‘ SO ME 0 fiEN'ZNL ALCOHOLS ERQM WITH PHENOLS Bag?“ 9? M. 5.. Thesis m- The E COLLEGE MKCH'EGAN 3'? AT 1H 53% fla’a/é a W IIBPARY d. ‘f‘ [C‘hyyxn 31;; In . /: /$‘ 6/ g1.” Umversuy . L - . mt... Ids’an.‘ch “Ir". 1'. 0,—1.0.) '1 :ruvr'. fi‘Ia-ea‘y? v ”(u-s ““vrn :m'ymry ‘513'51ir‘.’ .w ‘ .JL. C‘-“v l 'v. fl". In} C.9 ~ ,J . .‘v:\i." . Aunt“. ~ .IL‘ I' ‘ 1‘. g‘! D '1‘.-‘.‘. r- .3 ...¢'.'* :1: Yum; an A TW7VIR t‘iuimittod to the School of Graduate 99:11de of ‘.'1c?:1gnu State College a? figrlculeura and Applied Science in partial fulfillnant of the requirement- for the degreo a? “A”? ”5: :2"- m‘: PP? -: Department of rhumiatry 1943 b’éfl'ég am" ‘2”! mus-«I. MN! A‘c' ‘ .6 {V}! f * , '-a.i.;l. :1 ' Dn‘ t Th: writ»):- wiahm to express her sincere and cordial agzu'aclation to MW 3:. L. GU11. whom mzidanco and suggestions made possible the emulation of thin work. 00...... .‘lifii .Ctfi a. 0 331676 Abstract of Theell THE CO.‘.‘JEI~H3&T‘I‘.;)3 0? SJ 7:2 B'RUZQE’YE‘ZYL ALCC‘HQLS '«I‘I‘H FIZ".7£JT.3 by WU DU YUHG Parn-bromo benzyl alcohol was prepared by the reaction of formaldehyde with p-brcne phenyl magnesium bromide and subsequent hydrolyoiu. Crtho-browo benzyl alcohol was prepared by the electrolytic reduction of 0-bromo benzoic acid. The para and ortbo brono benryl alcohols were condensed with phenol in presrnce of slavinam chloride to give hehyd?oxy-U bromo diphenyl methane and b-bydroxy-2 bromo diphenyl wethane respectively. The structure of these two compounds were confirmed by the direct brominetion into h-hyiroxy-3,5,u-tr1bromo diphenyl methane and h—hydroxy-3,5,2-tribromo diphenyl methane which were ilontlce] with the products obtained by the condeneatlon of rare ani ortho brono benryl alcohol: with 2,6-d1bromo phenol. The condensations took place para to the phenolic hydroxyl groups with the formation of benzyleted phenols in 27-53°/a yields. Eo O-elkylnn tion was observed. The bensoyl and the benzene enlfonyl estate of the above phenol. were also prepared. . . .1 , . I; .I a... . . i o v: . u . fi— )1 I. I. r L I : w W . r!‘ U... c J . ... . «In. .. . . I v 4. . . . . ,. V7 I . . , I I I . b . . E . n1}. .1 .. 1 .cr \ .‘ . w , . O . ._ I . a .. . 1‘ s 3v. ., I u r I , . . , . .. ).. ~ . O a A e s 4 a ‘ a n. VI A! . J.“ u‘ , r. L . , . . : I : l .. . . a l c .1 ‘ . r U, . n: . u I 1. . la 1 u v . . . . . \I .4 , ’ ,A . , . 1: l n A l V A . I e ”I. , a. : . . a . . .n . g . u . ,. . l .. J. r ... : 9 | m If. . . o r n N .. , .. . . 4 .. . l . . : A V . a .. .. .T . . I I - . v e I o a . w I n . . . . ‘ . h. o . . . .. . r , .J _ v I I A _ _ . . :. . a: p . . , v .u v I a ,( r: . r . . . — ‘ B Fvn" m l '9" u - .‘*~ .0146) 4‘9”“, . J". - I ‘ l, E ‘ w r‘__— IntrOJUCiionooooooooetoe.noon...once-009000.geese... 3ifiturICClooeoeooeeoeeeeeoeeeoooeoeoeooooeoeoooeooee I9 .. .1 IXfidremunLfilootoooooooeoooocoobecooeooooeooooooeoooo :9. .: .9, ‘ 'E*bl.L1500000000600000500-00000000000000 -. , '3’. .t_. {can”nfiutnoflg...oeenoeooeoeon..oooaooeeco 1‘» ..1.-,§!‘1 wr03_wfiV‘LLQQQQOOOOOOOOOOQOOOOO000.09.... Hm"'..-'fi‘ 'v-L15 o LOmbfidu .oooooooeeooooeoeooeooeonee... “yiP01gfiifl 0f florivatlvoz................ . 1 .‘ “f IJbl;8.509.000.000000000000000000.0000... Discus.ion...oeoo.................o................o "unwary...ooo.so..............................o...oo ~~n~. m. .:.. wldliohfafiwJ00000-0000....-eeooooeeeeeeeOu0.00.0000. Vega 1 h) (3 M m M M H H r4 I“. u «q f.‘ in pa yr-uwpv-rvpmvm A _ \ . ‘ .‘ ' ' ' ~ this thesis in I report on the condoneation of ortho and porn brono bonmyl alcohols with phone}: uni gG-dibrono phenol}. fomidom‘flo nor}: has boon Carrie} out in this Inbomtm'y by Unoton and coworkers on the condensation by aluminum chloride. “on- Iyl alcohol. dnllryl substituted bonny} alcohols and halo ring aub- otitu‘oofl bound halides hum bra-2n condoned vdth phenols. A. on eldition to thin taro, it was considarod desirable to condone. cor- tnin broom ring substituted #:6311251 licoholl With phonolo. A comparison to: to be made botuoen tho yiolde and oroiucto ob. tnined b one of brono bonny! alcohol: 1nd those reported by other work—ore Ming the corroaponding ring inoculated honey). halides. -1- gt'r; T7355" a- 5 1’ ”fin earliest work on bought-ion of phone]. no pro'm‘wly b 25,, F‘atorno (I) 1!: 117.72 who proforma bong-'1 p‘mnol hy hoating- gently a mixture or berm-'1 chloride and phone! in the pro-moo of “no dust. ‘i'ho boozy). phenol obtain! hm! o manna, point. of 171'; 433°C. at 4-5 m and crystanuod out in mitts meals. melting; It 84"". ”any! nniaolo was prepared by tho some method auhotitutifin misolo for phenol. The banzyl uni-ole thus pray. r931 when. treated with hydro- 10:11:: acid, 5mm notm'l iodide and I bonny! phonol Identical with tho bonzyl phenol by dirocfi condamation. @653 Q (“£53 ¢ 311 '——‘ O C32 Don " (75,33. In 1874, Pater-no and I" {191:1 (3) proparod tho darimtlvao of beam. ayl phonol with Icetyl chloride, homey! chloride and bromina. 2y mam; oxoou bromine to 0. solution of bonny! phenol in carbon diaul- ride. they; obtained I. cor-19mm! whim of: 175°C. which {they “ennui in. o dlhronldo. Later Iowa" (7) howovor qme‘olonod thin omnmnl. In INF). Potomo and Filoti (3) prepared bonny]. phenol by condom- lng bony}. alcohol and phenol with a mixture of oulmric and cos-ratio town. They 0239;131:103 n mixture of crystal- nnd 03.13. Inter. Ronnie (4) showed that tho :rimlml onmfmnino command in the mfixtura mltod at: 840?. and no pun 9261:1351 phanol. The on was shown to bo ortho hamfi wand. marking and. :fo-ziglinoon (5) 1a 1630. datum! bonwl phonyl acn- tnto by tho action of bony). chloride on phony} cootnfio. Commutation .c. of tho bony-l phony]. acototo ylolood bonxyl phonol. 