‘IHIHIHIWIIH I TH _ SOME CHLOBO DERIVATIVES 0F PARA AND EZRTHO BENZYL PHENOLS IN REFERENCE TO CDNDENSATION 0F META CHLORO BENZYL CHLORIDE WITH PHENOL 2, 4 DICHLDRO PHENOL AND 2! 6 DICHLORO PHENOL THESIS FOR THE DEGREE OF. M. 8' Ralph Lawrencc‘Guile ‘ . \ ‘ 1933 ,_ 3mm CW DER NATIVES 0F PARA mm ORTHO BBNZYL PHENOIB IN REFERENCE TO COHDPNSATIOI W MA CHIDRO BEHZYL CHLORIDE WITH PHEHOL 2, ‘ DICE-030 PKEHOL AND 2, 6 DICHIDRO PI'EEJNOL A THESIS Submitted. to the Faculty of MICHIGAJ STATE COLLEGE of Agriculture and Applied Science In partial fulfillment of the Requirements for the degree of motor of science by Ralph Laurence Guile Juno. 1933 ACKBWIEDGMEW’! The writer wishes to our." hi. lino". upprooiation to Dr. R. 0. Huston who” mama and helpful attestation- m. pouiblo the completion of thin mt 331.593 Page to mmm1u-o------------,.-----. 1 I. lieterieel burlyneneyletionotmemlu-v-n-o-o-o 2 n.motorkorcnuu-.--.--.-.--.- 4 III. Aluminum (fluoride u Oondeneeting Agent (eJEarIJWorkou----~------- e (bl'meWorkotHneton ---~----~- 7 0. stete-entormbln---~---------~--- 10 n. Source, Preparetion and Purification of mteriele - - ll 3. Experimentelnete------------------ 14 1. Preparation of 8 hydron S'ohloro diphenyl methane end 3 ohloro beneyl phenyl ether - - - - 14 1!. Proof of structure offlhydroxy B'ohloro umw1mm-----anunouuéoo 19 (e) Preparation of 2 hydroxy 3. a. S'tri- chlore diphexwl methane and 3 ohloro beneyl 2, 4 diohloro phemrl ether «- ~ - 19 (b) Direct chlorination of 2 hydroxy 3' ohlorodixixewlmtlnne-~-~~--~ 21 (o) Ween o: 2 Mdroxy e, e. 5' tri- ohloro diphezwl methane es prepared in (I) end (1:). M M - # :E 22 111. Proof of Structure of 3 ohloro beneyl phenyl .mr----------------dca-- 23 IV. Proctor Structure of 5 ehloro baneyl 2, 4 ‘1m0"M1.tur-000-aeeeeadnon 2‘ Y. Preparation of 4 Matron 8' ohloro diphenyl mm-------~------.-Q--O 25 Po Ge H. nomadatrutteetehymxy 8' more dimw1m~~------.--- '(e) Promotion of 4 hadron 5.5. 5' tri- ehlorediphewlnetheneo-e----~ (b) Direct ehlerinetiea of 4 hydra: :0 0’11”. diMlICmm-oonueeo- (e) emerieenetebydrozq s. e. 8* trio ehlorodimmlutheneeeprepered m“, mdm‘b’.¢-nouuocnu VII.Eflmuiufimnonoaoaaououooan Mp1.t.!‘bl.ormmdflflhoouuocnnooo Mun-anqnonaooooooouua.-- Scheme of Mmutiun P38. 81 41 1. mired!“ in Thie theeie deecribee two netlmde of ccndeneine phuole with veete. chlorobeneyl chloride. The Oleeien nethod in which the phacle were converted to e eodim ult which wee mpended in e euitcble median and then treated with the beneyl chloride. loner meetigatorc showed that this method gave only the ortho eubctitnted phucle or the corresponding others, the yields of each depending on the nature of the median need. The Huston method in which the condeneetion woe effected by the eaten- lytie ectiu or enhydrcue elucim- chloride. The Note being pere lub- etituted phmcle and c mall per cent of the crthc derivetivee in cane cane. 'rhe chcwe nothcde will be diecueccd in detail in Section II (Hie- toricel) of thie thceie. 2. nietcrieel note I. Eerl: hauntien d Phenol m earlieet work on mutton ef phelele nidlt be welder“ to be by fluorite end nerte fr. 1871 f- l"! (Aeohr. Ghee. 1871, 7051 Br.. 5. «n e. no) can the: W dime-m htone. ulna pneumatic: acid ee e. «momma m. ‘ About thie ee-e tine B. reterne (one. chin. itel.. a. l - e; 1872) m haul phat“ by gently heetins e nixtue of muol aid beneyl chloride in the preeence of cine met. me conpomd hed a. melting point of cc. 0.. antenna in elite white neodlee end was eelnble in ethyl ether. elcehol. emcee. chloroform. or in elbline eolntione. substitu- tien We were forced with nitric ceid end o. enlphcnic acid woe gre- wed en treetmnt with euphoric acid. Ibis cane beneyl phenol wee we- pace by muting mieole and treating the nixt‘u'e with II. three me leter (We) Peterno and Pileti (Gate. chin. itch. o. my publiehee m erticle deecribing the eondmeetion of phenol and bencyl elechol eeing e mixture of euphoric and acetic ocide ee e. dehydrating m. 'i'hie time eryetele end In oil were obtained. Moe cryetele eere laid to be the bunyl phenol and the oil on ieona‘ probably on ieoneric beneyl phacl. . hrkine end Hodgkineon (J. Chan. Soc. 1880, 7843 1880) reported the ieoletien of beneyl phenol. The: heated e mixture of phenyl acetate and benerl aleride obteining e. coupomd which chewed by enelyeie to pceeeee the female eunfio, end upon treatment with alcoholic mu yielded an oil which when purified gave oryetele (m. p. 39“ a) analysing to have the female 01031 O. Acidification and purification of the slimline eolution 0 3. yielded e cryetelline mm (n. p. 80 . 0190! which had the for-ole dunno. nth-en: there wee e difference in ulting point of 8' thq eee—ee theircnpeudweetheeeeebeneyl phaoleeyreperedbyreterne end the lower melting new one d. to impuritlee. rummaweeorrtheeuetvoeeenmmenmmmu be treeting benepl chloride with phenyl eeetete in the meme cf elucid- nIe fluoride (.7. Chad. Soc... 87, m. 1880). Thie ie the firet work with niacin:- chloride in condeneetiene ee e dehydrating agent. Ite nee in thle Winn will be eieoneeed let” in file theeie. In 1881 Lice-an (Br... 15. 1583 need nolten some ee e dehydrating cent inthe condeneetimed‘beml elcchol endphmol endebteinede eryetelline W 11.1.00 «- e1. 0 and 3.1». are «- 322° 9. Bernie in 1882 (J. Ohm. Soc" 33, 280) chewed that the carpomd melting et 34' c obteined by Peterne end run: we mum: phenol and the oil wee ortho haul phenol. By nee of enlphnric ecid et boiling tnperetnree J. V. Bram the" es. 1m. 1910) prepared beneyl new}. other, beneylothyl ether. cvlyl ethyl other end beneyl ellyl ether by oondeneetien of the corresponding aromatic bromine derivatives and the reepeetire elcohole. Johneon end Rodger (.1. Am. Chan. soc... 36. 