* M Ran; + ROE In interpreting mm mam-emu in glacial nestle acid cam- mg mirogan bromide (10), Hughes and Ingold (1].) concluded that if the “1301' contained 3 5600mm m: fiertiary group , the reaction as of the «mm: 1611 W (Snl) but that if both my: no primary, the mm m a bimlomar meleophilic amalgam (3H2). War (12), in a my of «gum wfimfiflymd ether 61mm pound out that the reaction is generally ”Mod a 3 mm 1% prom proceeding through the. 1’an steps: R 3:1 Rmb: +£‘m {ugh-H m R++1R I * 5-H H H H 11.0 té-H: "twig-:3 m E~é+H+ mama which mapper“ this type oi” mec‘mnism is: 1) Ethan which might Em metal to {Com carbanium ions readily are “anally easily cleaved. 2) Band. m, highly branched ”hers, and metals are vary “the to acids- (11:). 3) Pain solvmta favor the mutations: 1.3., an aqueous magma acid dumbed in acetic mm is a batter clmaga reagent for when than a solution prepared from the mama halide m We acid (15) . ummgh the ‘e-arbemmn ion rapmution of aqueous. acid.- ca’halyaed etherii‘ication am? damage is useful and :2..th for correlation of informtion, Alexander swimmer! that it mat be an wmizmlificatima For M183, there 13 a grant difference in the rate at aleavage of ether: by the diffar-ent hale-gen acids (m1: MNHI a 1:61 on). Thu, tbs mum of the acid is more cmlmt than to merely furnish protons to the sum. mmwdmamdia cleavageoccura more mmmum media and ths mam rumbles an 3N2 displacement rather than u. Wm ion reaction. When an Wrioal ether is calmed w a halogm acid tbs primary products are the last branched halide and the me bra-naked nacho]. (15 ) . This my be the result. of a: mum hm a pmmtod stim- mlmle and a halide 1m (12), with attack at. the 1m ammud muons - J * .. GEE; can, If a carbonim inn were involved , and would expect tha alkyl Mime produced to ba derivaci from they alkyl group which would form the. most. “this carbonium ion-3 that. is , the most. branchad pomp. 61mm of animla by dry ludmgen chloride or harm-03w bromide in carbon mmflde cannot. be affected unless a amn wt of a halo ml: a ”rim, disasthylmiline, or aniline is added (16). In addition, the rate of cleavage in acetic acid. an: increased by than bun. Almdar (12) concluded that frequmtly more than tan mlemhs Micipafie in the 1‘0th of the Winch complm: leadw flag to etharificatinn 91‘ $168?an . Produced of the 5H1 or 3“? type can eftcn (though not: M!) be Wished by their stereochamicnl course (17) . Sine-e no genera}. may 91' the {warmehmnzy 016 other damages had. been made, m1]. investigated the cleavage of optically active methyl sec-butyl 9% by Ivar-agar: brmide md. by mm mfiydridaa (18). He. found that m cm)» gunmen of the optically active other and. hydragan bromde at. 50° yum“: mum brownda am 393 ubutyl aleohal of m m Manama: as the other , with little if any racemiutim . The band. mick m bmkm m therafora the methylmzwgan bond and. W has £1ng that the madman in of the 8H2 type: H c ' Q . 9-64.390033 + Mr “V..." {944%001131 0 Br (1) a , _ _ ‘ [E'IG‘HQOCHQJ ‘1' Br III-I." a-G‘HSOH + 63331. (2) The first step in the formation of an omnima salt. or something resealab- mg one. The mom step 13 fommtad as a bimolaculnr mclwpmne displacamnt by halide ion on the methyl carbon atom. Since the Maryl- 0mm bond is broken, the aec~buty1 alcohol has the some canfiguutim an the reactant ethar. Thus, a oaz-boniwn ion maehanim at the nec-butyl Mon am is mind mat, for this mum ham been mooted to. give Womble maximum, with some inversion. Attack at the prim ' (me-H131) man rather than the secondary (mabutyl) carbon is con- liatmt with all that is imam about SE12 reactions . 2~ » (7) on Mixed the atrium arm of a and at in an other new on the mm (3211 or SE” to be expected. mm both W are primary, or when 2-1 " is a eeoonfiam' alistyl mug) and R is mound, ohm]... or perhaps any n-elkyl group the am mohanim (8212) is to be expected at each anvil group. The reported clumps of prowl impropyl other which my be in dingo-omen with this are old and man be Whined. 35mm: 1?! is ally}. mud. R is alkyl, one may expect the anyl—onygm ham to be brekm, prob-ably by an 8N2 mechanic! (7). 0n the other hand; when n! in tertiary, the band mm the ternary alkyl group and the oxygen atom is broken (1;) , with the romtion of rm: and ROH even when R is moths-r1. In addition, tertiary other! are cleaved much more ace-11y by aqueous acids than other: confining only primnny'and secondary alkyl groups (25). This reaction, than, in the 581 type. Baton" ----e R” o ROH The carbonium ion reacts rapidly with manger: halide or halide ion to form the tertiary hanoo. When both ‘3 an EU are oeoomimr alkyl grmpe, it is quea’oionable which mechanimn will be involved. he date. bearing on the problan hive been reported. Bumll has suggested that a stash; of the rotation of soc-butyl alcohol famed in the cleavage of optically active aeo- butyl isopropyl other night elucicfiate axis point . If ‘5: is primary and R' is secondary, then as R is mgwossively Madame} by increased fiubmnohing, one might mrivo at a case where both carbon oxygen bonds or: broken . With neopomtyl other: , the principal product would most likely be noopentyl alcohol and the secondary halide. It. has been W that olmage of mu type occurs in cacaootyl imbutyl m (7) . a mechanism ”memo difformt rm than diseased my be involved in the cleavage of bonny]. other: or at least other: of odphonylotkwl ‘1”er Hart and flmW10.-. (20) investigated the clan-«Ago of optically ”the o-‘phonylouvl phmyl other by dry hydrogen chloride in bum. When (4») 6-1911le phony]. other in benzene was treated with hydrogen chloride, (-) o-phmyloml chloride was chained. Sims (0) «as-plum).- aflw}. other has the am configuration as ( -) o-phwlothyl chloride (21) , the process involved retention of configuration. The extent of mtivlty retained in the over-all process was calculated to be 37 .SS, with 62 .SS rooemization. These investigators proposed. the following moohmlm: mg I a) b) Q—C 4! - ~Cl\ / G H H /H v ' I \\‘~‘H/ 0--~-H G O 2 OF - r3. .- CHE, (3* © The o-sphanylothyl phony]. other apparently undergoes a. frontal attack by hydrogen chloride to give o-phemylothyl chloride and phenol. The hydrogen chloride may or may not be complmed with a phenol molecule, but frontal attack. is necessary to account for over-ell retention of oonfimation. A carbonium ion intermediate would be expected to lend largely to racmizetion with some inversion, whereas a bimoleoular displacement would lead principally to invereion. Neither of these mechanisms, which have been discussed in detail above, can moments the atereochemical outcome. in this case. It has been proposed that the rumination which won observed may be due to a partial operation of the onion ion mechanism, or may be due to reomntion of the «WI-- ethyl chloride by phenol and, hydrogen chloride, subsequent to its formation (21), or both. The mom of this present investigation was to make a more detailed , quantitative study of both the rate and atereoehmiltry of the cleavage of e-phmlethyl phony]. other by W. hydrogen chloride . It we. also decided to deterxdne the effect of solvmta of varying dielectric on the rate and etereochezniotry. Thus it was in hope of elucidating in greater detail the mechanism of this reaction that the work was maderteken. 10 A. Preparation and Purification of mm . This eloohol I» prepared as dmribed by flat end flatten (21). on yield at the 3.lier alcohol, b.p. 92-93°/25 mu (1:500 32.9") to (1:50- 3&2") from various apex-insets I“ 86-38% y. . - w 1 . . The optically active alcohol In. converted to the We chloride by two different methods. Hung mm). chloride (21), the yield of the love-e-Iphwlothyl chloride (01.2?“- 38.9°, hp. 69-71." m.) m 86% from lm‘phwlethyl alcohol (.350. 32.90). The other method on that or aux-well, Shields, and Butane when (1-911-151er alcohol (£350 9 27.50) III permitted to met with numerous hydrogen chlorido and phelphom omhloride, than u attuned u 705 yield at Mmmioom chloride (13.9. 7o—72°/10 m, .350.- 523°) Following the procedure of Hart and mentorio (21), thin We in W frm c-phmletrwl chloride, phenol, and petunia carbonate in Mono. Lm-phenylothyl chloride (c.1325fl - 35.33") yielded owl- ethyl Ml other (5250-- 13.92°). Dutro other (5:50.» 10.61°) In! eunuch-on datum-gnaw}. ohlorlao (0.35044- 29.610"). nMda-phwlomfiphmloihu,buodonthnmlotom- vat-d awlmn chloride, at nanny about 65‘7“. It. Ill mwmrmoymnmmhowmsflbymmumo: mnmuuuotwmummuumm h. mum 05. 