Document 7M7ywdvgMBbBZoDkq8MMQvmY8

RECEIVED - ; ` , ' i- V ' V, v,' Z . ,y '. /.'-ivr rs* 't -a '. 'A/ls , V1 ( V .( ;*. *. ii ~inv?t- -- --' - -*-''*-* , ..v>y- -a, -f... r*... ^ f ^ 1'1,7 ' fcb.. 1945 The Role op Oxygen in the Mechanism of Vinyl Polymerization 217 jjjjw.e.n Reactivation ( it cases by treatment lrogen cyanide or cy*. ;.cb inactivated by treatment with either of these was treated with iodoacetamide under conditions ,yl-mercuric reagents no longer gave a nitro- reported to be spedfic for sulfhydryl groups.1* -rasside reaction* and by the dose agreement The amylase was markedly inactivated under ipounds are specific re* cazvme inactivators is ey have no significant ginase11 or pancreatic bund between the concentration of p-chloroutTcunbenzoic add necessary to inactivate the 1 imviase completely and the concentration of sulfc ^ydryl* shown to be present in the untreated % euylase solution. these conditions and the inactivation was not re versed by subsequent treatment of the solutions with cysteine. fi-Amylase resembles urease in tfiis respect. ** The results with iodoacetamide in crease die evidence that free sulfhydryl groups are ; the influence of two upon the activity of ic first two sections of It UV SrECiVlC Otn.FUVUSYL ItRACnV/TJON WITH Cv* WtcAtilvt-eHr toft After V*activa(iOQ Aruvitv* %vt Usitt* ctrboiil* . T7ait*4 <wn tf* i fodoacetamide is another reagent which reacts .? with sulfhydryl groups. If the hydrogen-ion ac-y Critics of the solutions axe kept bdow pH 8, the % fraction is considered spedfic for thiol groups.11 ^ Certain enzymes such as urease* are irreversibly } r.ictivafced by iodoacetamide while the activity 'i % others such as pancreatic amylase1* is not ap* sociably influenced by this reagent. 4 The data given in the last section of Table II, ie typical of the results obtained when fi-amylase lit) (0 C V. SurtS(. /. Biol. Ckom.. 114. Ml (1934). (b) L. * tcliulinfnlH. P.Setaubot, iMA. 199,SS.M19S4).,; essential to the activity of fi-amylase from barley and from malted barley. ' Summary The results of experiments with a number of oxidizing agents and of other reagents which have been reported to be specific for sulfhydryl groups confirm and extend previous evidence which leads to the condusion that free sulfhydryl groups of the protein are necessary to the activity of fiamylase from barley and from malted barley, Ntw You 37, N. Y. Racsrvw Novsxatt 16, 1944 100 1000 100 V 0 1010 201 W* 100 mo , 7 0 0 mo S3 0 0 1070 So 1100 100 1300 100 430 80 *70 SC Mechanism of Vinyl Polymerization. L Role of Oxygen1 1' ' , . 1 f. ' , ' ,,4, ,, . .. By Carl B. Barnes' ... i <o 0.1 if acetate, PH 4-3. f "-.mates at 0*. * Amylase 11 if :ihosplutte, pH t)-S. la H at 25* for one hundred dro] wji treated in the sbjuc aide irius added. * Aliqmtis ritii distilled water. *Ali* *'l with a solution of hydroIii't^rmis oi maltose formed : "'ilitziam of etuyute actinff d pH 4,5 in the presence TM 'e'.iunj of amylase were ad'td as linearly proportional * Used. id SjnyLtie solution ad- If has been known since the very beginning of pounds has been observed by various investi polymerization studies that light, heat and air gators.* Moureu and Dufraisse'*' clearly estab \ 3ft effective agents for inducing the polymeriza- lished that &is combined oxygen rather than qxy- I tion of certain vinyl compounds.