—v— INVESTIGATDNS OF THE HrlGH PRESSURE HYDROGENATION 0F PHENOL AND THE CRESOLS WITH PLATlNUM OXIDE CATALYST Times for £410 pm at M. a MECH‘iGAN STATE COLLEGE Arthur F. Méiler _ 1953 L I B R A R Y . N ichiga-njbm. s ‘ 2* . Universuy ’IQJ. ”Liz”: fJ'Q t: 315%: . A ‘r.-:*,_t:’._ - J‘ _._- ..- This is to certify that the thesis entitled Investigations of the High Pressure Hydrogenation of Phenol and the Cresols with Platinum Oxide Catalyst , I presented by Arthur F. Miller A. has been accepted towards fulfillment of the requirements for ' 2 Major professor Date Decmber 3s 1953 “ A g 11.," “J“. w fl‘£\‘ it’s-A21 ‘1’}. ' 4 I g].— I I; "‘:..-l.a:&" . 4; V. -“ ' ’ 1‘ t c .P ;‘.‘I .33 . yfiu‘gw ’2‘ .1... 'II INVESTIGATIONS OF THE RICH PRESSURE HYDROCENATION OF ”01. AND THE GRESOLS mu PLATINUM OXIDE CATALYST 135’ Arthur 1. Killer ATHBIS Submitted to the School of Graduate Studies or Hichigan State College of Agriculture and Applied Science in partial fulfill-ant of the requirements for the degree of MASTER OF SIRE! Deparhent of Chaistry 1953 ACKNWLEDGIEIT The writer wishes to express his gratitude to Doctor Robert D . Schuets for his counsel and assistance during the progress of this work. W W W at! H i- Q "d C. Fan- \ v LI Pu} CI TABLE OF CONTMS maowcnou 1113mm ammrmns AND RESJL'I‘S newsman PAGE 1 2 6 16 22 30 32 3h INTRODUCTION MRODIBT IOU There being no recorded kinetic investigation of the hydrogenation of meals at high pressure with Adus platinun oxide catalyst, the purpose of the work described here was to note such a study. The problem was approached with the belief that a study of the rates of hydrogenation of such *cupounds and their stereeiscneria should give sue insight into the nechanisn of catalytic hydrogenation. The cupounds chosen for this study were phenol and the three iso- aeric cresols . The reaction nediun used was ethyl alcohol with glacial acetic acid, and platinua oxide as a catalyst. Hydrogenation were carried out at an initial pressure of 1300 pounds per square inch and a telperature of 500 O . HISTGRI HISTORY The earliest recorded catalytic hydrogenation for the production of an organic cupound is that by Debus (l) in 1863 in which he prepared netlwluiae by passing the vapors of hydrocyanic' acid, nixed with hydrogen, over platinun black. By the turn of the century catalytic hydrogenation began to be recognised as one of the major nethods of chenicel teclmique. This was due, in large name, to the exhaustive reseu'ches or Sahatier and his associates, which are published in condensed fore in Sabatier's book 'La Catalyse en Chinie Organiqus'!(2) . tabatier'a process involves pass- ing the organic substance, nixed with hydrogen, in the vapor phase over a nickel catalyst kept at the prepor taperature , under a pressure of about one ahosphere. Following, alnost i-ediately, Sabatier's work, a second process for carrying out catalytic hych'ogenattions was introduced. This involved the re action of hydrogen at one to five atmospheres pressure with the orgmic conpound as a liquid or in solution in which the hydrogen and catalyst were agitated. Hydromation in the liquid phase becue particularly useful with the development of colloidal platinun, platimu black (2), and platinu- oxide or Ad-s' catalyst (3). I The catalytic reaction of hydrogen at high temperatures under pressures of 100 to 300 whospheres with a ce-pound in the liquid phase was introduced by Ipatioff (h) during the first decade of the present century. * The investigations of Arnstrong and Hilditoh (5) were the nest systuatic of the early work reported. Their results indicate, in the absence of disturbing factors , that the velocity of hydrogenation is directly proportional to the hydrogen pressure . Anong those disturbing factors nay be included slow acting pernanent catalyst poisons, preferential adsorption of gaseous inpurities at the catalyst surface, and the presence of a conpound containing a functional group not susceptible to hydrogenation but having an affinity for the catalyst's surface . ' Platinun oxide as a catalyst for the hydrogenation of the benseno nucleus at low pressure and noderate tonporatares has been in rather general use for the past twenty-five years . Platinun is the actual catalyst when platin. oxide is used, as it is fornod fron ths oxide as soon as hydrogen is introduced into the reaction vessel. The die-- advantage of this catalyst is the ease with which it is poisoned by elonentary sulfur or conpounds containing divalent sulfur . A qualitative study of the hydrogenation, using platinun oxide, of a nunber of phonyl substituted conpounds was node by Ad-s and Herlhlll (6) . Their results indicated increased difficulty of hydro- genation with increasing nolecular caploxity. In 19115 , Snith uni ce-worksrs (7 ,8 ,9) node a quantitative study of the effect of structure