8017933 (23.21:) W «1- mm W ethyl alcohol (63.) in Mad over amnion ribbon and fraction-l]: distilled, 5.9. 78.3? c.- » atmophorlo W. _ ~ camel-l chlorobmcno (0.1%) m or!“ «no «1cm oblorldo and traction-m mum 5.9. 1.31-1.32“. W.nm melodiothylkltmul mum WmWMoforMhm. ‘Mofloluohlorflom mmmmmmummam It" filmed and ob. Iolvcm was distilled gt OW m.- nro; hp. 101.?°. va-nloohol, C. P. was, In drmuth mum oxide and Miami]; distilled; 15.9. 108°. 3% «- Wayne-cm" PM (o. P.) m dried over sodium mm: and {nationally distilled: b.p. 177.1°. W” Th. hydrocarbon, C. P. grade, no distilled at “masonic m. The first power: of distillate ( 10%), woo-load true. of tutor and was discarded. Concentrated Wommmuddoddrwduntonmof Indium cunt-locum! oomantntoa Willa-1o acid. Tho gamut! mogmomfidomtmmfimghalombbmoonmg mmmmmmmmmntemwmimmmo an. E. Kinetic Woman" on the Cleavage of "th1“er Phonyl by Anhydrm Hydrogen Chloride. 1-. mm All "to studio. we carried out in a thomaflthd bum in this): momma control a» mum to 1*: o.1°. A arm; a: the mm and for the moments 1- shown in Figaro l. The reaction nus]. contained a gas dispersion inlet for adulation of mum. hydrogen chloride, a gonad-glans nook to which an fitted u arr-loo om, Nomad-gm. Wrodnookformnlormlu. 81.1mm amino out by mm o: a mole flirting motor. The motor no houodlnamtcwughtpluuoboxmdplnoodbmthtbomum vmol in the boast-ant Worth" bath. Loud might. are and to Want the buoyant effect of the water. The speed or the rotor II regulated by a rhoootat which no cemented to the motor oimit out-ids the bath. a) Rate Datamation: mloying a Large Excess of Hydrogen Chloride. Solufioal of a-phmlethyl phony]. other we prepared by wishing 13 4 \.\J J .4. $4 I J \ «I c I 41 I 4 1% 4« I; K rd:.fi(_rll tr Ix fl .) _ .. . rvI_I «JP». _ o r A.\ x. .- 9 VI._< \ ‘ I 4 p! o ( Ix w,| ~ [J’s d7 1“, urH 20 Y...“ Fur) [‘1 .Jx _ .H {r o v 1 rl r I ._ o . _ 4 I Ill: \ 4 . x . v f‘ ( n . . m. 1 . - b ) . , .r» . 0.. r. r\ ~|r. i v\ - ' II II ll ’ <1: .munqpna ‘. 4..- h :0), . f: V”: pom 4).an ), T? r. L mspmpmam¢ .H mpswflm (by mime) the solid other in a voluetric mm the W solvent, which had been freshly purified and ohm-batted a: 20°C, was than added until the graduation mark of the the}: we reached. um making to effect complete solution a. known quantity of thin ”lotion m poured into the reaction vessel and placed in the 1;th bath. 1mm sufficient time had. boa: allowed for equilibration, Wm chloride gas was permitted to pass into the other solution. Ms this point on electric timing device was tripped to word relation fine. A volumetric pipette was used to remove l-nl. aliquots mick m medically transferred to a separatory funnel containing 20 ml. of 10% potaslmn We colu’dcc. Since may of the mum of phmol and phenolic others are the once, it was necessary to separate the phenol produced by the cleavage and the unreactcd other before deter-had- :Lng the phalol concentration. The analysis of the aliquot 10 Wood later under Analytical Method (3), which involved. a colorimetric determination of phenol and we the procedure finally adopted for all the robe studios . 13) Rate Datamation: Using Comparable Ammmte of Hydrogen Chloride and Ether. Anhydrous hydrogm chloride was pendtbcd to pass into the tram: purified solvent, which use themmttod at the reaction mature, will the desired concentration was splat-0mm. The MW we: determined by transferring l-ml . aliquots of the hydrogen ohloe'lde solution to an 3.0de flask containing 25 ml. of distilled Inter , coding two drops of phonolphtheloin, and titrating with standard 15 Iooiooahuoromido. When the solutions were of a greater norcnliby thou mo desired. for the reaction they mo diluted with pure colours and mdbionted. For each run the acidic solution, prepared and mnlyoed as described above, me poured into a volumetric flask which we Mud in oho‘baob coo coooeinoo.e weighed.qocooioy or oihur. when.tbe animation mark was reached. tho mm in quick]: W and Mn. 1 unple- wac removed imodintely and the W393: chloride «communion in again determined as a chock with the value obtained botm women to the other. In all cases there am: very olooc agreement and the» values wore used as core reaction time . At. various intervals slim“ me mad, extracted with pomeimu momma. solution, and mined for p’omol colorimo‘brioally es omribod under Analytical Method (3) . Because of the chugo in amid-5y of tho solvent with Moore a con-notion factor was applied to all aliquots accept those at. a re- am omeromre or 20°C,. which I” the max-azure at which on W v‘oro prepared . The mom and to oalwlete the émiw of balm at various moi-ammo is at .. m, . 10" «(t-c,» 10"6 Mt-egw 104x (ts-of» : 10“”4. The constants listod in on International Critical Tables (25) for toluene are: ‘ é a «0.922h8 , B . +0.0152 X '- 45.223 , A .. 10.0005 60 :- 0.83m 15 A sample calculation is as follow: “sob . [0.83h12910’8(-0.922h8)(50)010‘G(+0.0152)(50)“olo'p(u,223) 3 (5'0) I 511160 g: ‘ g: am (2200' 0.3653 (11%.) II 1 m1. V500- V200 . %% X l or 0.969 ‘81. from a 14-111. aliquot at 5’0" would only occupy a volume of 0.969 a}... at. 20". All volumes were: corroctod to 209130121 for the solubility dammimtiona and. for the rate data which will be encountered later . Methods Invoati mod for , ts. An attempt was made to determine the rate of cleavage of naphml- m1 phomrl other by following the: rate of disappearance of hydrogen chloride. A solution or know. memorandum of anhydrous hydrogen chloride in the particular solvent. at the dos-trod. Mentor-o m pre- pared, the concentration being dammnod by titration using various buds m indicators described below. One hundred milliliters of the motion was transferred to a volumetric flask containing a weighed m of other. 'rho- flank no flowered em": shaken while interned in m bath. At various time intervals who were removed and titrated 17 with basic solutions mic}: wore Mutilated with standard hyfirogm chloride f It had boon found that means solutions ooulfi not be used in titration of the reaction samples because: a nphonylafivl chloride, one of the products of tho oloavago, mmmad readily in the presence of filter . This as detected by t1 outing aqua volumes of atandufi mumgm chloride in the prosonoo and ohms of the organic ohloride. Tho volume of hose consume. m smalls:- in tho latter mo. It in .1” observed that won dilute solutions of strong hoses mob u potasu‘lmn hydroxide in methanol caused rapid doiworohalogonation of d-phonylothyl chlori do . To olindnat-o the problem of solvolyoio , non-aqueous system such as amme Mroxido and triotl-xylamne in benzene, toluene, isopropyl alcohol and acetone were investigated, using bromcrosol purple, methyl rod, methyl violet, and crystal violet as indicators. Moonium hydroxide solutions were found to be unsuitable booauoo of the instinility of ammonium hydroxide in organic mlvonto . Another undesirable feature was the prooenoo of water in the mononium moo-oxide, which away canned W138“ of the o ophomrlothyl chloride . Triothylanjne ' It: finally selected as tho baao because it is more stable in organ: I91“ vents, only requiring rostmdaxfimtion every two days, and because it did not cause o-phonylothyl chloride to dotwdrohalogmte daring the time required for timfion. _L._~‘_L_-— £6110“sz H01 was prepared by using froahly standardized (potassium told phthalate) MOB to titrate the acid solution . 18 Another problom encountorod was dom'drohflOgmtion of the organic. chloride in certain of the aolvonta uood for other cleavage. For . Mia, when isobatyl alcohol was omloyod , no change was observed in the. volume of ow triothylanfine roquirsod own after two hours reaction tim . rm. phosphomlybdio acid and momma hydroxide gave a strongly positive tent for phenol. Thus, it oppwod that cleavage mi donflmhologonntion woro proooooing otnnltanoously, so that the total alumni“. of Unix-ego: calorific prosont did not vary to w nignfl‘iomt extant . Thoroforo a solvent which did not cause dohyrlrohalogonation no required; it was also nocooonry that its boiling point be below 150°C, since its. soparation from ouphomrlothyl chloride would have: to be readily acoomlishoo for the optioal studios to be cart-loci out. Ono solvent mien satisfies: these dommis opponrod to bo chloro- bonzono . A tabulation of the data foumi for tho cleavage of o-qmarorln othyl phonyl other by morons hydrogen ohlorilo in ohlorobonzeno is found. in Table I. swam; triofliylamine in asap-mm. alcohol m usoo to titrato the reaction aarnploo (motlvl violot indicator) . Tho malidity of the mothoo. as o moo-sure of the rats of other olmago is illustrated by the foot that tho reaction appeared to have ruched oomlotion after 134.5 x 2.02 moods, althwgh determinations of phenol concentration showed a continued increase , thus indicating change was still in progress . Other; moo gave further inconsistent data probably‘booms of morogon chloride loss by the organic chloride TABLE I THE) RA??? 0F CLEAVAGE 0F n-PHQJMTPM P113311 ETHfiH BY AI'IIHYDRWS HIERGGEN GHLGRIDE AS FOLLOHED BI'TITRAEION .4 . . _ .. # ___ 4__._.