*. For example linyl chloride1 and vinyl acetate* may be poly* gwi (J^3f whic}f catalyzes,.the polymerization of acrolSnT' fHonflnt1* concluded that the catalytic utrized by irradiation with ultraviolet light. ! effect of oxygen in the pressure polymerization of i Both these substances also polymerize readily Upon heating to moderate temperatures, andqp ji "*s been reported frequently that oxygen, ozone i ^d peroxides have a pronounced catalytic effect isoprene is due to the formation of a peroxide. These conclusions of Moureu and Dufraisse and of Conant, et al., are undoubtedly of a very gen eral nature. During the course of this investiga 5 VPon the rate of this thermal polymerization. In JrfVt *t, it has been demonstrated repeatedly that in the complete absence of oxygen, many vinyl com tion no compound containing the vinyl or vinylidene group has been found which does not readily form a peroxide upon exposure to air under ordi d /`if 4.5 was allowed to 'r thirty minutes at 0* wciq tiu;n diluted either tioa of hydrogen sulfide I pounds either fail to polymerize altogether or the /*te is very slow..* . On the other hand li has been j *r*tab!ished that oxygen acts as a marked inhibitor t '"the photopolymerization of vinyl acetate.* nary conditions; furthermore these peroxides have all been found to act as polymerization catalysts. Less well established is the nature of the in hibiting action of oxygen in photopolyuierization. ^ ntifide was used fof `hi* paper is concerned with the elucidation of this (tp seemed to the author that this apparent anom c of phenyimercuric apparent anomaly and its relation to the mecha- aly might be explained very simply by assuming u cstd for the leactivat'twreuribeazoic acid* *ype P)ymeiriz&t*on rcacti011* of the vinyl peroxide formation to occur in preference to poly merization in accordiMg* with . the following he. first two sections * i"- aryl mercurc con*' y *- .t-amylase and that lv corupi*' L*ly ot largely reotnieuT with hydrogen ' i'i-.' n suits arc f'|r` 'i ii-i.-yl M-e ij"i >u l`*e !l` i-tivity of p-.MiiyluSe. of tbit ujiv.litsii'ti was wlii'ii ha*' ( *1 rr 4s.. 2 J.. 1 .1 444 ;,-u. t-a in The mechanism of the catalytic action of oxy- scheme IKu is undoubtedly related to peroxide formation, <1) M 4-UVL - M* llle presence of peroxides in many vinyl com- . (3) (a) M* + Qi 1 MO, (preferred reaction) uv*nauatl work dwritwl bwc wuourM ut ia 1939 . (b) M* + M MM* + M--- MMM', tic. `W U>I .Utkor vu witk tb* Nvtwi Coapmur, VtnMW, Mm. . I where M represents the unactivated monomer Qdw tppa/d i* {UitMh Ptst *40,234 (1*42). l idilfMi Cca4 Audio* utid Ziln Cap., CwVd , **rtthl* L1 m.bVowr^..l.iw___jr, BaM...t.wI. UVm1..U.. A**., 47, 113 (1943) 1 S*u a*, m molecule; M*. the active center and MO,, a peroxide. Qfy must be further assumed that the catalytic activity of the iHToxidr is due to it> 13 (14J3), tendency to generate M* (or siittiLr active ',.7> nu , 1,J, 3)7 (1973). " s`*(lincr, t miu SUrck. Bor.. WB, 1793 (1937). and Unit these active centers exhibit i! -t,,pe s, ' ua Mnaa BolL OUin . (41 19, 14 (1934): (8) iHftiMlii.gfr ft4 -Aft1**, <**9, 1 'J93*> u SckvalUck, Ah.. 443, 4 t(3U; B. L d mad i/'cm, iuii. / i.s f * Ca,/w, E4. CM-., a*, 11*1 (1WM), (i) Duffimw, t* !aA**l* y, 0, v IVAdl. ' r*2 , . ud 8*k4llMfc. O. -4; T*t4-- ha v----, 99, 99449919 (1991). <lu> Coftftat wa4 Taagitrg, Tin , MA, H {l*W. *2. '>* 4^4-^.4*^.*f*- .4..AJ*p, ucc 032091 iiuitii >,rvl reactivity with oxygen as thaw inr^ t ii !>'. i'-c Kdion of ultraviolet light.1* 'll, ilit't.ry n quires (a) that peroxides be f t.n it .n vinyl rnmpirnfJs by the action of ultra' Thus the inhibiting action of oxygen (t.r more aecunttely, preferential peroxide formation in Ute presence of oxygen) appears to be of a very gen. eral nuturc., applying to virtually all polymerisable 1 | ^ *0 riir'l % pp!ASMliTi .iithn ` j^ir wry -r vp ftn'l i.'xa'.i' *ho4'* '"`ni.r fro- .f t.ii|;V end .; that, ir. thtijirt^rncc nf excess vinyl compounds and to thermal as well as photu- ;rnuO'u' <f> -vjt. jio!viiirriinri<irl oc citrv^i" greatly re* polymerization. , Lwried. or TiTTiTvTy~~ rifcvenTt'd. Both these re- f (Ipmay be pointed out that B is this preferential ; Tiriiu'fTir!