on the hydrogenation, of the benzene nucleus with Ad-s catalyst at low pressures . They showed that, under the oxperinental conditions onployod, the rate of hydrogenation was first order with respect to the hydrogen pressure, sore order with respect to the wdrogen acceptor, and directly proportional to the aunt of catalyst used. The first recorded use of Adas catalyst with high pressures was by Baker and Schuets (10) in 191:7. they denonstratod that the hydro- genation of bensenoid compounds followed essentially the one kinetics as at low pressure , although the tine of wdrogenation was considerably less. There are a nunbor of references in the literature to the hydro- genation of the crosols. The interest in the crosols was due in large neasuro to the fact that the products of hydrogenation exist as goonotrical isuors. In Table I is a su-ary of the sterooisonoric products obtained free the hydrogenation of the cresols and their corresponding nethyl-cyclohexanonos . In general , hydrogenation with nickel catalysts loads to prodoninantly trans ismers while platinun catalysts yield nainly the cis isonors. TABLE I MIWIS! OF THE WATIOR PRODUCTS OF THE CRESOLS AID THEIR CORRESPONDII G HITHILCICIDEEXANIBS Conpound Conditions Hydrogenation Wasted Product o-Crosol Nickel at 175‘s . 67% trans (11) o-Cresol Raney nickel at 180°C. 68$ trans (12) o-Cresol Ranoy nickel at lOO‘C. nainly trans (13) o-Cresol Pt black, acetic acid nainly cis (1h) - o-Cresol Colloidal Pt, acetic acid nainly cis (15) o -Croso1 Copper chronito 100$ trans (16) n-Cresol Nickel at 180% . 82% trans (11) n-Cresol honey nickel nainly trans (17,13) n¢Crosol Colloidal Pt, acetic acid nainly cis (15) - n-Cresol Copper chruite 1001 cis (16) . p-Crosol Raney nickel, 180°C. 82$ trans (l2) p-Cresol Haney nickel nainly trans (l3) p-Crosol Colloidal Pt, acetic acid nainly cis (15) . 2-hottwlcyolohoxanons Sodiun , noist other 811 trms (11) 2-hothylcyolohoxanonc Pt, acetic acid 621 cis (ll) 2-ucthy1cyclahcxancnc aancy nickel, 130°C. 57: cis (12) ZJethylcy-clohexanone Pt black, acetic acid nainly cis (1h) 3-lothylcyclohexanone Sodiwn , boiling alcohol 86$ trans (11)- 3-Hothy1cyc1ohexanono Rancy nickel nainly cis (17) 3-hotrylcyclohexenono PTO,” acetic acid 691 cis (11) h-hotlvlcyclohexanono Ranoy nickel, 130°C. 59$ cis (12) WM. mm. The naterials used in a study of hydrogenation catalysed by platin. oxide nust necessarily be of high purity because of the poison.- ing effects of snall naounts of foreign natarials. The chuicals used in this work were: Glacial acetic acid Cyclohexono Platinun oxide catalyst Haney nickel catalyst Ethyl alcohol Phenol o-cre‘sol n-cresol p-cresol Cyclohexsnone 2-Hothylcyc1ohexanone 3-hothylcyclohexanono h-Hotwlcyclohoxanone The platinu- oxide used in all hydrogenation in this investigation case fra a single batch of catalyst obtained fru the Anorican Platinum harks. This olininatod the possibility of having a catalyst of varying activity. The Honey nichel catalyst was prepared frm a nichl-alwninu alloy, procured fron the Central Scientific Conpany, following the nethod of Pavlic and Adkins (27) . In a two-necked three—liter flask equipped with a stirrer and a thenoneter, 128 grus (3.2 noles) of sodiu hydroxide and 500 nl. of water were placed. The flask was in- norsod in cold running water and a 100 gr. quantity of the alloy was added in aaall portions to the rapidly stirred solution, while naintaiaing the t-peraturo at 50°C . After the addition of the alloy was conploto , the suspension was digested for an hour on a water bath at 50°C . , followed by washing with water until all alkali mid water soluble salts had been moved. The resulting finely divided nickel was transferred . to a 250- nl. centrifuge tube and washed three tines by stirring with 95 per cent ethanol. The one procedure was followed with absolute ethanol to m... the last traces of water iron the catalyat. The product was then stored under absolute ethanol . Cyclohexone, lastnan's best grade, and glacial acetic acid, Baker's C. P. grade, were found suitable for use after distillation. Ethyl alcohol of approxinatoly 99.5 per cent purity was prepared as follows (18). A round-bottonod flask was filled to about two-thirds of its capacity with 95 per cent otlvl alcohol. fresh quicfline , broken into lunps , was added to the alcohol using enough line so that the pieces projected doovo its surface . A. reflux condenser fitted with a calcin chloride drying tube was attached and the nixturo was gently refluxed for an hour and then. set aside for three duo. Following this, the alcohol was again refluxed for an hour and then distilled directly into a suction flask protected with a calciun chloride tube against the entrance of noisturo . Phenol was obtained as a 0.3.P. grade of naterial and was purified by distillation fr. honey nickel to