0 Osttarrl+ D—“C‘t'ftz—a C): 25-- o—c-orr3 zlooponif’lcot don OCT-:2 O :22 Loibmnn (6) to me use! zinc oF-alorido u a condensing agent in the condomotion of‘ bong-l alcohol with phenol. I22 19%. Tiinolro «:21 who? (7) proporod 4 hydroxy diphooyl nothano ( Q (“£33 0 C" ) by oondmolng hohxyl ohlorldo and. monol with zinc duct. 2'?in comma-.1 me than broaoimtod by tho groom] csg‘littion of.” tho oolc-ulotocl mount of bromine to it: chloroform solution. Thor 0329;212:223 I: dibrmimtol pro-duct, 35~dlbrono- 4-12fl Jroxy gjigfizowl 21223222212120 ( fl‘C) (2'2 CD: 37:13 ) umloh malted at 57°C. It my 'oo :20th born 1;? 711m} o'a dlb row: compound did no‘ 3mm tho coma Aing point on “at orno's (2). 'ttnolro no: mltor aloo comma: a tribromo command by adding; an axons: of bronlnc to 4 worms; diphonyl methane. Tho): assume-J toot lb 1:38;.4'-tribromo 4 hydrant; dip} 2mm; 1 means (" r DEV: C3427?! ) vtxlch melted. at 8:? 0C. 2r In 1916, ETuatoo and: ‘71an (P) cor domed benzene and boozyl alcohol in the gramme. of alumina” chloride. Tho chlof pro-duct ms diphom-l motimno. In 191E, Huston and Friedman (0) studio! the conslonoctioo of hen- nooo with tho Oéwbotltutod boozy! alcohols (phon; 1 not‘ [1 not incl. poo-1,71 ethyl oorhinol and diphonyl corblnol) lo prononoo of aluminum c3-.lor1;?.o Q-ganéQ ‘9“! Dog-C) it They ooncludo-l tmt the prooonoo of an «moo-t1 or ethyl grout) gore looor yiolla while the oroamco of an «photo-1 group gave hotter yields. I‘fuoton (13), in 15323. 0022212222301 ham 1 alcohol viH 32h '2’2'32201 and domino-i I 5003 yield of poorer-20 boozy! monol. In 1323, (”715132222 (11) m‘diohod work on the aliq'lotion of' phonol. ofmni‘. $2.29." won the sodium derivati ro of I manning-«Mia ohonol mo booted wit ’2 an 0212:“,1 holido in t 'nonfiioaoointiog" moan-'2. such to toluono. tho prodomimting moot-ion woo C-alkylotion in a position ortho to tho hydro-xy group. Efoorovor, whom a ”oil-sociatiog” 2220-3123222, moi-2 u toothy-l ulcot'aol woo used..ttzo trodomimting rocotion no Cu- alitylotion with tho tormtlon 0:" an othor. on 2“ ('3' ’2 fr: fr, 2 ’ ' 5 U 2 m." -—, fl (Ga-all: 1.22m) 3’ \/ G In: on toluono 0-131? _ 0 4' 9'15”}?! ——_) (F-alkylation) 'F'ho other and the phenol could be 0321221222232! '12:.- flouting: with aloo- holio potassium: hydroxide. Tho alcoholic 9022220221 2'2 hyflroxido form! t‘so ootaoaium phonoloto of tho phenol which no 301222219. T'to mixture was thon mrtrootod with patrol-sum ot‘aor to moon tho otiwor product. Fotrolmm nth-or was bat‘mr than othyl othor since tho lattor also m:- traotod a portion of tho phonolio proiuct. Tho mtrol own ooh-or diosolvod tho othan' groinct and loft ties phonolic promct in aquoous solution. 2'32. nquooua 1a; or on: than acil'. ioi w ‘232 hyirocleorio lcl'fl to litumto tho 32202101 from the phonolnto and them o-rtmctoi wit’o ethyl other. The oo‘mr 1mm“ was commie}, o‘romo other ovnftorotofi oi tho ghonol iaolatozi. T325 unison author! 0922:1911 as a process for the premmtion o." ortho 32322: ;,'1 932922013. In 1:224, :"ttgton {12‘ comma-2;! l mlo of banal alcohol with 1.1 2201-: of." {73222201 in {wotrolmn othor us ing; 0.5 “i018 of olunimo chloride to a condoming agent: and o bump-grown below 5307. 'r‘ob222m;,-l p‘mnol was obtained. 'E‘ho 21222:?ng 8T3. ethyl abhor. of the n-b-mxyl phonol worm also proper-9:! in good yiolda by oosadunsing bonnyl alcohol with aoioolo and phonotolo. “auto-.1 and fiagar (13) 1-2 DEC. o‘mdiod the notion of alljl alco- hol in banana in the {ax-(mono. of aluminum chloride. In 1027, f‘?~.2oton, tools and G-roto'mt (14.) condomol mthyl pf‘mmgl oorhinol, ethyl ohonyl cox-12122221 and bonzF-zyzirol with ohmol in Tulane. of at 2221222222 chloride. 3 H {21'1"}. I Q C o ("-7. d C) (.17 ——3-9 < 3 (7 “D- C“ "' 2120 R A rolntivoly largo yiold obtained in the conduit-2551.10: using; b92222};- drol co'd‘irwl tho foot nlrmd; booevoii (13) that amelioration on tho car‘aon atom, o'lfacmt to the alcoholic gram increased the reactivity of tho hytircnryl tour-1i tho d22E-2y22mting oi‘“'oct of al‘mirm chloride. In 1-329 (122) "ui'iold Itudlod the off‘oct of varying: proporti one 02‘ phonol. bonoyl aloof-.201 8rd aluminum chloride on tho yield and on tE-o relativo proportion of ortho- and ran bonzyl alcohol obtainod. P'o 1?an that throo 23012-13 of 322292201. one molo of bonzg'l alcohol and 322212“ tool-o of aluminum oT-slorisio goon tho highest yiold. LJ'f-chy (123) in 1330. momma! tho bromo-dm'imtivoa 0:" 32922351 922222201. Zia con-12322393 92292201 and go-dibrmo phoool with porn brow 1223:2231 chlorido and nominal 4 hydroxy 42' ‘ormo diphooyl motlmno and 44's,}!«lz‘rny SEQ-tribrorzo dipfioml motPano roan-actively. The lotto? coul a] ——o 474' C) L222 <‘__/ 2.5: (up 31.2.2 ‘5‘") ??r Er refé-r’rl "tr 0 .- / \ .. ,. ’1' _ , ., ".20 r \ f (.152 C2 LOCI - (c '5 (tap 14¢.A‘3u C.) grayamthoy (17) in 16231 prawns! the ortho brow boozyl 235922013. I’o com-imam! phonol and SIG—dibrmo phonol with ortho bro-20 benlyl .5. 