>mrr.vir"Hecn substantiated experi- reactivity of the activated monomer with oxygen ' 11 IM'S fjcidty o' n*:it''l>;-,. rm-. cliroinoie. I. i- . n, Lw.tti'Ity in the following manner. Tvro Pyrex which.accounts for the .erratic induction period hctizovl ]h-m.\iil.- ; 1- 11.J - , tubes were filled half wav with carefully purified, ('observed when pure monomer is polymerized in ? peroxide-free, vinyl acetate. One of these tubes the presence of air. The length of this induction 1 was evacuated, Boded for a moment to frec$t)of period depends upon Uic amount of oxygen prep. pttrifi-r.Von oi Mon^.r use! oidtTufi fro.,, unde rrui-. .J j...- r-.'re ti- S ail ii ill if .it m / ns w .|| air. <`oohd and fiien sealed under vacuum. The ent which in turn dc]smds ujion such eusiomiiHiy r,,[uliins ri-ii,.'li- i-.l(: , uiher tul"' uas flushed with oxygen and then con* uncontrolled factors as tlie design of the container, x :ic- ted to a large 11ask filled with oxygen to ensure the extent to whic.h(Tt\is filled, whether or not it is J, a plentiful supply. Both tubes were immersed i sealed,11-etc. ___t..' *-- t l.re'-cf)'"'", 'b- l.inn, i>. , -:igP wlii-h is '' ft.?* 1 |. xiolyntCf ton.i uiinds crylie aiih .'ifiidc. 71; i-. , horizontally in :> water-bath maintained at 0 '"if a polymerization is carried out in a vessel ? ter and *rrrc fcrl ioi-gam ami than irradiated with ultraviolet light. After open to the air the two competing reactions of * twenty-.seven hours the material in the evacuated peroxide formation from active centers14 and per- tnlie had become viscous. Precipitation with oxide generation of active centers eventually reach ' I It hat 1h`Xi previously itcrial exhibited tit? 'v,. dist'licd ttiroiieh .vi paikctl wnh til -- methanol showed the presence of 13% polymer. a delicate balance. As the eoncentratiou of per- * various pic'-sur . nr,- .j)' The liquid in the tube under oxygen contained no jiolymer but a test with a potassium iodide solu tion indicated the presence of 0.005 mole % per oxide. Similar results have been obtained with oxide builds up the oxygen available may no longer be adequate to react with all the active centers generated; therefore tire surface layers of the monomer exhaust the oxygen supply allowing the l ? i |7;i mui.). and 'IIs followinr I'-sis "us found t hy the above test 'The vmjJ i.-mi Carbon Cheuiieal, O-rti ;; methyl acrylate and methyl methacrylate. There fore, when sufficient oxygen is present, peroxides aie formed exclusively under conditions otherwise favorable to photopolymeriration. lower portion to polymerize under essentially i oxygen-free conditions, catalyzed by a rcla- V lively large amount of peroxide. This explain- t tion is consistent with the commonly observed \ ner. It "'3- k*p. dry ,r peroxide-free Ci-ndition, Formation of Peroxides, ir.erf as methyl acr>lit-, acetate could be sti-red in If the foregoing explanation of the action of oxygen is valid for photopolymerization, then tit should apply to thermal polymerization as well. In tiiis case 'it' is a well known fact1* that the - soft or sometimes fluid layer at the surface of an otherwise hard mass of polymer formed by the polymerization of such monomers as vinyl acetate or methyl methacrylate in contact with , ' * f in contact with nir tvitli peroxiiic conlcut. l.ndtr uttinhiHied jtionom-r sior tcmpcrai ore in diiTit'c daperoxide is present it; le1 s, catalytic activity of the peroxide is due to fits) air. 1 'i tendency to generate active centers. These ac Experimental t tive centers then should exhibit the same prefer Peroxide Twt--For this work a reliable sensitive test i. i-duttibute to the Kurnid',. eruuiitions a; shn.