ruovo aw trace of sulfur eupounds . o-Crosol, liner and Anond C.P. grade, was distilled fr- Ranoy nickel, as were n- and p-crosol, Eastnan yellow label. Cyclohexanone, iashan white label grade, was distilled fron honey nickel. The three isueric nottyl-cyclohexanones were prepared by dichraate oxidation of tho alcohols which were obtained by the hydrogenation of the corresponding crosols . A hundred n1. quantity of the crosol was placed in the 185 nl. void Aninco high pressure hydrogenation bonb. To this was added one gr- of sodim hydroxide , twenty n1. of ethyl alcohol and four grus of honey nickel. The reaction nixture was shaken under an initial pressure of 3000 p.a.i. of hydrogen at 180°C. until there was no further pressure drop. The reduced product was decanted fro. the spent catalyst and neutralisod with hydrochloric acid. The neutral solution was extracted three tines with ethyl ether and the conbinod extracts were dried over nagnosiu sulfate. The other an! otlvl alcohol were ruovod by vacum distillation. After distillation, the notwlcyelohennolls were oxidised with a dichronato-oulfuric acid nixture (19) . In a one-liter round-bottoned flask provided with a nochanical stirrer was placed a solution containing 120 gr-s (0.1; noles) of aodiu diohro-ato, 100 pa.- (5h.3 IL, 0.97 noles) of concentrated sulfuric acid (op. tr. 1.8“ in 600 nl. of water. To this vigorously stirred nixture was added 0. 58 noles of the netlvlcyclohoxanol in four portions . Heat was evolved and the tuporature of the reaction nixture rose to qproxinatoly 55.6. , and then fell as soon as the reaction was conploto. The resulting oily product was extracted with an equal volume of other, separated, washed with three 200 nl. portions of 51 sodiun hydroxide solution, then with water and dried over nagnesiuu sulfate. After moval of the other the nothylcyclohoxa'nonos were obtained by distil- lation. They were given a.final.purification.by'rodistillation.fron .Ranoy nickel Just prior to use. The cunpounds hydrogenated were phenol, cyclohexanone, the three isenoric crosols , and their corresponding notlylcyclohexanones . Bach eonpound was hydrogenated at a to-porotaro of 50°C: . and an initial hydrogonlprossure of 1300 pounds per square inch. A standard Anorioan Instrunont.Conpaay'(Aninco) high pressure apparatus was used.for these hydrogenations. The accunpauying pressure gauge was graduated in divisions of tonupounds per square inch. loadings of elapsed tine were nado with a stop-watch. The readings were taken as tho noodle on tho pressure gango'passod through the center of tho division lines. A glass liner was used in all‘hydrogenetioas and coup sisted of a.Ryrex;ground glass tube fitted with a glass stopper which had a hole ia'tho top to adnit the ludrogon through a narrow tube. The latter was bent in a nannor to nininiso the loss of reaction nixture during shaking. The tenperaturo was controlled and rocorded‘by a Leeds and Northrup hicruax apparatus. The tenperaturo during a hydro- genstion was naintainod constant with a variation of : 1°c. In carrying out the high pressure hydrogenations the general procedure was as follows. The catalyst and reactant, with the solvent, were placed in.the glass liner which was thon.placed in the boob after which it was sealed. 10 The bonb was next connected to the high pressure tydrog'on source by noans of a steel tube and ludrogon was allowed to flow slowly into the reaction vessel until the desired initial pressure was reached as indicated by the gauge. The hub was then disconnected and placed in the shaker, keeping the open end of hydrogen delivery tube of the liner uppenost. For obtaining initial pressures above those obtainable with con- norcial cylinders, a snall hydraulic oil p-p was used. The voluo, or hydrogen void, of the apparatus. was deter-inod by hydrogenating cyclohenne in acetic acid as a solvent . issuing a quantitative hydrogenation of the olefinic double bond and using the ideal gas law, the wdrogon void was calculated to be 0.0h81 liters (Table I!) . loch hydrogenation was carried out onploying a nixture of approxi- natoly 0.02 nolos of the cupound to be hydrogenated, 0.1 gr- of platinun oxide catalyst, 0.8 nl. of ethyl alcohol and 0.2 n1. of glacial acetic acid. A ratio of 0.191; nolos of acceptor per gr- of catalyst was naintainod throughout. Thirty n1 . each of o-crosol and 2-netl'ylcyclohexanone were ludro- gonated to doternine the sterooisaorisn of the products. When the hydrogen pressure had dropped to the calculated nount, the shaker was stopped and the running hydrogen was vented. After moving the liner fr- the boob the reaction solution was filtered to recover the spent catalyst. The filtrate was stirred with dilute alkali to renovo any traces of unreduced phenol, and with dilute sodiun bisulfite to ruove ketones. The solution