1014; 1913) prepared cob- etitnted phenole end ethere (by reduction with In amalgam end 301) of nixed ketonee conteining hydroxyl or ether radical- in the beneene nucleon Emplea reparation of methyl ether of e ethyl phenol by reduction of p - eoetyl enieele. 4. II. he Fork K cleieen In 1983. Le claim (he Me Me. 36. 478‘ published hie firet article on the carbon alkylatien a phenele. rho results of hie interti- gatien chewed definitely that men the eodinn derivative of nononrie phenols wee heated with an elm halide in . "non diececieting" medium each an toluene. carbon allqlation took place mainly in the position mm to the hydroul pomp mile» in a "dieeecieting' nodim as methyl alcohol the alkyletion took place on the oxygen. fouling the corresponding ether. Olaieen gave the following reaction" awe) MR ) (methyl alcohol) (1) 0 44203301 :x * A —7 O +racl one 0'33 e on mac - B 01 a mu mechanic: was built on llichael'e theory (J. pr" 57. 4863 46. 189) m- the reaction between eilver cyanide and methyl iodide. ' ‘81» N 9,-As+on,z-—+gx-—~+g+m m, ' [“0113 to explain the formation of the carbon derivative three different viewe hue been adwamee end were diecueeed by K. ten Aurore. G. Wagoner. and 1h. Bohr (char. tantra l. and? .. e. 1926) namely; (a) The initial formation of addition products rith enbeeqnent eplittinge (b) the initial formation ct normal erygon derivatives with enbee- q'cent Writ into the carbon derivatives. 5. (c) the reparation of the metal ae metallic halidee, forming free “of.“ 3“? end with the alight reactivity of the allql group partial or complete re~ alkyl and enel radicale Witt of the enel to the hate radical and finally the onion Of radicale. Of the above the fire. were formulated originally by China and le neat generally accepted. mic nechenien can be written. .'&a-HBI “039 am " ‘0.+nz—-+ ' I I .3... «one «am: ”web-n in which after addition a ehift of bald: taloee place making poeeible the final formation of a cenpomd with the alkyl radical attached to the erthc poeition of the ring inetead of the oxygen atom. Olaicen lieted the factcre mien effect the reaction ae followe: l. ‘l'he kind of phenol: Gondeneetione 1 complex phenolc were carried out with greater difficulty than the more einple once. 1. {he kind of radical attached to halogen. vaccinated. eaturated. aliphatic or aromatic. n wee found that eaturated alkyl halidee Mod the formation of omen-derivative” while mm... alkyl halidee pro- noted the formation of carbon-derimivoee a. the kind of halogen- 4. The kind of metal in the motel phenolate. B. the temperature 6. The reaction medium Discounting media mh ac water and alcohol give orygm-derintine ae condeneation products but in non-dieccoiating media ouch ae bmcenc. toluene and enbetancee lacking in oxygen than carbon- derivativee will be formed. 5e Related ecaiewhatte thewei'ketalaimwae then-earmemcntot W bmayl ether te give a beneylated final. J. Van Alphon (Eco. tm. can. Vol u. m. 1927). no heated beneyl phezwl ether with an.“ loo°otorommamro~m that it yieldcddhydroxydiphenyl um and a dyestuff. 11:. “mini. (fluoride as condoning Agent in) Baely work In love Medal and 02m! condoned ml alcohol and variou- lacro- eel-bone (ca-pt. m... u. mu us. no... '10, use}. they worked only with aliyhatie We but alt-inn: chloride haa tome a far wider nee in organic chenietry in flat it new be utilieed in almcet any we where the elimination of hydrogen chloride. bromide or iodide ie to he accom- which“. the action ie not well explained but three them-in have been evolved. {1) Intermediate compounds. (2) Catalytic action (8) Dehydration mam-y (l) was supported by Boeaekan (Rec. tron. chin" 19. 19 o 26, 150. 1.11) and the reaction unscented ae. am + 11013 ----9 ”man“: Bowman. + am --—-—-> Room 4101, + mu m, on“: * m0 3008' 4- not, + x 320 7e W them. 1:. W: 1800) and Bh'ttgeaback (.1. mm. Chane. loo. ace; 1923) eapported Met the wane idea or inetable “mince-organic We . 'sinee Mm (new... 11, 8151. may ieclated moral etablo coa- pounde of claim chloride with hydrocarbon formulae 113615-0535 and alarms“ which might account ice the large amounte of no), use. oteele (Trance chem. soc... 1470. 1905) tmmlatec the theory that claim chloride wee a true catalyst differing from other catalyete only in he tendency to become inactive due to the function of noble ccepomda with certain lubetaneee reduced during the reaction. the dehydration theory we upheld by the work or me and Weith (Ber... u. m. 1881) in treating phenol with almimn Novice and obtaining dd- phenyl ether and later by Janbert (count. nude. 132, 841; 1901) in the mention of choline em p-tclinnine. the action of gamma: with the hydrocarbon in the preeeaoc of Alan, apparently indicatce a dehydration ”‘5 ion. (b) The work of Man Using elm chloride the condensation of benzene and bonayl al- cohol wee carried out by Huston and Friedman (J. Am chem 800.. 58. 262?; 1916). The promote were diphenyl methane. come p-benoyl benzene and anthracene. however. at low tmporaturee and in a large exocee of became the yield of diphenyl nethane wee mg; and that or the by-prodmt lowere Later in 1918 the came investigatore extended their work to mine secondary alcohols (J. Am. Chem. SM... 40. 7861 1918!. Good yielde were obtained wing diphmyl carbinol but much lower yielde Ihli ethyl Ml carbinol and methyl, phenyl cartinol were and “thong: the retarding 8e effect or the ethyl mop appeared to be pater then that of the methyl. the nechwim woe given an n B oars-on 4» W .5331... own-gown 1' 82° euthenORneuemdhbeaoatalyete ' m (Sci... 88, I)” 1920) condmeed benayl alcohol and phone). in ' the presence of 1161. and obtained p-bonxyl phenoh Later he attended hie work neinc phenyl uthyl ether, phenyl ethyl ether and honey). chloride in- etead of beneyl alcohol Me An. chem. Soc... 46. 