m sm isaeHEK X sm o r urn s m o -a u q tu tio k o r phxkols, AHB o r THE CLS&VAGS ASB THERMAL R1SAHBA190SKEST Of ALKXL ASH. ETHERS » r H erbert 9 , A THESES Mae&tiod to th e Softool o f Gfcoduete Studio* o f Michigan S ta te C ollege o f A g ricu ltu re end A pplied Sciortce in p a r tia l f u lf llle e n t o f th e requirem ent* f o r th e degree o f HOOTCH Of FHILOSGPHI Department of Chemiota^ 1953 ProQuest Number: 10008297 All rights reserved IN FO RM ATIO N TO A LL USERS The quality o f this reproduction is dependent upon the quality of the copy subm itted. In the unlikely event that the author did not send a com plete m anuscript and there are m issing pages, these will be noted. Also, if m aterial had to be rem oved, a note will indicate the deletion. uest ProQ uest 10008297 Published by P roQ uest LLC (2016). C opyright of the Dissertation is held by the Author. All rights reserved. This w ork is protected against unauthorized copying under Title 17, United States Code M icroform Edition © ProQ uest LLC. ProQ uest LLC. 789 East E isenhow er Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 th e a e th e r idahea to eapreaa b is aincero i^io rs8istis& to Or* Harold H a rt, f a r hi* ©meuragaiaent, co n stru etiv o e r itlc ia w , and safcbm i s s t i s In te r e s t throughout th e ceurae o f t h i s ln re a tlg o tte n . Re alao wlahoa to asqpraee h ia g ra titu d e to th e Graduate Ccmae l l fo r fin a n c ia l a ssista n c e in th e fo n t o f a graduate Council F ello u ah ip . jm**L u.iHL.ifc«»Aftjfat a*m Tfifwinnif «### JA M ww • m i a t em m ets PAGE I« X n ti^ w U w ,, ................. X F o rt A. S tereo eh eaietry o f 0* end G -o^Fhonyl* e th y le tio ii o f Phenol. jM Jreeo l, uad M M H . m 2 !2 l..... 16 ( t ) B oeeiionrof Dieiyri E ther end %H % dregen C hloride ixt Aeetone C ontaining Suspend** od PoiaseitBs O m A f if tte * ,,,* ,^ ^ ,.* ................ 18 (f) lieactAon o f Sodlms jMSresexide and cK>f%e&^iatl^l P h ei^ l ®fcfe«r.... . . . . . .......... 18 U ) The F ro p aratim o fc^-jfcei^X ettiy l H se tty l SSther in th e Freeem * o f ^P heny letharl Phenyl E th er 18 (h ) Soto Meaeurewenie on th e ADorUti«Hi o f Sodium FDomd4e tgr ^B sen y leth y l Chloride in Atfapdrima E thyl A lc o h o l.. ............. 19 ( i ) Conductance H ea# u re» erite.... . . . . . . . . . . . . . . . . . . . . . . 20 ( j ) AxsAXyei* o f <<^PIief^Xe^ylftted Phenol H iac& ures.... 20 (k) Gom rel Procedure $#ed in O xidation o f K ~Fhenyletfcgrlated P henol*, ......... 21 XT. D le m s e s io a ......................... 2h M W t m c c m m s • CmUimd **« • KtVfc >* & •*«*«• P t "SMtikuWNt i^ w iP"8|(9arawl^n&sS2F VtmngrSl », »au*M ri«a...,.,..,,. . . . . . . . . . . . . . . . . . . . . . . .................. la **# «a*pwWTewePRwwfc#*#,..«#*.*••*#•«#*«**.«*«* **#*«•»#**•**#♦«*«**«•* *vf (§| °C*Fbii||lstiNFl Itwmjdl StSbroPji PtiAiioSt *f¥* B^dregeB 4? flm tfi Btfoar nod %i3vopi C hloride.,. Ii9 (fc) (c> K^Hier^rlet^rl ftaapSL Ether, %dr©#&n Chloride md it? • * ♦ # * * »******■#■•*< (d ) i ^ t n d g tb e r* flip C reao l, and H vdrogesi OldkAiii^lde* # . .* «**,*»*#*«•*«*«*«*»•*••«•*«*#* **.«»»*• 50 ptwac^rl E th e r m et P h e n o l* * * * * * ,* * ,,,* * 50 ( I ) O rth o <^~Pfa«EyXftilayl P h en ol mad Kydtregwn 6 t k f t h M . SO {«) i^ l O h M #TWwKyeL- ISl®MHrg rEtiwEtflML l i . #.M « * M (h ) (♦ ) Sj^J'r'QBu ............ 52 fhnmgrl M u r* r d f t m l mad SSt OtdAwiiki ( i ) ( • ) ^ ^ P h o s s r le th y l FheayX E th asr, t a r n mad Biydjfogsm 52 {}) W ^ ^ e s i y M i h y l PtioeyX E th e r an d H y lm rm C t& orlde**♦#****#**«•**«*#»#«##•*#*•«••«**+»**»'**» 5? (k ) (* } ^ ^ « a » l 9 % l J f e a ity l B tb o r, P h e n o l, mad ttEvwettitttim^AWfcL aamtfSj#0n (1) («) *C«r3aMMffl£L,,., (a ) IM M a o fs r .......... 63 (a ) Owioral Proooctare f i r ih o Baarraagwaeni o f ilia c< ^P h e3 q g rlo il^l B ih aro o f P h o a o l, p ^C reo o l an d t #6 ^X o i» o X * * , «**•,.#*»,,»•«»,*•,•#**#••*#* 6| (o ) (+) °C**Phoi^lotfeyl H ao iiy l E ther and P h en o l,******* 6b X, XX, XXX* f t t j e i t f u & m , , ................................ 6$ S&Mft&ry** •« * * * « • •* • •* • • # * * • * * • « • * • * « • • • • • * • * .* * • * • * * • » # • * * « • 7® R e fe re n c e # .. ............ 73 1 Although a l l o f th e eapariatenta in th ia th e e la a re l s l t m U t e d , and »ny be dependent lactam on# another f a r atereo ch en ical aaalgnaente « f con­ fig u ra tio n , « te M they have been divided in to tlira a p o rta f a r th e eake o f c la r ity l a preaeasxtatiiwu A eep arate h ia te r ic a l axel dlaeueelon geea a tth each aootion* th e th re e p o rta o f th e th e a ia a ra t A. S tereochem istry o f 0* and C-oC-phasyletbylatAon o f phenol, p~ oreeolf £#6-3tyl«nol and a a a lto l, B, Cleavage o f o ^ fc a iy le th y l phenyl o th e r by hydrogen c h lo rid e , 0 , T heraal rearrangOBieat o f th e c<~phenylethyl ath ara o f phenol, p o n o d l and 2f6**jqrlenol. The main eaneliieiena o f a l l th re e p o rta a re g i m in a w m m ej a t th e and o f th a th eela* and lite r a tu r e cgraphy. a re given in a eln g le b ib H - wm a JS$E&BQC8£KX3$IiC£ Of 0- AVB Of JHSKOk, p-CRS80&* 2*i6«d%3BKfX» AW HSSZfCXL iw & m m kh One o f th e a o ii general sethoda fo r th e p rep aratio n o f eth ers cons lo ts l a tr e a tin g th e ap p ro p riate a lk y l h a lid e , a*yl h a lid e , a ll^ a a ry l s u lfo n a te , o r a lk y l s u lfa te w ith « n a ta l alkea&ds o r pheatwdde , la anhydrous alco h o l, T his re a c tio n i s u su a lly e a llM the W iU lsaooa synthe­ s i s o f e th e rs (1)* K inetic stu d ie s by nsMerotts workers l*awe shown th a t th e re a c tio n la anhydrous alco h o l la second-order. S egallor (I!) has shown th a t th e r e ­ a c tio n o f a w r ls s o f a sm *1 and branched chain a lk y l io d id es w ith sodium phenexlde ie b im cleeu lar, Woolf ( 3) has shorn th a t n o t only la tho r e ­ a c tio n o f sediw s so fn a x id e w ith variou s a lk y l iodide* b lttc ls e u la r, b u t a lso th a t tits ro aetlo n proceeds alm ost ex clu siv ely by means o f th o eugenosddo io n , ra th e r than tho inadlssoeiated m olecule. lam er sad Shingu (it) stu d ied tho re a c tio n o f a l l y l bromide and sed im phsacntde la ab so lu te a lc o h o l. T h eir r e s u lts ore In accord w ith those o f Woolf. Wore re c e n tly Quayle and Royals (5) observed th a t in tho re a c tio n between scdlum phenoxtde and n -b u ty l bromide la so lv en ts o f varying d ie le c tr ic c o n sta n t, th e re a c tio n l a e n tire ly le a le In so lv en ts o f h i # d ie le c tr ic co n stan t (e th y l alco h o l)* l a a d v e n ts o f lew d ie le c tric co n stan t (bensene), th e re a c tio n proceeds v ia io n p a ir s , and i s in te ra te d la ts in so lv en ts o f in te r ­ m ediate d ie le c tr ic co n sta n t. th e re a c tio n o f sodium cthoadde o r n ethcaid e w ith o p tic a lly a c tiv e 2 -eh lo ro - o r 2-bromooctane proceeded w ith complete in v e rslc n i furtherm o re, 3 Hughoa and coMSorkare (6) *sl&o showed th a t th e re a c tio n o f sodium olboa&do o r metli03dd.a In absolu te alcohol wi th o p tic a l^ a c tiv e o ^ p lic n y le th y l ch lo rid e follow ed oecoad-order k in e tic s f proceeded w ith in v e rsio n , aad w ith higjh re te n tio n o f o p tic a l p u rity . Thun, I t seems apparent th a t th e re a c tio n between sodium aXksxlde o r pheuoxids and a lk y l halide* In dry alco h o l proceed* by a second o rder n u o leep b llia displacem ent mechanism (% 2 ). However, Swain (7) ha* shown th a t e th e rIflc a tio n o f trlph$*$rlm tjiyl clito ride in benaero by methanol i e term o lecu larj in p o lar so lv en ts ib is m m re a c tio n had been shown to obey aeoond order k in e tic * . Since th© o rd er o f a displacem ent re a c tio n ie ap­ p a re n tly dependent on th e experim ental c o n d itio n s, one must ex ercise e x tra s* cau tio n in th e in te rp re ta tio n o f k in e tic re su lts* C laison (S) was among th e e a r lie s t workers to e x p lo it the W illiam son s y n th e sis. He was p a rtic u la rly in te re s te d in th e re a c tio n of sodlua phenoadde w ith a l l y l , o ln n a sy l, and b eray l bromides in v ario us so lv e n ts. €la ie e n and Beth (? ) observed th a t in nondieeoolating a d v e n ts such a s beesexie o r to lu e n e , sodium phsneside* and a l ly l brom ide, oizmanyl bromide o r b eray l bromide gave jsredOBdnantly nuclear su b stitu te d phenols. On th e o th er hand, in m ethyl aX cohd and sim ila r a d v e n ts th e form ation o f th e a lk y l a r y l e th e r i s favored, th e e th e r i s a lso obtained In an e x c e lle n t y ie ld i f a phenol i s dissolv ed In aoetom containing suspended potassium carbonate and re flu se d w