-n hv since this work was do'ii, niri the formation of pitot ential reactivity with oxygen as those formed in for peroxide in monomer was required. Several common * the photopolymerization. Furthermore, the per oxide should be formed from the monomer and oxygen by the action of heat. Both these require reagents were tried and none proved entirely satisfactory , Ferrous thiocyanate was found to be much too sensitive , and rapidly oxidized by air. The liberation of iodine Iron * acidified potassium iodide was found to vary markedly t T Formation of Fsttoxnn Kxrosiin ments have been fulfilled experimentally. In one experiment, for example, a sample of methyl methacrylate was heated at 65 in the dark in contact with an oxygen reservoir bearing a manometer. During a period of twenty-six hours the monomer absorbed oxygen at a steadily in creasing rate. At the end of this time u&had ab* sorljed twice its1 volume of oxygen (at 65) and with different batches of the salt, being very sensitive to > variations in the iodatc content. By using a neutral solu-* tion of potassium iodide, most of these difficulties were* avoided, and the test finally adopted was as follows: * , To 4 cc. of a freshly prepared saturated soluiion ol r reagent grade neutral potassium iodide (containing It's ; than 0.0001% iotlale) in a 15 X 150 mm. test-tube was f added 10 ec. of the liquid containing the peroxide. The contents of tlie tube were then xhakou vigorously for oat j minute. A quantitative estimation of the peroxide present Tims, day, 1 2 S 5 ExensrO in 4 )tS'-wtt hull, at one fncii O.CKWi .IKlill .Hoar. .0311 By irradUting at 0* n i hail not visibly increased in viscosity. A portion was obtained by comparison of the yellow color of Uie - ictiiiu of light alone, /to of the. sample, at this point, was placed in a tube liberated Iodine with that liberated from known solutions under nitrogen and another portion was placed in of recrystaHized benzoyl peroxide in the particular (per- ` oxide-free) monomer. Although a definite end-point i' . similar tube under oxygen. The portion under , reached, the eventual deepening of the color (caused by the ! 'ion of jieroxiiic by Ir.-'m .. it will be observed that nooteut, hen was more cf'"i lormation of peroxide in nitrogen polymerized to a solid within a few hours ! slow liberation of more iodine in the Ught) made it (It- - f'-verse xvas ii-uc with viuv while uo visible change took place in the sample under oxygen. The ordinary ben2oyl peroxide caPdyziu thermal polymerization is likewise in* (23) Urn paiyflttriftttMni (dlbor photo* or lfacmi*J) ttraailvul in { ft sealed lube voder ftir4l)is very easily demonstrated that orjgitt it itoed up. Upon opening the tutie tmdrr tffttj*r when polyfnerif*- * Aii atteu.nt was mad. bom the two samples oi vi of th- monomer under redo of a y.-llinv oil was obi.or liilmi-il by oxygen us shown in Table IV. tiou it complete, oot-Afth the origiaul uir epace will be fiMed wnter, V'-d'-t lighi and i, sand!,a i >d Vvl{' obi-,,,,, |,y (ID II sir. |< >. til ii< i lint <>t m.ty nMneL chain *t (J41 If 'In ttf raiiffittlfil im the < gv itl i Im-hd'iI ihiIvhwi ttitiiuii tliui ' 'oi i,, ,,i. ,| ,i,.- .hat iin- i.f 4i iim i i. M M* or At M M *, n lofniiti only from iu iWf i tniFrk. in runtrmi.'ii, \% > (til/ *'i hifltr lOtl }Ju0*nmTin, Z. phytih, CAm,,, lilt, SiA (iOflfl); ever, lh*t in tin* chau eltu the active cgfititn, ebeihcr lht*y lit l.no^1 'i* -1 i Iv (,. i. Or* oml Ri4rfcl, proc. Jky. Soc, (Loudon), 170, 300 directly from the monomer or tfenernted by the do rettt U. t'. :'.ru,j;'; (lU3rj); MrlxiUc. yHnn. Htftt Chim. &*.,, M, fl (1030); Prwf mil preferentioHy with rayf#n, providing t* ** tifveflt ***') Karin-,, l.'nti.nlxUt Ml. Tutu Ioitai,. 