37753 1924.) and tron the reepective yields proved that beneyi alcohol wee not converted into benayl chloride before the reaction took place. no years later mm and Sager (Je A. Chem Sec. 4.8, 1926) applying the A163).8 reaction to oatoroted and unsaturated aliphatic and aux-cutie ale- eohole with benaene found that. in eronatic alcoholic derivation only‘ choee trim the hydroryl on the carbon atom adjacent to the ring react. that maturated aliphatic aloohola up to and inclining W1 do not react. and that maturation on the carbon atom edjwent to the alcoholic group in- creaced the reactivity. . In the some year Beaten and Bartlett obtained P-hydrmylel. l '- di- phenyl pentene by condensing phenol and phenyl bntyl carbinol and in l927 Boston and striokler prepared P41361013? - l. l -- diphenyl butam in the em m: by use of propyl phmyl carbinel and plume).- cuctcn. Lewis and Grotaout (J. A. Chem. Soc... 49. loss. 1927) con-- donned secondary 3,160le and phenol oomluling that noeeturation on the alpha carbon atom increased the reactivity of the hydronl group. About this time the beneylet ion of uremic was attempted and accom- plished by mane of the A1613 condensation. Boston and mm worked on the beneylation or o-oreeol. Beaten and Hank on the beneylation of h Il-ereeol and Huston end Lorie m e eimiler Nonfiction oi’ P-oroeol. This on): is «attained inleetuetheeee ee ieeuhottherellwine. to we Mon and Wield etwdied the effect at varying "proportion of phenol and 51615 on the yieldo of on and p- beml phonic. Yield: me inflected by harming the wt of mono). but not the mount of £1013. ‘ Fulton and Eldridge (J. Am. Chem. Soc. 63, 2260, 1951) condensed 2. Wiohlomphenol and bonny). alcohol by the £101, method isolating for the that time Ni other product! Along with the eubl‘titutod piano}. in an alt-'- Iim ohloride condensation. alceely roleted to the investigation to be outlined in thie theeie ie the earl: done in thie laboratory by Chen (meteoric mu. l930) and needle: (water's male. 19”). Chen carried out the condmeetion or c-ohlorobmeyl chloride and phenol by both the not, end the aleiem nethode. Using 11013 he prepared end identified 4 With“ ohlcrodiphehyl lath-no end ehoeed that em 3 tum-on 8' ehlorodiphwl methane Ice also formed. With Oleieom he prepared a hydrcnq 2v ohlorodiphexvl methane and identified it. Chlor- ination of either e hydra: 8° ohlorodiphenyl methane er 8 hydra; :0 chlorOdiphenyl methane he feud to take piece only in the meeupied ortho and pore position: of the phenolic ring. needle: vol-king with p—ohlorobemyl chloride and phenol in e einilar manner on moribed for the art of chem ere! practically the me conclu- eicne am prepared mlogoue conpocnde with the chlorine in the 4' poet- tion. However. no ortho eubetitution m domane’treted to new pore eobetitution in not, condensation» 9mm of the Problem me object or thie mhleu ie no folio-e: in no prepare. identify. and study the proportion or ewe W mint ieee of chlorodiphenpl methane. e) I hm It diohlm diphonyl Wm M e Mom at diohlwe diphenyl anthem I) 8 Mama: 3, e, 8' trichlcro 41mm mother) a) 45 more” a, 5, av triohlorc MM! nothme a. h We the yielde o: the above WWI. a. We 1W their outer derivativee d. Ea‘c amine the positions chlorine will time on altering the W O 3110:: Q03 m: ___C.‘. G1 H 0 r: "“2 <9 ‘\-~ ,’ ll. 8m. Preparation and ratification er uterine l. Mica-em dilution (a) Promotion of mta-ohIwotIolm m-ehlorotoloem was prepared by 1 method omioaoug to that deem hammweehlmtolmmw. nimloi’m-gmie symm- oiinn. ammummw1mme inetoedotartm «rpm-Mom. imetioa boiling at 161 teloa’voacmeimtebepmH-ohlmtolme end one need in the following promotion. 0) chlorination of When A eeighed amount of e-chloeotolnone anally ebent loo gone eel placed meromdbottonedtheeenoohedtlaottittedeithentlumme tube for the introduction of chlorine. chlorine cached with eulphurie eeideeepeeeedetthenteofebohblepermintotheliqnid,eenell pieoeofphoophomwntochloriaemoddedeeeeotuvetendenmion more a: no“ was maintained by use of on oil mm. me flack plne the n-ohlorotoluene me related et the beginning or the mlwinotion end at intervals through out the process until about 901 ci'thetheeretioclmmmtorchlorinorudbeeneddod. Quentin contented the (look were nationally distilled. The freetion distilling over between 2M0 e 317° one the u-ohlcrobonayl chloride need in the following econome- tione. new fractions were returned to the £19.31: with tree): Micro- toluene end mm dilatinetod while higher fractions undoubtl: e dichloro- produet tore dieeereod. mm: Miner: flannel on need eithont ”purification. “* . --X- -4 - 14-4.. .L-‘A 18. III. 8. e “011mm,. Ilse teehnleel a. e dlehlorepheuol III twlee sou-tum under re- ueed mum until A newly mite cry-telling product wee obtained. mums pom a! rem-mu mat we «.5’ to ee' 0. IV. I. e muuml Ximmb’mlflho‘otn. mumx. mind (0. 1.. 81. It“! Mtheneldewereweryloweomiatlene umuMm uuenI-wtrmewewemlnwhleh time “motion. mteteul- yhule all. wt or name hydroxide. one preeeedure were changed. However. no more than seven arm eenld be chained for each mole of m1 need In! eo the e. e «emu-em: need in the eaten-alone re- weeente the emu“ mm of new reeotlm. In genera the procee- me wee ee tone". 1.: melee or m: up treated with no éame a: concentrated eulphurle ecu in e. 8 necked 8 liter fleet equipped with e technical nine: and e tube for the introduction a: ehlorlm. menutureweeheeted for tourhaure onebollingwaterbethto in- me emlete enlphonatlon end then made ellmllne with 40‘ eodlu humus. m resulting eolid wee entirely neeolm by 600 ee or water and when the mixture had coolec the theoretical amount of wuhod chlorine nu mm by welghlm the flee}: and reaction mixture berm-e bubbling chlorm into it end then weighing et lntmle until the proper mt er ehlorlne ee “alumnubethupbythermflon. mmnmmtmnvmu into two portions In! men distilled to raw” the ”18111li which “Mental-med“ meant. “to: it flappedeomingowerthenlxture wee evaporated to (when, I00 ee or commuted sulphuric sell ended ml mam aletllletlen continued. the nu: being heated to woo . 