ith th e ap p ro p riate a lk y l h a lid e . I t should be noted th a t th e production o f th e e th e r i s termed 0-* lk y l* tio a # whereas the production o f n u clear alk y lated phenols i s tamed. C -a lk y la tio n , C -alkylatlor* o f phenols in b asic medium has bean used by ntuaGrous eo rk ers to o b ta in ortho alk y la te d p ia n o la . Ho s a tis fa c to ry laeehanisa has y e t boon proposed fo r G la ise a 1* O -aliqrlatioa* C laisan and Both (9) elim in ated th e e th e r as an in term ed iate toy shoeing th a t the allq rl phenyl ath « ra da n o t m m n g s ra d a r th e experim ental co n d itio n s involved in th e ir preparation* Subsequently, c ia is e n and T ie ite (10) shaved th a t th e proetuot obtained hgr h eatin g th e e th e r a t 200* m d iffe re n t fro * th e product obtained by d ir e e t C-aikyXetioa* Ifc* product o f th e therm al r e arrangem ent o f vhsreae th e prodweb obtained from C— aXkylatiom saa Proof o f s tru c tu re ean eiated in converting th e alk y la te d phenols to eouwirans* Am a lte rn a te meohaalen favored by GXaiaea ana th e M ichael 1 ,2 -ad d itio n hypothesis* th e a lk y l h a lid e *ea presumed to add aaroae th e orth o doable bond id th subsequent s p littin g o ut o f sodium h a lid e , and form ation o f the a lk y la te d phenol* The th ir d p o s s ib ility considered by CXaiaem involved "m etal tautcRserlon* o f th e phenoxide ion* Im m t aad Skknghu (W abate th a t 0 - o r C -alk y latlo n depends open th e p o sitio n o f th e follow ing tautom eric equilibrium * 5 C -* lk y latlo n can a le e be brought about under a c id ic co n d itio n * , ® w»Uy th e QORdiBflitlfla la c a rrie d o u t in th e preoexioe o f a k n i t acid typo I f th e a lk y l b o lid e and th e arom atic xmeleu* o re b o th ie * W U f t, th e preeenee o f e c a ta ly s t lo n o t necessary, Thus, Von Alphan ( H ) t Bomoatt and Beyaold* (12) f and Simon* and H art (13) bare rep o rted th e a lk y la tio n o f phenols m tfc te r tia r y « liq d halidao * M m re c e n tly . H art (H i) rep o rted th e a lk y la tio n o f phenol u ith ^ p b e n y le th y l ch lo rid e a t JO*. S tu d ies on th e a lk y la tio n o f th e arom atic nucleus w ith o p tic a lly a c tiv e compounds have been lim ite d to only a f e e e a se s, P ric e (15) and U nm an (16) have stu d ied th e a lk y la tio n o f benzene e lth o p tic a lly a c tiv e secondary b u ty l a lc o h o l. th e re a c tio n nee c a rrie d out in th e preeenee o f boron tr tf lu o r id e , hydrogen f lu o rid e , s u lfu ric a c id , and o th er ty p ic a l F rle d e l-C ra fts a c id ic c a ta ly s ts , Biace th e aec-b u ty l bensene obtained ace ex ten siv e ly raeam ised, th e aU grlatioii* se re thought to proceed by means o f a oarbonium le a in te rm e d ia te . Mere re c e n tly , B urnell (IT) alk y lated bem ene id th o p tic a lly a c tiv e secondary b a ^ rl m ethyl o th e r and boron tr i~ flu o rid e* Tim eecomiary b u ty l bem ene eae produced w ith Inv erted configur­ a tio n and o p tic a l p u rity g re a te r than 1$, Furtherm ore, B urnell e sta b lish e d th a t th e racem ication could be a ttrib u te d to th e ex isten ce o f a tra n s ito ry carbonitaa io n r a th e r than to ra e e a le a tlo n o f th e o p tic a lly a c tiv e o th e r (independent o f a lk y la tie n ) o r to racasaiaation o f th e hydrocarbon eufe* sequent to i t * fo rm ation, A lexander and K luiber (10) c a rrie d out O -elk y latio n o f phenols uitfa o p tic a lly a c tiv e h^bloro~2~penten© , in acetone and potassium carb o n ate. 6 9«m C -^ O ^ lo tio a ooeoRponioa t i * proeoMf a«S o p tic a lly o e tiw «CA ^ «•*!• jaethjjrlollyl phonal no* Jtansod* I t* oterooohem ieal co n fig u ratio n o r o p tic a l purity* M i n o t in w a tia a to d . 7 ex perim en ta l Propm ratim « f S ta rtin g M aterial* 1* RsjritetaUm o f s * 22,7 to °Cb ♦ 2 6 .7 , was obtained in as* Id e n tic a l manner. f to Conversion o f °C~fT*esylBthyl Alcohol to oC ^gtogrlethyl O hlsrida Method 1 > *«*» f o 9 .1 nil* (0,12$ to la ) o f th io n y l ch lo rid e (Bsagsist Grads) in a 2$ ml* roand-bottoiood H ack was added dropwiee 12.2 g , (0 .1 mole) o f lero~ o< ^hettylfitbyl alcohol ( ° ^ ~33.2°) a t roan tem peratu re. A fte r stan d in g f o r 1$ m inutes, th e m ixture was d is tille d to y ie ld 12.2 g* (S7$) o f la iio « e ^ ^ sM ^ lst^ y l c h lo rid e , fe. p . 70^!2°/X 0 mm., -3 8 .2 ° ). Method 2 . — follow ing th e procedure o f B urnell (2 0 ), to 200 m l, o f eh lo ro fo m th e re mm added 8? .3 m l, o f p y rid in e and 16,9 g . (0*b63 mole) o f anhydrous hydrogen ch lo rid e gas was passed i n . The m ixture mas cooled to **15° and 2b,5 m l, (0.20b am is) o f d o attro -o ^ p h scy lsth y l alco h o l (oQj ♦ 26,7°) mas poured i n . The tem perature mm co n tro lled between 4 S ° and ~XQ9 , and 18,7 m l. o f phosphorus osychioride so re run in dropwise w ith s t i r r in g . A fte r t o t a l a d d itio n o f phosphorus oay ch lo rid e, th e m ixture was s tir r e d f o r 30 m inutes w ith th e tem perature kept below -1 0 °. The m ixture sea stoppered and allow ed to stan d a t room tem perature fo r 20 to u r s . It was then poured over approxim ately 100 g . o f lo ef th e chloroform la y e r was sep arated and washed tw ice w ith w ate r, once w ith $0 m l, o f 85$ phosphoric a c id , and th re e tim es w ith w a te r. The chloroform so lu tio n was then d ried e tte te t A il ro ia tio n s in th is th e s is r e f e r to th e homogeneous liq u id la a 1 dm. tu b e , u n less otherw ise in d ic a te d . 11 over anhydrous e s le iv n ch lo rid e awl d is tille d a t ?0-7£°/10 era. A ?0j{ y ie ld o f lew -o C -p b scy letb y l ch lo rid e (<^iwl«rlliaA |*ereayX ether ([°C*J tM S*, d » &?# h m fti) led 1 g« e f aefcerlaX* )»«p# 1§0^0O/10 » « ftm el&eXl **3&bla frwfcl©** geve *& dleUlletio** 7,2 g* *£ p~ereecX and 3*2> g» ef ii*wthyi~ *1.77°). Sethed It. viia iMMiHMel laieMtediBNi fa r nmmrliktf o nfrleeirtim eerhmaetft^ Th# TiitHillfllf iMi^ioi freetlm Yielded 2J}*0 g* e f ^^hes^lethyl e&lertda end 0,$ g# ef ^t^hffinylettylr |ds*ayX •U m* . Th# #l)Mai«Ml»hl# ftraattea jd#ia#d 16.0 g. *f pfc#w»l, fh# iv w iw a w ^ . ..^ .-jy ^ o i h ^ t t e l ^ ° ^ I ^ B r l # t t g l ) m®ml OB 17 In th e so ld i# a lk y la tlo n a , efu im elsr amounts (0 ,0 7 mole) o f p-*ereeol and c^phenjylothyl ch lo rid e ( o ^ *22.9° ) se re placed in & SO m l. round bottom fla s k attach ed w ith a re flu x condenser, and boated on a steam bath f o r l i a s h e a rs . When th e so lu tio n s e a le d , petroleum e th e r mm added and th e m ixture mm estreats& w ith 10# eodiua hydroxide e l u t i o n . The a lk a lin e e x tra c t* m m a c id ifie d w ith so ld d ilu te hydrochloric aeld* The e l l ubicb sep arated mas ex tra cte d se v e ra l tim es w ith bcm eae and th e bensane e x tra c ts m m d rie d ever sodium s u lf a te , and d is t ille d from a m odified C lalse a f la s k , y ie ld in g 2 g« e f p ^oreso l and 2 .5 g . o f b«aethyI~2-( c< ^ h en y leth y l)p h en o l (°C$ *0*13*) • The above experim ent mas rep eated u sin g <«phex$rletbyl ch lo rid e (°Cp ~Wu?S°) and a 50# y ie ld o f ttrt»etl^l*4M <2#6-nilm«thylphaB0l CKp «0*1X*) mm o b tain ed . The same experim ent a ss e t t r l i d o u t using {♦) c<^phe#ylethyl c h lo rid e (°Cg ^ 2 .3 ° ) * (>) °0* p h enylethyl ch lo rid e ♦l.Og0) sad W cK - ^ b e iw le t^ l) ^ ,6^di»ethylphenol (< U 40*0^°) se re O btained. 16 U M itA m o t < » m n y l« 1 ferl Ptom rl E th w «nd 3 H S rfyogro C h lo rid e la Aeotone ConiiMLBing 5u#pended Carbonate tw enty »X* of a a o lu tto n o f 3 H hydrogen ch lo rid e in aeeta&a aero added dropwiae to * mirfcar© 0 .1 male o f °C«$»liox^X»ttQrX e th e r, 0 .1 » e le o f p o ta e a im carbonate in 20 a l , o f b o ilin g aceton e. Hoot o f th e e th e r wee reee re re d (0.085 n o lo ), and OS g# o f «*^phenylethyl phenol erne leol& t& d, Xt m e ehewsa, by ^ e o tro p h o to o e tric a n a ly e ie , to he btS th e o rth o te e n e r. R— o tK w < tf s o a m . p ^ » n s ld g . jM . g C ^ » ra r^ > » h y l m r n l ...m r n . to a euepoiarton e f 0 .2 nolo aodlan p-o reaeatd e i e So m l. o f beaaeae p -c re ^ o t prepered by eefX&sdtisg b .6 g . e f eedltai eeed end 18,8 g . ef^pfeam ft, wee added 0 .1 a o le e f o C ^ b en y leth y l phenyl o th e r. f o r f i r e ta m e . th e m ix tu re w fl refliw w d Oe cooling* th e ataftm e m e worked • • e e e a l. th e mnmXfcali eo lu h le fra c tio n gave 0.09 »ol» e f mnefaanged e th e r e td le th e a lk a li ee lu b le fra c tio n gave «*0y 0.18 molee e f p^eraeol* th » l» w » » » tton o f °c~ m m U V to X K«*q&x m m ..M ..r n tm m m e -n t ffee aynfcfcoale o f ^~ph© *iyletbyl n e e lty l e th e r on a OJt mole ac ale wee rep eated In th e prateeeae o f 0 .1 nolo e f oC-phenarlethgrl phony1 e th e r. A fte r refln ad n g f o r 2b h n m , th e m ixture nee worked op in th e ueual meaner • tw enty f e a r g r a e o f n o n -a lk a li so lu b le m aterial* b .p . 