was then extracted with ether and dried over anh'drous nagnesiu sulfate . Following renoval of the other the crude product was distilled in a snail Gleisen flask and the fraction boiling between 165°-170°c . was collected. Density and refractive index neasure- nonts were nado on this nixture of isoneric 2-nethylcyclohemols before subjecting the nixture to fractionation in a Heli Grid Podbielniak calm having a ninismn of one hundred plates. The nixtures of alcohols obtained fro. o-cresol and Z-nethylcyclohennone were fractionated into six and eight cuts respectively under a pressure of 3 -. Density and refractive index deterninations were nade on each of the fractions and are listed in Tables v and VI. ' Since the presence of an intemediate kotone had been shown in the lydrogenation of phenolic compounds using Haney nickel as a catalyst in an alkaline nediws (25) , it was of interest to investigate the possibility of a sinilar internediate using Adu's platim- oxide catalyst at high pressure in an acidic nedim. An attenpt was nado to detect the ketone internediate by ultra- violet absorption spectra, using the Beck-an D U spectrophctueter. Solutions of known concentrations of phenol and cyclohennono in absolute etlvl alcohol were prepared and the per cent tranenission at wave lengths between 260 Iillinicrons and 320 nillinicrons were neasured. It was detenined that the concentrations required to obtain an appreciable absorption spectra with phenol was 10"“n, and for cyclohexanone it was 10-5! . It was also observed that the absorption peaks for both phenol 12 and cyclohexanone were very near to one another . Both of these find- ings were unfavorable, even before considering the effect of cycle- hexanol. There is an adverse concentration factor. The anount of cyclehexanone present would have to be about one hundred tines that of the phenol in order to contribute appreciably to the combined absorption spectra. Since such a high ratio of ketone to phenol was not anticipated, this nethod of detecting a possible ketone intermediate was given up. Since deviations fru first-order kinetics in the Ivdregenation of phenols and the crosols had been observed after the hydrogenations were about two-thirds ccwploted, the reaction products corresponding to two- thirds hydrogenation were investigated for the presence of ketones. Suples of phenol and each of the three isomeric crosols were hydrogenated at high initial pressure in glacial acetic acid with platinun oxide to, a calculated, two-thirds capletion. The reaction was then stopped and the catalyst filtered from the reaction nixture. The filtrate was neutralized with dilute sodiun hydroxide and extracted with other. The ether extract was dried over nagnes‘iun sulfate. After renoval of the solvent, the renaining nixture of substances was fractionated using a snall distillation flask oQIIiPPOd with a short Yigreux colun. The distillate was collected in fractions of about half of a nilliliter each. The ketone intermediate was shown to be present in one or nore of these fractions resulting fron the partial hydrogenation of phenol and each of the three isomeric cresols by the preparation and isolation of solid derivatives of each of the corres- ponding kotones . Table II lists the nelting points of these derivatives . 13 TABLE II WATERS CF ETONES ISOLATED FRO! THE PARTIAL HYDROCHATIOI 0? m PWOLS II GLACIAL ACETIC ACID WITH PTO; AT HIE PRESSURES _‘ w Phenol letone Derivative H . P . of Derivative Mounted Interaediate of Ketone Observed Reported Phenol Cyclohexanone 2,t-D.N.P.‘ 162-3° 162° (23) o-Oresol 2-Hethy1cyclohexanone 2 ,h-DJ .P. 136-7° 137° (23) n-Cresol‘ 3-Hotlwlcyclohexanone s .c .b 178-9" 178° (21.) p-Cresol . h-Hethylcyclohexanone 8.0 . wit-6° 196° (2h) a) 2.1.4) .11 .P. - 2,h-dinitrepheny1hydrazene b) 8.0. - Senicarbasone With the presence of the internediate ketone in the hydrogenation of phenolic conpounds in acid nedia with R0. at high initial pressure confined, it was desirable to obtain a quantitative neasure of the concentration of the internediate ketone throughout the reaction. These dotsrninaticns were nade at intervals of each additional ten per cent hydrogenation starting at ten per cent hydrogenation. The nethod (26) used to detenine quantitatively the recent of ketone present at any given per cent of cc-plote marogenation was based on the f deternination of hydrogen chloride liberated in the fornation of the ketoxine with Io'droxyluine hydrochloride . The equations for the reactions involved are a Py CD- 0 + mph-301 ——-—-? RD- 11‘“. up + Py-Hcl R breuphenol Py-HCl + llaOH hm Py + lfll + 3.0 . where R - H or 03,. Thus, the amt of hydrogen chloride liberated was a direct neasure of the ketone present and could be deternined by titration with a staniard base, such as sodiu- hydroxide, using bron- phenol blue as