210° 0 en 15. a eil bath. The 8. e diehlorephenol em on: ee en on which eol iditied end wee matinee ”I new meme. m purified prodnet M e mung point a: 57 «- 57.2“ a. 1‘. ”than“ Beta 1. mmutmav ehloreiimewlnethmeendlehloro- beam. mi ether 1:; claim mum on I ‘01 out») a: OWO O’MQ ""°‘“‘”< Q W53“ 0% Wuhflfleeheuimmmpennedmmezooeeot tom in I three no“ one liter rem hottand flak. equipped with e tent: menu: end e new eealed etin'er. Ehe eontente of the fleet m mm mm the toluene hence we the Indium menu rieing ummumuw. menthe etirretene etartednnathe «dim team to bird ehot eiee by stirring. All time were tenant hen the vicinity of the resetting mixture and one half hole or pheul in toluene tee sued. A Vigorous venetian amt-ea with the evolution of moses: eat the {Mien of e. white me ei‘ Iodine phemlete. the Min we hung“ to empletim by heating the flank on an oil bath at 100° for about tour hom‘e utmmg continuum lo the hot Ielutioa one half nole or Mhlonbeneyl chloride end in theee maneu- time deeeribed n definite wt of 8 ehlorobeneyl phenyl other we we. Pmione work en a Deter“ wheel! by In 3. Ban! and work by nu- eel! m given very poor yielde at a my S’ehlommwl mm racing from 8.4 to 6 gram there no 3 chlorobeneyl phony]. other we m- et. renewing the work of who leeley “some Bruno Derivatives of We em Pure Beneyphenole". betel"- 'meeie, In equilibrium wee semi to Clint between the much at 2 turn-on 8' ohlorodipheml methme and I 16 chloro bmeyl wml ether and it wee thought the addition of 8 chloro- hemoyl m1 ether wouln remit in an inoreeeed yield of 8 hydro” 8' merceipheewl lethene. rho condensation after the addition of the whim benepl chloride end a chlcrcbenul yum ether wee can-Mm by heating the flask for eighttotenhcore onuoilbethetetemperatureofW-lWO etirring continually. After the epecifiec time the mixture wee cooled. washed twice with voter to remove the H301 and iietilled under atm- pherio mum to m" 0 to rencve the toluene end trace- cf weter. he reuniting oil we treated with 300 cc of Gluien'e reagent (550 grme of m unsolved in 400 cc of weter end made up to one liter with nethyl elochcl) to form the potoeeim cult of the {tool derivative which it he eolnble in petrolemn ether. the mixture woe than extrectod with three loo co portion of petroleum ether to remove the 3 chloroboneyl phonyl ether and the reeidue me made ecic with concentrated 801 end ice 1 | 1 after which it we extrectcd with three eepcrcte 1.09~ co pcrtione of di- ethyl ether. i‘he eolvehte were dietillcd off in the case of both the petroleue other out Methyl other extracte end the one that reeultee from both extraction were neotionetcd under reduced preeenre. the re- suite "1‘. M £011”! riret cosine-mica (15 areas 8 ohloroheml W ether) Ethyl ether extract 10.1 gram (mostly phenol) Uptc 100' O et 14/- 11.6 gun, a hymn e' chlcre 11 Ml uthene 19004100 et ulna 3.2 great. tee Above 810’ at le/m 16 Petrol“ ether extrect “.7 gree- (hoetly eachlcro bunny}. chloride) Up to 160° ct “In 1541 green e microbuerl phehyl ether ”8'4”. et “/13 1.6a- ‘ tee ‘ebove noodle/m m ounces-emu (to green 5 chlorobuefl m1 ether) rem ether extract 0.9 m .31, phenol Up to note ee “/1- 10.? gene a moron av “Mimi mum 1000410“ 0 et 14/. 7.! green tor Above rim et 14/:- .Petreleoe ether extrect 4.2.5 grant noon: w-ehlcrobeeeyi chloride up to 15890 et le/u 20-10.: grate a dumbenerl phenyl ether Weno- c .1: 14/.- e.e greae m - Above 190% at le/ue mire ocueneeticn (30.0 green I chlorobenu'l m1 ether) Ethyl other entreot 7 gram eoet them: up to 1m et ie/m 33.0 game e hydra: 00 chlorodiphenyl nethene 1000.31.00 a ct u/ue ' mt grate tee Above 21000 at 14/31: Petroleue ether extrect 16 gram mostly e-ohlorobeneyl chloride up to 153°C at li/nn 80-10., you 5 chlorcbeneyl Ml ether 1539—190" 0 at 14/m 2.). gree- oer - Above 1900:: et 14/».- Fourth condensation (47 gram 3 chlorobeneyl phenyl ether) mm ether extrect e.e grcme mostly phenol ‘ Up to 180°C at “film no.2 gram a menu a! chlorodiphenyl methane 1000-2100 0 at ic/ue 8.8.3111“ tee Above 210 0 at ie/m 17 Pemleue ether extract 98.6 game mostly n-ohloroheneyl chloride up to 13300 et ie/m «eh-3.8.2 green 3 ohlod-oheneyl phonyl other 1839490“ 3 at 3/- e.e W tee- Above 190°!) at 14/!- Iitth amnion (60 gram I ohlorobemyl phenol other) Ethyl ethee extent 5.5 great mostly phenol Up a. 19000 et 143/.» 10.1 gm- : more It ohloeodiphnnyl netheae 1600-210“ c at ulna 4.: me to: Above 210% et ulna Petroleum ether extract 42.! green moetly n-ohleroheneyl chloride 09 to 158% at 14/:- ooeio.o We a chlorobeneyl Ml other HEP-190° a at xe/u 3.1 groan tar Above 190°!) et ld/m , Iron mete condemn ione naming the norm yield of 8 hydron 8 onion diphmyl methane were no 3 m honey}. phenyl ether is mad at the beginning of the reaction to be 4.2 grade. the ”sedge of the yielde 2.4 to 6 grams already nontioned, it can be em that was 15 gram of 8 ohlorobeneyl m1 ether name: the yield of I hydrous: 3' ohlm din may! methane about 5 times. 30 grams immeing it about a tinge, 41' grand doom 9 time end 60 gram e little more than twice. meeo {note em to indicate mat there ie come sort of an equine. hrim utebliehed between the enbetituted phenol and the corresponding other tomod en a result of the mat ion and they 3130 point to the foot that perhape too mob ether 1: present m5 interfere with the production of the enbetittaod phenol. Mew work would be mum to demonstrate thie and find the equilibrim point. _ rh'.