1b0-4£5°/ 5 « . a**i 1 .5 g . f b .p . l80*220°/5 a n . were Obtained* th e a lk a li aolubl© f ra c tio n gave 7 .0 g . e f n e a ite l. to oC ^hesyletfcy l phenol wee d eto o ted . 19 W m M w M m m m to. m th e A lkylation o f Sadttai Phonoadds fry «T«»rheiaylotfryl it h y l A le d fa e l *>t*d l e g a te S e t ^ ^ t lo s i Set© determ inations were s e rrie d e u l t o i therm o stat m aintained a t t9 .5 ° * 0*1®* Sodium pherm ide soluU ons (o.5$«fc H) wore prepared fr m weighed ta a n tiiia s o f th e phenol and sto ck so lu tio n s o f sodium In abeoltfta e th y l a lc o h o l. th * c < ^ h e « y l« th y l e o la tio n s (0.5000 H) in abso­ lu te ajSOfofl H f f prepared fro© Weighed ^ were combined in w elar ratiogfo o f l t l , 2*1, and J t i c< *$fr*nylethyX chloride* E naction* m S o lu te . EdSOtSOitli phsaexid* to allow ed to run fo r Measured tliae in te r v a ls , a t th e e nd o f O d # h j $ m l. all<$&ets were withdrawn end tra n s ­ fe rre d in to 100 wX. o f 58# a$asm e a % l a lo e h e lj th e amount o f base un* reaotod wee determ ined t$r t i t r a t i n g w ith 0*099h8 W hydrochloric a c id to a Xsameid in d ic a to r end p oint* I n i t i a l co n cen tratio n s were chocked by w ithdraw ing a sample iwm&diabaiy a f te r combining th e re ac tan t* end t i t r a t ­ in g w ith stan d ard a c id . P recaution s m m token to p ro to o t e l l e o latio n * from m oisture end o i l ©|jhoeylothjrl ch lo rid e w « combined end th e re a c tio n see allow ed to pro ew d a t 19*5® f o r 2h hour*. th e m ixture wee worked up as d escrib ed in Method 1* 20 D ie ilH a tlo ii o f th e i» ii* a lk a li *eli2&l« fra c tio n &*** 12*0 g # o f on* ro ta te d c ^ -p h e ^ le th /l chlorid® and 2 ,5 g , o f o ^ Q c y ls th y l o th e r. Mo* U U illo f t o f th e iD a U o elo b le fra c tio n g m 7 3 g* o f p l m l and 1 .0 g , o f o* and p ^o O p b an y latV i phenol* filBBlM lilfflSfc O M W M W H t Can&MtuaM m tw ntK iW 1 m Md« using * dipping typ# o a ll a t S53° on th e follow ing aolu'M^PO and * (a ) 0 ,1 mala o f phonal di#«& *ed in $0 m l, o f aeeton e, W 0 ,1 mol* o f pet&ealun ©arbenate added to 50 a d , o f ao«tono# 50 s&« o f aeete n e, to id&ch f i l t m t a o f euepension in (b) * (d) 0 ,1 0 ,1 mala o f phenol disso lved In nolo o f pifrtawiiiwfr ©wbonata wee added, (a ) f i l t r a t e o f eaapenaien in ( a ) , th e fallo w in g rem dtto were obtained* (a ) gl*0©G aha**, (b) g re a te r th an 100,000 aim *, { « ) g r e a te r th a n 1 0 0 ,0 0 0 a lm a , (d) eisae* and (a ) 35 *b ofena. fb a iaaam rla miaAuree o f o G p h es^ letl^ l phenol* ware analyeed spsrotrop h o to m etrically aocerding to th e procedure o f H art (2 1 ), th e u ltr a v io le t ab so rp tio n ap e ctra were d e tr a in e d w ith a Boatman apoctrophotom eter, model ** Measurement® were node by B radford R. fhoqpaon. a M § mg ta g 1 m * wmrtm c e llo * gfrjmtbol&ct wtij&mm ootvfcalalng w t o u * m# fHfflNg fflpfehft Ami ttA y * * . 4m urnm p n p H n A . a p lo t o f w itw e tla a w e£C U **A ft* *$? m - m& a?3 A*» ftMfclttHMftBt UM JUttfe iftilllilrfr'lillftiiiilf MlW Mftfcl iaM 4 ko. 4M %lHin'Tla3»IPI» |~if jftfti VwvB* JIh IMM awFtW #VfW AW I m PAm KAVI W lrWHiP’^jiwBPMA Nfrtl ftftlftF ABB' (MUut b p Pm B P UUP tWPfc1 ift*TllrU f!>»WIAtuniwfciiaat Am>lFj«a»fe. Iftfctt fffflrt *if l iA ltlM W h i W #*Mkm4l.4a*mtt44iH*tt far Vl)M *,*If **«>..«'»» ^KkBmwaajh Mmt"l>ijMii. awt ., , f # * orihrtion co n tain in g 04$ f * (0*<3H5 m%*) a t ei IHQr^ imapi aui6llBi»S aa&jfao'fc aaat f^ 0$r**ir0 t r a a tfHflttftfl iftth l^ tp 0$ a l # jMHrildni <|0 benaene, % ^H yB upW yJi »wi^H MPW l MiPW k i iPMW MW lP iW t «0ttK0Jlut ilfejiU0kK%iiii >AI41 0 MlKVB» wK4ww S00T3t!^™JMflMMft wfPr SkWlkfceiillllilito^tlB w OBSmSB IW l^*^W naNi yy >yf * 1S1-1S20 # u ta ft m x tu r* o f tb i» oo®- fto&ft obftft^nod f ipyw ft fcymff* tffwpT-* o f p te sy JjB rtb y U w rtla «e*4 a n lta d (A 35L A 52® . If%4*. 'vS.OlLS j«# artfcn ta aw ft.jfrrt**.1*** ihMl«§ «£*£§ #»# tial . 23 «<■ *» ttf s? W m*\ IT O s>+ * 0% + rl Wk O * . *n*$ * # *> % 3 •f «i^SS1 ■#**'*© * % • * % n§ S#k «« 2k m m m m The as* o f o p tically a e ti m compounds in alkylation studies involving the aromatic nucleus hee been H alted to only a few oases. Theee w e concerned with the alk ylation of benxeae by o p tically active secondary b utyl i M t o l o r secondary butyl asth y l ether in the presence of etrong sleetro p h lil* reagents n e b e» su lfu ric a d d , boron triflu o rid e and hydrogen fluerlde* The extensive raevslsation vfeioh ©haraeterixed these reactions m s o lted as evidence fo r the formation o f a planer earboni\*i ion interm ediate during th e reaction* The very m a ll amount of o p tical a c tiv ity o f inverted configuration which ua* obtained night be interpreted in tarns o f shielding* A# the earbeniu* ion reeete v ith the solvent, the departing group eereena m i aide o f the carbonic* ion* I t hae long been known th a t in the OH&kylatlon of phenele f allowing any one of C laieen,e procedures, there ia usually eene unclear or G*alkyl~ a tlo n , provided each positions are available fo r su b stitu tio n , Althou^i Claisexi9* methods o f alkylation hate enjoyed widespread nee in organic Synthesis, m re su lts have been reported on the study o f the stereochem istry of the reaction using an o p tically active halide* I t aa* thought of in* tc re s t to study the reaction using o p tically active c<-phenylethyl chloride fo r the f o i l i n g reasonsi (1) ®rk«ra (23)* th e reaction followed second-order k in e tic s, By using anionic displacement reactions which lead to inversion, (in conjunction id th reactions which do not load to Inversion Since the reagents employed do not d ire c tly attack the asymmetric carbon atom) Hughes* e t ml. , ©oneluded th a t etfcerifXoatlea o f «C-phsziylst^rl chloride resulted In inversion o f configuration. They fu rth e r concluded th a t the methyl and ethyl ethers 26 o f o^q&ongrletlQrl ohlorliSe were fam ed w ith high o p tlo * l p a r ity . Than th e s th e rlflo a tlo n o f o ^ p h n g f U % l ch lo rid e m w n to be • ty p ie d 3,2 reactio n * In o rd er to bo c o rto to th a t % a iu ilftr Walden Ixxvoraloa accompanied th e o th o rlfic a tlo a o f c ^ ^ h e x ^ lo tlq rl ch lo rid e by aedii»B pfae»» oa&de, kitt& ilc sotsw oB eaito eo re tttxhartftken, TbdUs e ffe te one to ee tftb lie h th e eogsfigpratten o f th e o th e r i& tb r e b o o t to th e h a lid e . Roto »eaeure»e»t» mere eftrried «rat In ft th e ra o etftt k ept a t 29.5° ftt th ro e d iffe re n t I n i t i a l eottte& txatlono o f ro aetftftta , varying th e pheaoxlde io n co n cen tratio n th re e -fo ld , th e re a c tio n wm follow ed by removal o f aliq u o t* a t tftriooft tin e In te rv a le , quenching th e re a c tio n t l | d ilu tio n , end t i t r a t i n g w ith etflmdftrd hydrochloric a c id to e j eeptajd in d ic a to r p o in t. f e to o t fo r aaeoad o rd er k in e tic * , th e in te g ra te d form o f th e eeoond o rd er r a te exprefteiott w&* used. a * molea p e r l i t e r o f sodium phenoxlde fe * melee p er l i t e r o f cO p h en y leth y l ch lo rid e x * melee p er l i t e r o f ftodiua phenoxide which re a c t in tim e t* (t« x ) * rnolea p e r l i t e r o f sodium phem xide p re se n t a t tin e t , (b*x) * m alm p e r l i t e r o f o<^phepyl»ihyl ch lo rid e p reae n t In tin e t . t » tim e in niinutes A sample oftloulftU on i» Imp f e llo e s t 5 » 1 . a liq u o t req u ired 8.05 m l. of .W U 8 W HGX, (a-*ar) * 8«05 m .®99li8 *7 * » b * X• (*"*} • 0 , (M • 0 ,llt7 6 %• X * j ” * fg g (jfcjha&y k * 1*03. x I©*1 U l x ttaJk** 1 b - 0.2S90 «wpMPX /4tIif kz 10 Hb>t0 1.20 0.0063 0.0062 1.17 0^CSlli6 1.16 0,Qlt|l 1,01 0.902 0.906 t 1 0.06 * * 0*f6$6 m&Xm/l, - x lii. * * x ©*1663 0.1602 ©*1392 U a «• m 0.3079 0. b » 0.1607 Mltiyi, 0.0711 1.120 QJMk 1.093 0.1679 o.ns 0.1836 0.906 0.3075 0.90b k ft*ai*g» • ©*9S8 £ 0*09 26 XtX 1300 8H 7 IftfO ,3939 *ole*A . b • 0.3250 0.3^87 0,3#® 0.3880 0.3800 0.3063 0.10S5 0& $$ o jtm isf • o.**P t 0.0® h 0.1025 a (a r ta ^ .) O.M86 0.3#® 0.39J9 1m A> 0.985 0.908 0.906 0.995 0.885 k C l-a^ la-^ ln .