an indicator. The reagents used in this quantitative procedure were Wulaine hydrochloride, 95$ ethyl alcohol, pyridine, and M alcoholic bra-phenol blue solution . Approxinately 0 .5! hydroxyl- uine hydrochloride solution was prepared by dissolving 3S grns (0.5 soles) of the Wehleride salt in 160 al. of distilled water and diluting to one liter with 951 ethyl alcohol. The solvent nixture for the ketone containing s-ple was prepared by nixing 20 ll. of pyridine and one n1 . of hi alcoholic bronphenel blue solution and diluting to one liter with 95% ethyl alcohol. The standard sodin hydroxide solu- tion was prepared by dissolving 20 grns (0.5 noles) of sodiua hydroxide in 100 nl. of water and diluting to one liter with netwl alcohol. The alcoholic sodiu- hydroxide was standardised against potassiuu acid phthalate using phenolphthalein as an indicator . In a pint pressure bottle , 30 n1. of the wdroxylaine hydrochloride solution was nixed with 100 nl . of the pyridine-indic ator solution. To this was added a 5 n1. aliquot of the twdrogenation nixture ,, which had been nado up to volue with etwl alcohol in a 10 nl. volunetric flask. Sodiu- hydroxide was added to neutralise the acetic acid, the 15 equivalence point taken at the point where the color of the snple corresponded to that of the blank. The pressure bottles were then stepped-ed, placed in wire-nesh safety screens and heated on a ate. bath for two hours, and then set aside to cool overnight. The ample solutions were then titrated with the standard sodiun hydroxide solu- tion to the one end point color as the blank which was identical to the hydrogenation suples except that it contained no ketone am had been treated in the sac way as the s-ples. The results of these analyses are s-ase-ised in Tables mm to m. ' Since the kinetic data obtained on the hydrogenation of phenol and the three isoneric crosols showed sone deviations from a pseudo first-order rate egression as the hydrogenation progressed, it was decided to investigate the order of the reaction. This was done by holding constant all. but one of the possible variables in the reaction and detonining its. effect on the reaction. The factors investigated were: count of acid, nount of catalyst, initial hydrogen pressure, count of acceptor, md rate of shaking. The results are tabulated in Tables VII and VIII . CAICULATIWS AND BELTS 16 CALCULATIONS AND MITS It has been shown in several studies (10,21 ,22 ,23) that the ludro- gonation of benzene derivatives over platinwn oxide in the presence of glacial acetic acid is first order with respect to the ludregen pressure, sero order with respect to the concentration of the hydrogen acceptor, and directly proportional to the count of catalyst used. Thus, the rate of the reaction for a given count of catalyst can be expressed by the differential equation - ‘1 PHs . - k PH. T which, when integrated and expressed using logarithus on the base ten, gives Pg' kt . 3 1" ‘5;— " To where k is the specific reaction rate, t is the tine, 1933 is the initial hydrogen pressure, and PE, is the hydrogen pressure at tine t. To calculate the values of the rate constant k, the slopes of the lines obtained by plotting log POE/PH. against the were nultiplied by 2.303. Since these constants were deternined fro- different counts of catalyst, they were referred to one grc of catalyst in order that all values nay be couparablo . The data and plots for the detenination of the rate constants are shown in Tables I to XVII and Figures I-VIII in the Appendix. Since the qurogenations of the ketones, cyclohexanene 17 and the three nethylcyclchexanones , did not obey the first order rate law under the conditions used to hydrogenate phenol and the isoacric crosols, a ccparison of rate constants for the ketones investigated could not be nado. The rate constants for phenol and the crosols we recorded in Table III. TABLE, III SPBJIPIC REACTION RATE COISTANTS FOR THE HIM P3333183 WHATIOII OF PEDIOL AID THE THE ImRIG WIS 01‘” of Initial Acceptor Holes PtO. Pressure (1) .s .i .) k x 10" Phenol 0 .022 8 0 .1175 13m 11 . 6 0-01‘0801 0 .0191; 0 .1000 1300 8 .32 n-Cresol 0 .0191 0 .0985 I 1300 10 .3 p-Cresol 0.0192 0.0989 1300 10 .h 'Hydrogenation carried out in a 0 .0h81 nl. Void Aninco Bonb in an Ethanol-Glacial Acetic Acid Solvent using PtO. as a Catalyst . In order to detonine the relative ease of hydrogenation of all the ccpounds studied, plots were nade of the noles of acceptor hydrogenated against tine and are shown in Figures II-IVI. The tines required for the initial 305 of hydrogenation of the acceptors are recorded in Table 1'. since it has been shown by Jack-sh, Macbeth, and Hills (21) that a linear relationship exists between the densities of the isoneric 18 TABLE IV was mom son THE INITIAL ram: pm cm W macaw-ml III the am: museum: HIDROCEIIATIOII' or PHHOL, m m Isamhlo cancels, cmmmnmnh, m rm: mum lsanmc mummmamuoans fine in Min: . Grcs of Initial for Initial Acceptor Holes PtO, Pressure (p.a.i.) 305 of Hydro- genetion Phenol 0.0228 0.1175 1300 12 .h Cyclohexanone 0 .0197 O .0995 1300 8 .0 o-Cresol 0 .0191; 0 .1000 1300 13 .5 2-Hethy1cycle- hexanone 0.0152 0.0788 1300 ' 11.1 n-Gresol 0.0191 0.0985 1300 12 .7 3-Hotw1cycle- hexanene 0 .0159 0 .0819 1300 8 .5 p-Oresol 0 .0192 0 .0989 1300 12 .7 h-uethyleyele- “hexanone 0 .0119 0 .0771 1300 8 .h " Hydrogenations carried out in a 0.0h81 nl. Void Aninco Bonb in an Ethanol-Glacial Acetic Acid Solvent using M. as a catalyst . 