‘ - 18 the rive lone-210° oneottoneerrhymxyet chloro diphemrl lethm were oeebined end manned hide et 14 m wee-ore. eon- tageeerqute eenetentlyet iu'eiet°oeeeeteeaee1orea oil. A totel yield at 41.! gene of the purified product no ohteined for the flee mum. we meet!" en ever-ego yield of 7.781 bend on the w 0! m1 need. he 8 €111le m1 ether {teatime on re-dmilletim one one et e meant taped-attire or mo . 100° 0 et u. an preeem-e yield- ing 89.! ere-e of the purified ether. It memlieed on etutding and efter re-eryetellieetlon eeverel time from eleohol toned in tranelu- «at pletee having e eon-teat melting point of 86° - oe.e° c. The over-- age yield of ether bend on the wt or pheml need tree 10.89%. 19 n. free! e! etruetm or 8 hydroaw 5' ehloro dipheuyl mm. i‘hie pree: depnee twee the prepdretion of 8 I 3‘ triohloro diphwl nethene by eondeneing 2. e diohloro phoml and a ohloro benzyl chloride endoheoking theoonpomdthnemeredeimthesesi triehlorodipheoyl nethene tuned by direct ehlorinetion or a hydroxy 3' chlore dipheayl nethene. (e) Preperetiee ed’ 1 hydnq 8 e 5' triohlore diphemrl methane and 3 ehlorohenerl I. e diohlore methyl ether. aluien oondeneetione similar to the one. elreedq outlined emept for the adding of ozone other were carried out rim 3 ohlore beneyl chloride nd 8, e didtloro phenol. The reaction we considered to take pleoo ee follow: on 01 e1 /“ m. 1 ”0* mo ----~ Om “MU“‘C' 01 01 ale-halt nele quentitiee eere need and the following results were obtained. Piret Condensation Ethyl ether extract 10.! me I, e diohlorophml 1: grams 2 hydroz: 5.5 at trichloro diphenwl methane 2200-2250 et 3/- Up to 100°C: at 16/. t gene tor 1.7mm 225°C at M/m retroleu other extreot 81.8 gre- o mmbneyl ehloride 8.! an a ohloroheneyl l. e diohlm 2140-3200 0 at ie/m phony). ether Above 220% at 14/. Up to 11000 .t le/m 5.65m!“ tar new damnation Ethyl Ether mm 26.3 ere-e I, e dichlormnd 7.! green I hadron 3.5 5' triohloro “M1 methane . eel grew tam retreleu ether ertrect “.1 green I chlereheneyl chloride 1.1 creme 8 chlorobeneyl 2, e. dichlero phetwl ether ‘e‘m tar mil-d (laden-cum Ethyl other extrect 19.! am I. e dichlcrphenol namihydroxyaesi trichlore diphenyl nethm 8 grme tar Petr-elm ether extract 29.8 gram 8 chlercheneyl chloride 8.6 awe 5 chlorohencyl z, 4 dichlcro phezwl other ‘e‘m N Up to 100°C! at lit/m 220'- 2zo°c et le/m Above 225°C at 14/11!!! Up to 110°C at 14/m t sir-220° :2 et lt/m Above 230% at 14/11.» Up to 100% ct 14/m 220°- 2ze°a at 1e/m Above 2290:: at 14/11!!! Up to 110°C at le/m 214°. We at le/m Above We at le/pe Both the a hydroxy 5 5 5' trichloro diphenyl methane and the S ehlero heneyl r. 4 diohlorepheuyl other being crystalline they were repurii’ied by that moo. from the three oondeneotione 19.? grade or 8 hydroxy 3 5 3' trichloro diphemrl methane eere obtained or smell 'reddieh yel low needles which upon 21 reported reeryetellieetiea from petroleum ether hed e content melting point x 61.0 e to. a. heel at the nae-mt of 2, e diohlorefitenol need the average yield wee eel“ er the theoretical. the 3 ohloroheneyl 2. d didflorophwl ether upon, repented reme- tellieetion from alcohol came down no long white needles with e conetent Itching point e: 42" . “.8. o. rho total yield at c chlorobeneyl 2. e dialer-om}. ether from the three oorldeneationo wee 6.3 gram or en even-ego yield er 1.451 teeec on the mount of phenol me. (It) Direct chlorinetim of z hydrory 8' ohloro diphenyl methane. tee an or a hydroxy 5' ehlcredipheayl nethene ens dieeolred in eheutfioeerehlcrommineIOOeethreeeeekedrmdbette-edfleek fitted with e uncommon stirrer and e delivery tile for the introduction ei'ehlorine. i'heeixtorem cooledinenioeendeolthethendaeeeone fluorine ewe with flirting util the theoretical amount for Cubetitl- timertwoetomeofchlorine inthephemlhedreoctedee mmhythe cheese in weight of the fleet end ite contentee . 1 M thie point wee reached the reaction mixture eee poured into e teeter end the chlorotore emporeted of! leaving an oil which oryetcllie- ed on standing. 7 Since Chem Warren end needle: had been meble to introduce chlor- in& in day poeitione but the ortho and pore of the phenolic ring the re- eotion tee considered to he. i on Hgl a ti 0m< >+01,--—-—-v 010m“ >+mal \ cl Ithe meteie were preeeed between filter paper to remove the oil and rem-reunited In time: he. yeti-elem ether. After which they hed e melting point or 58.8" a 59.2. a. to) mien or eubetituted pheeeie from (e) and m the I Won 8 6 8' triehlm diphmyi methane prepared by the china condemnation of 8, d diehlore phuol end n-ehlore bensyl ehleride 36.95 me e melting point at no.4." - to“ a. WWW chlorine, name 3 hen-e11 eeter with uniting point 62.5° - ea" c enelyeie 87.171 chlorine. end eryetellieed in fine brewnieh tinged needlee. the ow prepared by the direct chlorination or the W 3 hydrexy 8' ehlore diphenyl methane had I melting point at 68.8. .. 69.80 0. min-e “.727: chlorine. yielded e Denney]. eeter with melting point 62.5% 65' e. enelyeie 2709;: chlorine and emtellieed in fine bremieh needlee. Pm thie date it was named that the compound prepared by direct ehlorinetion of the euppoeed 8 hydroxy 8 ohioro diphenyi methane wee I when 8 I 8' tri ehiore diphenyl methane end thne the enhetituted phmol fro- the Claim eondeneetion of phenol and Moro beneyl ehloride wee ee expected 8 hydreq 5' chlore diphenyl methane. . m. Proof od' Structure of 8 ehlerebeneyl phenwl ether. willie-en's an. A consultation of phenol and 8 emcee bueyl chloride eee m in lethyi elcohel in order to were the etrnctie-e of 3 chlm beneyl M1 ethc fer-ed by the albino. condoneetion (in toluene) of medial and B ehlue beau]. chloride. 90 76 ee ct nethyl elechol in e 500 on three neeud fleet fitted with e etirrer end condeneer wee added 2.76 pm of eodim. After the venetian lied nbeided 11.6 arena of phenol nee edded. the etirm eta-ted end efter eight more of heating to 100‘ to 110° 0 on on oil beth with autism eta-ring the mixture was poured into e beaker end the elcchol mponted of! on e eteen bath. when the residue]. oil was mailed 11th enter to relieve the uni formed and then extracted with :00 cc of ethyl ether in no on portione. The ether was driven off end the remaining oil wee mun dietilled. 