13, 270* (1041). *iMOBt. s.,r. j*. a ;b tr.iiri *,*r r** ^^ \ s L-u` ucc 032092 tc os scc'jn/iary ilandardi,. solutions of (.'.H|!ii Oirjrommi which could be diluted to match the *' .Bi;. very a; curately. A series of these standard! *'* rTiadi' up and matched to the colors produced in the menner from solutions of known concentration ' - aoeijf O.OOH to 0.01%) of i ecrystallizcd benzoyl in iiermridc-frce methyl methacrylate. Higher , o ii tn'uuinvs uere determined directly, owing to the dif* \ii-iy f matching the color of these solution* with di- .i,rici*'e- It: rr.siltf por-sible to detect Jess than 0.0001% * (, ,.o' pfusidi- hv tlii- test. ' puifitation f Monomer*.--The methyl methacrylate w.is obtained front du Pont and carefully distilled i mi(ter i educed pressure to remove the bvdroquinonc (added - 3ii inhibitor) as well as any other impuritie*. The " -olnui`1' artuailv tiserl were of the type developed for .cvv.ithi; the formation of polymer in the column, a de- l,si nhrn i (amentia! for the distillation of such easily "1/iuertr thle compounds ns ipettjarrylic apjrl and metha- atiltvdrttlc. These columns were one inch in diame-, ;,-r h'l'c fret long ami arc packed with copper doth." J lit had I'tan previously established that the distilled ma- . tittil exhibited the same polymerization activity a* that ,;,,tiilnl through an eight-foot column of one-half inch bore, our'acu with glass helices.) Boiling points obtained at , v-tli' cs pressures are 49 (130 mm.), 43* (90 mm.), 39 ,p; ,nm.), and 24 (33 mat.). The material used for the Mlnving tests was found to be completely free of peroxide* ,'.lie shove test. The vinyl acetate used teas obtained from Carbide & * Paritnu Chemtcais Corp. and was distilled in the same man- ' nrr. It was kept dry to avoid hydrolysis and used in - prrovide-free condition. , formation of Peroxide*.--It was found that such mono- -1 jjers at methyl acrylate, methyl methatrylate and vinyl acetate could be stored in the dark at 0* for several days i- ia contact with air without developing an appreciable peroxide content. Under ordinary room condition* <i. ' it,,inhibited monomer stored in a colorless bottle at room * mnerature in diffuse daylight) a measurable amount of * p, fuide is present in less than a day. 1 Both light and heat r. i-.iMinbute to the formation of the peroxide under these ' ...millions as shown by Table I. Farmer" ha* shown, v .mic this work was done, that heat, light and catalysts ,* dd (he formation of peroxide* from olefins and oxygen. >. Tabu I ._ * Tahu II Relativ* Effect of Light and Huat on Pbfoxidb . _ Formation* Monomer Peroxide ctiotfrtit, molt % UVI-, 0*C. Dork. 0*C. Methylmethacrylate 0.003 0.03 Vinylacetate 0.004 0.001 * Treated for seventeen hours in Pytex tubes connected with a 2-liter oxygen reservoir. Heated tubes were kept dark by wrapping completely with tinfoil; illuminated tubes were immersed horizontally in water maintained at 0 by refrigeration and irradiated at a distance of 15 inches with a G. E. type A-H4 mercury are lamp with outer glass removed. amount of the yellow nil on a spatula was placed in a flame; it exploded in much the same manner as docs benzoyl peroxide on simitar treatment. Other vinyl compounds in which peroxides were ob served to form are as follows: methyl and ethyl acrylates; ethyl, n-propyi, isopropyl, w-butyl, isobutyl, allyl, methallyl and cyclohexyl methacrylate; methyl a-chloroaerylate; methyl wbromoacrylate; acrylonitrile; vinyl iso butyl ether; vinyl a-propyl ether; metltyl vinyl ketone; and butadiene. Inhibition of Polymerization by Oxygen.--The inhibiting action of oxygen in photopolymerization is ahown in Table III. The amount of polymer was determined Tablb HI Inbibitino Action or Oxvobn in Photofoltkbbization* Pmxldi Mombv ' AtBMpliffi coocSm ' Po<ymr, aoU % : % Methylmethacrylate O, 0.0025 None ' Methylmethacrylate Vacuum .....1,1 6.48 Vinyl acetate O, 0.006 . .. None Vinyl acetate Vacuum .... 