-1) 1.07 * 10** 0.788 * l<£* 0.738 * I T * K» AhA that tba m n ii ardar MAa anatw la «r* «$p*ejdNafc«]jr eonatm t •« r>* AtoaafaM m m m M U w m nga MMnub that W» raw tlon la .PritS kW dllM SluW Si S ftM I&H SbpStt0 *^H nV^*w fctlKSAIHw fe '4klfc&^#^piB S VvAVdQ hSB S: WsmMp* jPSsP S^SPSJW ttSSSipS lMti^ fepP sfttfk SitiM SSsW M hSfK ciV tkstk #WMI0Ip TpK W Wfe PW V mM ^U pS i isfijfi' rW H PIJIIJP P^^W RM PffcJW Ms jfflHBf- ^piiHW i# *s Slsst ilusibs0 f InfsM^ sts* fbiisd siife sbtisjElds AwH aatbaadde $m* I t is U»f«l0W «tf* t<* m tw tfesfc tbs rsasiloa ocmirs Still SSW SfSSSII & C$StSli£lPSd^&S&St ibs si^swsWis skv^ss ston* It irtXI b# astsd tbsi tbs vtts ssostasts dserssss stout 15* stih ty^ttnfl ttoiwillt^ti^QI of SSdtW phORBOSide» fMy |&$g&oa$ii&hiftS boss pm t.im M ftp sspsptiA (#*$*!2Uo%IH t| Suayl* sad ^ t n f 1^1*2) sad has toss sttHbnatad fc@r tbs Isitsr to suit offsots* Is ti&dsr to sirlataisb ttst tbs rosetto balog fsilsssd ktmtioslly mm tbs istsfttltfii of c<^hoi^iothgri pbst$& etbs* said sot sisp lj tfes do*0Tirohslog*nafcion S3f oGphs^lstbyl &&M&M to styrfsna# tfe®resstlsn S& 8 * oINiiit SISSSS litiit SSHSSSW o ■HrW IMnV mm d issssd sdvm m w lttd m i on a e f f i c i e n t l y Xargp ecale to p e w it pvodost ieclatXoi* and id e n tif ic a tio n . used m 8eveniy~five p areeo t o f th e •^p h B n y letb y l c h lo rid e recovered unchanged. The <~phM!gfXeifcyl phenyl eth er* id e n tifie d V means o f i t # b o ilin g p o in t and m elting p o in t # e*a obtained in 2$% y ie ld a f te r a 2h hoar re a c tio n tin t* th e mm n lk iili solvable fra c tio n y ie ld ed onraaeted phonal (? 8 0 and a IC# y ie ld o f o<*ph«nyl»thyl phenol, th u s* th e « ti» re a c tio n i t th e fe m a tle n o f oC-^pheayletbyl phenyl ether* Hhea ( o^’^ phenylstbirl oh lo rid o nag re fla a a d n itti phenoxide in anhydrous a lm h o l ( f) o^phogylaldbyl phenyl e th e r a s s obtained* <♦> C^OTBB, Cl a sodium e th y l >■ <♦> 6 A P C .K , <50* sta so e th e r fo rm lio n i a presumed to take p la ce a ith in v ersio n # {#•) oC -^hopylethyl 4 t e l 4 t baa th e aaa* co n fig u ratio n a# W < ^ $ li« iy l« |} y i i u * e • ce, fft* S b * e *e% I f m e raf&xats* (*> *^**jbeayletiayX ch lo rid e and phonal in a sus­ pension o f acetone and p atm ^ lta i carbonate one ag ain o b ta in s <♦) ©C*gi*eayl* « ||y l phenyl ether* fin e s th e earn e te re o o h m la a l r e s u lts a re obtained in th e to o d iffe re n t m adia, m e i s tempted to m m dtsie th a t e th e riflc & tlo n in acetone and potassium o av bm eta, g tm o ed isg o iih in v e rsio n o f configura­ tio n , i s probably a lso a e p i c a l % 2 dispXaeenent re a a tlo n involving ta o rd er to fu rth e r to o t th e hypntheei* th a t th e e tfc o rifio a tio n in oeotcwoe nee lo n le* eon&o&iiOBee ipi«ilflw *,-m eiyf U P ■»'*■" »>■ 11 " I p |* none witrfo an mImHaimi . gl&trahiinne o f th tiie onnoef&intte o f ohotiol mul iteetene.. b p p h w f^ p *■■ *" w w p ^ p ^ p b p t W im pfc ~ ipnaup J W lr ^ i r # i ^ w r f l i i * ^ n r» * '• w w w ^ i w Jl ftotMoolOM oWtseiBSto met Seetoieeji otH p$tenoX# jWP*aftiffwf> eeytPMtiftte aw* aceton e, A {tuej^ne&esi o f ffiaffltfcll air* ifiirii.^fffi eoyiyaflfflto in sootono tun 2 #900 Stem* mwt* oondooting then a e o la tio n o f phenol in tootom u *8mt in o f g re a te r ol^dX ioenoe 1* th a t th e f i l t r a t e o f th e erapeaedan o f potBssism oefhoniito in tfNMMwfli nee H jf^ y to a ttr ib u te th e iii^ipaefffr in ^ , j a : h^m* $£ ag .. end f t eooee reeeiendiXe a mi potneainn carbonate i n *m%&m to th e tw m % lm o f pfemogUie loser* th e fu n ctio n o f th e potaeoiun w to en n te As th e re fo re tw K fo ld j to ro a c t m th th e hydregon ehleiiO.de eeiirae ttf spoe&Mjfm^ nsa®^oaoifae®o^9 faaav ttttd ep^^^en deein# ^npooie■n^augi th ^one^e^p u soso^pnao^s* e n^e fofe* ^eono^e •n own^nrase^ theapebir ^npumwo* ^ni^avsntl-ncr gne iro^^seumsmrobp^ eXeneege « f th e eth er* te d to im m pfcansonlde to n e . F u rth e ra o re , attem pted eyntheei if o f th e e ld w eofng p o tn ssin e bien i^oo ate in pH*a* o f p o tssstn n oAatNenete ra s n lie d in a eooow sy o f aee*nei a ity e te y tin g ra ta rie X , Although potaeeiun felearfcoaaie would ee*taA*sXjr ebeorb th e hydrogen c h lo rid e tm m od timfimg th e reac tio n * i t in apjm rantly n o t m jffie ie n tly h a sle to fe m enough p lm m d M im » to allow th e re a c tio n to preened a t a aeswsttrable ra ta * th e o O ^h eeg rleth ^ eth era o f f^ ereao l* £,6*uqrl«nel and n e n ito l were ain o prepared in aneheaa end potascdUst carbonate m edian, u sin g o p tic a lly 31 a c tiv e o ^ p h aig rlath y l c h lo rid e . Altlumgh tb * sig n s o f ro ta tio n o f th ese e th e rs d if f e r , i t i s assumed th a t they a l l a re formed w ith in v e rsio n o f th e c h lo rid e , The la rg e magnitude o f th e ir ro ta tio n * tend* to land sup* p o rt to Mil* assum ption, th e sign* o f ro ta tio n s and eonfigw ratiou* o f th e e th e rs a re summarised b elcv i ch3-£-& (4 (4 (-) (~) In o rd e r to study th e stereochem istry and p o ssib le mechanism o f n u clear a l l ^ U t i a i i t no* n eeessiry to r e la te th e co n fig u ratio n o f ^*pfeeagrlsthyX ch lo rid e to th e » < ^h an y leth y lated phenols. In stu d ie s which to lu d id n o t w ily s u b s titu tio n reac tio n * b u t k in e tic stu d ie s a* w a ll, Cowdrey, Hughes, Xngold, Kasterman im& S e e tt (23) were ab le to e s ta b lis h th a t (*) ^ -p h e n y le th y l ch lo rid e and (+) °C -phe^ylethyl amine mere ec m flfu ratlo n al^ r rela ted * B ernstein am Whitmore {2k) , in s tu d ie s based m th e stereo ch em istry o f X ,t s h i f t s , were ab le to r e la te th e re la tiv e co n fig u ratio n o f (♦) p heuy lsthyl amine to (•) phenylmethyl* a o e tle a c id . Here re c e n tly , tii lm r and H e ftie r (2$) in stu d ie s involving m eltin g point--cQmpoatiion diagrams o f j& e^lm etl^X acetic so ld confirm ed B ern stein and Whitmore1* assignm ents o f c o n fig u ra tio n , Furtherm ore, th ese have been re la te d to a la n in e , which has been used as a co n fig u ratio n al standard* These r e s u lts a re summariaed in th e follow ing form ulae! 32 O%OGB CQOH I * c * h z oa# - 0 - h I « da* <*> {+) (-) (~> In o rd er to r e la te th e <<-ph«nyl8ibyl phenols eo n fig u ra tio n a lly to th e © O phenyleihyl c h lo rid e from which they v«re prepared ( e ith e r d ir e c tly , by C *«lkylntion, o r in d ir e c tly , l e w in th e th e sis* by rearrangom ant o f th e corresponding ether}* i t seened p la u sib le to take advantage o f th e c m w ith which a» arom atic sin g containing a hydroxyl group can be o x id ised , th u s* in th e *13grl*tod phenols* i t should bo p o ssib le to oxidize tli© phenolic r in g to a carbonyl group w ithout fu rth e r a ffe c tin g th e m olecule. 121 „> w*$wm Since th e o x id atio n does n o t a tta c k th e asymmetric carbon a tm o f th e ^ •p h e n y le W I group* th e asy ao stry o f th e ® <^hei3ylethyl group should not bo a lte r e d , fw rth a m ro * ae we have Whom above* th e product o f such an o x id atio n hoc alread y boon conflguratlonalX y ab lated to our i n i t i a l re a c ta n t* c<^henyX eihyl c h lo rid e , Aneoh&ta (26) oxidised p~t~butyl phenol to trin e th y l a o e tie acid by means o f a lk a lin e perm anganate. However, attem pts a t o x idation o f (1) (+> (♦) th e et»re< ^b«»t*try o f th e fo ra a tie n o f C -alk y late ir m aceto n e, phenol and potasgdun carbonate o r fro n sediua phenoxide end e th y l alcohol o r trm sodium phenoxide benzene mm found to be tine ease in each e a s e . (♦ ) « C ^ h e a y le th y l ch lo rid e gave (*) ©<~pi*enyl«th3rl phenol o f th e sane isom eric com position {88-9256 n t b o ) , Since (+) « < ^ h e j$ rle tiy l ch lo rid e has th e oppoeite co n fig u ratio n to (<*) c<^*pgi*syXetfcyl phenol* n u clear a lk y la tio n has tak en p lace e ith in v ersio n in each ease* 1* potassium carbonate* acetone phenol 2 . sodium phaooad.de* e th y l alcohol 3 . sodium phenoxid©, benzene 3h 3n attaMpting; to e sp la ln th e s te re e e h e a lstry o f form ation and th e o rig in o f th e C -elfey late, tfc* e th e r lm e d ia te ly suggests i t s e l f a s m p o ssib le in te rm e d ia te , C la issn (10) however, was a b le to shoe th a t in th e ease o f a l ly ! m i beiw yl b ra a id e , th e o - a lly l o r o-beneyl phenol fam ed was n o t produced th r e e # tb s e th e r a s an int«naed±ai© sin c e th e corresponding e th e rs s e re s ta b le under ssndtt& ens o f th e aU q rlatio n . f u rth e r p ro o f we* fwmaished hy CXatssxi fcy in tro d u cin g a s u b s titu e n t in to th e a l ly ! group. th e product Cbtataed by CM^Usylatleo follow ed by r e airo ag ro m b o f th e e th e r gsve m ^ - s u b s titu te d o - a lly l phenol, whereas th e product tr m d ir e s t alfcy latio n m e a ^ -s u b s titu te d o - a lly l phenol* 3b o rd e r to v e rify C lairo n 1* conclusion* w ith re sp e c t to tb s p re se n t ease under etad y f s e v e ra l enw risexite were perform ed. oC-l^enyl e th y l phenyl e th e r was found to be sta b le wader th e condition* o f a lfe y lstle a i I t was recovered unchanged a f te r refX m lag f o r fiv e hour# in th e presence o f aodiw* p-cresosld© in fesnsena* 3b sa e th e r eaqperleent, «<-phai$KLeibyl w e slty l e th e r was prepared in th e aseteiU N petassIm carbonet# warmer, in th e presence o f sows © Ophenyle th y l phesyl eth er* th e mssltyX e th e r i s , o f c o u rse , incapable o f giving any O-alfcylaffce, sin c e i 11 o f th e a v a ila b le o rth o - aw l p a ra - rin g p o sitio n s a re alre ad y occupied. th e o ^ s f y k H y l phenyl e th e r s t i # t , however, rearrange* 1* C -alh y late was found, however, and s in e s these co n d itio n s (fh h em s re flu x ) a re wore stren uo us than those under which «<>phsx$rletbjrl phenyl e th e r I t s e l f was p rep ared , i t seews vexy sa fe indeed to conclude th a t tb s e th e r w ill n e t rearran g e under th e co n d itio n s o f i t s p re p a ra tio n . 