2: 10:21:19 on! o «mi-mi 4-h;~l:°o::,*-2" 22220-229 di;2:2.o'-~l 222299.222: and 4-H; 32.23:;— ”7“ -tribromo fiifihyi;l Hot 21o r2~v¢< 331;. 5&3 lafito? couli also b9 c‘...-t:21:2.<:,3 b. the LIE? 22.2. ‘32""2 . 2...: 102‘. of tho foraor. ‘Z‘E‘ao bonsai ostor ‘3 22-, T076“ 3' “"6220 dirt 22.2,; 1 2*. {22222.22 was pronto; but 210 “W331 mtor cool-3. to 2222*... .2221 92202.2 21-h;Irot=:;-L"2'7.'f"tri‘3rc~:o dish-22:1 m—otl'flno. 7;}. < >f‘17 < _\ r'f~”.r ” 2 ' u 5 T (no ECG-CSO') «,1. l‘ r j ‘12- :1 l ’ 0 2:. ”’2' r {2 22's,~ “or 0 '2‘) 1 ”0 bongoyl onto? :12 l‘I'ZCp Flor-20.2222. - ‘52: on! '12torm.-v {If} 82.222191 the anti'actor- ital action of di Vera” .. holomu 811. :sti‘cutod boo“ 2.;1 #22222013. A 22222-23222“ of‘ mono anti. lilmlof m unrivntiwm of t 222 3 an! 6 222212203; diphsmggl mot- 2222222322 on} thoir a 1:51 homolor‘o had boon oyntE-moizozl oithor ‘22)! diroc‘: {who lotion oi‘ hologo 2n :2hez-3: 0‘. ea or ‘3; holngomfion o“ b2’inz;,,'1ato-'l 222223220122. Th3 boozyl group was diroofiod to either the ortho or para position 59 union tho f‘laiorm mythod or by 252220 chloriio no a coodozmoting agent. In 1733, Eaton, “991-33. fagnar‘wwtfior, "’t'P-rcy, ‘h?t!‘i°’ 2. I, ""221 Mm! and. 12222221 (1.”) 22121211932 2:! on article on brow mam-2m. of bonzgl 523122120122. 732252.201 was cordemaegi with 2-brmo 322-3223;] chloride, 3421:0220 52323.31 c‘zloriin 9.22:1 4-hrmo $22.23;! {3"1102'1i0 b; that; 321222.322:- zmfl by tho 3121221132222 0121222152: 2222223023. 21. 21 222-22139 of dataminlngg 2:21.23 structure! 02‘ the 22222122222122.2221 91"???223‘92-‘2 1:2 2.32.233 22222212210223, conic-2222222310223 of much of than brow aarmtituted hon-'41 o‘zloriim ware ms}. with Efi-di‘nrono 2221-3201 by tha filial-2m martho-fl 212127! with fifi-di‘nroaug‘wnol b" than 8121221212122! 0221022130 “23".?201. 732.29 trio "21‘0'20 323223;;1 322922313 o‘atainei by those: can-dansati 2.2223 mm also Marmara-:1 by the: (30121 321-0211 2221131321 07' t‘m carrots 22012-11253; nondwom 32:33:21 2231 322-121 in chlorafcrw. In no c5323 22.22.13 M 2.302231%. 9:0 introJuoa bromin-w into "ti-:0 bang-1 2220122223, the ”222022.223 9222;322:123 only they uncomphd ort‘wo or {Jam 220312.103 0'." 21;. phenolic r1223. . . ‘ . wrug I'Y‘OJ' . a . . . “fig.“ nék- * “a”. I "htnrinla mi“: 1. 3:”?0710 hangs]: Bled-:31 p-hramo haazyl ulca%ol was wraparai through thn onIOVQnt ra- actions. 77-? '“r 1".“ I (3‘40 & 1' mfg??? a L, hr “1‘ C 6r (‘5? {7' "2% 2 f' 2'; . M o 2 7 ¢ 2 4 ——-) 2 9‘ ”k"! «b ‘5 G “r ‘ ".2, “ . _ é" ‘ .i .' ‘ ‘ J (A: r-wmmiicn o dawn-thaw» :t-rma w _. .19 m wmrv-en- h «1 -~ uh.‘ m.“- Savwfi hunivai 10$ thirty grar; c? krona banzana uni 23 g. or iron $1112: warn Glace: £3 a tirma mack thr:o litar rouni motion flasx I r 3’11: .1 1:11-13 u re: law: can. 1279.3! 12' and e. drojwlnj ftmml. ":1 553311: Liv-1.11mi (m! twrty rmm n." 1ruw1vw u. are: 111:”?! 0.1 1nd to I‘.» rand; 1m”: ’5" means of‘ flux drowizzf f‘tmits‘. 11': the; f‘olIm-cinzj raw-.10“. “I'm-2. cc of? hmn’m warn (11.10:! cm d an film‘a: h-m’mi an a mtmvt 111‘}: for a few Nantes: 1". ordar to utnrb tVn reactinn. 33 soon an tho raarhion L33 afiartod, EMT" in ms an» v2.2 jm.l;.ze.11;,* war I; 1?er hour mricvi. “PM tram-tam: ma ezznb‘nrrfic er“! 000'me ms nocnemry. A (201’ tomfl xm’w"‘e:1 armnd 1:1»: 71021: of fur! {lurk 1.1:1 313'! ca..r-’*-.-‘:x'o?. 9.3m reaction as: it far-tl‘tctn!‘ C0‘:3§"3n‘:ficn withmt Tfit'lt‘lallj fieatt-raaszlmt the rmctim mtn. fu‘tar $111 the bromim 1a.! Tia-«m mlzlml', the film}: we heated For 13-2.. mix-.mfim an It atrmra ‘mti. to cam-113123 Um roar-Mom ”mart mount, the r-mrtion moiuct mam-ate! as a solid was. Tim mm: mm mafia! 1‘! rat with {37' 90:11.1“: him}?! t4 n013t10n to almt-rm- 1mg! mamas brmhn, . .. .a r“: and t: «m with mt‘ar. The liquid ms remand from '9 a. ‘t‘na" W122- the solid mu: 1); doc-ants: ma. 'flaa solid ms 30330:! on a porous plat: to rm'ncv-m was; aiharinfi amtxar and unrmrcta'l brthn’mwzn'm. Tho (2:11:13 firofiuct me than distillefi. It: diatillod VHF-10:11; deacon":- *oaH‘m at alfi-O' f. at: 7&3 “1*. Tim (115*.111911 wro‘iuct may remnxatallimd from alcu’xol. ”an. 115°C} The: 1:14:11 van- '9’: {I 371. (7'1" 01‘ 4:54, than)? 99:1- cnl awmn‘; ‘* . (b) -ra*nmt10n of n-hrmo W‘ my} mmwshm jprmfi dc: “*w-u IO-h—u-' . "our “1.-...m-l In a three 111;»? throne me}: roam! bot-Pom flask fitted with 8'13?) cc drawing fzmnol, mcfmnical stirrer and reflux conimer mm Placed 3:5..‘3 m. o:‘ mmaamm (1.13 male) in 2J0 cc. air-minus othar (the aim- drouu at 201* from 1:39 flock room was dried war 3031.221: hof'ora mm). -17)- Thu r-«mcfiion ms tire-tartar! "rrfi 'myirttum and car‘pm dioxide by a dry- im‘; tuba at 1:339 tow a? co'fimsar Sinai with saint-A limo an! ‘1»: a 513'. cm‘irm 8913161 stir-ram A few: cryata'la of 1011.40 «mm. 9161:“. aids?! as a easily-139:. A nixtum 01" 35",? (3-11 (1.5 7301.3) o“piihrom‘mwzorxa in 5’)” cc RWJ‘ dream Iat'mr ( or 0"0313‘1 a':'1;.rirma fish-var to dimer-m fiha d'ibrmo-‘aensone3 were than 91:11:31 in t‘m drorpfing mural. Thirty fio fifty co warn added mat-mar: stirrhr. “he: f‘lnfi- us '33er with hot: mate)? until t'rm iodine) M102- dimpfimr-xt mien mu (m finiwntim t‘mt 1:21;: rmafisf on 512.2! started. "‘1 . :3 rrm‘irul'zx' 0'? the Smith $011.29. on ma thy: aside-d slowly Witt}: fl sfirring at a rat-'3 5;".th ms swat .2191: «with to mlvzfiein. a ganfilo rs:- f’lnx. 30:30 axfzez'ml cooling; with aunt-’2‘ van ma'fsloyad' but; Hm variation mixture was kept mm to facilitate $239 raacti on. gift-3r all tha Emilio had ham @1in. stirring: ma confifnuzfi for 1’! P‘s-nan Him-1’3» or unfifl 1:319 u hear- no long” ”Slum-i. The. remit-.1215; nroéxmt far t‘za "105?: part was: a Im‘aomnoms solution but; t‘mm firmin- od tnaco: O? unraartnd magnnsfirn. (c) Th , firqmmfii 3n 0" o-F-prnw-xo “mm! 131007101 ‘— ‘~ -“- —- -—-— -4. *‘ “L 4...... Tho drommz funnel was now renlacad b; I. this glass tube ahmt 1?.