13.0 I * Samples were placed in Pyrex tubes which were im mersed horizontally in a water-bath maintained at 0* and irradiated for twenty-seven hours at a distance of 8 inches with a type A-H4 G. E. mercury arc lamp with outer glass removed. The evacuated tubes were sealed and those under oxygen were connected with a 2-liter reservoir, ' FouunoN of Fbbcxidb in Mbtwyl llnuavun *,:> Exfozsd to Am at 27* 1, 1 v Tine, '* iiyt ------------------ --Pwmidi, mol* Exposed to * UKKvtrt bull* t n fool --'......... .' Dufc by precipitation with methanol and drying. ' The inhibit ing action of oxygen in thermal polymerization is shown in Table IV. Tablb IV :i J3 0.0003 .0010 Less than0.00005 .00005 Inhctitino Action op Oxyobn in tub Thermal (Cataltzbd) Poi.YMxaixATioN or Mbtnyl MbtkacbylatN* S :5 .0035 .030 .0001 ' .00015 rkmpM *.. 1 AIsmw- 1 BB9yr phm% ' pvniA.%;,/ Ns ' 1 0.01 ' Solid polymer /; i ~J By irradiating at 0* a peroxide may be formed by the , is d**u uf light alune. A comparison of the rate* of forma- v. '4> f peroxide by light and by heat is given in Table II. ' *tid he observed that under the conditions of this experi, - lit. heat was more effective than light in causing the '"'luiion of peroxide in methyl methacrylate while the e-vi't-sc was tme with vinyl acetate.. ^ 4u attempt was made to isolate the peroxide formed hau i Lr two samples of vinyl acetate. Upon evaporation " "f 'hr monomer under reduced pressure about0.005 mole % *' " x yellow oil was obtained from thq tube under ultrax `.'`I't light and a smaller (unweighed) quantity of a yellow ,, ; es obtained by evaporating the sample which had " seated in the dark. Both these oily residues liberiodine rapidly from potassium iodide. A small 2 Oil'',' 0.01 Viscous liquid ' 8 0 . None . . . No polymer but 0.001 (' mole % peroxide All three samples were taken from the same batch of peroxide-free monomer, and Samples 1 and 2 were pre pared as one solution and divided. All were heated at 65' for four and one-half hours in the dark. I t.iSi ' f, 1 Acknowledgment--The Author1 wishes to thank Loring Coes, Jr., of Norton Company for help with the experimental work. - Summary ,! ` " 3. Patent ap2Sl,t7 (1*41). 't i * Bkmngeid, 8v*dnUinsliuii ami Satevw, Fmss , ' ' .**, X4g (1043). 11 An explanation has been given for the frequently observed inhibiting action of oxygen on the photo polymerization of vinyl compounds and some addi- t ' 1sK4\ fi *; i il hi t . V. 032093 3 .ivi n il ijii iher* ence to polymerization. ,-1P r< liter of t.ir "7 `.tt V-"`Vj standard taper mal polymerization as well, and that Loth these Easton, Fa. Rkkvto Swibob to , ' ' * ,1-uJe ad l tne q !<{ .*">asw|l ,^ gr* raduated tube f,,. ' l ilpl tubc R 1 -|| scaling all....... (CoirruurnoN fsom in Department op CinttnsntY, Noxthwiitbrn Univxuity] '* ..aiul po'1^ lnd '* t: Racemization, Alkylsulfuric Acid Formation and Exchange in the Reaction betw. * 'VriLi. j5.11 iwc if' liaiir Wi Sulfuric Acid-dJt. and Oopticallvy Active 2-Butanol1 By Robbet L. Bcrwbll, Je.u . , (l forirr:ics(tia:rni dtoar1d0mtamp^,ia" \ -.(wiled in s ground joint ti '' that the reaction fla.+ <om The racemiration of optically active s-butyl alcohol by sulfuric add was recently reported.* In this paper further data on this reaction are pre sented and a hydrogen exchange reaction is re ported which accompanies the racemiration when sulfuric add-dt is employed. The interrelations among these and the other accompanying reac tions, dehydration of the alcohol to butylene and m the alcohol was produced. Tbit process require*] 1' one and one-half hours. Upon its completion, stetq* passed through the residuea (toa Mcaerrmy aoivmewr aAnnay* u>n_r_ecowl" 1 alcohol. The outlet of the apparatus led to a gas , The alcohol, isolated over saturated potassium *, \*attee solution, amounted to 3.09 cc. or 0.0328 male- It. + 1.56. 