35 A» mm ftdilttoaftl felt eiridefus© a^portlog thin conclusion, I t mm tmmI tfant tdwn * t^dregga chloride *o*t jffteftft th a t ftt XOOPw 9i% a£ ttw athwp and QK of a-allyl pfemal mam tonmd ttella at KJ®, they aMaftM* «Oy 79.53* a# tka attar and 89.®* a t tte a-aUyl phonal. tiagr a^tai^ww# tiio ljr iwfteMft' ftft th e bftftta ft# t h*y1 fty»l11htrfB!ii t *dftftnotroptcM 36 A aor* modem in te rp re ta tio n M l w oom tfdorftilm i o f tfe© contributions of fte W im m mmmmm otructwso 6 6 i^H^P TiMRjftf ^NQhwVCv-n In ilm qfommm Qf OlOt)itgI&0g| f lit C M tfiJ^ftiioa QflHlHid $$|§g| bO fOiSbShttttll ftft t ffoff IfafttliilMliOKlftl fftftOilftft^ ttlO ffolllFO ff dju^ iifNwHiftt f oil o f ptiOMoX ii&iit ftonftotto fftitoftiXftofaoftft* § ‘2# ♦ 0 m fc-a. * ''* * • ' ' ^ ^ 3 V -C H , M 0 ttm m i# mm m%*Am$An$ im teem m i C -oligflailon sfatoh «ooh ft ^ h rojgot oa^ ia lnj ilsfti i#$ tb s 9 a t Xa««t 8W , of ortho al&yX&tioxi« fla « $ u ro ly fttattfttiOftlL bools* ons * i$ ti oa^not it t» l p ro fsro m e o f o ^ S Jc^ lsiio a m m - p -ftl^Ifttio i* * M to £11 os*o* m portod in torn lito r f tts r c m tmXk m in t!d * tem m te& & tm § O n orib o p aaitiogi i* I n m d s i lo s s t i s ft S«X w tilo* Aitboagh m mt&Amimfimm « o l « a i l t e fan boon devised f o r t h i s phfloaim a^ i t i t m m m tvatitm th a t tbo m s^ m d m mmmt in to pXegr only ftt th e in s ta o t of a tta c k ftnft «*% th e epeeles e ith th e n eg ativ e charge 37 e l t t e t* tin* cwp'goa Tm&d fe* U Im port*!#* Sa tb t im m ite m #t*te» I t i t a f " I x t e r t t t t® jxa&**t t u t t&ftt ttd n a* ofiho patXtl®** i t t t t l i * «kl* t t in gpaqp tH ^ U lta t l a tfee p*r* potittiaA n i t t %■# flifc £ ^j^|^felfciByj|iai^|| |l ^ ^ fft||g||[jflft tSlSS jfflBlf MHUflni •to*** tto frudhytato to to ito M t «tto lito to N M M t o , cm m b mow tft ttfc itttt# ®j£ tli® totofejMHife Q? jnto^ maMBMsitoiMg sicdJtttkK IT waiwiiil«aMart MA n o t toi^>» em *Mte»n®vierit, trettjasm t ®£ ltd * t i l t H it i t t t t s i ttm sq aiio n i m i i t b® j a t M J l t i . H it r t t o w t d lM t# t M t r M t fra » t b t la re p ti^ tio n o f -$^W 0rXitbyXi^M srl ttbtr tit ths m i tio*lXsr irar* e^«iM inrl*tftQri efclorlde ia n o t booimoo i t bum tikm&w toon prepared from ttoo corrooponding i I m M t f reac tio n * rbleto n i ^ i t p o rw ii ro o o iio o tlo n , fho ULgboot r tiu o in tfe* lltaim tav* io th a t o f M r a r d <§8) 1 da* tonogonoooo, ffear* £* **34*»eo, to w w v r, t i n t th io vain* I* lo o . Inrwoll ( 8 0 ) , in otodioo on ttio oonw tilon o f os>ti©aUy M ira ^jjhou^letfegrX oloohol to ohlorldo too* obtained 0 maaiaaa oo)v8twioB m tio of < § < tW ‘on tba bfifffl1of °C b . «bN » rotation*, • tbo lo n e th of rr r r " dwlM Otk^. '**yi® ['•00 QloPB^BWwWww^^ oitMuOL^lMkOuttiAMaiia0 j* ^^ 4iwmW 3bun ^MPRHBotr^yr o*mMirff*^on Wot jJHHpW 4ook*.iOium %Ajpqq* ■*. ooo^t Oc^ lpoBNBI r o ta tio n , lnrio&13* oenetwaloii rw tl* iihhmmi** a t 20^ ^ ^oH hSo oKoFW wBo jlt ™ wW NQ 3* tlii# oeio a value o f l°Or) of 3103*5^ for t$* ^ * a d opeoifie ah3)djpl4a.* lb aba fi.mopa mUPL bo used as a p tlea lly p m -^ ^ ^ o p o o ( o i ^ ^ o * o ^ ^ p j th li vottm #*» tha m «iiifirn jfePuarifm—»4 ja# J| mam wiHmm— fatlaam | a 4ka f*tlfcft&l01£ Vi^MNIt (1) 1% i« m «3Q>0Ti»«ttiia mud (&) i t H ill gfrflft «**!»»» Wvm {®C||^ *$k*9$? <**s0W6^1top% cbloritte* lt*mfepl«g<»( «? • X 12,13. * $ 1 ,? # . yy ^yjtf jjjirtdot %%l# ihtibfl# by bbo iN^pNirbad value (|1i #6|®) for flp ii^ illy pw# KNitilo o&id^. an# olyfesizui a vel&e fo r iho 0^ at opMeol jnafl^r* tbe f*obe**tiort o f oj>*te*l parity ooold ihes fee 9t*5# or a m&Kiffiu» o f $<$$ wmmim^hm baa m ootM U ftoi** invereion o f esss** f igaratico mb bigh tm m im o f opUeol purity fur»i*h atrtmg evidence f bo jjjpoooBtb bubs j^oosiSUfe an ■■n'lgrmant e f a mxImm m ta* to tlw »>ta~ %tm t f fttM d lr pm? < ^ b w g rteii« l M n U » . fto f t iln t a g « v n n ia a bo oood for ttfoff* ,-iiTt_ 1*0 [ oC ] jj f o r o p tic a lly pur# eiO orida • /j« c jb * I s ’a n r ) * ( l °C 3n * e ld a c tu a lly ' o&ttiisod. A m aftlm ttoft* < 3Df on© ***>■>* *$* above *********■! it* b*e€M«* mwimiwiA that th* «a>i* mdurtted « O m to p t t a o p tiM U jr y o n oKtorldo dopondo on tite t« m tn tb * (teanalwtagr, amljr, «t» wdw {oCJj> fw pbeqrlwttyl «m*1« ooid a<»t.tta 3 iv . fk U tt* . ***** iMtow m e t O ft nftMMHwr ate«*«S iB jB ji t4 « < t am M j* o f t l * mwOmm m & m o f aj»^|a» roo&vofwi $i&&£idQ t t wtt foyi# t^lsito ii -A IrOHtoT X&fe&t o f m m * W m m til torn ft ap o o lflo w lslto n i. o f 2X#6C waifcAiytaAMp m2|a®B o f m w M m m « f 3J9i*S>° tf«* i t » agw elfte ro ta * te m and t t » o«lJ jjhos^laol& ylftoetie a c id obtaiaad from th a Offjrfo^rtn “ & J X X J M -1 6 .7 8 lil S lattfltr c a lc u la tio n can be c a rrie d e a t to tf th e cawe « f p * e r« w l and S ,6 4 0 M a l, 8«(c^benylethyljphow l (88J8 artto) ®”C§* 16.78° ll.S O ° l»-£<^pl»*Hyl#tb23.)»2#6-dimtfc0rlpb«wfi. These vb&ms $.89° afcaaXd be reasoaefoly eloee te the correct erase, beemee the lutyametvie eeater 1* s e t affectw t fty the eoddfttiea proeedore. jPhosifcX 1© t t e pPWetNS# &$ * m W ^m % <&£%* rn&M&p »fiif|teenl l e i s i l e f e d l a Mtdfjiwit H u e l a el^ M a * aedltse* Tot* th e ff*r>e sterecNtihefldatey la etao eiied l a e ith e r eaee fo r $ f6"aQKKoool» An *jiwiiijttfMiiaii<*w a# th eee fa e ie le n e t cfevicafl a t thdLe M ae. Fofthcaf lewle Ini nstHtai^ jpeettaoflaMrifcgr fOf* th e eeee o f 2 »6*xylen0Llf oeeaa h ig hly d ealrah le* FASTB 1*3 HXSIG&1CA1 th e transfo rm ation o f a lk y l a ry l eth er* to alig rl phenol* ha* been aeeenpllahecl fey nalxsg a v a rie ty o f Louie type ad d * * Beagente which h im bean employed in clu d e iiydrochlorlc a d d , «ino c h lo rid e , aluminum c h lo rid e , a c e tic end euX furic a d d s , gaaeou* hydrogen h a lid e * , and boron t* i* flu o rid e . h i g e n e ra l, UQ onduy and te r tia r y « h y l groups m igrate w ith g re e t cm1 ease then prim ary a lk y l {pro***, th e varlou* m ehaaim * which is*** boon proposed nay he divided in to tfeme wwim d as* * * ® ( 1) im tram lein & ar, th e m igrating gr©tg> never lo e in g co n ta c t w ith th e m olecule to which i t iw riginally woe joined! (2) d isso c ia tio n end recom bination, th e a lk y l group s p littin g o f f ae e m olecule, io n o r ra d ic a l and then recom bining w ith th e arom atic nucleus* ( |) sX kylattsn by th e e th e r, one e th e r m olecule a c tin g ae en alfcylat* in g agent tow ard a ascend arom atic n ucleus, Evidence f o r th e in tram o lecu lar n atu re o f th e re a c tio n i e derived from a strawy o f o p tic a lly a c tiv e ether** Sprung and G a llic (22) tre a te d ( 4 aee*butyl p * ta ly l eth e r w ith e ith e r s u lf u r ic acid o r a im c h lo rid e in f a c i a l a c e tic a d d , they obtained a product which was s t i l l d e x tro ro ta to ry . IdI th o aec-b u ty l group capable o f m igrating w ithout to ta l ra c e o isa - tlo n although l a theee a tu d ie e , th e ex ten t o f xueealaatlon mm n ot do* term ined. When a n& xtwe o f (+) eee-b u ty l n e a lty l e th e r and p -c re a o l m o tre a te d in a a ln lla r warmer, however, th e ero o e-ality la tio n p ro d u ct, e-a«c-toutyl p ^ c ra a o l, m o coapl*rtely ra c e n le . in a c tiv e F in a lly , when a aiaefcar* o f aec-toutyl phaoyl e th e r and iaopropyl p*ere«yl o th e r m o tre a te d w ith a u lfu ric ami g la c ia l acid* a t 100®, th e product* obtain*# imm- a*ioopro|^l*W w t^yX phenol an# 2-*eo~butyl phenol* The in a b ility to ia o la to crooo product# in the above eaperl& etit, c o a le d w ith th e in a b ility to ia o la te o p tic a lly a c tiv e product* when th e re a c tio n l a n eceeearily X n io rao lecu lar, give* otrong eupport to th e in tram o lecu lar n a tu re o f th e reactio n * S hort anA Stew art (30) provide etro&g evidence th a t wader