14 crane or 3 chlore beneyl phenyl ether wee eh- tnined coming over in the fraction 166‘ - 180°. et 14h. mi- frection eelidii’ied end ei‘ter reputed metellieeticn melted et “.2" - “.0" o e uniting point which ooi-i-eepondod closely to so“-os.4° a given by the enppoeed I chlore bony). ether obtained in the. cleieen (toluene) condeneetion of phenol end e-ohioro beneyl chloride. Chlorine when of the two We checked very eloeely. l. 5 ehlere bonnyl phenyl ether (Mien) Minnie Beanie weight ee .1 I i chlorine x chlorine mo, Pond coloomed . 1 .2176 . 9.8? 16.00 16.23 2 me Me ___ “.le 16.30 I. 8 ehlere been). ”1 ether ‘Wfllimfll'l syn) Alleluia angle Vela“ 00 .l I f chlorine 1 chlorine AGED. loud colonleted l .83“ 10.” 15.25 162: a .2590 12.3 16.16 I! Mdsmofldllmbuqlt,ddichlm .Wether .1 eondeneetien in methyl elochol minimum syn.) eimiler to the one described for the preperetion of 8 chlcre bowl phemrl ether (above! wee node wins 8, d dichloro phenol and n-ohloro beneyl chloride. 1 yield of 13.3 pane wee obtained which upon recryetellieetion tron eloohol melted et 42‘ - 4.2.50 o e melting point corresponding to that of a chlore my: a, 4 diehloro phenyl ether obtained in the clocieoi condensation or 2, d dichloro yhennl end n-chlorc beneyl chloride. Chlorine ennlyeee c! the tee compounds ere no follow. 1. I ohloro benlyl 2. 4 dichloro phenyl ether (Cheien) Analyeie 3‘91- WOiQIt ee .1 I f chlorine f chlorine MO, round eelcnleted l .2656 27.86 37.2 87.01 I .leto 87.69 ”.19 Am 5’ e! I. 5 chino beneyl 2, d dichlore thl ether Willienecn'e Syn.) Anelyeie Sample Weiglt cc .1 I 1 chlorine 1 chlorine 56303 round Calculated 1 .8310 24.01 36.96 57 .01 8 .1120 22.1 “.96 Y Regen-cues: of t hadron 3' ehlcro diphenyl methane min) 0+ clanz CVMI' mem 4- reel meenduehelflolee ofphenol were eupendedintOOcoofpetroo leu- cther in e cone-motion cylinder fitted with e mechanical etlrrer end imereed in e weter bath need to regulate the tonperetnre of the re— ectim. re thie eolntioll of phenol one-belt mole of 3 chloro beneyl chloride m added. The etirrer was started and when the deeired temper- ature had been obtained by nee of the weter bath Mouth nole of 11013 mudodwithcentinnel etirringmreperiod efonemdehelftetvo hem-e. During the edditicn of incla large mount. of am eel-o evolved. ihenixtnreweethenetirredforteohonreeoremdellowed teetendover night. It m then decoupoeod by pouring it into ice end hydrochloric cold 1 t 1 Ind oxtrnotcd three time with 76 cc portione'ci’ ethyl 0th.. Afi- ter dietilling eff the etbr the remaining oil wee treeted with 600 e. of Choice" reagent and extrectod three time with 7! co portion of ”mm other. he roe idne from thin titration lac thm ”would with concentnted hydrochloric and ice 1 e ‘1 end extracted with diethyl ether until all the oil we removed leaving e clear eolntion. the eolwente were driven off from both the petrolenn ether and the diethyl ether extrecte end the remaining oile from eech eelvem were freetioncll: distilled. Pour condeneet ione were carried out at different tmperetnree to deteninetheeffectof taperetvreontheyieldcfdhydrcnct ehlcro dinnewl athene. The reeclte were ee folloee. 25 um attainment-1 e’ - 10' a 1mm ether extract 115.: pm I. 1 nonhuman up u 110% n 14/- 18 m i may S'Ohlcl'cdiphenyl o methane 199° ~21: a at 14/u 4.2 gnu tu- Abowe 215°C at 14/.- aeem connection 10" «- 18° 0 Btlwl ether extract «.7 an: a, 1 dichlorcyheacl w to 11000 at 14/- 37 an O hydrcn I'chlercdiphenyl methane 199° ~21§°O et 14/. 3.1 grams ta: Above 215% a 14/».- mm conamuucu u“ . 10' 0 m1 ether came ”.8 gram 3‘, 4 ummpmnu up to 110% ct 14].: 80 creme ‘ hydrowar lichlorediphewl mthcne - 199° «213% at 1e/m 1.: arm tar move 21?!) at u/m Fourth Gena-unsung a. . u° c Wletherextreee 76 crane 8. 4 flamencpheml Up to 110°C at “In $3.3 grams 4. ham-e17 B'ehlcrcaiphewl c . nethcm 199 - 811% at 14/:- ‘J grime tar Above 315%. et 14/“ he nuclei-ether mm 514m yieldnyecnpmenemm- rented 8 ehlere m1 ehlcriae. m. mute recovered were. tint 27 condensation 49.2 grams. second at me, third 47.6 green. and fourth 41.3 grace. hell preview work in thin laboratory by Philip Stanley Chen on the claim chloride conduction od’ phenol with 2 chlere Meryl chloride both the mm end the pen ccbetituted phenol: were formed. mm: me leele: reporte elee nine nelogm bromine compomde to the chlor- ine oompcude need in this work not more in evidmoe or crtho eobetitw- tin. following these ideas the fractions of the ethyl ether extracte be- M no“ and 199° 0 ct 14/2“ were combined and refractioneted um the ebJect our obtaining a moron :1 chlore diphomrl nethono boiling at 1'1“» 191’ o n 14/“ mat a: an. oil am over between 1940- 1990 c at 14/- chewing it to be impure 4 213'qu S'ohlore «phony: methane. m eater (benmyl) melted at 3'. 6 the melting point of the bemoyl eater prepared by use of pure A mm 3' chloro diphmyl methane. Not enough eubetcnce was obtained between 192° ~ 194' c to prepare an ester and so no definite proof of ortho eubetitntion wee eetcbliahed although it nimt have occurred to e. mat “tent end wee not detected. i'he fonr 1990 - 2100 0 ct n/m trcotione fron the chore condone» ticue were combined and ”fractionated twice a 14/1... procure. coming over quite content” at 300° . 202’ o ee e etrew colored oil. A total yield of 6914 game of the mitied. 4 hydroxy 3'01!!!" diphowl methane wee obteinedu 'rhie repreeente an average yield a: 15.841 bleed on the account of 8 ohlcrc beeeyl chloride need. no. the an n eppeuc that e temperature of 22° .. 