137 cc. (27*, 730 mm.) of butylene was trn> v or 0.00535 mole. Of the original 0.0426 mole of s-w!^', sulfuric add, 76.7% was recovered as alcohol, U jJb'y butylene. ** * ^.Siit allowing water vat*^, h the reaction flask in p ,,n *pd liquid air about th* ^ '"' .uened aornd by approp.in "Tf 'trioxidc was sublime.! m n"tuf f a...dImmiihshsiOion of dry air , ..i,bed. The proper q.innJi ^.V.1 in 1,10 Pradu:"ed nlc , .he walls of the tube sbov. V-ktir* manipulation in a i i'.<--r writ aAllioww^'dJ ttr> tir..crUtt .., formation of s-butylsulfuric add are considered. Unacidified barium s-butyl Sulfate was oegfigjty..J- from a niicroburci p, ; drolyzed in one hour at 100 . ^ .acid cooled in liquid u .1 Experimental Materials.--The preparation of rf- and J-2-butenol has been reported as has the origin and analysis of the sulfuric Preparation from Chloroeolfoolc Add.--To 9^ a i e+t5h.y2le9n*e) wdaicshlaodriddecd.. 0.T0o169thima omleixotufred,-2k-ebputtaant cJl(Lf | *"oiijing of alcohol and m k- i * y-jr alopco' hs ami the Ix/,V) M With Apietou Grij., add.1 The rotation of the alcohol in equilibrium with a 0.0167 mole of chlorosulfouic add was added. }j.j g in lust otir ruit, >. saturated solution of potassium carbonate dihydrate will gen chloride was evolved slowly and in an hour a u"a .lifer a suitable reaction tk be denoted by $. Such an alcohol contains 3.3% water layer separated. The reaction mixture was pro3 i were |K)Ured into 'vntr- afj. and its rotation is 02.7% of that of the corresponding an like that resulting from the mixture of sulfur trioxidc,); ; ^ mevioosly described.' Ti hydrous alcohol.' hoi and dioxane to yield 5.0 cc. of an aqueous solute. / * w iivlroxyl group the i crown Sulfur trioxide was distilled from 60% fuming sulfuric barium s-butyl sulfate, o*o +0.16*. A one-cc. n*.\ times its volume of wstiv acid. was hydrolyzed at 100* with the addition of 6 M tj,. . l( s< technique described u.u*; Deuterium oxide (00.6%) was purchased from the Ohio chloric acid and barium chloride to yield 0.3158 g. a,* , >y| aulfatc. This was fwio Chemical Company. ium sulfate. The direct addition of sulfuric aad in. V i he alcohol was measured; . Commercial dioxane was refluxed with 6 M hydrochloric cc. of sample gave 0.2536 g. of barium sulfate, whcacti)..*: laippcr oxide, the rcsultuig add. After separation by potassium hydroxide and drying was 4.1 X 10"`mole of barium chloride per cc., andO.^ 7 ,,d,b alsmtard walar, and the with potassium carbonate, final drying and purification 10*4 mole of barium*s-butyl sulfate per cc. Wbeotq v ,, -l hy the float method* were effected by fractionation in a 12-plate column of the Peruke glass-helix type. Preparation of Barium d-r-Butyl Sulfate yield was 40%, [a]"D +0.60. In an experiment in sb I. dioxane was substituted for ethylene dichloride asth.,' vent, reaction was fouud to begin only at 100* and loiq^, to a yield of but 7% in an hour and a half, amo 0.00. > a'strmization and Exchscqr .,Cinrv of the follov.ing coni-' ** .latiol (dBn --2.01)'), Oil; o 0392; heavy water. 0 f- Preparation from Sulfur Trioxida in Dioxane Solution.* Preparation from Sulfuric Acid.