___ WT ‘ l w - ._ . ‘ _ . -w H, _, "T “—4 . _r_..L,_. J. . . - '—‘A .. ‘ ____.__.__ .. g v w _ ,A . w w z r, . V—‘v wvv—v— Tmotnro: {£006 , Solvent: 5%aorobonz one Ether] : 0.0.990 molest/litm, {H61}: “0.1610 moles/liter, [may]: 0.11m min/liter r. m.— ‘ , w _.w._ W.— w —,_ Time a 5:1; 315: no). Males H61 soc. x 10" $31.) 4— 4 # w (1-3/1) ‘ “(0:WM # 2 0.7? ~ 0.1073 0.0532 11 0.76 0.10634 0.0%6 2g. 0.70 0.0980 0.0630 53 0.6? 0.0938 0.13912 70 0.51 0.0351; 0.0756 81 0.59 0.0826 0.07315 10 0.56 0.07311 0.0826 12 0 .53 . 0 .07h2 0 . 0363 13 {:3 _. 51 U .1071}: 0 .0395 1L5 , ' 0.145 0.0630 0.0980 3.5.2 0.545 0.0630 ‘ 0.0980 16.5 0.3% {3.0630 0.0930 20 Wurmmocaam. Mmmuwmmwl mahtwmnmflcormofclw. 81mm sodium $110th and heater-brute «Mons we prepared by the usual procedures. oéhonylomyl phuvl em solu- tions m wwod rm nomad mum of tho solute. Reactions mollondtomformud time intervals, attho and ofwhioh 141. aliquot. mo withdraw: and pipottod into 5 125411. separator: tum]. Mg 20 ml. of hormone. Than 10 ml. of 101 am We collation m added. imodistoly, to «ta-wt the M]. Wood Melange otths other. This actuationmnoouurym mm1plmfiflmcbmmcnothmthm-umt ma tho phenol. mum. The Main «tract in poured into a 250ml. iodine flak md «manna with mutated morochloric mid. . A calculated cacao” of standard bmido-bmto solution was add-ad Along with airflow distilled water to make the carbinod volume 130-50 n1. Commtofi Wufimafidodmthemwmmmwr @39de a waste. Tho noon We was destroyed by 10 ml. or 101 Main iodide and after crashing the flask all: with distilled mm the mo iodino ml madam: titrated with standard sodium thiomlfcu using a starch indicator for end-spout detection. Although this broninction procedura- ror determination of. phenol gave mute and‘ reproducible remit. for high concentrations of phenol it we not accurate for W101: of phenol during the early 21 “ago; of the change when dilute solutions snobs: 0.1 H ammo and. Thisomboobsowodinmgurozwhiohiscplotcfstmiul can’thadatcmtchulatcdinrablon. mpomucarmm WafmmtimfmsbovoWoclOpobmuthotummtc «Mlpnmtctthuommcmldnstbcwmlym. 1. The consulfrogm The gonoul procedure m to dilute the phenolic solution with motto mid, add sodium nitrite and soli’urio acid to tom autumnal, no that: sad access alcoholic amnion hydroxide . The solution» In. memo: stmdforaunimoffivehmsmthmminWWof transmitting coloredquinoidultmmoddthaphotoolm «muster. The intonsity as related to a calibration our" W undo? identical condimona by varying omactutiom of a “We! m1 owls. 2» W Reagents required in this procoanro more prepared as follows: W - 800 ml. of glacial acetic acid, 150 an. or 10% mwmm, WSOnl.o£um1-orcdud to give 0. liter oohtion. .c ~A liter of solution was puma byflxingtSOnl. o: anhydrous othylsloohol, 300 m1. oclhn mains Worlds, and 250 ml. of at». swz;;.eL w “2-. r‘ ,.:_ ~ n: ~ Sodium nitrite, 73 3., m Wtolmnl. ofdistillad utorctromtmtnn 7’) l—l. rv“ l l L 1 23 MEI! THE RATE OF CLEAVAGE w ui’HMETm 91mm. m B! mews 315006311 CHLCflIDE AS WED 33 WMTIGH anaa=auaaa========a=================a=====fi?-w* ‘ “2-1;:=====:======== Tsnperatnrot 5090, Solvents p~Cynnnp [Ether]: 0.3.076 halos/11w, [301}: 0.21.10 Holes/11w 1.-- -1- “ ~ “Wm“; m.W. 1‘ ‘~‘~ w. _ W rm 4, 111.3,0, Esq. Br. neq. Br. and By th Kola . ‘_ 10 { 91,131.1«231-1 U ., _ P , .1115 =— w 0 3.1.16 0.9820 0 0 0 0.1076 8 11.00 0.9680 0.9820 0.01.2.0 0.0023 0.1050 16 1.1.10 0.9768 0.9820 0.0062 0.0012 0.1061 18 11.00 0.9680 0.9820 0.01.1.0 0.0023 0.1050 20 10.00 0.9363 0.9820 0.01.97 0.0076 0.0997 30 10.50 0.9260 0.9820 0.01.20 0.0070 0.1006 06 9.3.0 0.8272 0.9820 0.1580 0.0258 0.0835 97 8.69 0.7665 0.9820 0.2155 0.0359 0.0711: 122 8.10. 0.71.26 0.9820 0.23914 0.0399 0.0671. 151 7.87 0.6926 0.9820 0.2891. 0.0082 0.0591 196 7.00 0.6582 0.9820 0.3.038 0.0500 0.0533 233 7.07 0.6222 0.9820 0.3598 0.0600 0.02.73 ga— mi the moons oolste was filmed iron the ammo. WW - 900.01, 0.1 t 0.01 3., ms wished, wourotolymolmrml.volumotrioflukufidihudto «only 100 ml. with the buffer solution. After thorough male-al.1nquotmumrumusmloo-n1. volumetric flask and dilutod to the no}: 01th the but!» ”lotion. if mum accuracy is desired the phenol and so the otmdorfl mot be the on» that is being detox-mined. m3 ~ Solvents mm by two: of phmol veto mm twice with a 10% potassium W00 taxation and when! nth mm. The can.“ loyar was then filtered throw: a dry fluted paper. Fag-mammal. 2,3, 1., («005301. or 0.. Itmdsrdphonollolntioa no fumed into “you” 50ml. WW M. 3m mid, Wforlolo‘uonmaddodtomootomvolmoISfl.oudthontho color development was carried out by addition or We acid and sodium 110010. as described below. A blank was also run. A non-00mm photoelectric calorimeter and o No. 342 violet filter were employed to We the intensity of the solutions. In Table III is the dot! for the calibration curve (Figure 3) for tho sundsrd phenol solutions. That this method as satisfactory for analyzing minute unm- of final with the desired accuracy was domtrstad as follows: 0:» m1. of a 0.1100 molar solution of phenol in banana was trans. tamed by a volmtrto pipette into a separatory tunnel containing 0030.0 III ‘ mu m 00.me 002m 00 09.00000 9mm. omens 9081103. 30:10. Scale corrected“ 3012mm (mac/509113 ““1“! __ “KW. 11 O o 19 O 1 0.1011: 93 7h 2 0.2028 156 . 137 3 0.30112 21° ‘19]- 1‘ . 0.14056 250. - M 5 0.5070 . . 310 291 a'zl'h0 value obtained for the blank was subtracted from :11 finding:- to comet for may due to the 000101 nitrite solution. - "i (10 n .— I . L J \-' I ‘ ’1 27 10 ml. of 10% potassium 1W9 solution. Romano m added and tho womb Wow was oopwatoé and amlgood for phenol oolorimotrioally u will ho dooorihod. moo trials gave tho following ”moo: 1) 0 .000099 halos 2) 0 £003.07 males: 3) 0.000112 1003.00 t 1.1 Pro 000.00 U000 ~ ‘ Since o-phonylotkwl phom'l other gives the mo yellow-goon color as phmol upon nitmoation, an extraction operation as required to ”potato tho phoml and the unroaotsd other . At variouo intervals loul. aliquots of the reaction Wm were rammed and 1000001“on inn-ammo into a. 125-401. ooporatory mmol containing 10 m1. of 10% potassium hydroxide solution. Thou 5'0 .20.. of bonoono was addod, and the mom shaken for i‘ivo mimtoos after 511100ng the more to settle the «mom low was Mormon}. to a. 100-003.. volumetric flask. To the oopmtory _ formal m 00000 55 ml. of 10% potassium hydroxide solution and Again the We no oinhon for five mimtoo. It mo allowed to nettle and the aqueous layer we withdraw into the 100-011. flask. Finally 5 ml. of distilled mm was added. to tho bones-00:0 solution, shaking in carried out 1030 two mimtoo and tho aqueous layer m withorm into the 100-101. M. To the combined extracta,‘giae1a1 acetic was slowly added while tho flak no 000150 in 10 tan-avatar . Addition was stopped before tho 10091. mark as reached in condor. to pox-mt the contoato to reach room 28 more. Then the final momma mo made to five a total volume . of exactly 100 m1. at room WWW . A 1-321 . aliquot of those solu- tion! (doairablo that the phenol content is 0.05;? to 0.5 mg.) was pimttod into a dry 50ml. flask . Acetic acid buffer solution one Added to who a total vohmo of 33 of)... Color developmmt was carried. out as fonowo: To the above 373%. flask. was added. five éropo of 36 H soJImfic an id and 19m drops of saturated sodium nitrite solution. M «on fixed by mung am ponittod to stand 30-25 mm. Alooholic ammonium hydroxide was added slowly while cooling the flank in ice-outer to make a total Voimao of exactly 50 ml. at room tompmturo. The. final solutions were permitted to stand over-night or a minim of fivo hours . Thm tho ooiorimotrio readings were determined. By the above prooodum tm blank dotominotions wore also carried out; in one the sodium nitrite solution woo matted one in the other it w imlucioo'i . (only the om oontaining tho nitrite solution gave a. significant reading and this value an: subtracted Iran all 3min road- ings . S . Detormination of tho smouuv of I oro on Chloride in Tolum - Since the solubility of hyclrogm chloricio varies inversely with tho Wanna it me noooasary to determine the concentration of hydrogen chloride: in tho "901th at all temporaturoa at which the mm were 131W . Hydrogen chlorido ,. generatod and. dried as described We, no pm'mittod to pass into the themstottml solvent until “Wation m offootoo 3 that is , until tho voluno of standm base 29 Wbyniimteofthowhxfioomoomh Mom W to rowing 1-1.1. :11me the reaction vmol, tum-.