c e rta in eJroumetaneee th e re a c tio n can be o f th e d ia e o ciatlo n -rac cab in atio n ty p e . Barney! phenyl o th e r, when tre a te d w ith tin e ch lo rid e o r hydrogen c h lo rid e bS (o r b o th ), a t \od* gave a m ixture o f e* and p«heneyl p b en ela, beneyl c h lo rid e , and phenol* Com petitive ejqw im ente uaing equlssoXar amount# o f b t s i j i phenyl i t h i r and an ieo le wader th e m m e e a litlo iie gave come mob®* and dl«hiM ylate& e n ie o le . The f c re a tio n o f benayl ch lo rid e and th e Im Ia U m « f benaylated an ieo le a irp o rt* th e contention th a t th e r e ­ a c tio n eatk he la le n e lio e S iir, f u rth e r auppori f a r th e in term clecu lar n atu re o f th e re a c tio n hae been re c e n tly provided by S&dlee ( j h ) » Benayi ©••tolyl e th e r gate a m ixture o f 6« b ^ ^X ^2^airlhy1tph»»oX and h -b ex ay l-t* taeibylpbenol* When iso b u ty l phenyl e th e r uae tre a te d w ith elt^wiirw* c h lo rid e , p ^ te r tia r jr ^ u ty l p M l e a r obtained* th e l a t t e r mould he th e eapeeted prod uct i f th e la o b u ty l group e p l i i o ff in th e re a c tio n ( 32) , preaumabXy aa a to n 4 X lM ito d (3X) obtained phen ol, cHLaopropylphenel, 2 ,k -d i-ie o p ro £ y l- ph en o l, f #U,6~tiXie<^ropyXphcisoX and th e re sp e c tiv e a lk y la te d ieopropyl eth er* from th e re a c tio n o f heron trl& u o rld e tao prepy l phenyl ether* gteith (32) ob tained iaojw ^ylbenaene from th e notion o f aluminum ehXerido upon l*©propyl pi*«*yl e th e r in benscne. The eapertm ant* lend a d d itio n a l ounriart to a a******** e P t |n f l y v r i v an ew y ^ e Cbmbeyg w e e e m e w w a n i i i ^ a ^ H f l T w w w P 'e imMiwa iw o h ijsh e. e e p ^ re w *ow H pw ^^eB aa^^*w e Bubbler (33) thought t hat th e o h u p nee a necessary Interm ediate in th e form ation o f benaylated phenol* $mm sodium phenoa&de and henayl chlo rid e* fa n Alphen (XX) r e n t e d th e rearrangem ent o f t r i - phecylm eihyl phenyl e th e r and diphenylm etbyl phenyl e th e r by sin e c h lo rid e and hydrogen ch lo rid e a t 160° to th e corresponding alk y la te d phenol*. Since th e cleavage product# is o la te d m m id e n tic a l w ith thoee obtained k6 from th e d ir e c t a lk y le tio n o f phenol#, Tan Alphen f e l t th a t th e e th e r wa# am eaeam ttal in term ed iate in th e a lk y la tio n p ro cess. Behagel and F reienaehm r (35) te e la te d o-> end p~ teraylphanol#, 2 ,U-dlbeiwsylph9n o l, end phenol by refltu rijig benayl phenyl e th e r a t 275° fo r fe a r hear# in th e preeemee o f H ue o r copper. When a m ixture co ntain­ in g aim# o r co pp er, h am y l pfaeayl e th e r , ami »»ilyX ~c/~*»pht)^l e th e r eft# r e f lu re d , Behogal end Freleneehner is o la te d m ainly |H & e»*yl<^~m phtbyl m ethyl eth er* th e form ation o f 2 ^h-dlb^isylphenol end p*fea»»yX<- -^n o p h tiiy l m ethyl e th e r me# e ite d ae evidence t t e t th e e th e r i e th e a lk y la tin g ag en t. Xm view o f th e meaningly c o n flle iln g evidence etdoh ha# been c ite d , th e p o e e lb ility e x ist# th a t th e re a c tio n any proceed by acme com bination o f th e «ischoni*nie d isc u sse d , o r by any o f th re e moehaxslaa*, depending vp&n th e re a o te n te and m o t t o eenditione* f t i e in ta re e tta g to n o te , th e re ­ f o r e , th a t T a rb e ll and fetro p eiile# (36) found evidence f o r th e sim ultaneous occurrence o f both Imbro—and Im texm eleeiilar nrooeess#. Btnasyl ofrattvl o th e r nee feaiitt to he eemverhed by el ’iwdaeie femeide in elileyotHmaMsme #q1u — iiom to a m ixture o f about h®$ p h en ol, $8$ o*ham yl|shen#l and d ic h lo ro diphei^ljftcthaneo. The o-b $tat»& ex lg taaH y i r a i » t . a t tSBS liitiii n l i &£ te a The fiittiHllfitll Yw» fw eU w w t a t **» eijct^r stiMeetes# i'rgm the ten ada&te m& gene 3.-5 g» t f a Q ite ig M lv l t i M * , 1 .0 ( , o f M m N l <. B lrtlU atla& t f t t e *\fc*H wflwtte CmmMmi i m 8.0 g , of phmnX. c^ !^ aB r? ^ iirA _ .aw » 3 . Stftwr. w C rw o l. mA. g rfro jw a gjtorM o. H i Jroaoto»t«# 10,0 | t | 0,og io ^ ! of phony! «HMrf $t*0 g** 0*5 *0X0 , o f *m*m& ixid hp&m&m w m cw bim d In *be »*»»«» dftjfttirlbod wytwrlaaailg. Tbo Ftttetl&n ittta mi^iaidt to Bfflfiftd fcr O&NftQr j&iiaitoo* ii!|iiy^t l^.^,i^|.fflpij g£ tb o imfcOfcXJmljL fmot&on a im 3 g# o f int^rfaX ^ b .p . 180-880^ 0 *» * fJn ilto iU iikltM t li'tBU oa d m on d& oilllotlott 5 0 ,0 g , o f s tw o o o l ML $ g , o f > m t^ l* W < < ^ e i y l« tly l ) p h o n al, »«p, 1 2 5 °, liiom fcoro m liao » 4 u I 2 5 ° p f ) # ogr^awlertteX ItoBgyl x Horn* mwMtMmg $5*0 g* (0*M iw lo) o f phonal and 1 5 ,0 g* (o,o?5 nolo) o f phmyl othor mo plooodl In a ttamaiofirtat ot t 0,1® for m i fe w , fit* s^tatax* «i» Mrlml aanal m om r. « ^ M i tm M m gam 3&*0 g« o f vommm& <~phway:utharX fbo «fch»r# b ,p . X£2*Xffe®/li a n . it^^feogm ami hnli&od IffQo j* g # o f < w , mi 1*9.8° for two hour*, ffe* alxtur* w i m M t$> in tho nm ol m m r , B iotilloitcm o f iho *3&a&i aolofelo fraction yiolded t,5 g* of n otarial, fe,p* 1 6 0 » l^ ° /5 * » , which o m ly tad 98.55 o rth o e< ^h« i^rl«th yi pho nal. 51 mmmmm m m m m w m m t j» x w % h m m m m m m m 8.868 8s8» 888 *&7 a ,iM 0 .1 7 8 366 m *82 *81 880 m 8?8 877 878 87S m *71 873 m 88* 8<87 1*$ 2i 3 *& T,fra]t 52 lkm &g* ( 0*075 »&Xe) mf phe^l mthar * 3&«Sb*)# f|* S &* (0*t5 *»&t) o f |&«!ia3L# and Isydrogen et&0«t^ <10 . 7*) and 5&.0 g . (0 ,5 m l*) « f »xHn«t»l m ofclart.de for rtstjr M att** *fc h9.(P . th# i t d m tm atod with hydrogen m * worfcod 19 m usual, th# < ^ b «p i«M vl* 1»d tM M d was wworte. tmI oC^n>«Bftottea rhtnarl Hfeor. Jwrnem .jad Srfeogm gfeiartde c<~i>feeaBrl*topl ptamgA «tt«f (20.0 g ., 0.<# mA«) (<<$$ 4>J,°) » 30 g. (0.5 Mi*) of kMHM Md tydrogoa ehlartde were a&lowod to roast for sixty alnirto* »t tO.0®. MMUMIm of to# bbMUbIU soluble fraction gave 9 .5 g. of «<<*iM»p2*t!vl < U m U i (e^® «0 J»*), S3 1*1 p • xixture o f phenol « « x e e ito l, md 1.5 g . o f o - end p^^hragOobborl phono! which eaelyeed 38* ortho. Tbo •O p h eiyleth yl phenol wee op ttcelly inectlTra. to ) oC^hwaXottiyl itooity! Ether m o A M ^ g m m * * M * Hydrogen chloride wee bubbled lata 5 g. (0.08 a slo) o f Ksphenylotfcgrl aealtjjrl ether far ten minutes a t $0®* (fee hundred m illt* lite r * e f le v hailing petroleum etber ma* added a d the reaction mm worked up in th» uaual manner, the xiia-aXfettXi ac&ufeXe fraction gave d ia tilla tio n 0.7 g , of athyl ohlafd.de 4X1,15°) X-X/2 dcm,# no eolvent) n|? *1.5280, th e a * w ii aolub le fra c tio n gave on d is t illa tio n 1*5 g. o f m e e ito l. 5U DISCUSSION T ta rearrangem ent o f a lk y l a ry l e tta r e to t t a corresponding a lk y l a r y l phenols ta g been stu d ie d by aasgr car ta g e , b u t s t i l l poses aany problems* f lo r e l a only one rep o rted oaao l a «hieh axi o p tic a lly a c tiv e a lk y l a ry l a t t a r baa boon stu d ied (29) * Xb attem pt cas made to study th e e te re e e ta m istry o f t t a re a c tio n from t t a p o in t o f v is e o f co n fig u ratio n o r t t a a c ta n t o f re te n tio n o f o p tic a l p a r ity . I t nan thought o f in te r e s t to in v e stig a te t t a behavior o f © C -jtanyloould t a c a rrie d o u t taaogeueouely. fra th m io r e , t t a m igrating group could In­ volve an asymmetric m a te r d ir e c tly attach ed to t t a a t t a r oaygen, enabling mm to stu d y t t a »tersocta«& atry o f t t a re a c tio n , d t h p a rtic u la r ©mpliasla m o o n flg o ra tlm i and t t a e x te n t o f re te n tio n o f o p tic a l p u rity , th e p o ssib le r o le o f t t a a t t a r as an interm ediate in t t a uncatalysed a lk y la tla s o f phenol node i t o f fu rth e r in te r e s t, P re liirin a ry experim ents staved th a t a m ixture o f «< >pta«ylethyl plumyl a t t a r in phenol a t i*9.8° c ta n tre a te d d t h bydregm ch lo rid e fo r te n m inutes gave a h it y ie ld o f e< « p tacy la^y l phenol. S p eciro stato raetrio a n a ly sis o f t t a © <*|taJ^lethgrlated f t » d proved i t to be an isom eric sds&ure co n tain in g MW o rth o chAxig»d & th e r (J*Q£ o f th e anotxat need)1 wee fwonswred a t thy and o f one hoar whan only ana—h a lf th e naoant o f hydrogen ohlorldia rep aire d was p re s e n t. Phenol l a n o t needed f a r th e production o f c<^henyi©Abylated p h e n o l.....a %$% y ie ld o f o rth o ^ p ara °^ p h ftfly h tliy l phenol o rtho ) wee a tta in e d when th e e th e r wm tre a te d a t 1*9*6° w ith hydrogen ch lo rid e f a r s ix ty minute®. wm a t two d iffe re n t tin e in te rv a l* in d icated th a t the re a e tio n occurred in two a te p e j (1) cleavage o f th e e th e r by hydrogen c h lo rid e to g tm c^^benylethyX ch lo rid e and pho nal, and (2) re a lk y la tlo n o f th