2-netwlcyclohexanols , the stereochenical structure of the 2-nethy1- cyclehexanels resulting frc the hydrogenation of o-cresol and 2-nethyl- cyclehexanone was deternined by density and refractive index neasure- nents on the alcohols before and after distillation through a Heli kid Podbielniak celcn at 3 - Hg pressure . Heasurenent of the densities after a sinple distillation and before fractionation indicated the 19 per cent cis isoner in the hydrogenation of o-cresol was 75.21 and, in the case of 2-nethy1cyclohexanene , 77.21. In Tables 7 and '1 are shown the densities and refractive indices of the various fractions obtained by distillation using the Podbielniak colunn. TABLE V DEBIT! AID museum IIDEI W138 (I THE Z-BWIDHEXAIOL RESILTIIG PRO! THE HIGH PRESSURE HYDRO-ATM OF O-CRESOL IN AN mama-mom ACHIC ACID comm USING PtO, A8 A CATALIST FRACTIWAL DISTILLATICH WITH A HELI QID PODBIELIIAK COLUHI fi Traction weight in than n ”‘0 1).. ($11)") 1 5 .759h 1 $6147 0 .9339 2 b.7502 1.h6h3 0.93311 3 h .7156 1 .146110 0 .9326 h 3 .9861; 1 .h636 0 .9315 S 2 .3012 1 $633 0 .9298 6 1.71116 1.h629 0.9282 a) Before fractionation 9,. - c.9313 and n” - 1.1.638. TABLE VI DENSITY AND 11mm max W3 on m 2mmmnor. Insomnia FRO! THE HIC‘n‘i messiah HIDRDGEHATIOI 0F 2-METHII£TCLO- muons In All mmm-cmcm mane 1cm 30mm ‘ USING rte. AS A CATALYST FRACTIOHAL DISTILLATIOI arm A HELI cum PODBIELIIIAK comm Fraction weight in Grcs nub) Dub) 1 3 .2360 1 .héhe o .9338 2 6.2072 1.11615 0.9337 3 2 .5072 1 16112 0 .9331 h . 2.81190 1.116140 0.9332 5 3 .0990 1.14638 0.9328 6 3 .6138 1 .h635 0 .9319 7 3.7126 111631 0.9300 8 1.1097 1.11628 0.928h b) Before fractionation D30 - 0.9315, nag ' 1oh637 - , . , . y a - , - - > - ’ ' - - u - . > s , \ ,. -. .-. . . , a . . . - - . s . . * e ‘ e s o l . v - . . ,_ . . -... . - , O . .s .- -- a , . c . - -a-.-- . -. c . . .- . . - - .- . . . . . .7 . . . ' . o ’ ' . . - . I 1 . - . , H ‘ 7 - The plots of density against weight of alcohol distilled for these two hydrogenations are shown in Figure XIII. The reported values of the index of refraction and density (21,22) for cis-Z-Iethylcyclohexanol are nan - 1.h6h9 3 D30 -r0.9336 g/i1., and for trans-Zenethylcyclo- hexanol are n” - 1.14616 3 D” - 0.9.237 It is evident that the product is predominantly the cis-isouer and that approxinately the sane percentage of cis-isoaer is obtained free either o—cresol or its corresponding ketone. . The percent ketone present in the reaction nixtures at various degrees of hydrogenation are tabulated in.Tables XVIII to XII. Graphs showing the percent of ketone at various degrees of hydrogenation are found in Figures XVIII-XII. Assuring there are no interesdiates other than the respective ketones present in.the reaction nixture, the anount of alcohol present can be calculated free the hydrogen.uptake and the quantitative detenination of the ketone by the hydroxylanine hydro- chloride nethod. Since each nole of ketone forned has consuned two noles of hydrogen, the additional soles of hydrogen used divided by three yields the noles of alcohol . The noise of unreacted phenolic conpound can be obtained by substracting the stat of the neles of ketone and alcohol free the noles of originol phenolic compound. Graphs of the percent of conpononts, phenolic compound, ketone, and alcohol, at various degrees of hydrogenation.are shown in Figures XIII to XXV. The data.fcr the hydrogenation.of phenol under different conditions are shown in.Tnb1es XXII to XXVI. Figure XIVI shows the plots of these lmirogenations according to first order ldnotics. The values of the 21 rate constants obtained from these plots are recorded in Table VII. Plots of the noles of phenol ludrogenatcd against tine appear in Figure XXVII and the tines for the initial 301 of hydrogenation are listed in Table VII . The data for the hydrogenation of cyclohennone as the conditions were varied are shown in Tables XXVII to XXII. Plots of the soles of cyclohexanone ivdrogenated against tine appear in Figure XXVIII and the tines for the initial 30$ of hydrogenation are found in Table VIII . When phenol or cyclchexanone were hydrogenated at a shaking rate- of twenty-two cycles per ninute , identical data was obtained