- 1”me to on iodine nu}: oontaining 10 m1. of distilled voter, md titutdms with 3th sodium worms to a phmolphthalnin mo. point . m volumea mo oomotoo to 20% by W carnation footers mm from to. form. for thy clung“ at various tamer-atmo- . In'lnbh IV mtho at: for tho solubility at Wm ohloride in some at mot-1mm from 0" to 60°. The comma loom We “hum tried to timto the min In: 0.10% norm. It m owned by the m1 grooms winging pom biphmto (28). 6‘ W Into. amending tibiae the tem mowntoradmybo defined“ follow: (I) anti (1:) 0 Initial mien per liter of bank-om chloride and aaphanyfiiothyl phony). other respectively. x «- Moles pa‘ iitor of phenol at time (t). (vac) and (bun) :- m» on iitsr of hydrogen chloride and other at time (t). t 0 Tina in We. tables to as am; obtained by mm a saturated Wrogm chloride ”lotion; the hydrogen chloride concentrations represent the solubility of worm-on chloride in the solvent (toluene) at those mam. ‘ 30 WE N m 3mm 0? mm cmms III M Gan-actinn Gan-acted Humility _ ._. reg. 0.1022. R N003 A (10.1 0.)(a1./1 3:1; cliques) new Vol. (-0.) ._ of 301 w. 0.0” 7.35 0.982 7.22 0.7375 21.6 0.13 ......... 0.13 0.1.229 1.0.0 2.70 1.022 2.76 0.2829 50.0 2.28 1.032 2.35 0.21.10 60.0 1.91 1.01.6 1.99 0.2005 u _ ., 31 Tm V THE RATE OF CLEAVAGE W «emf-arm rm m B! MEWS MERGER! CHLGRIDE trauma-am: 0°0, sour-nu roman, [m1]: 0.7375 Mom/mu- _._A H44... .4.. A. m. h... T1,. 1“,...“ v—v—W—M— *— fiu _, Beale Corrected Phenol 00.9 W Ether 29319 3% finding- W11 . MM°- W11... m 21 0 0 0.1001 0.1001 0 23 2 0.0020 0.0981 0.0995 11.5 28 7 0.0035 0.0966 _ 0.0980 20.5 01 20 0.0106 0.0837 0.0850 1.0.6 75 51. 0.0266 0.0735 0.0751 72.8 109 88 0.03.1.3 0.0558 0.0572 96 128 107 0.0557 0.01.10. 0.01.53 1.25 11.3 122 0.0638 0.0363 0.0375 150 153 132 0.0691 0.0309 0.0315 180 179 358 0.0851 0.03.30 0.01.32 -_ ---_, .*R.H.__.:m:1;_m.___w Vfifi? 0...... k :- 7.2. x 10"“ no. km In 1.01 x 21.0“5 1. :00)..."1 m. M ____~‘ _. - ._______ A“ A _.. _ A M .4 _. _.. .. . ' ____. V,‘ —-.‘ ww— . _ mw “ ‘v—w —....——— w— _ w -1 H I! TME VI TEE-5 RATE OF CLEAVAGE OF awmm PIERTIL m 21.0%, salvm: BY WW?» WWW 6312(3le 1‘4er .. omwut‘m‘. »- —‘r’F-W—' A , ',.:— ‘ kxmj m .3 x ‘I'M hq ‘ .1 .3 m. x 10 (0/1.) (0/1.) (0/1.) (1.001. 000. ) L. 0.0021 0.129;. 0.1989 1.26 12 0.0003 0.1272 0.1967 1.31 20.8 0.0105 0.1209 0.3.901. 1.37 1.1.5 0.03.1.3 0.1172 0.1867 1.25 55.3 0.016? 0.1108 0.1303 1.27 75.2 0.0195 0.1120 0.1815 1.20 103 0.0273 0.3.02.2 0.1737 1.20 i 337 ' 0.0580 0.0735 0.11.30 1.25 1-: - 1.25 ~1- 0.03 x 10"” 1. 301.4300.“ «mm 38 1m III THE RATE :1! CLEAVAGE 0P «emu-an. Pm mm 8! 180201088 mm 01001180 1mm: 80%, Solvents 10:11.00 (mm: 0.1208 Mam/11m, [Ether]: 0.3085 rum/11m kxmfl‘ The J x m: h-‘a -1 a no. x 10 (8/1.) (rs/1.) (8/1.) 1. 001. m. 7.11 0.0031 0.1177 0.3011. 1.115 32.5 0.0151 0.1057 0.2892. 1.1.8 87.5 0.0221 0.0987 0.1821. 1.119 81.6 0.0301 0.0887 0.2081. 1.58 100 0.0399 0.0809 0.26116 1.38 151. 0.0530 0.0678 0.2911 1.39 180 0.0571 ' 0.0630 0.2178 1.35 21.0 0.0683 0.0585 0.2362 1.2.0 .0 -1 kwerago - 1413 i 0.06 x 10 1. 8101. no.“ 39 TABLEXIII m RATE OF CLEAVAGE 03' 04mm 01mm. mm 3'! 83511130133 11111000027 CMIDE 10111010000210! 179°C, solvmt: Toluene [001]: 0.1217 Mom/um, [00:00]: 0.0979 Holes/11m Tins J x 0-: be: t 3:30.15 «0. x 10 (bl/1.) (ll/1.) (Ii/1.) 1. m1. «0. 6.3 0.0015 0.1202 0.0961. 1.37 36 0.0071 0.11116 0.0908 1.05 53 0.0002 0.1135 0.0097 1.1.1 ’ 0.0106 0.1111 0.0873 1.25 109.8 0.0121. 0.1093 0.0819 1.30 120 0.0167 0.1050 0.0812 1.31 0.0215 0.1002 0.0771. 1.30 360 0.01.35 0.0782 0.050. 1.60 .1 .1 kammga - 1.35 t 0.08 x 10"“5 1. .01. 000. ho TABLE XIV 1112;; 0120 or 01.017100 00 0431013001111. 000011. 173.03. 01 1101110000 1111110051: 01101100. W4?“- 5 - .1- Au Tweramre: 310°C, Solvent : Toluene Em]: 0.2230 Helen/liter, [Ether]: 0.1006 Helen/11m- M J x 05% b-a k 1:30 7.; 000. 310 M (H/i.) _ (ll/1:) A ‘ (1-1/1: ”1. m1. 003* 3 0.0009 0.2221 0.099? 1.36 12 0.0035 0.2195. 0.0971 1.20 18 0.0052 0.2178 0.09511 1.32 23.2 0.0060 0.2170 0.0906 1.20 26.9 0.0071 0.2159 0.0935 1.23 33.2 0.0082 0.2108 0.0921. ‘ 1.36 38.8 0.0106 0.2120 0.0900 1.31 03.9 0.0120 0.2110 0.0806 1.32 167 .7 0.0365 0.1865 0.06111 1.33 2811.5 0.0521. 0.1706 0.0032 1.27 Mal. ___ —-—-—- ._._‘ A... __.‘ #fl ‘4. - A. _.-~ ...‘._ ‘.—-.._ .-__._ ._v fiv— W W v...“ ‘w “- ww w r — -——— ~—,—— —v—— 2. ._.__. w “w . w w... , .1 .. karma :- 1.30 t 0.05 x 3.0"8 l. 1001. 000. A M A...- ._-._ _._4 A...“ __‘ ...._ , w .7... w.— w —, INN WE RATE OF WVAGE 03‘ «0mm mm m 3! W000 MOSHE CHLORIDE Toma-nun! 00°63, $03.va roman (001]: 0.2931 Mum/110», (0000ch 0.0975 mom/11m rm ‘3 x us: M k 330.5 ., m. x 10 (Id/1.) . (bi/1.) (3/1.) 1. 301. m. 5 0.0020 0.2911 0.0955 1.01 11 0.0000 0.2889 0.0933 1.37 28 0.0102. 0.2827 0.0871 1.00 33 0.0117 0.2811. 0.0858 1.35 05 0.01143 0.2788 0.0832 1.28 52 0.0160 0.2771 0.0815 1.21 63 0.0200 0.2731 0.0775 1.29 76.8 0.0201 0.2690 0.0731. 1.32 35.6 0.0273 0.2658 0.0702 1.38 93.5 0.0319 0.2612 0.0656 1.5}: 206.3 0.0093 0.21133 0.0117? 1.31 Average a 1.32 i: 0.00 x 10‘! 1. marine.“ ME IV! 7 21m RATE OF CLEAVAGE N” adem mm m ‘ BI ARE-1111110113 mm 00100100 Twat-awn 00°C., 801va 0:1er 10015000 [1101]: 0.1580 Holes/11w, {Ether}: 0.1000240100/1100: Time .3 x 2-: If»: 1‘ 11.1.0; .1 loo. 1: 10 (PI/l.) (bi/1.) (3/1.) lmol. Duo. 7.3 0.0021 0.1559 0.0079 2.57 13.9 0.0006 0.1531: 0.0950 2.32 15 0.0071 0.1509 0.0929 2.50 20.7 0.0090 0.11.90 0.0910 2.1.6 28 0.01.00 0.11.70 0.0090 2.67 35.8 0.0120 0.11.60 0.0880 2.31. 0 00.5 0.011;} 0.11137 0.0857 2.08 51.5 0.0167 0.1013 0.0833 2.39 50.5 0.0180 0.1396 0.0816 2.53 83.7 0.0258 0.1322 0.0702 2.118 227 * 0.01.95 0.1085 0.0505 2.50 k .1 0 average in 2.118 :t 0.07 x 10-, 1. Rolflm 1.3 2131.0 1711 1'03 RATE or 01.01va or 041mm mu. mm 31‘ 0100000: moans Wm: 310°C, Solvmtt 019001 1500000 [001): 0.1250 Mona/11m, [Ether]: 0.2003 Hons/11m Tim J x 0-0: 114 k If“ _; 000. x 3.0 (ii/1.) (Id/l.) (bi/1.) 1. 301. m. 2.9 0.0010 0.1232 0.1905 2.29 9.3 0.0052 0.1198 0.1951 2.60 11.8 0.0071 0.1179 0.1932 2.51 11.6 0.0080 0.1170 0.1923 2.30 101.1 0.0106 0.11111. 0.1897 2.66 23.1 0.0120 0.1130 0.1883 2.25 27.0 0.0102 0.1108 0.1061 2.26 30.2 0.0160 0.1090 0.1013 2.36 89.8 0.0006 0.0810. 0.159? 2.51 126 0.0651; 0.0596 0.13119 2.1.2 kflfi‘lge . 20,42 1‘ 0-12 I 10‘s 1. ”10‘1”. .1 THE RATE OF WVAGE 0? «00mm PM mm mm XVIII BY WW8 HIEROGM MOI-IRE \ \ 0mm: 10°01 501ch 010000. km {1101): 0.1350 flan/11w. {Ether}! 0.2981. Ham/11m 21m - .3 x 0-1: 0-0: 1 k :30} 7 000. 1: 10 (PI/1.) (ii/i.) (Ii/1.) 1. 1001. m. 1.0 0.0021 0.1.329 0.2963 ’ 2.37. 5 0.00116 0.1301; 0.2938 2-30 8 0.0071 0.1279 0.2913 2.26 12 0.0111. 0.1236 0.2878 2.31. 11: 0.0130 0.1220 ‘ 0.2351. 2.116 20 0.0181. 0.1160 0.2800 2.27 21. 0.0200 4 0.1150 0.2701. . 0.31 25 0.0213 0.1137 0.2771 . 2.3? » 1.0 , 0.0350 0.1000 0.2631. 2.35 09.1. 0.0680 0.0670 , 0.2300 2.05 “E -1 .1 “amp . 2.3:. 2 0.06 x 10 1. 1001. m. TTEKI'K .f Ydm sun}; 02‘ WMJIAUU U} dw’leifla&fJfla Pdm’fifln w ' ’ 113’ “I. 5.51-3.3'Lufm "3'32.”“1‘1 'J:.1.';i1.i}£ Tewwammn 30%! , 519‘}..th 7711:1150, 1900015 [1101}: 0.2071 Moles/11w {am—J: 0.099? wan/11m- Tit-.00: :‘x 5... 1: bus: k :1: £150: «a. x 10““? (10/1,) (FL/1.) (Bi/1.) 1. m1. . 9 .1 0 $1012 0 .2132: 0 .0955 2 .155 ‘ '3 L‘. 0.0071 0.20% 0.0926 2.30 22 0 .0106 i: .1905 0.08.91 2 .06 30 , 0.0131 0.19.0.0 0.0356 2.39 51 .1 .0206 0.1865 {7.0791 2 .39 109 0.63153 , 0.1726 0.0652 2."0 129 0 .0022 o .1519 0.02.175 2 .31; k .6 .1 .1 “rum-are :- 2.340“; 13.1.1": I: 19 1.. 1001. 300. TABLE XI THE RATE a @EAVAGE OF a-PWM mam. 0mm 8'! ANHIEZOUS 323106371»? CHLORIDE tmamre: 00%, 801va 0100131 km- [301]: 0.2610 mom/11m, [00002]: 0.09920 nun/11m- m J x. 0-0: 0-: k 13°“! «0; z 10 (Ii/l.) (Fl/1.) 04/1.) 1. :01. m. 2.1 - 0.0050 0.2550 0.0902 2.25 17.8 0.0110 0.2500 0.0882 2.1.1. 29 . 0.0150 I 0.21.50 0.0032 2.1.0 37.8 0.0010 ' 0.21.00 0.0782 2.5:. 07.5 0.0250 0.2360 0.0712 2.15 56.7 0.0000 « 0.2330 0.0712 2.37 81 0.0370 0.2200 0.0122 2.31. 90 0.01.97 0.2113 0.0505 2.35 haul-ago - 0.1.2 it 0.05 x 10“” 1. 3.131000.