e phenol tgr »honyXetbyl e th e r, loo* phenol th a n in th e te n adnefco v m and a 35# y ie ld o f -< ip h o i^ le th y l phenol. Although th e cleavage appear* to ha d e a n , I . e . a m a te ria l balance o f $5$ oar b e tte r wee u su a lly a tta in e d , th e re was always obtained an $6 m M m fo iiim i l& gi ta ttlin g re s id u e , $1*1 * zHm*aXk*Xi so lu b le n s ts r ls l * l# fc &$ a*jgr « f or * »£*ture of ti» feX lw ingj pfaeael* sllQ&ated *ttar er ps3$*tp*Btgft« m m y M m & $m m % w m is o l a te *l*m ^ - ^ e a y ls tty l aoluUon ww traaUd p to r n y l e th e r li9*a° irltfa l^iro«w* c h lo r ic . festa sd , s s $ r s la im g s p ro m o te , n«Ksely# ^ -p h e flF le tb y l ehltw ld* *a& plum ol « * » ■tftttiftfrff._ ttio SflSbttliijBHStii &£ . ia*t2xr!L «» ethei* eges i^^ybQflX. ipeSoXisSm AimiiiNiEdfcilar th e ttoiM ts^tffttiQ ii *£ c le s’vee"© e MtSyP^raww feJ&bWJltai^JAf X ^1jR iMk £ jftMB l^l<$ iw lfetSS. pwWw^ *RkdlMttl^Jl"fc. U lityw $MlipflfrUSfcm lt»pfcwi®thrX lfft% S f '| ^ fl1fflIM j ffal%jli.1frll %** SSSIMHPSd $M HbS flliS V ll^ WBttSSFI 7j, S w ifw * ' tb s iX J^yisiloii s£ ytMMSfll by £♦) o<^*$to£Eg\m SSEgf* pOSx^* SSflSr jgWfw Qpi&OSiWy «©lCfcfS «MMMito#4!Ldfctoft-dtaa, to# rtrttttiflTT pfiWwX lllw fhtotoPriatofiirifliftli||||mtfiH fltttitfjFttiJI fif tfas alW lata^ pltssSi stwsssi 44 to %# sini 4sssn#4s sdWhsps tio«l setlirity* fbs fs s t 4I»4 s ssssnle pm*» ©C<«pb«3grleti^X sss Sb4«4ss4 l^sn s» np44s«Xly se tiss Is m ris s d a ^ s »a^ m tin t mily tbs (d 4 ) purs a s d illo itto srystiOXissod m%, or tb st tb s sptisad sstiF ity sss too swtiU. is iMgiridtods to dotsot* Ths I s tts r sesas 60 wManH? raaaomtiXt in v im « f the axfteaMUw n M d a U n and lew a » "P W i *a*att«» wbteh efceveeterleed unMtal^ed aUylaUoM . Bwonle t i l g l i M phenol wm A m M M m I A m the nm U m a f (-> •C ( A n f M l l neattpl « A w t phenel and tgrdvagan dblaa&da. Ttan aligXaftad phenol wm ebewa M he Jftl ertho and 68* par* hr anaIpafta. I f Aim #%Vlfli*li#AllMif witiMiMBtt m 4V jk r^MManeM'i#dA ItaMi fcltM FtPHJ AW DUp ^p#p 5'4klll feft.£#fl ^Ae# 1v> ^0ti#tf1flA#fcfl#tjP ###A^^# O ^LftfcAhH# tflMA^A•^^0##Ap4#A#1 iA t# ti# ii9 S llllS iF 1b# ttii t w4Vvir^ «wV%^am*!rfa e«)hi»a— Op jMHa) AWlAiAA^pm0Ah |n i|||0 tf£A eAB^p##ilAd#0 ^^fcaAi^JM#M ^pA ^^A aA f rjf #|r##% jaM f# #|i^3Atlo&* f h i# mt*# l a fm ot, tb» q im a il# «h#tyl OIImwp^ tut* 00 tMNM00M(Nt pll0l$0l#e A$fc*ERpt* £&}$& ox^dl fdoKBflSUi l^poo idbiiloi* 1bni8 $mmss1» o f oHaro* nod holoN* hmmstl phm&l oHmm *ats& M M U «F0j0*|g^ti» Attain * *"■»ilfiilpWfiltWr f MMlPifw» jkWIWiWWMPittwA- iwW n»Iil*ttWMkJoJr Jrtt1* arranging tem p i phony! attar la poor yi& da, t t e attar aaa raflnnad for night tunar* to giro an iaoaarlo nlatara o f ortto and paratem yl phonola and awao S,fc<*Ubaat]rlpteMl. Bomyl attara o f o -« r« w l, gain ed , ®G> aa» ^?-oaphtbola warn aim aaooonafsUr nnnfnaatgr* to piro tte dealrod benaylatod pbaaola. Xa ardor far tte raarraaaamat to ta te plaoa tte mtfaoro •AaAm that tte w aotioa t aapari tnro m at bo aalatalnad ateaa 2JW°, fbo raastian m found to te a n t rapid and eonplato t e a i t e or oappar n atal ana addad. Whoa a nixfcuro of aiothjrl cK-naphtbjrl otter and bantyl 62 I t a o r l f ttta r « « i hoatod a t ISO0 fo r te r n , oapJitiqrX aatM L e th e r aaa th e o af* product ieoloW U A m ixture o f s(« fl« |A D al ta d bottsyl p*areaol i t a r tro a to d in n a t l i r faehion | i i i 3N*«i»3L» e< * d ^h tb o l «o$ Behagol aad M a u a i f f l t r pr*$»o*ad th e Ida* t i n t th e o th e r a m i a a th e «13grXatt&g a g e n t, in otjdor to tagftaSa H a o rig in o f th e ami ^b « i» y l^o (^n ep h th o l* SiOldhaMHkteii fhflfr oavrlod **«**- th e aoffftraint o f b u ttv l tAffinorl jipo s at 2$$^* Benairi •tbar. ia ohecol and toluene oaro fanned. in 4 J b o a rtl^ t1, 1ft* &» to a ndjdosra o f the ortho and $@hp 19w& |^pe»4 sus1sjlcMi ® jf # to bwwgl froo radioalo* 63 P relim in ary Banortmottta P relim inary experim ents on th e th e n sa l rearrangenents acre c a rrie d e a t by h eatin g 10*0 g , o f th e ap p ro p riate raeos&e e th e r a t 270° fo r n in e ty m inutes, The tem perature o f th e liq u id gradually dropped to abbot 380P. Buring th io tim e about 1 .5 M illilite r s o f liq u id , b .p . litO-1600 , d is t ille d ou t o f th e rearrangem ent m ix tu re. The n o to r ia l, 0.25 m illil i t e r * , l».p. ag° l *5fc>0, appeared to bo sty re n e , c h ile th e n o ta r ia l, b ,p . lh t* ld $ * f wm n o t id e n tifie d , fh ara aaa obtained a 205 y ie ld o f o^opbaayletbyl phenol, b .p . 160-l?0®/5 wm., (655 o rth o ), 0 ,5 g , o f phenol and a h ig h b o ilin g re sid u a , b .p . 18O»22d®/10 mm. The high b o ilin g resid u e aas n o t Id e n tifie d , b u t m ight be any o f o r a M ixture o f th e follow ing* e th e r, p o ly sty ren e, di~ alkylat«d phenol o r Mono or d ia lk y la te d Mhan (*)c< -phe-nyletbyl phenyl e th e r 205 y ie ld of (~ )^* q d » eiiy leth y l phenol ( ♦ 5.08) wm u se d , a B *0.62*) ah ich analysed 855 o rth o , aas o b tain ed . ( - ) ( g<-Phenylethyl) 2 ,6 -x y ly l e th e r ( c^-12*57°) gate an 185 y ie ld o f (♦) ( *21»0O/1 0 am. ( »)o # « ^ « ti» y i)* 2 ,6 -^ ili^ tljy X p h e m l, b .p . 175~185°/ 5 mss* (* ^ £ 4 0 jt* ) f • 21# y ie ld , i m JSm A S ig h t gram* (0 .0 )3 xvele) e f (♦) < ~ p h * n y leth y l n e a ity l e th e r (°Cp*3?*25®) end Hi g . (0 4 5 nolo) e f phenol e w e hooted fo r eeoen h ew s in On o i l h a th m aintained a t 200°, th e re a c tio n M ixture nee worked up ee described p reri^w ely . ft» xm^oOJotli soluble materiel eee obtained, D istillatio n e f the e lfrf l t notable fraction gore 12 g . o f a mixture of phenol end xseeitel, end ) gf i f « i ioonocio mixture e f erthe end |we«0 . 00° ♦ o.og® ). 65 mmuBBtcm t he tltartoal rearrangem ent o f hensyl phenyl e th e r bos been attem pted by se v e ra l workers w ith a view to w rd causing a rearrangem ent analogous to th e G lalsen rearrangem ent o f e lly l phenyl e th e rs . th e r e s u lt s , h o v » m f in d ic a te d th ftt beasy l phenyl eth o r d id no t behave In a fashio n analogous to th e a lly ! phenyl e th e r s . th a t i s , th e y ie ld s o f b eray lated phonola m m p o o r, and m ixtures o f orth o and p ara isom ers, as w ell as dl~ a lk y la te d products were ob tained. A H yl e th e rs , on th e o th e r hand, u su a lly give ra th e r good y ie ld s o f in tram o leeu larly rearranged products * Furtherm ore, to lu en e mm o fte n observed among th e product*. Presumably, Warn l a t t e r was formed by hydrogen ab e treo tio n by beroyl r a d ic a ls . Free ra d lo a l and o th e r Interm oleoular mechanisms have been proposed f o r th is re a c tio n (1*2)* I t was thought o f in te r e s t to re*lssveetl$ate th is rsa o tio ii using o p tic a lly ao tlv e -pharyletfcyl phenyl e th e r , and sim ila r e th e rs , In vhleh th e o p tic a l a c tiv ity o f th e m igrating group could be followed* Furtherm ore, th e stereochem ical co n fig u ratio n s o f th e e th e rs and o f th e a lk y la te d phenols which B ight a r is e from than had been e sta b lish e d a s in d ic ated in th e f i r s t p a rt o f th is th e s is . Prelim inary eaperfm sats in d icated th a t a t re flu x ( i n i t i a l l y 270°), c \ ^ h e n y le ih y l phenyl e th e r ra p id ly decomposed and a 20$ y ie ld o f • t t e oC'^mhastfXatiuri sternor! o tte r a lso item approxAjnrntoly D a am * faam lt* a ltte u g h only 8$* a rtte * T t e , in ttsla aaae* t t e praam*# la te # ptem# #X*k a a la te n t itemaftUm a f o p tic a l jrari% o f 37 M o r a aaateam rao««i**tioii a f 62*6*. I t m i o f t x t e t H to te te r a la a s t e t e t t e iterraiiaM M int mould occur to ih® p m p o a ltlo r^ i f t t e ortho p o sitio n *ar* b lo ated by a u b a titu o ttta , asm i f ##* to * M )r te a a to rc o eh ea iatry o f I t e praam*** f t e raarrarjw R aat a f (*} M ^ p te s y X e tb r l) 2 ,6 -* y iy l a l t e r maa a a rrU d mat bgr hooting th a aaMpamd a t t o ^ f a r lim a te a n u f te r a ma* fom ad i s Z$$ y ie ld , (♦) 1*« ( ^ « $ te * y te t! y l) ~2 ,6 -4 i» a tl^ i|> te a tl • 66 Wot «gO? *** m m a e U rity ro ta te * * , b u t th e o<>pho»yletfcyl W P bM w eiitay a&$mt*4 i& th re te n tio n o f atereoatum leal c o a fig o ra tio n , Cte « ia c a lc u la te th a amount o f re te n tio n o f e p tie a l p u rity in an id e n tic a l fbabieo to th e e a sts p rev io u sly discussed* The observed ro ts* M m . o f th e fo*< ^-•pbenj'lsfchyl) 6 ,6 dinHsthyl phaneX im ld have bean ib is i«to» bsr that o f optical% p n h«*( dlMl&ylphoiieX, tfeo m »I o f retantlon o f optical p ritgr maid bo • t?