- m intent-v11 diameter this}: rmchvi ulnoat to but mt balm the cur-- fam of.” the liquid. The tube Gama-acted directly with a 5’37) (so round gotta-a flask containing (‘0 mm. of paraformldahydv wm ch had beam pre- viousl; (triad for em day. in a vacua deuce-later aver rahonfinorua mafia- azida. This drying in important: since cmrctal mmformldahydo co“.- mined 3-5... Mt‘flf. -11. T139 Itirnr was 31:53:“st n21 tun £19.91: containing 1:133 {arafurmldg- 3 up: Ow. byzio mas Mat-33.1 in an oil bath. or by a 1:332:11: to I -390 f. "'an for-r a:1.1:3?.;'.1:3 .omad we carrier: We: into tit-a frigzmfi real-cut. ‘3‘ a 910*: cu rrent 0!." try nitrcmn. “rm ins-art atncmp‘wra of nitrogen ~23: Foam to partially 1:11;” -1311: ‘s‘uu p131; carnation o; Oflfiul :1 33-. "in: reaction ma cat-rim to cor-11319131031 no sham: 13;,» a nog'gfitivc ro- tation to ”Sclalor'a 1:910:33}. To 1331! cc; “33.3731: 0 t1 a ram cti or; n1x1:.1r-zs. 03-3 I'ml' CC cf. 1". ”11:11:31! '11 woo 9 111613“; 1312212939 3:238 9.1419510 0‘ t3... what-.3333, 1 cc 03 main: man 13.1.1331 slowly and them .. cm:- 33-11}. drofn of 0.2.7 volatiun (3. 1033.333 in glacial 110.3131: acid. is characteristic greenish blue color is a noelflva 2 4:3 ”or tin 7"?)3‘11206 of." (frigmz‘l reagent. flit-Jr tho reaction ma contflo'm, tho 1‘m:.:~.':1em n1 rmro W31! nolroi 1r:1..o I 3 :1. ‘ma‘mr cont: 1min: £3 ".0 rm. 0? ems“ 3:0! ice. 117nm hydrolmia m: cmnlatc, u shown 13..- loch 3" nu: ma: reaction, 1130 an. of sulfuric acid (343') cc of 337 2’2““- '4) w: a 8131:! t) (11:133301": 131.4 magnw‘ufl 1:31:01!- 1-1-9. Em rum-cw: or “maria acid was usually requirod in arr-1:3? '50 hydrolyze the form} forns's-J if an carer-.198 of" fowl-1.911311: 3mg used. 9 301111;! on an than ortrsrtod ‘rdth ethar, the other Ingmar casin- mtoi an! 1:.. aqua-mo 1am? ma wtractai 0:373:11 1.1m: with .3113 3r. ‘I‘ho o1:' or o:rtI‘ncte and 1:13: athar layar war: combined and t‘m ethoz' ms l‘=):*eO“Ia'-‘1 by distillation. ":1233 crude nroduct m 021‘: 3:39:: 91 to mourn 01.11 41131011 at 15 m The ”312111;: of cm fractionation were u follow: up to 1000". F1 33":- 1::°-110°«7. 17 m. no” . moan. 5.: {7%. 133° . 1430?. 29 go. 14)“ 0 143°C. 0“ g*. 14;“ . -a‘:. :2 gm. 143° . 1730:. 13 5:. Tn: lower boiling fractiona‘woro bromooonzono and p-flihromooonzono r-r rm 3” _ L Q C u , to: hlgfxaor fractions waif-:1; :m o—x;l;.'lrmo glycol . “Poo frac- r“& 0“" {'9 tloo 50111:» Eefiwoon lé3¢14307. at 15 no. was coonldorod to he too on bw'wo 1333:1371 alno’wol. ”1:15 f‘PMtln otrotmlliao'l m Man-ling on! ma rucrjafiallizol tron othyl Alcohol yieldlnf 92 an. o? 9 our: oroéoot m3lt1o: at 7C-?7°r. The fractions bolllng bataooo lfifinléfiflf. and 113- 1430?. at 15 mo. alno cogstollizod anl aura coooload and recrystallizod tw1oo from alcohol to give 33 go. o? n-brono bonayl alcohol molttnq at ?3-?2°P, Total ylolfi of o—hromo boozy! alcohol was 133 gm. of 4C“ bonod on dtbroonkanaano. inothom two triall ware carried oufi'with 4?? ani 4?" yiold Po- 3 met. 1:'-31.! . o 2. r-E‘imarw; 1 6710:1142 ”r< >C‘L5f‘.“ 4. 31'7“). —) :13- < >r'".,"1 33 733.15: g b l. Twonty grofin of p-brooo boozyl alcohol hora allowod to react with 109 cc of concontratoo hyirocilorlc acid first 5y choking rooctoous t cothor for one hour and toon roilnxing than on a :toun bath for ~13- twotmar om hour. f'inco 1.3m gram in act‘rmterl by the banana nuclms an! 1:33 ‘3 cu 'm‘.'t1tad "r, randy rmctton trim 1131;003:113?” 11011 was expectmi. The rrohcfi mo Hum coola;.,m ahai 1:1 ’31-: col] 1": ’ "a it“s Isolation and than with mtar. 1’12. cm .1,» crystalline Telnet was recrystallized tron alcehol to 31.311 27) m. o" max-om ”urea 1 chloride 71.x). 41°F. “ho yhl-l was {31'1 ‘mrml on nun-bravo hem- jl GICOHOI. The: crude nrofluct urn rut-11101 by distillation. ‘1at111ut10n at aft-103110.010 prewar-:3 a“ 235°; . cemwzl alight: dacmzaonitim. In order to toast for chlorine», n Ila-12:19 ms roi'luxal with «Ico- Iic potnrr-hzm hy1roxi'10 for a few minutes. '.-"..-a Health: solution ram- «mg/ma with diluto nitric acid gave n acuiti'm taut for 07210113.: with 911:“)? nitrate. 3. !~-*‘;ro¢-fio ":‘Hzl'l .10‘}3‘.01 “P ‘4*‘ Hr A<:::>r£9” ; <:::>?”2Tfi 1'fl‘0 cal mt rolyti c rmhcti on The o-hrono have}! alcohol can "rammed by tbs olac. rob-tic rainctioa oz” o-‘oromo hwzoie acid. "an afimz‘ntus una‘l was nearly thy saw: as that given Jy 010mm and Morgan (2')) wfit. ..‘-:e wcofition that one callwio used inst-aw) a" four cans convactari in r) '19:, a 15 volts ’-. f. cut-9231:5113 um"! I’m-.981 o:‘ 113 volts, 111-11233 cn“ cath‘o :3 our: ace lax-mph}: use} 11931109.! 0'” 173 «:32. ""-.1r?;;-£'1'm 3mm of -o-’3rmo hearts-air: nc11.'pr-;:'~am1 from avt-‘xra- .1‘ 1c eel-.1 12111-01171: 1:. :aaotuatim 55.119111 rm «1:' rm: t1 2*! (21) an igni- 1'13 ‘biy 1' 95:01:11; in alkali an! rnwruct flint 91 1!: act 1 mm inched -14- 111 2‘3? er of 83" alcohol. ”Twia'2‘f-;.