“ ’27 TABLE XXI m RATE 01" CLEAVAGE O? a-PHEI‘I'ILE'IRIL mm mm 32' mamous 23131200323 323.012133 =5 Wm: 00%, Solvent: 2.0mm Alcohol [301]: 0.1275 Holes/liter, {Ether}: 0.1051. noun/11m Time J x 34 0-0: k 330‘” *1 one. x 10 > (ll/1.) (re/1.) (0/1.) 1. :01. m. 2.3 0.0050 0.1225 0.1002. 3.06 36 0.0102 0.1133 0.0912 2.96 1.5 0.0167 0.1108 0.0887 2.95 81.6 0.0261. 0.1011 0.0790 3.11 99 0.0290 0.0985 0.0760 2.91 126 0.0370 0.0905 0.0681. 3.21 11.7 0.0390 0.0885 0.0661. 3.01 k .1 Ava-ago . 3.17 :1: 0.10 x 10'” 1. 0101.21.00. 333.31.??? XXII THE RATE OF CLEAVAGE? OF fl-oPFFEFEETm PHENIL 0mm BI 11342511210333 11“me 0011.100an Temperature: 1.005 , Solvent: Isabutyl 0.1002101 [001]: 0.1005 Males/11001», [001100]: 0.2000 Hahn/liter ”21:00 .3 x 0-0: 13-9: k xii-C. .1 m. x 10 (ii/3..) (Fri/1.) (0/1.) 1.001. m. 2.9 0.0010 0.0987 0.1932 ' 3.10 8 0.0032 0.0953 0.1908 3.0). 11.3 0.0071 0.0930 0.1929 3.07 1}.- 01.0080 0.0025 0.1920 ‘ 3.01 18.1 0.0106 0.0899 0.1690 3.02 30.2 0.0150 0.0815 0.1800 2.98 ’06 0.0250 .07., 0.1750 3.31 87 0.0100 0.0005 0.1000 ' 13.10 __h _.._ A m..— LL .- .._.._ W— Wv in. ——v w k -0 -1 .. war-030 - 3.07 t 0.08 x 10 1.2001. sec. _____ _-'_ ‘w—w WWW . ”—7— —__v *1 4 TAEiE XXIII THE. RATE OF CLEAVAGE OF 0-PEFENEE'I'E‘IIL PHENIL ETH‘Efi BY W033 111020010 WIDE m T 1 _ m :1. a _ ‘ - _ '11 Tmparaturm £1000 , Solvent: Iaobutyl Alcohol [001] 3 0.1250 Moles/liter- , I Ether I : -.-.__ 0 .2861. Mala/liter _‘._ —_._.. Tim 3 0-5: b-x k 1‘30 .1 «3. x 10 (0/1 ) “A 91/1.) _ (LI/1.) _ 1.1301. «c. 1. 0.0006 0.1202. 0.2838 3.3-0 7 0.0071 0.1179 0.2813 2.93 10 0.0106 0.1101. 0.2778 3.15 12 0.0120 0.1130 0.2761. 2.98 16 0.0132. 0.1066 ' 0.2700 3.53 20 0.0200 0.1050 ‘ 0.2681. 3.13 22 0.0213 0.1037 0.2671 3.05 01 0.0350 0.0900 0.2531; 2.96 60 0.0500 0.0750 0.2381. 3.27 72 0.0605 0.0605 0.2239 0.01 1: map I ~35 0.1 . 3.21} t. 002“ x 10 lowlc 3.00 50 TABLE XXIV m RATE OF CLEAVAGE 0? 00mm m m E! ”131303008 “HEDGE! CWDE mm» 00%, 0mm: Isobutyl Alcohol [001]: 0.2256 Halal/liter [Emu]: 0.1000 Nola/11m- 21m .3 3: sun M k :30.“ .8. m. x 10 (3/1.) (0/1.) (5/1.) Lysol. m. 14.7 0.0035 0.2221 0.0965 3.35 12 0.0002 0.21714 0.0910 3.17 16 0.0106 0.2150 0.0891; 3.00 23 0.0102 0.2110 0.0858 3.01 30 0.01014 0.2072 0.0010 3.12 31; 0.0200 0.2052 0.0796 3.15 1.9 0.0280 0.1976 0.0720 3.00 66 0.0355 0.1.901 0.0605 3.21 100.0 0.0575 0.1681 0.0025 3.20 .1 I‘M”, . 3115 i 0.10 X 1.0.a lawlagsno TABLE XIV ME RATE 0? GLELVAGE 0? am PHEN'IL mmws mm mm Wm: 3.0%, Solvents imhawl mm]. [001): 0.2000 wales/liter, [Ethan]: 0.0981. Mala/liter Tina _, a; mm: M k {110“ .1 no. 1: 10 . (ii/1.) (ii/l.) (Ii/1.) 1&1. m. 2.3 0.0021 0.2779 0.0963 3.32 6.7 0.0062 0.2738 0.0922 3.50 20 0.0160 0.2600 0.0821. 3.21. 36 0.0261. 0.2036 0.0720 3.26 30 0.0280 0.2520 0.0701. 3.22 51 0.0300 0.2060 0.0610. 3.20 55 0.0390 0.21010 0 $5913 3 .55 75.8 0.0591 0.2209 0.0393 0.95 .3 I kwmga II 3.51; :L' 0.33 x 3.0""6 1.301.“.00 52 TMEmI IKE RATE OF CIEAVAGE 01' «WEM mm. mm 32 mars mesa: WE Temperature: 00°C, Solvents Eta-y). Algohbl (0.st [0011: 0.1175 Holes/1100: {Ether}: 0.2013 Malena/liter . k _ an The a . x 0-9: _ 1m: ' x30 .1 m. X 10 (Mo) (Mo) (Mn) 1.1001. 368. 5 .6 0 .0033 0.11140 0.1935 3 .56 1.8.2 0.0116 0.3.0.32 0.1575 3.50 1.0. 0.0291 0.0881; 0.1727 3.1.1 98-2 0905113 0.0532 0.11075 3 069 125 0.0655} 0.8515“ 0.1362 3 .hO .1 km . 3960 i: 0.06 a 19‘s 1. 301. m note: Mommy ammnto for rate studies in ethyl alcohol me undo with dutch-out 0.110 than than and for motion of tho calibration curve and than 00me with other solvents are m Mid. EMI TH3 RAT: 01" 61131113313“:- OF 04mm HIM 3131323. 3'! RTE-3’." 3230138 m..0m GELGRIDE -— Hanna-u- .W.M. -JFH~._~_¢4,4‘L- ,. , Tamarature: 30°61 , Solvent: Vithyl 11001101005) (1101]: 0.1253 11.1103/111031- , Mar]: 0. 0969 Holes/liter Time .3 1:. 11-1: k 1&0 .1 sec. 31 10 (1/1. ) ( IE1/1... ) (0/1.) 1.1161. 890. 2,3 3 313 0.1210 0.095'6 0.57 8.0 0.111516 0.1207 0.0923 11.36 19 0.0090 0.1163 0.0879 - 21.115 33 0.0160 0...» 0.0809 1.59 ‘1 use .1 "average =- i..53’:3‘; 0.3.23. *1; 17.“ 1.4103... 300. 511 c .. Gloom of Optically Active oéhmy'lsthyl thyl Ether by Anhydrous Ween Chloride atypimmmmminthotomm. Tooncliter ~11: 611351111561”: mndummmho" thou-om W105 t. (6.25 mole) of euphwlethyl ohm mar (11:501. «311.88%. m allow mathomticntoprooosdfor msomunzthoftimthcmtim mmmwmmmbamm manna 20:11am magmas 3111111111. The mm nym- m nah-1 twice 111111 200 :1. of ant» and mm mm sodium «Hate. mo 11W). chloride all distilled a m and its refractive index no option]. rout!” m W. All cleaves! reactions of optically active «not we Wont inan lanthanum accept tor-variations in thaulmt m router-y pom of the em. 2. '~ fact of ' o 1.13 1.161.331; 31.1.21- -'-.11:.‘-::. ' :12, in ~' 331:1. 1 1.! r The mat of nomination of optically active a-phwleflayl chloride: reuniting solely from. the method of isolation was dotorodnsd . 11 solution of c-phwylotlwl chloride (known rotation) in pure oolvmt m mm at 119° for the desired tine mm. The reaction mom a. that «treated with M museum We solution and the organic has! III mod twice with approximately 200 ml. of water. It as dried over sodium sulfate or calcium chloride, the solvmt was distilled at atmospheric pressure and tho a-phervlotlvl chloride was distilled am. The real-ts are compiled in Table XXVIII. 55 ME m1 PEG“? RACWZASIOH 01' ”CALL! ACTIVE «mm mama IN 1113 1331:1103: or 11111101., 1.0 aolmt blouse 0 1 + 19.98 + 26.50 211.118 1. + 19.90 + 26.50 221.92 6 e 19.60 1 26.50 26.11 26 o- 19.h6 1. 26.50 26.58 DW1 0 - 33.92 ~ 1:11.115 23.50 Km 1 0 33.00 ~ 1:11.15 25.26 26 - 32.75 - 1111.15 26.11. Wtyl 0 0 13.95 0 19.30 27.75 Alonhol l 4» 13.60 19.30 29.50 26 1 13.39 19.30 30-59 (e Rotation of a-Phenylethyl Chloride after tins (t) WWW wi—WV ___ (by Original rotation of o—thlothyl Chloride ._._ 56 3. o- Rec»... 1 o '1111 11111 .1315: ' 2.1. 31o mount of nomination of optically active o-phavletbyl 111131-111. due to the We of phml as determined by permitting :1 «1111111111 or 0.1 m1. m1 of 11me 111mm, pom, and. Wm «111111-1111 111 one 111m of mm to mm at 111° for tho «sired 1m. mom-unmomst‘w c-‘phwleohylohlommflwmu WMWMW). ammuwmmmm Mod and the pa- cmt rumination. no «11111111.». The results an mum in mm. 11:11, 11:1, and .3111. h. . . In mm mm, “1111,1111: mm are found the 1 ~ rotation of ooni'iwation of omwlotivl phwyl other m cleaved by 1, hydrogsn ehloride in tel-am, diethyl kotono, and 1:0me alcohol . TABLE XXIX 57 PMGM MG-EMIZATIW 0F (ETIGMLY ACTIVE «mam momma: «11.90? ~33.22° 25.15 433.65" «33.22“ 30.00 -23.2s° “33.22” 26.81. .22.:11" ~33.22° 33.90 411.2" «33.22" 35.36 V. ——.—-—— w. ——_.7— W (a) to Iagofor e-phwlothyl chloride am tine indicated (111») Original rotation of cephmyleflryl chloride 211.92 26.11 36.58 (c) Total nomination due to phenol and mark-up procedure (11) Extent of mmimtion due to the mark-up procedure (9) Extent of rwwution due to phmol 3.92 7.79 3.15 58 TRBLE m1 1’me mommnw 6F CP'I'IC-ALLY ACTIVE 11-131mm CHLQIDE BY P1111301. AND 111111001311 mmmc Tomorchro: 310°C , solvmtz 1111111111 Kotono 0 ~— 43.6110 ..... . 1 .1s.7o° 1-23.61? 29.50 25.23 21.21. I. 2 ~16.28° 413.32. 31.33 1. «45.78" £3.61." 33 .118 6 45.311 43.131." 35.12 26 ~11..71° «2.3.61.‘3 37.36 26.11 11.72 (.1) (1112? 1.1 e-phmlothy‘l 111101-111. m 11.. 111111..“ (21) Original rotation 11-911leth chloride (c) Total mmfieflon duo to phmol am‘iwrk-«zp procedure (11) Wt of nomination due to the work-up prooecmre (o) Wt of newest-don due to phmol 11311313011: PEROM MCMZRTIOH 0F WTICHLY m1: 11-19mm GHLGRIDE BI I’EETEEOL .5115“- 133.310.1311 313.0911?” amuaumag ;3 rt»_oeawv~>»mwreamzmaaaas Tmermre: 11008, 3111111111.: Eaclmtyl Alcohol 1 _ o -o “1.1 W __ f i D O ' m 1.130.300 an. m «In» 1 120.15“ 130.20a 33.05 29.50 1.30 2 +2o.§9° '+3c.zo° 31.35 a. +1350“ +3320" 33.1.0 6 +19.37° +30.2d° 33.80 .51 25 113.679 133.2. 33.32 30.59 9.33 __._‘.._4 ——w— —. “1—w— w (a) [3:12; for o-phonyletéwl chloride after time indicated (b) origoca1 rotaioan-aaphcmyoatcyl 11101131 (c) Total mmioatipn duo to phenol and mack—11p procedure (:1) Wt of reomioetion one to the work-up procedure (a) Mark of marination due to phmol TABLE mm: Pmcm gamma or cmxmflofi IN THE CLMVAGAS 0F MIMI ACTIVE (gamma JXL mzmm "-'::‘1‘£-i 43“" BE 3.337553332sz Iflmflfi‘éfi GmGFID-E I _ . ‘ . 19W“: 110°C, 301mm ram. Percmt.‘ Pore-ant Rotation Pmt Rae. of £301 3mm of 3-04: 9mm (Wed) (Corrected) Rotation of Rio]. Tim - 0 (rm-a) (am-:12? mm? 