as when these coupounds were hydrogenated at the mud rate of thirty-four cycles per minute . DISCUSSION 22 DISH 3810! It had originally been planned to obtain kinetic data and infornation on the geonetrical ismerim of the products resulting fru the ludrogenation of o-cresol and Z-nethylcyclohexanone in both acidic and basic solvents. A conparison of the specific reaction rates of morogenation and of the acute of cis and trans Zaetlulcyclohexanols obtained should give intonation as ”to whether the nechanisn of hydro- genation was the sue or different in the two nedia. Unfortunately, hydrogenation of the crosols in basic nedia could not be achieved. Along the bases investigated were sodiu- hydroxide, piperidins, and —oniun hydroxide. During periods of tins of fru eight to ten hours no appreciable drop in hydrogen pressure was obtained in am of these solvents. However, in each case, it was found that if the catalyst was washed and used in the hydrogenation of a fresh quantity of o-cresel in acetic acid, hydrogenation was obtained. This was accomplished by stopping the shaker after several hours , venting th hydrogen and recovering the catalyst by filtration. The catalyst was washed with water and alcohol before returning it to the reaction vessel with the ' fresh o-cresol in acetic acid as a solvent. It thus appears that the presence of a base poisoned the catalyst but such poisoning is not pereanent since it could easily be moved fra the catalyst by washing. men the ketones were hydrogenated under sinilar conditions in the presence of mania hydroxide , a rapid drop in hydrogen pressure 23 was observed. This reductive mination took place at a faster rate than the lvdrogenation of the corresponding phenolic compounds . The course of the reductive uination can be represented as follows: NH n-un. + Q—o: 0:0; ;_-_-» Q-n-a +n.o H H Q-u-a —-—-*p: C>< NH, )1 on u The presence of cyclohexylasine and dicyclohexylanine was confined by the preparation of their twdrochloridee following fractional distil- lation of the. hydrogenation products of cyclohexanone in -oniacal nadia. since the hydrogenation of the ketonos in .oniacal solution proceeds readily, it is evident that the poisoning of the catalyst ob- served in the case of the phenols was selective. This could be explained either on the basis of the relative attraction of the base and the acceptor for the one type of active centers on the catalyst surface or by considering the catalyst to have nore than one type of active centers. It is possible that unonia is held to the catalyst by stronger forces 2h than phenols and does not pernit the latter to replace it. The Schiff base type of conpound resulting fro: the reaction of the. ketone with -onis. nu be able to replace the anonia on the catalyst, or the ketone nq react with both the mania and the fidrogen at the catalyst surface . The geometry of the active centers nay also account for the selectivity of basic poisoning. Phenols , as well as other aronatic capounds, have been found to hydrogenate only on certain types of catalysts (28), n-ely, those which have a certain geonetrical pattern of active centers . The flat wise adsorption of phenol could be pre- vented by the containation of sons of these centers by the base while a hetinine would require only two adjacent active centers on the catalyst . Since the rather extras conditions, for Adus platinu oxide catalyst, of 1300 pounds per square inch hydrogen pressure and 5060. had been used with the phenols in attenpting to carry out their hydro- genation in basic nedia, it was decided to investigate their hydrogenation in acidic nedia under sinilsr conditions of initial pressure and tenpera- ture . Under these conditions both the phenolic capoufis and their corresponding ketones were ludrogenated. Considering first the geonetrical configuration of the alcohols obtained fra the hydrogenation of o-cresol and 2-nethylcyclohexanone , it was found that in both cases approxin ately seventy-five per cent cis-Z-nethylcyclohexanol was obtained. This indicated that, in the Wdrogenation of o-cresol , the ketone occurred as an internediate . 