24° :1 1o ore—- {arable to lower tcupmturea for the reduction or 4 hydroxy vehicle “m1 -filne. not would be the effect or even e higher taperetu'e we not cleerly «team. but tron an earlier condmeetion a u°-u‘o the frutiee 199% zoe'o at 14.]— yielded 5.3 gm:- m1 the frection eoe’ - 250% et u/m yielded 2.9 gram. 29 '1. Proof of SW of 4 hydroxy 3' ohloro diphewl methane me hotbed edcpted for the proof woe similar to that employed for the proof of the cm formed in the Glacion condemnation of phenol end 3 ohlorc hurl chloride. It consisted of mporizg d hydrow 3. I 8' trichlcro diphewl methane by on Alcla oohdmeatmn of 2. 6 dichloro Ml end 8 ohloro Merl chloride ud checking thie eubetitnted phenol with the mend prod“ by the direct chlorination of the supposed 4 hydra: 8' mm dim nethmeo . (e) Promotion of 4 hydroxy 8 d 3' trichloro diphezwl metlmle. m 1101' connections eo already described in this thesis: under the preparation of 2 hydra: 3 I 5' triohloro diphewl methane were run using 20 gram: of 2, 6 dichlore 311101101. 20 grams of n-chlore bmzyl chloride and me or moron dlcls. rhe temperance of the first connection wee bytet eI-ioooauthuoeomu u°~1o° c. iroeotiawutotm place eccording to the following equation. m 01 c). on 01 °1 0‘“ + more D --—-+ ‘ oi an. (3 However none of the 4 hydroxy 8 5 5' trichloro diphenyl methane woe tamed but the original 2, 6 dichloro phenol and the 3 chloro benzyl chloride were returned elucet mtitdtiwely. we more oondcnshtione were carried out at ea'aze'c. the tunmmmmamtmmmmooxr, a dichloro phenol with the correaponding mount- oi’ 5 chloro haul chloride C” W £01.: Th. “8111138 wore as follows: liret connectio- lthyl em extreet 14.! clue I. e dichlerclhfllel 7.3 are“ 4 hydroxy 8 I 3'trichlorediphwl nethcne 13.! area tor Petroleu other extrect No product ieoleted 80cm “emotion Ethyl ether extract ool arcade 8, d dichlorophenol 2.. arm 4 hydroxy 8 d s'triohlorodiphenyl methane 9.1 gram tor Petroleu ether extreot lo rodent ieoleted Up to We et “/2111 190° 42090 et 14/:- Abore 220°C at 14/3: Up to 12000 at 14/m 190° We at 14/.- Above 220% ct ie/m the fraction or the «m1 ether extract coming over at 190° - 210' 0 ct n/m cryotallieed immediately. It formed white needle 11m eryetele from petrolen- ether and had after emrel reoryetallicetione a content Inning point or 10° - oo' c. the total yield of the mum product wee 6.1 creme reproeehting e 11.54% yield booed on the wt or I. I die ehlero phenol need. lone of the oorreeponding ether woe ieoleted in theae condeneetione. 51 (b) Direct chlorination of 4 hydron 3' ohloro diphenyl methane. hie chlorinetioo wee carried out or deeoribed for the chlorination of I hydron 8' more diphonyl anthem 1.1118 10 gram of 4 hydroxy 3' chloro diphaiyl lethuio. The reoction woe euppoeod to take plece ecoord- ing to the following eqution. w 1 . 1 * noQoa,< °>+ “12M nobmdo 2301 cu When the chloroform woe evaporated e enbetence cryetollieed out which no oeeuned to be 4 hydroxy 3 5 8' trichloro diphem'l nothene. After preeeing out the oil from the oryotole with filter paper and recryetellie- ing cone eewen times from petroleun other e melting point of 78.50 «- 99.2’ c was obtained. to) couporieon of 4 hydroxy 3 I 3' triohloro diphonyl methane oe prepared in (e) and in (b) The 4 hydrozy 3 5 8' trichloro diphetwl nothono or prepared by the A1613 conduction of 2, 6 dichloro phenol and 3 ohloro bonzyl chloride hed e melting point 79° - 80’ c. analysed 86.95% chlorine, yielded e benooyl enter with melting point 130° 0 130.4." 0. onolyaie 27.4” chlor- ine end oryetolliood in fine white needles from potroleun other. The compound prepared by the direct chlorination of 4 hydroxy B'chloro diphenyl nothnne had as melting point 98.5“ .. ~79.o° c. ennlywedm chlor- ine. yielded e boneoyl enter with melting point 139% 1290’” onelyeie 87.29; chlorine and eryetolliled in fine white needles. u the ebewe «in apparently offered proof that the compound prep-wed by the iireet chlorination or the eeemed e tum-on 5' ehloro diphmyl wee e hadron 8 I 3' triohlore iiphmyl nethene end hence the enbetitutei phenol tr. the A101; «much of phenol end 8 ehlore beneyl chloride one the expected 4 moron l' ohloro aiphewl methane. Y. Betclflmm the butcyl eetere of the echetitnted phenole were wowed by the nethod or Einhorn end Holland (5.. 501.. 95: 1898) (Method of Organic Chen. W. Stevert. end Drench page 181 - 182) no follow; 3 great or the metenee tee dieeclved in 5 grace of dry pyridine and e 10% exceee or the eeleuleted uncut e: beneoyl chloride wee added. After etending over night on eqml telnet of enter one elc'ely added end the mixture church un- til no odor of beneoyl chloride could be detected. The mixture wee then poured into cold dilute euphoric cold and extracted with other. After be- ing wcehed with cold dilute eodiue eerbonete the other one dietilled or! end the enter ellceed to cryetelliee. Reoryetcllieeticn from alcohol wee then resorted to mtil e ocnetent melting point wee obteined. For the promotion of the pore tolyl nlfonyl end the benzene enl- m1 eetore, pore tolyl euli’onyl chloride end benzene eulfonyl chloride were euhetitntcd respectively in place of the beneoyl chloride in the ebore proceednre. The beneayl eetere of 2 hydroxy 5'chlcro diphenyl methane, 4 hydrcq 5' chloro diphenyl methane, 2 hydroxy 5 5 5' trichlcro diphenyl methane end e hydron 5 5 5' trichloro diphenyi methane; the benzene eulfcnyl eeter of 8 hydroxy 5 5 5' trichloro diphenyl methane. and the para. tolyl eulfonyl eetere of 8 hydroxy 5 6 5' trichloro diphemrl methane and 4 hydrov 5 5 5' tri chloro dipheuyl nethene were prepared. me beam “Howl eetere end the pore tolyl eulronyl eetere of 2 hydrcn 5' chlcrc and 4 hydroxy 5' chlorc diphenyl methane failed to cryetellize. for father informtion regerding the melting pcinte, chlorine enely- eie. crystalline etrocturee end tomlee or the ebove eetere rater to the denerel able at corporate under the heading of Rotors. VI. den-rel reble d’ We MI. 1. 