'w v— w . m w—v—. -—v—— —-—— rwn—v v—r— “ w w 029.10 25 .15 90.11 1 «16.30 ~lis.88 61:36 2 4.25.25 «5.30 whaa 62.50 30.00 92.50 a mm «55.: ~m.sa 51.110 23.31; 90.21; 5 +£7.08 455.30 «mas 59.71. 33.90 93.61 25 “25.25 45.30 “11;.83 53.50 35.35 93.86 A‘___L_J_'_‘._L - - AA‘MLA- —v— —,_- v—w r—-——-- w w—v—q w- _. fi—V‘ __ (a) Rotatiun of u-ghmlafivl chloride after the indicated (19) Original rotation of a-phanyleflwl chloric‘ie used to prepare tha other (3) (“322,0 for amhmlouzyl phml other V. rm mm Pmcm RWIWI 0F SWIGZRATIW I}? THE CLEAVAGE W WTICALL'Z ACTIVE a-P'Emmm HEM. 33'1" Z25... BY HEHQRCRIS 1mm {KEGIIBE «*w- mvN-n-H -‘ mun-M" *flmflou—rvaw- v,u"“-' ‘w‘4q‘-‘.«.«“«4 r'd-II-l'rtum»-'rt*l%AW-fl-Hnfl*-'ww-4~‘Wk-..A¥‘¢lfllfl-ww , .-.-— Tamerahxrex 1.0603 , 891.va 131mm. KW Parent 4? Percent mm Mo 2r” Reta, ion Parent Etna. M: ’«i-fll 3mm (Hmra) (a) [a]? (b) [a] :33 of R—Q-R Retention (Determined) (Corrected) Romtimz of EEG]. 1 «23.65 +35.25 +1235 61.80 29.50 91.30 2 «22.55 +38.25 +1233; 39.3.1 31.33 3-23.73. L. 42.21 +33.25 0.2.75 58.00 33.1.8 ‘ 91.1.8 .5 mm 438.25 +1235: 56.11 35.12 91.23 26 was +£6.25 4.12.75 55.25 37.86 93.11 __ _; .4; w .7; 4*" -;__W W” ________ (n) Ratatfina a! aiphmlsmyl chloride me. time indicated 03) Original rambler: of craphwletfiyl chloride used to prepare the ether . t:° (a) [51233 for a-phenmafiwl 1311mm. ether 62 TABLE 30111? Pmcm-r $231"me 0F C‘mew 11: rm: 0 12mm: 0? 0191101511.! 5cm 423333.23m'n. mm *1. :3? mm" mama "meow warm :E'w “2:3“; ~_§' _ ._ E“ : W *" L” “1:” ‘l‘samratm: :;.o°c, Solverrt: 130mm Alcohol ‘ Fment Percent Time ,0 ,Eio Pwem‘b Rae. of R-Cl Retention .0. ‘ ado . (110mm) “Ned‘s mm“; of "i'i'aEJ-de. mtmticm (DeteraineL-" '1.) (Corr-acted) ._‘. A.’__..| A -L w — .—_,_ —...__.~ ,__.——.fi..._ w-w—w '- V ~— __ 1 «3.3.50 +3045 +1150 «50.50 32.05 92.55 2 A 4.17.77 +3045 +1150 ‘ 53.22 31.85 90.02» E. 46.92 +3045 +1150 55.55 ’ 35.1.0 - ~ 90.95 5 916 .70 +30 .16 +1155 ' 55!...75 35 .80 96.55 215 ‘15 .97 +30 .155 +1130 52 .33 39 .92 92 .30 (a) Rotation of n-ghwlaflwl ciflnric’ie after tune imiica‘ted (’b) Origixml - mama at“ auphatwlathyl claorido used ’59 prepare the ether (0) [05121530 for a-phemdetivl gnaw-‘1 ether 6.3 02301.25 M113 0100030103 A. This Kinetics 0f the: Cleavage The; method 3330 ramming; {2'10 2:003 0 i“ cleavage"; 0f 0 finixewlemwl phuzxyl ethar by Im'zrogmz 0201012100 was briefly as follam: A solutian 025’ know; concmtramn 02‘? hydrogén chloride in 15110 particular 3011:! 00%; was pourm 314w *‘ v01um0tric £105.: containing a waigmec: (500.3 0103* 0:? 04-33 magi-2132;}. 0011321 00 .200 00010120. nastier: ms 0110230000 2 «0 91200000. At various H.200 intervals 1-011. 01.101000 of tha remtion sanitation 00:20 220020000, clilutasi with 3110020210,. and extracted Wit} 3201;000:3220: 15.0 3024’ 32;; 0 . 3‘00 {2220210110 002150000 tam-3 acidified with acetic no": 21:"; 800101": 11210;" 5.300 022.2 001202.010 acid m0 nag-523.2. 00 3501-0: 21100080121103.0121, $011000: ‘22:: 02:0 250 0.000001%“ 20.220101111221022 ro;.:§.<10, wiich yielded the fillet-«@000 93.2.1120 5.2-."- 001‘13. 0:7.“ nit-fuzaoyhenol. kit-014 the solution had been 03.101206? 130 0-20.05 27’0”." 3; 2:01: 202 *0 02: 0030 its 12100213103“ was measure-.3. (at 1.22.“: mu) using; 0. . i-3ti.~mmersmm 020000300132‘10 calorimeter. T110 intensity 0120 0010.00". ‘00 a cflibx‘ation 0121020 p222 902021 in 0.21 1.21021 01022.1 00.21002: from «0010.0 12} 10110.. 001012100 . The first rate .Wmmwts that. 002 0 20000 were 00:05.00 out by treating a solution 0160-9110252101‘220 l xfizmwl 001002 and 001210110 with a conmmm straw: of Emir-0:201: 0210:1012 gas . The procamre for datum- stun 0f tin-0 93101201. was '00 0023021000. above. T0 determina mather the reactinn was first order with raafimt "£50 £320 01.11012, a. plot of 1MP! ~ F) n (t) as made, when P f :- phmol 00110000200100 at 1C0??? auction, 63.1 P a panel 0000900101000 at time (t), and t. m 01.00 in 0000000.. Figzra h m 00 mien 222115.012. line 02.2.22. no 0000100121 :2. 20". 3mm Might 3.1000 0020 obtained at all tempwatm'ea at which the: reaction 1200 001121012; 2.11., 09, 20°, 012°, 12'0", 2.00 0. 22.115 2.2-. 2.2 clear that. 012 01830150 50 i‘irat 0121017 with reapwt '00 13120 22121201“. ‘20 0000011332 the rate 1m 22.2.... respect to 30-0012 r000 120000, 1.1122 rea- mm was 0130111013 with 12310 ether and. 3010-0an 0hloric10 at 00052010010 but. varieci 00110232012005.0110. .3. 12001:. f0:- 000000‘. order tine-1.100 000 22:00., using 1-200 11200310000. form of: the 000000 01201012 raj-".0 0220120031031, Th0 gimbals are 0013000 on page 29 . A 30:11:21.0 001001220100 10 as follow-z 11. 1-011. 03.121002; was £01.10; 220 have 0. 0012000023 00010 reading of 33 $15.01; , "0:; 00220201000121 with 1.310 Mum-CL 121102.101 calibration curve, indi. . , -2 000021 a phenol. oomentra‘oion of 1.570 ng. or 1.0? x 10 moles/l. a II U.203.U b » 0.1315 :1! a (1.016? (0-0:) a 6.1843 (02-02.) a {3.3.3.118 1; 0 55.3 2: 103 sec. -53 «.1 0-1 k3 . 1.27 X 10 19 m1. 88c. A. test for third orflar kinetics m0 cam-33.03 out using 2.310 equation, . 1 :2: 2 ""3 b’a “3 ' “5-105 {030-225 * (gm; log 0,502; I ‘ 1., \ L)“ N’”.? 53113111011. XLJL‘: THE.RATE 6Fm1av 2 GF'a-FHEEXLETHXL PHENIL Efflfifl BY. M¥iwfi"c* W 2T 13M" E‘i €0.41; Lin‘ T010300; [1:331] [Ether] 12111210: K3 310 301‘; Gilt :WL 1 O mm/l a 6-." if; .z “fag/’3. a {3'34 ‘. 1 0.11333. Q 3136 I: ~.. . Ag... ......_ h _‘ ,_ M 4 ' ' __ ____ _._. 4“; - 4 m- Tolnena {1 u. 7.17:1 .1003. ‘I .125 1.01 21.G 0.;229 $.1OQ0 3.2? 1.3S 00 0.2829 ’9.1030 0.31 ‘1.52 50 0.3010 0.10?3 0.53 1.60 60 , LL2“hS 0.1033 01?? 2.31 Telumle 3.10 0 .2312; 1') . 91113 .1 . 2E? :17 .03 0.1217 0.3352 1.03 + .05 0.1.217 0.30512 2.1 O 10.1 Kn. HP 'I 8 ‘2. f “. ‘1 P ‘5 r‘ I' : -. J 0.32;U 0.1000 1.30 i .05 .-. (1-23 2 ’ ~ _.. ,9, ,--... -..' 01.1"”,1. ’.. {_r' ‘3’ I" 'J .2. 0,311- .2. . ‘13.; ’ Q. ' , -Pl 1 01.02.2313... 310130110 ’11?- "1.1173 ., 1.1135711} 51...? :2; .97 0.1250 0.2003 1‘13 NI 0 2-. E3- 1+ 0 k; . 1 c... ';. 2‘ _- é' ’ 1.1.1.351) 0.29621 .33, f: .0“; 1", f“. :'. F' 31:."- . ‘1 (v I. ‘3: 0.aJ{l 0.0yyf 2.4M % .vv ‘2) Ho 2) I 0.?wlfi 6.0992 2 IfldbufiYI 30 0.1275 0.1050 3.17 4 1+ 12 E; 71 '1“. .. ”.1 .. - . 1.00-01 0.1005 0.2000 3.0? 0.1230 8.2860 3.23 i .23 0.0256 0.1000 3.15 1 0.2300 0.0980 1+ + C 1.; c: .33 H‘ 0 a 3 11112101 alcohol 120 0.1275: 0.1018 3.60 (10001120) 031031 alcohol (70%) 4—- _‘. .— _.___ _._. ._..__.- M A 32“. (:1 0.2153 0.0969 11.33 !+ .11 ‘_ _.— .,.—, w .fi—r _‘Vfi 2—?- m _._. _._. _— ‘7 ”33000 in.athy1 alcohol 0000 measured with airfarant 00113 than 20000 0000 for praparaticn of the oalihruttun.0urve. 6? uwmmt‘wh. mumnfltmnanmmm mmwmmmwmmmmm. am mk.mwmmmmummumm- nuwmmmmmww.mw ammummmmmmwgmm memmma. Mmufwuwmrwth-WMWW wwwmmmmwmmmmm mm :- AR «In/fir (1) - 11.1-11.6 Amatmupumwruamtmmmmww mwormmmummmmammm,mm WMMmawmmmemmu-lm.mwm (II-AWE). mammarwmnummmmmlm mum Aflw A I tar/h a (3) um.»mmmm,aumm1mw (1.38xlfl'fl'wwaw), hurmww (6.621;me um.)mdnummmma.mm.mmwm¢ mmwummmn, ammnmmor he“ a. an 1-32.6 0.3. .0 w 0" ~90 -V o F 'I'Lo‘ The large negative entropy or; native“ and. fine 15v mg of Clementine indicatee that a precise static orientation is required in the minus: state- and when this static reletimhip has been stub- 3.1m. the reaction meme easily. In those cases where excess hyc‘a'egen ehloride we used, 11:. was necessary to new the solubility of meager: chloride in toluene at We matures no that the true specific rate constant. for the cleavage reaction could be determined . In Table IV are fmmd the rate looms m hydrogen ehlorifle eclubilities for reaction twee-amen ef 0°, 21.80, bo“, 33:0", and 60° , 0. Although the pseudo-met ore-er rate 3mm, k1, do not vary directly with tampm'ature, it can be seen that. the amondwrder rate commute, summer: by dividing k1 by the hydrogen ei'zlaride eoncmtretion, increase regtflnrly with temeramre. The enlubiliti-ea of byémmn 21-110mm in toluene named. in the present investigation agree reasonably well. with Y the mall amount of data. previously available . wage"; and. Sinshelmoci (29) found the solu- bility of Megan chloride in benzene at 20°13 and 76° m. pressure to be 0.13608 miles per liter time Eeirbretber and. Belkin (30) obtained a value of 0.3632 mien per liter. The procedure of the latter was to Inmate the benzene with mere gem cbloriée for about three 1W: . me want of dimlvec! gee was determined by misplacing it with a mt of carbon. dunno-free air, absorbing; the hydrogm chloride in. VIII-Mr, and “eating with normal sodium hydroxide. Bell (31) Items 3 method similar to that of Feirbmther, determined the acluhflli'hy of Wm chloride in toluene to be c.4423 males per liter at 20°C and 70 760 m. pressure. The We the damning the scalability of ‘ Wm chlorine in this meant immigntion has been described mwionaly. If. we found that at 21.5% 041229 males of hydrogen chloride diamlve in one liter of toluene. maximum of Tablee V to X33311, finch list the reaction rates for the cleavage reaction in various when“, indicates a eurpriemg’ly ml]. solvent effect... An average of the second Ol‘dér rate constants four-xi fer varieue concentrations of the reactmma in min uolvent 311'". 