-"n97-m cc 0." conceatmfifi sulfuric new 1mm than £41131. The aol'xt‘ion ms blacai 1:! a 1333 cc bezai'«1r anrl oarva‘i as the cathode liquid. (1m hunk-31 and twat-g; cc 0:" 21‘. 1' 7; w:.‘e tZ-mn planer-J in a porous cup and natal as tho anode liquid. Pk) . M the strong 0113 my co: A11 ama iron salts! which 121‘111'111: ra'luctlm, 1%: arms thorcug-jé'aly clamno‘l by Porch; first I dilute aeluticn oz“ 301- 5.1m 1:.-,12‘c1113 and than 31.112141: 11111312210 acid thrcmsj’l the) walls to 1'9- mova any matalllo 1'1911‘1131535. The shirt-«2r ma start-:31. tha current turned on an) tZ-m r9919- tanca so azijjztad that the twat!” recorder! 13.12 mm). "L’he tar-anal“:- tum wan ketwt at about: 330?. by surrounding the beaten? with u col-i *8 he! ‘ 173th. «r, The titscretical aware hours regatta} mm» 4 5331"") 2: $1 3 ‘f . -" ‘5 u .1 J x.- 1?.fi anfi. hrs. .-‘-.a the currmt efficiency was wary low, 3-4 than the) rm. hrs was usuafiy remind. 1.?th the detominad amount 0‘.” current had I‘m-3m manna, the current was worsens-1 and the outfioxio 11:21:11 was used for 1:72» 1301:1135.ch of‘ 0-3.2er tmzyl alcohol. "119 alcohol was that emaommfi of‘? at; low tmmmtum. TM 901::- tim was than. nmtmnam with anfiom'm hy-Jroxida. arm-w nmtmlization , tfva sc'lzzticm 1132.19.11}! aofnmtoafi 15:15:) t‘cro 111mm. The: upéor lagear was an alcoholic Ioltztian of‘ o-‘uro-no 136'133'1 Macho]. and tho low)? Ieyar an aquawo 111;th contaiF-‘ing wronhm sulfate; and any unraactad (an-Eran) byznoic 803:? as its amenity: salt. ~13. The two Iago” wore than infiltrated and the alcoholic lug/9r ma momma-.1 It 16': toenmmtura to a r1311 volume and nracipitatod with too water. The 0.51.610 bonzyl alcohol .9911th as a solid mu and was futamd of‘f. The flux-91o mu natural-,6?! with awwoni‘em sulfate and extracted Ber-mm! tl'ma 11:16:: affix-11'. 'Z'ho other was o'mhcrl‘atal and the roaiduo cor—blood with tiriro min yrocipitate. T‘m crude pro‘tuct was le'l 1’10‘1 by Fnix'lapsandingfgln tutor, nmtmlizing with aowonium hyirox- 1:10 and :‘iltorlmg of? tEva/x'breclpttato. "Z’ho weclpi tats ma hushed wifih water and recrystallized from alcohol mp. ne.4-ns°r. {literature 5306.1. The yield was;’13 gm or 43' based on (kimono bonzoio acid. “Tho lquoml layoffws than acidified with. sulfuric acid. wring acidificatim, the uorinctod Oubrono bane 010 acid was proclrwflzatorl. he proclaim” no filtered off, wound. with nuts” and than recrystal- lised from hot water, 5.9. 143°C. T’ho recovered o-brono Mosaic acid could be mm! again for refluct'lon. Another two trials were car-rial out with 311911: of 157:7 rm! 3’)" ran pact 1901}. 4. 2 (3 «d 1hrofio_33t.mo_1_ r. 'flxe EIGA’E‘nromo phmol uaoi in this experiment was pramrui accord- in; to the method of {fasten and T0313," {22}. A redistilloj and morgu- talliaod pro'mct boiling at 131°C. at 15 W1. and with; at 56°F. ms used in the following «pr-rtoenta. -19.. ‘il II Few‘ Inora‘310fl m»~-"‘—“ All condonantIOfil' warn Carrie} out by a l‘taotmrzi procafizro do'mlonoi in thin laboratory for tlumimm chloride ec-ndonaa'clr.'n. Tao fire-"to boozy! a} 0.0“:01 no.1 phenol urn-o 11191372301 1:: putt-clam cthoz‘ km: below 33°C. «mi {holy riivldea lulu—11mm chloride ma ad. led in port! one. l. {1331 wgattoo o“ ofarg-xo 13mg? alcohol I131 :32_oool I. ‘- 3"r C} {"2267 .5 CD- Ire—v.1 13 or C3 {”2 C >111! - 3’25 “mow-four 52mm of p-‘orono benzyl alcohol and 5‘) m of nhavzol were IUBPG'TiGC’. 1n 1?.) cc patrolman nth-9r 1:: o 57)"! cc threes neck flask fitted with I mechanical otirror, a rorlux con-imam- and a theme- tar. "foo gram of clumimm chlorldo mt. added in roll portion at such I mtg that the tmparatura wan mlotoinei between 23-3301". After all the Mutt-11mm chloriio has! boon 3.11101. stirring; was con-- time-.1 for another hour cm! 1:31:11 the; roactlon mixture was 11110on to stand over night. “She rmction man was decomposed with ice no.1 hydro- c‘;lor1c sol-:1. 'fi'ho organic lagor ml separate-1 no.1 the oqzooun laym' utmrtoi throo 1.1 was with othr. T’ho or-wmf-Lo laser and the other ex. tracts wore 00151.net! and the other rowod by distillation; 'fhe r991- (ho ohmho'l was w‘vjoctej to mono distillation {3 ml. {motiom collects! mm as follow-1 up to 99°C. 17 m. 93° . 170°C. 2 5:11. .1 7. 173% . us 3 33. .33 first fraction was un.r3nctoi $33301. Tao l’?’l -l73°(. frattion was the ezjocfial pro$zct'wfli c“. solllif-31 on cooling. fiaorjstallizn- loo Tron owtrolwnfi at or "3'3 3 'ro‘uct ;‘lt133 at C£.C-£fi yloli of l? 53. corraafioullng :o 23' o‘ theorafiical won 03131331. $1303 11; 3511133 point 0” tho product 111 not chonk with that rewort- [3 e! B" .‘ircv -;) two more conio3ogtlofis wore corr£31 out to ~1eld 4 d O prolsot3'3.o. #5 P. in yiallo of El 331 477 rnsvoctivaly. ”he arolnot no: 33313 a1ijsctod to refinatod vaoufi d1 tillotiro 'oar r3113t ”ll qtion,and two rosrystnlltzntloa from patroloua other gave a orolnct still 331113: at £507. Is t3 333 313% u have baan 3033 o-alkvlotion torotfior with F-clby- lotion to y1313.a.:dxture of phenols and otfiorn. Q r“? {:3 ”r C) .3321?" (D —> 2 ”1' D “big" 0 the trofiuct from tho 313“ 331 chloriio con£3333t133 fine traatai with an 333333 of '13: sq: ol.or-hollo 301333 solut103 (3:0 :3, 9'? dissolved in 623 cc. of wntxr 3'1 3313 u3 to non lltnr 3133 33‘h;l oloo'3oll a11 torn extractel udtfi yytrol333 ofihwr. 