3 hydroxy 5' chlcro diphenyl nethene Structural {oracle on ____Ol 0““ U \ Oryetellinc rm straw colored liquid Boiling point: 192% 194% at Milan Yield: * 7.73% Ana-1:“! , Sample weight cc .1 l x chlorine 1 fl chlorine mo, Pond Celccnted 1 .31» m V 15.31 16.13 2 .2816 10.“ 16.“ 16.23 Am 16.38 2. 4 hydroxy 5' chloro diphawl «them structrel fondle no Om. Q“ Oryetelline torn: straw colored liquid Boiling point. 200' - 202° 0 at 14/“: Yield; 15.84% W1! Steeple height co .1 l f chlorine fl chlorine 8630, I‘m Calculated 1 M": 11.17 16.01 16.88 x .2140 e.“ w 190”.“ Average 15.00 5. I hydrou 5, 5. 5' trichlcro diplunyl methane (tron Oleeien condeneetion) ctrccttc-el {oracle tn cl cl 0 m, Q 01 crystalline form. Smell needlee from petroleum ether mums point 1 59.4’ - 50" 0 Yield 1 4.56% inelyeie Sample Weight co .1 l 1 chlorine 1 chlorine 5603 Pound Gelculeted l .1999 20.85 56.99 57.0l 2 .2339 34.16 56.69 Average 56.89 4. e hydroozy 5, 5. 5' trichlore diphetul nothnne structural fondle oi cl QB: O Oryetelline form White mall needlee from petroleum ether Belting point 1 n" «- 00% Yield 8 11cm Anelyeie Sample I'eiart u .l H t chlorine f ohlorim 1&0: Pound calculated 1 #22“ 23-29 “e98 "e01 2 .1986 20.67 56.91 Average 36.95 Ethere l. achiercbeneylmether Structural rem-Ill Owed cryetelline:rorn¢ ~ Melting point . 36° e 36.4° 0 field- I 10.39% Analytic hlorine xiehlorine 3.... W or to... m... l .2176 9.87 16.00 l6.25 8 .8080 9.51 16.21 leercge 15.10 2 5 chlcro bonnyl 2, d diohlorc phony! ether Structural flornnle 01 Ol c1 <3 Mao Oryetclline torn; mlting point , 42° ~ 42.e° 0 Yield 0 1.4Q% inelyeie chlorine Sample weight czgagbl' flighlorine ghiculeted 1 .3858 27.86 57.8 57.01 2 .2840 27.69 ‘___§Z=£!_ Average 87.2 57 xetere l. Buoy). enter or 8 mm: 5' chlore diphenyl nethene. Structural fondle 9 r3 ., . \ . Oryetclline farm. ehite flekee from alcohol mum; point . 57° .- 57.4° o Anelyeie Sample weight ee .1 l S chlorine S chlorine mo, round calculated 1 .23! 7 11.17 10.” 2 .m 6.4 __ A 11mm t Average 11.13 1. Deneoyl ester or d hydrery 5' chloro diphenyl methme Structural formula ng Gourd! mum torn 1 Pine ehite needlee from alcohol Inning point . 57.c° - 580 c inelyeie Seaple Weight 00 .l H 5 chlorine- fi chlorine A6503 Pond eelccleted 1 .20» 6.20 11.03 10.99 8 .2088 6.41 10.89 Average l0.“ 38 5. Imeyl eeter or t hydrory 5, 5, 5'trichlore iiphmyl nethene Cl Gmtelline form Long mite noedlee from alcohol honing point . 534° . 54% lnelyeie Sample lifeight co .1 H X chlorine fl chlm-ine mo, Fond Oelcnleted l .5055 16.58 87.15 27d? 2 e1998 “.3 27.15 Average 27.14 d. W actor of 4 hydroq 5, 5, 5' trichlorc diphenyl netlune Structural formic C>°=o o 01 O 01 l “at dryetclline torn. ehite mall flakee from elcohol uniting veinte 130° «- 1.30.4.o o inelyeie Sample Wemt co .1 n 7: chlorine fl chlorine £8305 room! calculeted l .50“ 15.94 37.51 27.17 8 .5050 15.75 We” Average 27.45 _-_" A ‘u ALA—“uh _ . __ . ______";__.A_-L‘_.L_~'z_—l 3. Me tom nlfcnyl eater of 2 rural-on s. e. 3' trichloro diphcnyl nethue ° cl “er 01 Oryetcllim tome Brood white blunt neodlee from alcohol mums point 3 135.4" .-. 125° 0 .Anelyele Sample weight cc .1 H % chlorine a: «aloe-inc A5303 Fomd Calculated 1 .8053 18.71 85.93 24.09 2 .2056 15.97 M 24.09 w. Arorogte 24.01 6. Pure tolyl cnlfonvl enter of 4 may 3, 5, 3' trichlorc diphorwl asthma ‘ Structural formula ! wac>§=o 0 01 U m l Crystalline tom: Lone: mite needles from alcohol naming point . 104.50 «- 105% Analysis Sample weight cc .1 H g chlorine % chlorine mos Faun! calculated 1 .2174 14.71 24.01 “.09 2 .2418 16.59 24.00 Average 24.01 7. Beneene eelrwl oeter at a hydrcaq 5. o. 3' trichloro diphmyl mm strmtm-cl foe-uh - ~ 9 (.1 3” cl 9‘ 0:13 01 .._.o1 emu-.111» fem: white tronelucent rectilinear mule from 11100le Melting point 1 11M" - 1150 c Anelyeie some weiaxt ea .1 r :2 chlorine x chlorine M31303 Pound Onloulated l .2100 14.7l 24.64 24.08 8 .2078 1‘.” 24.86 Average 84.65 41 11!. M l. e hydrery c' chlorc diphenvl lethcnc and e loci-on :1 ehlwo a1- phoxvl methane and derintiree have been prepared and identified. 2. Ho widence of ortho eubetitution in the elminm chloride conden- eetion of 5 chloro beneyl chlm-ide and phenol who obtained. 5. Mpenturee above 50‘ a core found to favor the formation of the phenol duiutite by the elminmn chloride method. 4. Chlorine roe tend to cater the unoccupied ortho and para peei- time of the phenolic ring of 2 moron 5' chlorc diphenyl methane end e hydrcry 3' chloro diphanyl notmnc. ' 5. Ho ethere me ieoleted from any of the elmimnn chloride conden- entione. 6. A relationship was donmetrated to exist beteeen the fomation of 2 hydroxy 5' chloro diphenyl methane and the amount of the 5 chlcrc benzyl phmyl ether present in the reaction mixture. SCHEAE OF CONDENSA TI ON C? c? .59“ OH 0 a a . a (1 MP I30 -/3a4 0 am £211»ng 9 MI? 79-80' Cl «6 )QC 1 MP /04.5 105° :0? 00 0“ CH3 cl 1 0+ «OM» Qwaon a. P. 200-101“ MP. 57.5—58‘ H'MM OHM 0+ ac @1401!» Sand MP. 36-364. (HM! (1:0:d MP6? 67+° or. 091-1943 MAIM OHM) 0+ (ICHQ Cd MP 63.5- 6+ d CI 1. (3 e” w MP 12515415 .EJ::2.d—» M-P5a4-60 ) HM) c 0.....dmaQC3 UQ MW m? 42 415‘ CI 4.2 .. w _ I .,‘-.'t‘,t_) ,8 ski-v: ’3" 5.3,? ;;-; i” c ' '- ‘M .3: ~ .‘9‘ I! o . \ In: .. I . 5 i _ 4. ['41‘.“ .' .1: .fi“ |'.~ ‘4 “ .N-JK'LV' - V; _ '} Q ‘. -! :‘ 3f}. .- ~. ‘1 4-5-1 U7." ~, ’.".J.’4,',}"' .2} 33" . 7'" ' -. ‘1 4 . . t . Rf. I U - 5.1;} g 1 1‘4?- (‘2 '0 . ;‘ .3“ ‘A.’ . ’. , g1! ~ . ‘ . £1“ i._'-.I,"- LI 3} c3 Vfi’ffg: l- -y ~33: ‘ ,Lnai.» t" ‘u .' ,F&‘ ‘4‘. a" ‘ fid'flfiy 14’: 3'?‘- ' 5". '- :1 .vl.$ " 0.. atwgff eL ‘.$V’_~U£ VL(-‘ 9856 I l l l l l l l I ' I l n' '- l I ' Ill. 1 II II '6 l '0 l i