340° in indicated balm Quiver; k x 10-5 telnene 1.33 1.no1.'1¢ec.’1 Methyl meme 2 .143. isobutyl alcohol 3 .13 efizyl ale-03:02. (absolute) 3.60 91:13:11 113.com}. (70%} 3.53 It may be new tint there is an increase in the rate of reaction with increaaing solvent pouring; but it. is an unexpectedly mall one. 3. The Stereochaeistry cf the Sleavage Hart and 1‘3.th have 32min that (+) e-phmwlethyl chloride yields (+) a-phawlemyl phenyl ether when refluxed with ”dim phenoxide in Wrens 31001101. 31 m vzia Sines: tamer formation is presume: to neeur with Winn, (4.) a-pherwl- new]. dflorido has the 5mm c-ezli‘igun...tien an ( .) cr~phew1ethyl phenyl ether. {3]. 91:635., 1 v s : Ruth-2133113 43' 3-6-0153 2 1 (4 i (“J Wan (n) eaphemlnml fluoride am} phenol were refluxed 1111 a mapenaion of acetone anti wtnaafiam cm'emtn thwe was obtained (+) a-phwleflvl phanyl eater. Sigma the name s‘eerne-ehwdeal newline was new in the We Mfmnt mam, Hare and fiflazterie 33mm: that nth-nrifieafien in acetone and. potassium ewemte is a typical 3H2 din- planmt mention, mick present-En me: inversion of configuration.- my!” ant! 1:an (32) established that (+) naphnwlwhyl chloride and (e) «memlnflxfi amine new configurationany related . I33" atmo- ehanieal amdiee ei‘ l", 2 shifts Bamatein end Ehi‘tmore { :33} were able to relate the cenfiggma‘bion 0:? (-1» } phenylnti 13:1 amine {1.0 (-) pixemma W1» acetic acid . Latent" Minion emf: .Eeffler (31;) , by stuziies involving melting point ammunition diagrams of 1i: :2 whamkvlac-etic acid. , canflnaed Bennie-in and 'fififltmre' a cenfignmeioml nesimnmta . in addition , MMWheefic new. and. anphewlethyl 2:31:19 were related to alminn, Ihieh has been new as a eonfignmtional standard. The resales we swwaariml in the following fnmmlas: 8 9' . a»: 60022 I I I M 4‘ t. ‘ fi 9-: Q '(+) v wt ‘- $32.3 utb'-i€}d-I if; C 5E: l 313 93 C | «nu-u- not. “:2 m + v firmer: Herb one. Elmberio broaboci (+) o-phwlobhyl phony]. other with a. .1 - 8 I v. «a o. 3!! 72 a H «5" ('3 I pun-Inn-.. ! M H G ('0' hydro gen chloride in benzene they obbninnci- (-) o-nphewlofizyl chloride (21). Since (+3 czdphonylothyl phomrl other has the some cenflmbion as (9-) o-phmletbyl chloride; they concluded that. the cleavage ooe‘urrad with rebonbim of oonf igurabion. The mark of Banter (35') and of Wanner-mm (36) , which no new moment to this present sway, deserves nonbion because of the Immr name of the prone-goo involved: £1.11 all three reactions. 33m abwiod bho ammonisbry oi: bho not? hydrolysis of £29me Stilbnm. oxide, am fmmi the process occurs with robmbion of oonfigm-abion to yield the three-glycol, “a" ~1,2-diphe3vl~l,2-proponooio1, 'ul' 3 His finwme differ from blouse obeemred for bese-oaielyzed rim! up: 1:13 sags (337.) and for acid-oatmed ring; cinemas of :1. number oi‘ nonupheevlebed socomiery epoxjdee ( 38 )V in bib-1b in bit-e313 bee-ea mar-aim is the rule. BrWBer propoee". b31111; one of: 12111 Embers contributing be we emceee appears to be b‘: :9 generation oi :1 11mm]. emonium clwrecber at the site oi" the react-110‘. ;. it is hemmed fleet bwbiery or cup-perv]. eporldee could develop a parbioulerls“ .11 .1311 (38; wee of carbonimu b‘rareober, men to the paint ea: ere a reem'erfi moloop’uhc "131131" was nob required for the reaction. The obereoohemioel outcome of the reaction would depend, than, largely on b‘rzo locatinn in Space of: the moat ewe/3.311111: Lewis base capable of reacting»; 111111 the. developing carbonium center; if 111118 base were weakly one 13032313111. 11:: 3;ree erivenWe wool-:- eocrue from on inversion process as bggflbm be one 13W3; be bhe retention. of con- figuration... Brewster ebebee that en "Jonqm' fume; 3.11:1. “ “01mm.— cage" by reaction of a. proton donor m ‘1 an. e :ide mule be oriented as that the pe-efeb ed retention oi coni’is rabies: would occur , provider 9133:1531 commune chamber developer: at the reaction site. The following balm we: prepared for b21ereeebion= H 1“; /£1e£3* ‘6 ecu: 1‘) \ /0\/1m"0/:\a \Jx'\/ \G———-C/ 17.10 33"; + 6 It. as also mbionod by Brooobor that retention of configuration in acid-catalyzed oloemgoo of omepal 233119137'1ox11'oneo ( 38) indicates that a omglo phony]. group is sufficimt, am probably necessary for this result. Ho has mgggoebod that a phorgl group mot be attached to the reacting; carbon atom in accord. wibh bio-:1 pioturo dwelopoo above. bios sermon treated oio- arso brauo-dypnono oxides (I am: II) with hyorogm chloride in acetic ac: lo or ethyl elem-101 am: observed that fmnation of the roamebivo olioroh'ydrins occurred with retention of oonfirgarotion. The scheme mandated. for b11113 reaction is as follows: 131 '3‘}! “ff-5”” ('04, 111100113 (Itobmbion) . 11 (Inversion) - 0 9‘.me ‘1; ‘ 0 ¢-~‘ flflmf xxacxfl‘moo r3213 11 o . . (:13 (I) \ / 11:31 113L313, -, I” (fictonbion‘; \ (immion; / ' \ :1 t') 33 h I! d‘ W“. \“ $01.. as 3&8”me omen-m bhab bin: (13111nt of: tho opoxioo ring; takes place with retention of configuration, Iguanas the ring closure bivalves wait-ion hover-sign. He cited mologias :01? :sstsnt" ion of comioaration in the sewing of mm similar to shame oxide we}: as the rose ties of afihmylswl alcohol with i'arfimgsn bromide at ice momentum (39 ) . am the alarms of asphalylefizyl pawl other by dry hydrogen chloride ( 21) . It is Massimo shat the ammo-ms]. foatum mics. sakes mess mums sass optima to t? :18 type of cleavage appears to furrolvo the attacnment of“ a Wow}. you}: to the swoon undergoing... =‘" ’35 f isaioa. moors-sen belim'es the mpmna miso- a}. ohms-in conversion aroooozis by a moose similar to that saggestefi bv Kart one mentorio {20) for the cleavage of a: 11‘s wiethyl phony}. other . The results of this present invest igatism are in Jigsaw" tuith those of mm and. filmterio. Cleavage 5:»? nag-angles; v1. poem sthw by warms )“Qfairogan ehlorifls was 33012115 to oomr with retention of con- figuration . {ma percent racamisation was -:?‘.etomin or} to he appmxisstely 30 to .1;me the resist-ion was a rifle: out in the solvents lists-i in Table mm. This :mcluot ad! 329 .2”. or, m: u the racemiaation of? the Opttsslhra Mi 3 ohhorios 6311:9335; ‘ she *- . 7' .~; ~up ores 6353 an." also 39-1.. ' «has to the 1332522101 am: ,r region "low. jars-52122 :--1 m the r22 3' tier: "21.221132 as a remit of tic-s classega (11:51:). “in Tab sari“ $311}: an: 23:31:; are fans-.3. the percentages for the fumigation resenting from the method. oi‘ isolation at: 9% rscoefisation by the mono}. and fights-egos chloride, respectivaly. These values were silos-"1‘ to 22o po-rccm amt retention, as show: in. Table XXXVI, in order to correct ior recesses tics occurring subsequent to _. s-phmzylothyl clflorido fem-tics. it will " ousted- tb t the c _.ssvags processes with approximatsiy 90:: retention of configuration in all ,...I 1 i“. .fi .. . ifig.‘i.~...' 76 1'" seem RET‘EHTICfi‘i 03'? (KMIE’SU 172411310133 31 xii; GL7." a‘J’AGE {3913‘ OPTICMLY ACTIVE? a-Pfitzfl‘MJEM: P8151533, 52171-1 53.13. M MWIIRCHS HYDROGEN CHILD '" .E Solvent Toluene Liotayl kotoao Isobutyi alcohol Tiler-2 (Hours) o~ 3’ so t4 P3 I"\ LE 26 '1‘ superstar ?eroent 'fiatantion 61.80 ‘50 .5510 58.22 §S.VS Fho7§ 52.38 Percent Racomisation (fiotanmines) [0 t? 1 h J I '50 ' kg (2 C CD k. N CO v 4:. L2? 'uo \A} o \t C v sarcoma Retention {Correctoifl 9Q.ll 92.50 90.2h 93.61 93.86 91.30 90.7h 9l.h3 91.23 93.11 92.55 96.07 90.95 90.55 92.30 v.— 77 three solv out: Isaiah we stained. . sis is consistent with the kinetic (fits. obtained for the cl swag, use in the 3 solvents, Ln maios the second- ore or rate constmt-s were of about the same mammal-s . Thus the results of moss storeoohoaicsl Sissies fart: 1:31” iaiioate that. the reaction is not greatly affsoseo by variations in the solvent dielmtrio . {I , ”oasis; 133.111.9(321) as. Lie-scribes} or; inn-333:1? as a acetylene of tm ions Which is .311. “beget: in; 53‘ electrostatic astracticm , in a solvent firm}: does not have sai’i'ioient solvatj ;: pomr so fires the ions from each other. He »:s:~znt..ons that it is not aim-ye pose-.3313 to distinguish between an as. “6 9.2121 ion of two ions to form an ionugsdr am? are assooiation "to fom a covalent compo-um; . It is qm to likely “bl-sat the type of bones former} say vsxgr waifnale out? contains L. 531}? from ionic to covalent ones . 