753 got333133.3alt of 333331 13 135013313 in rnfirolsna athwr fihllo the @633? la soluhle. ’h» p~trolo 311 3:11" w~ss 333.3311313nl ovaéorntoi but contnlnol no othor orofiuct. ”‘ia lrlicntol t :3t no o-al“m'le 1C1 h31 occurroj. Sh) lower 33330113 la «r woo tt3n trw £31 9:1'h ice 333 not: trallzed wl‘h c03033tro£31 h,.rocklorlc acli. £?t?r cooling, the 333331 dnvi7ntlvo -1 7‘. Ln rnwovad 3y extraction mfi‘fi ofih3r, tfia QTOGSS atfior distilla! 0‘? cm! tire ramming? .0113 32-0.!th racrtvzstanizol rm intrcl mm ex: 3: 0 .7 ,0. A z r. '1. 1. C‘J.'~‘Cg.£. C. :- C) {“2 O . - 2-3:- Cj) r": O r3 alrn‘m'! 1c ‘ I as: T :‘r'. 3+3" 33”. ‘1‘?! —-3 4‘ ’ l ‘ u-‘I fi‘veg‘u‘lm} 1 Elm-MP attracted with athqr and flurifiad 2. "031333973! 3:15;." «Parana hmz‘yl c-‘ilm‘L‘m with 332.3301 “—0 Vine» W’Arc; 393i 3-5rono hnq'yl chloride in candoflsutlso ufith 35a331, anothar trial an” 3310 3313; this substanao as the starting 3nferfia1. '1 ’- 31.? -.. Fa: r-Y v.03». r<>M31+Q-- )rQ.2»C:>...-vl *333ty r3333 of n-Erono 503331 cfilorida Q31 33 33. o“ nhonol were 31?}, u 03333333! in firenqfirfi o” 1‘ f“. 0” £1"13 b” 5&0 3199&1J 01t113°4 “’0‘ ' U Cofurv. ”303 Fractionati’fl at 3 33, t53 follewinq fractions W3"“ 05- . 1 t3!ne.a -1,“- 1 0 up to 170 C. 2.46" 173° . 175°C. 11.1 5W» 0 175 up 5 m. _ o . . The 173-175 C. tactic". 5011:3151” and was recrystalnzed twico from patrolqnm ethar to yiuld 13.4 5%. (47!) 0? I product melting ‘t c4.c-c5.:°r. "5m melting mint with the nrohzct obtahei from ths ems-swat! on 0" :vbrmo brmayl alco‘wl id‘s-h phraol gave no da‘u'aasion. 8. FCfiihfiznt¥Ofi o? T~¥fnéfl a": 1 61cc 01;.fih -6 i15r0fio*53631 3" .111 . 96W: + C)?” " = <3 <35 hr x 'I Twanty grams 0” w-hrcwc Hafizyl alcuhcl ware coniafisad V th u2.4 FW. 05' SIC-di‘wmwfiwncl (3'3" arcane) 1n presence 0.” 15) gm. of alumirum cE-elor‘i 1: according; to ‘?m (:12- 01., 09415113er iproc-aiiurc. ":‘ho {cunning fmct1om mro obtainol b; vacu'a (113‘ dilaticn at '0‘.“ (i \,. 1. up to 19’30‘”. 3-5 5"“ 0 O 133 . 129 C. 2 gm 120° - 213°C. 1 two 0 213 - 223°C. 3.5 an. ,, ,o _ ‘2‘.) m) 6 Fl“. (:6 decon¢u1t1m ma noted on $3.9 firs-n: 1113* 1llnt10n of this t3. 9:) 0‘? h1g3}. boiling rostrum mtxmm, the follovdng; precautions vmro o‘roervoai: (a) A natal alloy bath ma used hat-and of mantle.) 3‘1an I. mas-111a cause": more local heating than a mafia] but?» .2 '3- {13} '72:? flan? was c3013! 1:0 rols'i': t.:‘"p-):‘~;xf:txr‘a 12330.”; ‘farml'hg t'n vac-1m an! 111d". 31% a1”. ~r ‘3‘»: rwrfivor was cumin”, 1:33 ril'zflltt‘fiim af‘ “ranks: was «n'rnc‘":a‘..--::1 351.21"? 2320.55 was a“ 1101 $0 tfi> distillifif f1£3?. “n she cur? wfinra thvra ””1Cflzt19'8 u::1rt Oz‘afvet, ceunllarnqu 5nC‘ fian.;1cn mq mat”: as: :‘rm:*;101 ‘r oiling ‘.u.+‘.':!~->vsr1 21‘} {$305.} ma firm react ctullim! fro-a mtrc" ram 31133-1? to 2 '- -- Ion '. ‘ V .T‘. - '.~.. t. ""213 (‘O"'!"§3T"O'\.xfi to a 4"." ".191! “4290‘! (m 33-wa bartzyl alcolol. In Grant“ to (it‘s-ar'nim '¢.-".-.eti;.ar them was any at“. r fur-ohm formal 3'12"- “3 L". .9 con ‘cnsatiot, the; pro 1 c‘; was 1r ‘flufl‘! M”: P‘- aha n“. roar-cant 6.21.1 thud extractm 811111 in ..o‘. am 912.1232“. ‘0 «has: proluct err-11.1 1m isolvtol f‘ma ‘? :0 yr.» trolam a“ 31" 1a or. “an mom and-man W m ur~re carr1n1 cu u. an} can) a 721°01th malt-.1"; . f at {7. ". 1:253; v1 13.13 of 4... tan-1‘3” rmepostiv fly. V 0-4 ¢. .nn“mwr‘_on 0? n-‘)r0“o ')*:i3f1 ulcohc a? ilt'l 13 “I" Q r. .2 . * C} . “an grwu m3 (an‘tt'ow Swag]. alt-0T 01 w-ax'a c-VJ-‘l'rfizzrl 2:31". 2.“) 5:1, 0.? fix-#147. in :31“ 'Eirh‘o o" F‘ SW. 0‘ (2.1.1.1911?! diarifa. .:’\.‘.";-:z‘ d»>c".‘s°>osi'fi.an (1'21 mtraa'fi ., t .o 1' mi‘ .m rm: 5 172;”. mini to vac-:1": -V11:sf;11.‘~.:‘.t1m at 3': rm. "“3: ."l‘ucledrm COITm-tc} vmrm - o - Hf: 1:3 ‘3 f". 12...: g; '1. “’30 ’ 13’3") 1.” it". -12!- 1?? at. am 5 E30 '71:!» fraction boiling: hntmnn 1623-1 .7150 ’. ms rocc-atmlliml Imaml thoa from mtrohum 01:. at to V1011 5.7” . (41 ) of 3 00'1- Doan-Li melting; It 64.13.45.205 ‘mn 011;; aroma was iaolnt a} from the 1110-1710) F. “act? on but (“f-o arts-mt was '01“ r3111 M15 1:‘.. erafora it was not identif" ma. 7‘0 et‘mr pro-Met could he Isolate! fro"! the 1C3 0'1 J70 C. fraction 2: trrmtlng with Claim-m Merv-wt fo‘lo'md by mist-action W11: ‘1 pnrz'ol- mm at"; 1:‘. 5. fontmagttm oi' a-bro-w Lac-mag} 81¢”)th with. tic-(11‘. :ro- «o *1 .mol Br ”r “r -=r <36"th « C) r"! ——#> ." a. '3 fir " “r Tun grams of ortho bro‘m b35551 Ilco‘nol ware Graeme-J with 27 an. of ZIG—dibrmo gheanol 1n rn'ns'mco of” ‘7 m. 0? 11121721111": chloride. Aftar decompositim and extraction, the) maid-w: ma uu’ajectn! to vacuum distillation at: 3 m1. “he fractions collacte) were: up to 1330‘”. 18- gm. 131° . 213%. 4 m 295° - 816°C. 1.? in. 215° up 4 :71. 7‘310 True“ 10-1 “011121;; b 31.311931" c. 35-2150“ 1. 801133.1'1433 7.1;! was rm- crgntnllizod swam} 121 am from petroleum ether to yiel-f. 6.0 3:1. (20" ) o. I ccmwcund meal inf; a191."-‘.‘-2.’}°:‘. 'I‘T'm proluct ma than tr 2:31:31 with {‘ lain-3:1 f‘vfitgvflt i‘ol’mmj by 0‘2'153'5161210fi mt“; mtrolwn et'mr. ‘To ohm-r profiuct cmll‘ m isolate}. ”’7 ”\IIhV-ge,“~’u.!~n *-m- "iv-1. 1 ¥'_n \ ‘1‘..1‘.."?' '29-!” T” w- (WEN-3'33”. “mt“, 1. ,3 W3 m r 4-,01. .. 6*411..j.u * 5'13 we .. ww— - hut—.u-n-r. nan—- 2"‘1'3 ‘. 1:2: :-“.‘a..-1s 01' 4-1;;12‘073-43Brown)«11-132237331 methane wwh; diaaolvad in a") cc. of chlorofom 1:: an .r‘»3~3-:a,-'er flash: «:3! 