--A mixture tf i in' liMiusat 25* the aleobui i --Into 20 cc. of dioxane cooled in ice, 0.0638 mole of sulfur butanol (6bd --2.09*) and sulfuric acid was prq*> '> ahnhol after drying ui n' trioxidc was distilled from fuming sulfuric acid. To this, in the same way as in earlier racemizatkm studies' (a,4 r- 'l 1 dl'3 K. of water. To 0.0545 mole of d-s-butyl alcohol (flBi> +6-29) was added alcohol, 0.0525; acid, 0.0538; water, 0.0128). After;/ qf i w:is added. Tlie rerultfi;1 at room temperatures. After ten minutes, the reaction hours at 26.9* the reaction mixture was poured into tag ai.Zi>m hrnv)' at 26..S*, whenett mixture was poured into a suspension of excess barium pension of barium carbonate in water. The resulting*^ vrd'ugoi substituted by rieutCi ft carbonate in water. After filtering, tbe solution was ture was filtered and the filtrate was evacuated. Pn.^ 4- 'tin exchange and for the placed in a distilling flask in water at 35* and aspirated for both processes the exhaust line led through' liquid i; l-o|,,Ayl hydrogen, 09% of tie six hours during which the volume was reduced from 70 trap. The initial volume was 60 cc. The final voln/ *TMI" wot the heavj' ivrtopr. to 18 cc. To this, 14 cc. of water was added and tbe was 24X cc. h*o had been 9/ 'O.dO or r>.' volume was reduced from 70 to 18 cc. To this, 14 cc. of Tbe condensate in tbe trap was distilled to isolsttn>' It nunilar cxpiriim'nt tt>Ji. water was added and the volume reduced again to 23.6 alcohol which was recovered over a saturated solutiurk` - d `J-hiitanol (flop f.`i29 cc., o*b +1.91*. Rotations refer to a one dm. tube potassium carbonate, 0.0292 mole; 6"n --1.77*. wt4ah arid, 0.0409; fthd lii.i' v save where otherwise noted. One cc. was evaporated and Five cc. of the barium r-butyl sulfate solution r* e 'V-n periial of eleven and *tie f ignited to yield a residue of 0.2306 g. of barium sulfate, evaporated and ignited to yield 0.3607 g. of barium mrfc- eu- --ie-1 an ulcohol, risi> i--' whence the yield of barium j-butyl sulfate was 0.02346 The rotation of the solution was determined in a Jt ! - * wus burned. 0 *CVf j,....' mole or 87% and (a]"o +4.34* (on the anhydrous salt). tube, 0*0 --0.105*. Whence the yield of barion ; ,..d'td with 2.1C.1 g. of sTan.'nii,' Upon adding water to the solution and revaporsting, butyl sulfate was 32%, (a]Bn --0.38 , and the ieaf **'* vr! was diluttd ni'h ,V'<t a similar specific rotation resulted, thus demonstrating of tbe alcohol was 56%. ,' ^ 7Y.- tesulting watei Mill li4 , tbe absence of d-i-butyl alcohol. Hydrolysis of Barium d-i-Butyl Sulfate.--To 22X5 cc. Exchange Reaction* ' be-1uTrrtpond'i to the nibsm" ; ,, -- t-i uM exteul of 55 7%. Dr of tbe solution obtained above was added a solution of Procedure.--To prepare heavy sulfuric acid, ta s. i. * pa--] trim 56, Thu:, d.i 2.4 g. of sulfuric acid in 30 g. of water. The precipitated glass apparatus was constructed consisting of h 1 ! ' an* 1(V)% barium sulfate was removed by centrifuging. The dear containing sulfur trioxidc connected to one outlft *,r emi/etion (D(| Ey-hxig v t solution was transferred to a small fractionation apparatus and so heated that the alcohol-water azeotrope distilled (1) Prcacutad at the Buffalo tneetifif, Septaabw, IMS. manifold by a valve patterned after that of (4) Willard, Tins Jodumi., IT, 324 (1436). Willard'i n)w. opened by taaitiaf and blowia) out a Pyrex capiUary cocltacd vd-^ r 'time of thr lollraiug r r aitauul -(.5.29), * :' *w, ruul heavy .rdti* tif ftmr Innirs at 25* t tv (la) Prwaut eddrtw, Naval Research Laboratory, Washington, qiiarta tuba. It waa cloaad by baatinj the quarts and tbuilaad'-^ * ---f fVi.- third was prort . C. ,, Pyvex apiUary tip. Id tbe pmat reacareb it waa found diibi+ (2) Bunrtll, Ten JooaaaL, 44, 1024 (1943). . (S) Suttr, Bvaaeasd Elder, iM3., 44, 630-4*0 (ISM)'. The writer lt a Yacuun-tixht aaai at tba tip of tbs Pyrux omUiarr SB % a Pjiu soft (law ssal, a left (law uapUlary waa aubatittaair-; tM- sa.1 ,'ikihw], Tun J a/V 't* * *aa.--.a iv0|tw I, .: a iadehted to Dr. C M. Outer far auggssting thia rwSioa. ' ant rwulta were obtainad. ' -' rf -*< Mr. Wllliaai Uoirs t