5 Bowman (.' :2) points out. that "one stcmoor‘hmasl capabilities of? ionfiejrs are not yet. cl or, but («“0'3": {1 is acoamhtz’ m: that .nfisr aorta in con- mittens both cation one." sates , -r- 74322.27“. 3.}: asymmetric: arc: 3.3artielly capable of reintaining t": 2 213‘ fixer-2.1.3”: i; :o extant of loss of ssmflmetry Lapwing or: the 212151.: oi life, m see '2; so also salon, and .. (113316;; of intense]. solo-causation of 622.1. gs . as evidence aomnmlzroes in Mi a stay. or supposes an ion-toss: meshes-v ism. The kinetic stud. 103 some am in aziilute solutions the rats of cleavage is slow; this has boa case: "or. freq * entity 3‘01: react-Loos mach spar to via on Miami.“ mot-2:21:22 ((42)). The High negative mimopy of activation, oalcxflatod for the other damage, vain-ates that the staric 75 wirmts are quite rim . If the ciflsricio ion becomes attac‘nsi to the aids of {as inn first: of. 110?. “bi-112 1’: 3.1 :1 misc-111.0 leaves a Euggfly origins: trmsitian state is requires. Sines the cleavage has bssn fauna. no occur with satsntisn 05. 00313119 firstifim a 1.153110191311151 dismissa- msnt can be ruled out as the reaction panama: haemss on; would expect imam-aim in this instance . In was similar motiom, in mic-h. moms-‘9 f s embonaomvgan bani occurs wits sensation of configuration, the most. suitable nmhmiams flmi‘; Ems bssn proposes are ion-pair processes . It hss beam statsd- first was simcun'm. fsa‘mra which permits these reactions to um’iwgo olssmggs ms newsman of configuration my be he grasses of a sham-v1 group on the {2mm bonded to the: mqrgm atom. the sham group may be nos-693m? to donation c-irhonmn eksrac'ber at the rssctisn site. It wulr— appeasr was tint one of was factors that contributes to the 12139;“.ng of saplismrlsfiwl phwl other by Was-n ohlaririe with Mention of coni‘ignzrstion is the: presence of the 1331sz ring 111 tho aliwl carbon. 0n s11. basis sf the above counsel-sums it is promos-11. fist the mantis-:1 -1: mm can best be rspresmtss as follow: 7—? ,_ E1. 1-- F \ .. . fast ‘\ (.33.. ," . ufiu’l + /‘L’_ ”-4) m /'d. ".J-“¢ (is as: W 4) tens. + ' 79 It is suggested that the Species, - u -! :53. .53: _.‘.3‘.+. - - 5 -45 '. mi; may rsprssmt an inmmimts 01:- a trans itisn stats 5 1-5 . Buggimtsj Fume ‘iiqnwjmsnts 313133 .2 525:5 3:15.11 mlvsnt .5530th was observed, it W13... a: spear tiist 13:52 ionfiaair samples; mat Ls tightly beams-i . Stmiies of the cleavage 031‘ wbstimtsd swfiismrlstizyl pussy-5r}. stizsrs Bimulfi. ts 5235551215? interesting. .75 J Om- .muii sxpsst s. 5 ”sat ssh. amt s ifs-c i. in those cases ”Eras-was the alsstzszzis fleets 0.?" tin. subst. Ummts Bi: 3.; muss a. change- :in the: attractive fem-es of was ism-mix .. fittest ha rate ans stereosbnis ry of the slssrags maul-ii. be more: 55.1.11 59in Amt. If ti 9 p2: sass-as m". s piisrwl ggmzp on the aliqyi. st. ' i.» is. is necessary for cleavage to occur with reis- tim , by stabilisation 0:“ t. as past carbsnzinm ion tin ough remnants 05‘2" tisa Tr electrons of the bans/star: ring, 1‘. :32": any substimants on this pining-l 5:15; at only cause a. manna: t oi. angs is tbs rats and stsrso-v cimnista“ . The: s: is st of subs-t Meats on the 3221s.. 3.. ling of the an plumsthyl group would wioubtsiily sans-s ‘ s. more stars. affect an the charsschsmistry tlmn mum wtatitumta on the other 911ml ring .- Hmrsvsr, it mid ts fruitful to wire studies in finish both rings were subsumtafl with else-tran—s‘t‘lwscting and slas-tronfltinirauing groups . Answer axpsrimmt which 8350111551 "as 02; value is wbstwtiating the. wopossti assimism mm consist of carrying- out tm reactisn in the 80 ,. .,. ,A 15 - o i . .9 -- .4 ’r . ”a. "i ,3 . ,' an? , \.. ._. 3; ’ . .n pressrss m. adorns 5.3: -.+.- arm-5.555s 5s. .5 “1.35.3 $423.35 malt its 0:. v; .9. .' .5 ,.- ..~-.._.-.-. -5 -1555. . .4 'r . a. -. 9.35.: m itstemmum 55:53.55}. 1...; g5..*sssnc.2 0, 45-55-35 5555+ _ um.» gas}. as Gill-Drills was smashis ion fumrsass t: s rcmstion rats by ixzc'r'*sasifig the ionic strength 01’ tm: -2555:le ”wiml +03? 13;; attack 05" the anion at tile i! ammonium ion site . MW! 1. The clear-go of aqhewletml pew}. etha- by numerous hydrogen: chloride at 0°, 21.8°, 150°, 50°, and 60° in tokens and at 140° in too- ba‘Wl alcohol and diethyl kotono we studied kinetically by colorimetric 31313815 of the phenol formed during cleavage. ' a) Pseudo-oft“ order rate constants were obtained. for the reaction, when a. large moose of hytirogen ohloride in telnem use need, by plotting the log of the other omemtretion versus tine. The cleavage was found to be first order with respect to the ether at all tempewemree at which the motion was studied». is) Second order rate constants were calculated for sales in mien the reactants were of approximately the same concentration. The «imitated constants for the 01W in the three solvents were all of similar mgzitnde, increasing slightly with increas- ing polarity of the solvent. 2 . The worm and. entropy of activation for the cleavage of euphenylethyl ohm). other by Wagon either-ids over the Waters was 22" to 60°C were calculated. The large negative entrapy of aotivetion and the 1m: mesa of activation intimate that the tmition state is highly ordered, and when it ins been established the reaction can proceed with relative me. 3 . The stereoohemiatry of the elm of e-phwletharl phmyl other by lurcirogen chloride in toluene, dietlvl ketone, and iaobutyl 82 alcohol at. 130°C has been steadied . The cleavage occurs with oppressio- utely 90% retention of omflmtion. is. A pouible reunion mochmm mob fits the kinetic and stereo- chemical mum is described below: n - H \cl H RC]. + )e—o—e /e———-o-—— ‘1’ 61-13 We Ii, 'r . - ca. 3\6* ¥ (9/? """ °‘-‘P CH: 33 .— mom (l) minim, A... inn. gag. 325 (1851)... (2) Wolff. 0., m. 331. 129 (1863). (3) W, 0., Ann .132, no (1865). (W) Michael, .11., and Wilson, F. 3..., Bear 32, 2569 (1911:). (S) Bane-or, A», Bee. 2.3g, 2560 (1893). (6) 3m . R.- Rmiy if. B. and Schlitz C. G. . J. Am. Chm. Soc. é}; {:26 (19111). a i i s (7) Bureau, R. 1..., an, Chem. Rev. fig, 625 (1951;). (8) room, a... and. Foam, in, 2. PM. Chm. mg, no (1937). (9) Igongiwfms K- Fit and Raj-“J 0., Z. Wik“ 631“. m 1113 O (1.0) W, B. In, and momma, L. v., Ber. gag, :2th (192.9). (11) Boga-so, g. 12., and mm, e. W., J. Ohm. gem, 251 (1.935). (12) Alexander, E. in, "Principles of IoaioOrmio Reactions,” Joim mley and Sons, ii. 1., 1950 CH. II. (1.3) GOMmr'Q-I'Ay, Le», mid. Wbm’ Jr Chm. 306., 5'6 (1938). (11;) Looms, A” and. 5m, G., Angolan, Chen. 5;, 916 (1938). (15) Bull, 3., Manning, J.., one mm, H. 3., ignorant: of Papers, p. m. E, 98th Meet-mg of the American Cimfical Society, Boston, (16) MVflmr, Mo, PW, 8-1, and. 3211(33, Re, J. mm Ch“. 500. g9, 13-1 (191:3). (17) Simifiriener, i., an, Chm. Fm. 5g, 632 {3.956). (13) W, R. L. Jr. Elicia, L. PL, and Maul-y, L. 6., J. Am. Chem. Soc... g}, 1769 (was. 8h (220) Hart, 11., and mantel-in, a. 3., J. in. Chm. goo. 1g, 1379 (1951.). (21) Win, H. 3., Ph. 12. thesis, .i'flo‘hlgm auto University (1953). (22) Bel-well, 21.1... Shields, A. 13., and Hart, $1., J. Am. Chan. Boo. 19,. 908 (1952.). (23) Elm, L. 27., ”MW in «an-mic Chmiatry," 2nd Edition, Beaten, Heath, 1955 . (21.) Holman, A., "Techniques of Organic comm-y," Vol. VII, and 23mm, How York, Intweoionoo, 1956. (25 ) International Critioal Tables of Win]. Data maniac, Chemistry 2mg Technology, Vol. III, Homo-Hill, Na: York, N. L, p. 111 1935 . (26) Spliethoff, w. 1..., Ph. 9. theeie, Elohim State University (1953). (27) Lykkm, 1..., Wm, H. 3., and Mm, v., Ind. Bag. Ghee. at}, 103 (19%). (23) Kolthoff, I. 31., and Smell, E. 8., “Tambook of mentitativo Inorganic Analysis,” go. 3, W. 2., momma, 1952, pg. 1.2.0. (29) Knight, 3. 1.1., em? 121113116le61, 0. 19., J. Ohm. Soc” 2466 (1927). (30) Fairer-omen, 9., am: 38.135111, 2-1., J. Chem. Soc”, 156:. (1931). (31) Ben, R. 38., J. Chem. Soc.” 13‘?l-1332 (1931). (32) Hughes, E. .D., and Iagolci, C. 35., J. Chen. Soc. 1252, (1937). (33) awn, H. 1., am": Whitmre, F. 0., J. km. Chm. Soc. 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