51:32:31 in M loo .9132 M + .3." but 3. ‘f‘wraha gram of bromine {about 113’”: mess-ma for 1:24 pramratim o“ triflrowo dori mtim} war) 3113310131231 3.". diagram“: am! ’ 113131 hora-31:23 1313-3 11‘133 31:33:31 “.31- 2.931033. “9m noluticn was stirred cowfimmsly an! 32133139310331 9:0 81391'2‘! err-3:“ night. 7“an 'aixture ms t‘zm 50:33-35! 1"": o a ”an? 31‘ a A 1:539 c zlorofon 3.. move?! by em: mmtim. “he 3-3311!va was make! with 35;” sodium biauli‘its to death}; any omens Ezra-311nm, .. m with 3‘.’ T’n'~r~_«3 to rmms any 2'73: uni fiml‘sy wit-3 m! 3;- to frame it frm my alkali. If 1:333 cru 1:3 mtar'fi. :11 was colore ~21. it ma (113301de in ot‘aer ani docolorim'i with. maroon}. 73m emf-coal may {'11’; 32231 of"? (m1 9:33: 051213? Iolzzfiicm rmnoratod 2:0 dry'finrfi. 11.9 ratchet me 1:115:33 rat-'1" at 11:11 3! frm mtrolesm at ”.m- to form color-1.9.53 333.313; vi W41 1'1: a". No“. A 3101:} oi" 73.5 r"! (’77 ,1 was obt.-im31. can :a “trainee my m? 3. in: thrmrfla the for-mt: an 0:” on-Itallina Trvmzqyl an? hangs-3:13 sulfa-1.1 enters €011 cvmfl by nu: ssaquont hyirolgail .0. to 1: cwwmni Hakim at. [.1'.s1-"'".&e 2.7113 tints”: will be dis 0.153363 1th.". "13:33:: melting point wit} the) nroluct 044152331 fro-'3 condflwn' Eon of p-brono bonzyl nlcohol with 26-d1bromo nhencl gave no depression. I 2. “rowhstim 0‘." 4—-!~.;;:1rc~.x-_.r— 2'- Emma :21 zharjgl maifiann fr 2 9r” 3r “r b . . C." CD Cu! ——" ’7'? Q '5'?" Q 2 Q 2' ’2 1 232' Thraa {franc of 4-h:,r-.iroxy-2'- . :‘orm dinhan.:1 methane were bromi- natod with 4 an. of bromine according to the procedure alreaiy dos- crlBei. The wrodnct after recrysta1lization from petroleum ether '3 . . melte'l at 91.3-31.6”6. r011!" gram oi‘ colorlass mac-31193 were ontazned which was an F33” yiali. .Ta'izej melting; point with tha product obtained from condsnsafiicn c? o-brono batty} alcowol with 23-diaromo phenol I gava no degreesion. 5M 2" Div-1. m7-‘v‘v-fi -- ~9-~io'.--A 11-. ‘9 .~ 3...! my 4-. .-.-“‘~. 955-1% ( A I} 4“: ‘2 ’ ... . _ " ' . .. - ‘ .fl rr~ . . *4 ---- ~ ~— ,, 4 __ G 3:31.: unv' h) 1 2":J5 urUDLJ 7:0»- .051 O. (“F.- :11:““ “(‘1 43.1.1; m. i319?- 1 '1 ‘2‘ as: m 4.9”?“ mgmjim __ 2";"1311 __‘._'::3 .-.- 2-. .1: __ 17.131’Elt'3133 . . . ...' .., .. O- ,. 0 45-13312'10 '..c:'3.:o:;.-.m‘;;::-n or? 4L-mg: exam-3.3.2 (. E’E-rl‘: F. {1'3} ark-rows 133-3.le alco‘. £1 with P11971131 . .. ,.,. o . cum-mo Coniamation 0: <3: . {34.‘;¢..£‘.2 C. cz-s... "-'° .(17’) f3-"3z‘o‘.o ‘)J?1.‘.,'1 ' chloride with nhonel 9,. . .331 ' ' '5 o » ,‘_ o ,.3 (ye/os'otl'lffl'ofi'fl ."O'fit‘ffit'. f‘?‘ Of {7 57.‘§o!'9.4 -. {Ln-2 r. (.1 1 C" .".1:‘o:r;,--4'~ ‘ r030 :12 pE-.-3r:;1 methane D of. O 3:;¢'-tr1‘.3ro-*w Conlamation of 4-3-4433 F9.P-GO.4 1.. F142 1". (13} jxo'ar'o'zo benzfl alcohol with 26 dibrawgplmnal . 0. .- 2!_brcno fonlnnsa‘ion of 41K 64.3-F3.2 ". 71-“3°€. {13). o-brmo bent/1 c .01 M523 phenol . 0 o SHZ'- trl: mono firm‘mtlon of . 91.0-91.1; F3. '75-'00 C. {1:'} 4-1;; lrcry—E '- brcmo diphtmfl Miami: 04-. ’ On . q “I“; Ltrias‘o 30 (fortification oz" :27. 91.63-72,? L. 'c’Pw’WCF. (I...) o-brcno bang/1 ‘co‘..c;1 with {35-3- dibrmoi'figranol —— 3““ R: 1"! 3-31“: vat 17:38 1- ..._......"‘1'"3-"1;1...E::i':1 Th» lmnsoyl ”flora of all t‘ma 03133301: warn Draper's-.3. no follow-m To 0.5 331-5. 02‘ this phrmcl, 1‘5," SIC-(MI of banzoyl Chloris}: was added and than 6-10 cc. of 1:"!7 coitus: hydroxide. Thu mixture was aha‘mn vizier-0.351;; and the benaoyl eat-33's usually crystallized out nz‘tuar' sm'cnml minutoa. Tim czvamla were 3'71! tare-l az‘f, meme! W1 th water, than with dilute) acid and finally with mtm‘ and than ”crystallize-2'. from alcohol to t coast-0.3!: melting: point. In com mam, the ”tar: did not crystal- 11.2.6 out. mating but adhered to the gin-m tuba u a sticky mos. f“:.1u Otis}? material ma mrhal with Wharf and than oxtmctci with athar. aft-Jr which the at’zmr was mragwrahed and the rmiduo rocryatallizofl from alcohol to a constant melting: point. Thu stick"; mas. 13"th 11:31:35; tharmghly slashed with water by da- cantat'icn, could he cimngje'l into a monastic}? fem by treat-“3:33:32: with a few cc of alcohol fellatio: by stirring. The soluticn m5 then diluted with stator, washed with diluta 1113511 anti mtm‘ mm rocrg'stnllisod frat-10 alcohol. 2. 1333313293133 azflf‘cmk'l eaters nun—‘- “—— 333 benzene sultan-1 aatcar'a of tin 'mrimo phcmula were prepared 01th:” by the cam procedure) as that; for they benzoyl oats)": using; ban- mm culfzmyl chlorids as me ac;.1ating want or n; the; oytiiim mama in tin» case of «wily h;.:drol;-xzablo asters. '2‘2'30 furocmiur'n for 1:333 {33111331119 mums ms nu follows: 'fl cm 5mm: of if») :35; 210‘.- m'zz'a dissolved in C (in. of dry 33:1'111'13 an! a 172'. excaal cf the calculate} afiount of Transom) sulfa: 1 c‘lor- wt“ 113 a;le3. Aftnr standing ov.r night, an sq a1 vcluna bf watur was 31195 slowly and thn nifturo 313504 urtil all tho Eafltfifis tulfcnyl 6' 10:13.0 hag ‘fiyg-rolg'nal. ‘1”: mixture has 3022er into dilute {zlfuric acid and oxtrnctci with ethur. fiftar being washel witL cold dilute coliua.,arhonnta. the athar'ubs ruxovwd from the attar extract by disn Lillatloa an: Eta profiuct recrratallizcd frcm efih;1 alcohcl to a con- stant malzin point ~27- ...b' t‘fi"~.n.. 3': 1!“!‘6 {. 3"” . (fin.k~n".o.~‘,r I.: ‘ l "f t v' .. ",ng .fi.r‘,‘.u’. ,.~.' ‘. ~ . .