*6£ le s e v e r, lb s aigaificmiw® o f th ese re su lt* ay© ojwm to Me© q u estio n , s t a t s tte o o c a lc u la tio n s a re based m observed r e t s t i s s s o f la s s tb a a ©*5 o f a degree. Although tfee o ^ ^ e n y le tb y l e to M moot trader®® oocie therm al disseei-* iH v&dse of re a c tio n , a m ixture o f {^) o O fh ^ X s th y l m aettyl o tb tr and fteie X ia « t e i e d a t SOCP fo r i m hour#, waftttgdl e th e r could n o t, o f s c o re s , r©~ arrang* SMra»aX^«X*r3y sine© i t t e no a v a ila b le o rth o o r p ara p o s itio n s . I t c o u ld , however, «33?yXafee th e phenol. I t inroad c u t th a t a hh% y ie ld «9 ** m ixture o f ortho and p m pbenola m obtained* fh t* product wee com pletely ra c e site , eten though e th e r o f f a ir ly high ratable® Audi o p tle a l p u rify w*e weed* ^ ra tra j& o to m e irle tmalyalai o f fclils m ixture « M i t to he 7i~7® ertfco and 2&-S&£ p o re . Ik t i w o f th e f a c t th a t a fre e ra d ic a l meefcaxdn® f o r th e dX eeoeiation p m e e e h as been n e ith e r p raw d nor disproved, th e eaaly ei* o f th ie iro * r a ric m ix tu ra i s open to m * tm b ia& * I f d leeo o ietio n occurred V » w ii o f fre e ra d ic a ls , th ee m te a lfy la tlo n eoald o ccu r, and th e r e s u lt o f th e m lc r e it would be in e rro r to th e ex ten t th a t th e method cannot d is tin g u is h beteven ortho end mete o^phaisyX etfyl phenol*, Bow th e n , ^ion th e re a o tio n i# n e c e ssa rily in te ra o le o u la r o p tic a l a c tiv ity ia n e t retain ed * ffel# f a c t , to g e th er w ith th e f e e t th a t th e crf^pfeei^Xetfcyl group m igrates w ith re te n tio n o f co n fig u ratio n in th e caeca where i t could bo in tram o lec u lar, stro n g ly rapport* th e suggestion th a t an intraitto lectdo r rearrangem ent can Indeed occur w ith th ese o th e rs. th e rem&b* which hero boon obtained o ra c o n siste n t w ith th e 77«o4R0tac fyp« »»cHanlaB& of /Dewar* th e m igrating group new * leav es th e in flu en ce o f th e Tf e le c tro n cloud o f th e barmans rin g then en ab lin g th e group to r e ta in i t s o p tic * ! a o tiv if y , Who® th is la not p o aelh le as $m th e cane o f o ^ ^ e j ^ le l ^ r l ® *»ifyl e th e r , o p tic a l a o tiv ify i« lo o t* m w ax X. The c<-ph9nylet}iyl eth ers o f phenol, p* ♦ 01" 2« th e sign* o f ro ta tio n and co n fig u ratio n s o f th e e th e rs w ire detezminad* 9 © 0 -© -® , OH, - G - H (*) (*> CH, - C - H (-) 3 , C onfiguration* o f c^jdiQoyXetbyloted phenol* aa w ell as th e ir magnitudes and alg ae o f ro ta tio n s w ire ascertained* OH 71 t , th e a lk y la tlo n o f phenoxide io n by ^C -phenylethyl ch lo rid e pro­ ceed* w ith in v ersio n and w ith a t le a s t pU.5* re te n tio n o f o p tic a l p u rity . Tbeae foo t* fu rn ish stra n g evidence fo r * earbanlon displacem ent re ­ a c tio n . Q 0 + ex m $• A M dJHui value f o r th e e p e e ifle ro ta tio n o f ^ -p b e iy le th y l ch lo rid e hasI boon determ ined 6. ( ©Op " 1®8*2°. fh e Y ttreoelM B iflty o f th e cleavage o f tho o p tic a lly a c tiv e <<-j>henyletliyl phenyl e th e r by hydrogen ch lo rid e hue been stu d ie d . (*) Cleavage o f c<-jdw nylethyl phenyl e th e r by hydrogen ch lo rid e occur* ra p id ly to glee ^ -p h e n y le th y l ch lo rid e end phenol. C onfiguration o f th e < * g ^ eay leth y l group le re ta in e d . (b ) Experiment* In various w lim t# in d ic a te th a t th is , b71 (1930). 88. V. 0arrwd, 1 . Ohan. S oe., ?bl (19b6). 89. K. K. sprang «nd S. S. W allie, 2 . A». Chen. S ee., J 6 , 1715(193b). 30. W. r . Short and 8 . 1 . S fcew t, 2 . Cbon. s e e ., 553 (1989). 31, 9 . S. Sm , 1 . B, Stolra and <7. A. Kieulaad, 2 . An. Cbon. Soe. Sb. 2019, 369b (1938)* 3b08 (1933). 38. E. A. south, IMjd., 71? (193b)| Jgj, 8b9, 3718 (1933). 33. X. Qawerg and C. 0 . Boohler, Ibid. . 12. 8659 (1980). 3b. 8 . A. Xddlee, W. S. Cudwjr, I , B. Hagw, 1 . B, Perry, and B. M. Pike, ib id .. tb . 5b5 (1958). 35. 0 . Bebagel and S . Preieneehner, Bar. 67B. 1368*?? (193b) . 36 . 8 . S . Tocfeell and 2 . 6 , Petropolena, 2 . Am. Chan. S ee., 2k*8bb(1958). 37. E. Alawmder, 1 r iM t |t a o f Zonio Organic Beaetioaa,* John Wiley and Sana, 8 . X. 1950 Ob. U . 38. » . 1 . Spliefchoff, Pb. B. tb eelo, U d d |M State College (1953). 39. * g . Ph. B«*4fol, H. To Biban and t . Binon, 2 . Org. Cbon., 1J, 8b6 (1958). bO. B. S. T atbril, Cb«o. B ow ., 87, b95 (19bO)j "Organi© Beaettena" Yol. XX, p . 1 . 2dm Wiley and Sena, Bow Xark, (19bb) . b l. S . 6 . Powell and 8 . Adana, 2 . An. Oban. S ee., b£, 6b6 (1980). b2. V, 2 . BbeSdabotten, fc ta w , kkaL* 580 (1939}. THE STEREOCHEMISTRY GP THE G- AND O-ALSXUTXOH CP PHENOLS, AND GT THE GL&AVAflB Aim THERHAL REARRANGEMENT or A im Am ethers By H erbert S . KLeuterlo AN ABSTRACT Submitted to th e School o f Graduate S tudies o f M ichigan S ta te C ollege o f A gricultu re and A pplied Science 1n p a r tia l fu lfillm e n t o f th e requirem ents fo r th e degree o f doctor or pm osoiw Department of Chemistry le e r Approved >*— 1953 —\~\ •'* H erbert S# E leu terio THESIS ABSTRACT I t has been long known th a t th e Q -alk y latio n o f phenol# follow ing any one o f C laisen ’s procedure# i s u su a lly accompanied by some n u clear o r C -alkyX ation, provided such p o sitio n s a re a v a ila b le fo r s u b s titu tio n . Although C la ise n 1# methods o f a lk y la tio n have enjoyed w idespread use In organic s y n th e s is , no r e s u lts have been rep o rted on th e study o f th e ste re o * chem istry o f th e re a c tio n using an o p tic a lly a c tiv e h a lid e . I t was thought o f in te r e s t to study th e re a c tio n using o p tic a lly a c tiv e <-pfaenylethyl ch lo rid e fo r th e follow ing reasons* (1) ^* p b en y leth y l ch lo rid e has been shown to a lk y la te phenols in n u clear p o sitio n s in so ld s o lu tio n , w ithout added c a ta ly s ts , and i t was o f in te r e s t to compare a c id ic versus a lk a lin e nuclear s u b s titu tio n . (2 ) The oC^phenylethyl phenyl eth er m ight be an in term ed iate in such a c id ic alk y latio n * ! th e re fo re , i t was o f in te r e s t to sy n th esise I t and study i t s rearrangem ent and cleavage w ider a v a rie ty o f c o n d itio n s. (3) The e th e r most ex ten siv ely stu d ied prev io u sly was secondary b u ty l phenyl e th e r. T his e th e r re q u ire s vigorous c a ta ly s ts fo r rearrangem ent and cleavage. I t was suspected th a t benayl-type e th e rs should be more su s­ c e p tib le to such re a c tio n s , m ight cleave or rearran g e homogeneously, and th u s bo su sc e p tib le to k in e tic stu d y . (It) Bensyl-typ© eth ers m ight be analogous to ally l-ty p © in undergoing therm al rearrangem ent. I f s o , th e example chosen should be a good one fo r stw fylng th e mechanism o f such rearrangem ents, fo r th e carbon involved in m igration would be asym m etric, H erbert S* E leu terio (5) th e stereochem ical ©onfi guratlon* o f many substances co n tain in g th e < ^phenyletijyl group i t w ell known and i t migjht be p o ssib le to de­ term ine config uration * in th e p rese n t eerie* o f reactio n * • (6) th e p rep aratio n o f o p tic a lly a c tiv e o ^p h esy leth y l c h lo rid e 1* r e la tiv e ly easy and ha* p rev io u sly been d escrib ed . th e ^ -p h e a y le th y l e th e rs o f phenol, p « e re s e l, 2 ,6 -jy le n o l and a e s lto l were prepared in good y ie ld follow ing C laisen** a lk y la tio n pro­ cedure*. th e k in e tic * of the e th e rlfie a tio n of «phei$riethyl c h lo rid e , t h i s value i s [•{©] * 10 8 .2 °. th e stereochem istry o f th e cleavage o f o p tic a lly a c tiv e «^phcnyle th y l phenyl e th e r by hydrogen ch lo rid e has been stu d ie d . The re a c tio n ta k es place very ra p id ly and homogeneously to give phenol and e<~pk«ayietbyl o h lo rid e . -pheuyletbyl phenols, Experiments conducted a t various tim e in te rv a ls in d iffe re n t so lv en ts in d ic a te th a t th e re a c tio n occurs in too s te p s , cleavage follow ed by a lk y la tio n . Experiments in which o p tic a lly a c tiv e e th e rs were employed shewtfd th a t th e co n fig u ratio n o f th e <-phenyl~ e th y l group i s re ta in e d in the cleavage s te p . The <^phexayletbyl phenyl e th e r ap p aren tly undergoes a fro n ta l a tta c k by hydrogen ch lo rid e to give <<~phsnylethyl ch lo rid e and phenol which subsequently re a c t to give «<-phenyl©tbyl phenol. (a) OS CHa H-C-Cl oh ■> The o p tic a lly a c tiv e <<-phenylethyl e th e rs of p h en o l, p -c re s o l, and 2 ,6 -a^ le n o l were therm ally rearranged to give th e corresponding a lk y la te d Herbert S. Eleuterio pheno ls, phenol and sty re n e . The alk y la te d phenols re ta in e d o p tic a l t a c tiv ity as w ell as co n fig u ratio n «, An intram o lecu lar rearran genan t la proposed. CH-CH