‘ '3‘,“ “w" M “A“ . . .L- .' ' '. .' I on a- I 5. - ’ .. . J '. . .t 3 L ‘3 . ' '. b _ ‘ .. __-4 ' - O‘ , {.09 .II“-11.'" |.-s gn- I 3 -.' Q a. .. 9- D g .'- 'r... . . l nu, .13 4 fl... 1.! - .t .l "I §' 5 II a I it} 4“ k ) V1.81 1’; '1 a: I .1 e 1:1‘.f‘~ .F “-I; I!» :30:- a!) ' ”4:133 sum»), Trurtwwss 12:" 5.; - rate? “" fl " “W 441;; irov." dip "km.- 1 nhanj'l 33:12.": r: tr'rmrud "filfiin" was»: on L‘w '1 .4 ‘9 *fiyr—aa-u o rig-d»... .-l:-’--:.- m- non-m W4;-{4.u—_:_' ‘_.__ - _ _____ - _ ‘ J- "1 ‘H : g .t} (-95—- ‘ 3:.‘5‘. ' ".15: '-;'_ _‘- ' 3...- -. 1,3. 91. .. ‘ aw nu ,. :5 ~ A O 4 -.n (3.3:) CLAY‘z.vI‘:§€~uiU’-1 hmzcgl 1.. ~1..‘:°' . 11:.s..;.-1;3 CA1?) 3;;2utribromo cam-3 ".11..“ b'mzogsl 1:: “.14 .. 0'. 1:.‘:.1«-.:;°:‘ (115») 36‘; '-trih:'o'ao In (mi: nation 1mm! 031 163-14701?) Dbl-161305. (I?) l‘ ... . 1 ‘ r- .fj," ‘l ‘ o -‘-'.‘.;80 .0 CO‘ 5on 31-6311. ‘0'} '35}‘.“.30;.1 77.F‘IFQ‘$ '1. L‘...fi..5 C. (19) HH- 33.)).{23'13'910 con. imsat.‘ '3 392305.} 195.5-1‘3’1.2 ‘T’FIE'.‘;:*1‘-'sromo 11-1‘Q33 mtiun ‘..r:-?':80_;..'1 13"31513’ '50 '"' 4'.- 131'030 cordevxn'tlc'r: lznhzeno 1’!2.’}-.-"‘.;.; C. .. a*1110f:;1 1 I}?! _ ‘rl rows couflat'mzti en humane 14;3.3-1-18.2‘t'. a. lulf'onyl '5'?ng tnfl‘m ., L ' as- ' n }» " "‘ i 9 0.. .73]; ~. . .. John .Jrom vn mnsrmo AwJ-l‘rs L. - uu 102-1321 “I: ogv'. V “drab-33:) of ‘wigptivas 1. '-f;-72: ————9 :3:- Q 0'12 < ‘>—r::'r ('2'!) '4‘ Tfr (.7! :1" ("f 3:!- "r < >P"2CTI «- Q ___. "T ( >r'f‘22 CE (7) gr Fr Accorihg to ’E'Arcy {16), (bring brow: nation, brmina avatars-:1 into 179:1:ng manola In tEm unoccupml ortho or para postman of‘ the pheflolic ring. ~33- h... . *‘r T“? C3 "'f‘. C) '72! (‘3) ___2fi ’=r C} Fig —C>m .r ‘\ ( If _' r, 5.15.1 , “"1? "r C) #22 C) (3:) _i_, ‘jr ( > rrtflQ (1;) " 31‘ Vhda, If (1) were tha prohact in the condensation o? ?—bramo benzyl ulceiml with 1231121201, afmr 312-0121311203,it'armldrivu(ic-')which would be ideacical uitfi tn) pro;ur1- U «I . - J v 0,. . . 5 ‘.*,~.‘orzo difil'a.1:);,'1 222-.2t?£.rw 2222?.) armor-2.! i) "c.7223 022212222222 :22 ()1 372.21. 22w? 03'520 brrrm “ma-'1 2.12:25'0‘2. h"; 5.1 :_ '-;_Ei"..z'(.;'21;: 3.2-;"2221. ‘o M-1.1T.“-".¢.2‘..1.}D. was dunno} in 22.11 t as; c:- -..‘.2u;:.>..';.1...;g. ‘3“..22 ohmotu'm of 4 12.213217 ‘1'..'=.:~ro-.22 .11 21...,211 l 2222’. 52.2222: 2.21 4.42, 12012:;- 2'2122'2‘20 41:22:23.1 "‘25.. 22:2 2 ‘.'-"-.‘--."-f: lio:=2";1.‘i'e.i '2),- t".2 .‘iix‘oci.’ brainwa- 2.5.02 2.“ t' 229:2 to“) coax 2.12.1.2 122‘ «1 1“."11‘29‘13’ 3334'- tri‘n*o=ao 2112;222:231 2222.22: 22122-2 2m! 4 ‘" droxy 313:1 tri :ro2o 23.1 2122 2,1 .231 :23. (in) 7’. 5J'fizz'331 223522!“ of £3.23 Io..2r :212271918 €23”..i £2.22: 1102132221222 M1f23'g1 oatsr of? d 22.,«11‘022: 4' bro: 2» 1123222221. .22....21...) 9.221 4—1-23,» 12-21;..- 3:241. tri bra-no among—1 22222322223 war. 11' two}. The mterificabioo uni armooquent hydrolysis of 1.2.2 0:24.22.” was used an : mathoi for the 3122* ficaum‘. of cox-min ct‘ tho 32522220112. Th» {Ir-23292269 oz“ impuritiga in tho pcrmza cup 1232fbtta tr.) e} actre- ljtio reduction of tau-brouo-bmzolc said to o-‘grorao 1:92.211 alcohol. Condom-“1m of tho 2-22-22 pubrorao b023,?! alcohols with 23.922912 gave 122*ng 3,212.21 .222 t: on them rorcrtad 2261.2: tho ortho 2:3 mm bro-2.20 1222222231 ctlorilos. ‘3 '3 1?. 11. 12. 13. 1‘1. 5. 17. 12'. 19. 7"15t0-"'. “o "o If”. ‘rieivmn, J. ’7'. .3. 127's. f‘he'n. "oc. Faster. T. C. on: "agar, D. a. 2. Pi. fham. ac. 4? W, 155 (1"; =2: '2': :Z‘“ r ' w Fatsrno, 7. Cass. (him. Ital. ’. 13C (1572). rum-no, '-‘-'., 2.22:2 $112.2. 72.22. “2.2-". 32291. g, 1:1, 271 {1:74,}. Vatornc, $., and Flint! Cazz. rhino Ital. _, 3?1 (IFTSB. Refifi1w, ?. 8. J. CVFfi. 70¢. :1, if? (1?”332 E‘Jrlri'a, "-.. ". 9.91211 "c:'.g11=.*=mrts-, 1". 3. J. ”V72“. 7760. L, 7242 (H.733. Lemar-w. A. Mr. - 35.. 1'53 (1""270 ”1 c.~, ". owi nl+~r, . :nv.‘§:£, 3F7 {14.4}. "unto”, 1‘3. 4". evil 1‘! (2:3;3’182'1, J. r. J. ’1. ”hen. ."CC. 3.”, 25?? {1916). i 23 J .' ?;E (lfilfl). ! "1:32:12“, 1‘. 6‘. "dance 5'9, 2112:? (1"29}. r. 7101.011. Y. 7.. AEZJ‘NQ "260‘s. 23:. 478 ( r23). met-on, :2. r. .2. 2m. Chm. Soc. 4?. 27:5 (1324-). \J O faster, .-‘. 12:52:25, 7. ("a an: Frotwmzh .3. An. rhea“. "ice. 4". "EX-”131:1. fl. VII. "Ilfitfil' ‘11.}31.’ ‘..'..C. (1923). “Arcy, If. 2'. "112.:th 'Thmu, ‘-'.".C. (123.3} 1“a;.-'o*‘wv. ether. 3". 2’... “hate? T112013. "3.2". (.1731) i'rlarnZ-“O ”'0 ”3.3930 T--o on 9"} "‘1" 2.9?"07: ’9". A. C. In. The“. "00. i, 2:15 (1fi02". ff-reton, "-2. 1"" “6:91:13, 2‘... intramentfrzar, ”E. Y... '2'.'-'=.rc;.', ". "a. ”be1011, ”allurfi. ". ”a. unfl 3.0 02‘9. ;. F. J. Am. 6 ' . F'iufl. fC‘C. 55. 2149‘ {1‘2234 folamnn, T. W. and Johnson, -. L. frg. ynt‘22soa 21, 1“ {13 m1 ‘ojgson, F. ?. and fiulkor, J. J. than. "2:30. 1C2] (1‘33). BS (‘3 DJ 0 F’ustcm, 1?. f‘. and Ywmloy, A. J. Am. "mm. V-‘oc. 57, 21'“) (135-5). Lam, J. 7'. rad ”rod-enon, 1?. J. J. Am. Chem. Soc. 5“, 2963 (1317). 31?”,5'. 3‘. J. ‘nd $11151" ;. Li. J. Chg”. "300. 1‘34 (1334). Fyorfi'. I. Y’npubnah as} cmmica‘c‘lom. "'. 3. C. alumna, 5?... Fucks-3r, 23. J" arr! Jonas, ‘1. 1.. Chem. Nut. 23, 4-353 {1:329}. fl P3 53315.3ft. A. and Frumar. 3?. (Then. A’m‘c. "3, 1:13 (1779129). Carothm‘a, '5. H'. ‘1'“! Adfl'l, H. J. NE. Chfi'flg 8m. ‘6. 1:75 (1:134). ”urge, ii. uni :"olkm'u. E". J. Am. Hm. 53°C. 13. 229 (1%? ). ~43. .« 3. .. Iltllummmm rmmumumnumnujmnum 293 03169 00