25 The reactions involved could be represented by the following equations a ,on ,03 go 4 pt '_' ‘cs, ‘cs, "'- ‘cs, to 31%» \CH’ The specific reaction rate constants for the lvdrogenation of the | OH. OH (75%) crosols and of their corresponding nethylcyclohexanonos could not be cmpared since the ketones did not follow first order kinetics. A further indication that the ketone is an internediatc in the hydrogenation of the phenols is shown in the plot of the hydrogenation of the phenols according to first order kinetics . The initial portion of the curves, to about seventy per cent, is a straight line in every case . however , the maining portion of the hydrogenation curve shows a deviation fru this straight line. This press-ably could be due to the relatively higher concentration of the ketone than of the phenolic ccnpound at this stage of the hydrogenation as is shown in Figures XXII to XXV . The actual physical presence of the ketone internediate in the re- action ninture was shown by interrupting the hydrogenation at sixty to seventy per cent of conplotion and subjecting the reaction nixture to fractional distillation. For phenol and the three crosols a sufficient count of the corresponding ketone was obtained in each case to prepare 26 and isolate solid derivatives , thus confirming the presence of the internediate ketones . Since the rate curves for the hydrogenation of the phenols did not follow first order kinetics throughout the latter part of the hydro- genation, it was of interest to deternino the cuposition of the reaction nixture as hydrogenation progressed. Assuning the ketone to be the only stable internediate forned, the conposition of the reaction nixture at aw particular degree of hydrogenation. could be caressed in terns of noles of phenol, ketone , and alcohol. Figures XXII to XXV show that above sixty percent hydrogenation the concentration of ketone present is greater than that of the phenol. Thus, since the ketones did not follow first order kinetics, it is not surprising that the conposite curve for the hydrogenation of phenols and their ketone intern nidiates are found to deviate from first order. A conparison of the relative rates for the hydrogenation of phenol ad the crosols can be nado. The order found was, phenol 7 p-cresol - n—cresol ) o-cresol. These results can be accounted for fru a con- sideration of steric hindrance. This nay be of two types. First, the steric hindrance between the catalyst and the adsorbed nolecules , and, secondly, steric hindrance of the type which interferes with the approach of Mdrogen nolecules to the catalytic surface. In the first instance, flat adsorption of the bensene ring requires that the nolecule find an area on the catalyst which has sufficient sise and suitable spacing of the netallic atons . Substituents on the benzene ring would be expected to decrease the possible nunber of areas where the nolecule could be 27 adsorbed. Adjacent substituents have been found to decrease the rate of hydrogenation to a greater degree than the sane nunber of nonadjacent substituents (7). The second type of steric hindrance night be inportant in govern- ing the rate, since the hydrogen nust pass through the substituents which extend any fro. the catalytic surface following adsorption of the acceptor, in order to be adsorbed and subsequently react. The rate I. at which hydrogen is adsorbed on the catalyst nay be rate deternining fer the qurogenation process. This would be in line with first order rate dependence on hydrogen pressure. In order for the internediate ketone to be isolated, the partially Wegenated phenol nolecule'nust have left the catalyst surface. Since the ketone nust then be readsorbed on the catalyst for the final stage of the hydrogenation, steric effects could cone into play at this point. The hydrogenation of the ketone can be pictured as involving daprption of the carbonyl group only. Here again, an ortho substituent could hinder the approach of the carme group to the catalyst surface. This effect would not be as peat in the adsorption of the 3- and h- ntlwlcyclohexanones. lines the btones did not yield straight lines when plotted accord- ing to first order kinetics, the rate constants could not be obtained. In order to have a basis for the conparison of the relative ease of hydrogenation of the ketones, the tine required for the initial thirty per cent of hydrogenation was detenined fren plots of the noles of ketone hydrogenated against tine. The relative order found was, 28 cyclohenanone ) h-netlwlcyclohexanone ) 3-nethylcyc1ohexanone > 2-nethyl- cyclohexanoue. hen the she conparison, that is, tine required for thirty per cent hydrogenation, was applied to phenol and the crosols , the she relative order as that obtained by conparison of rate constants resulted, as is shown in Tables III and IV. The effect of varying the conditions in the hydrogenation of phenol provides evidence that the hydrogenation of phenol follows a first order rate expression for approxinately three-fourths of the Wogenation. As is shown in Table VII, decreasing the mount of acid by one half had no appreciable effect on the tine required for the initial thirty per cent of the hydrogenation and no effect on the rate constant .' when the count of catalyst was increased or decreased, there were changes in both the tine and'rate constant in all cases in the expected direction. Decreasing the initial hydrogen pressure by a factor of tee approxinately doubled the tine required while the rate constant renained unchanged. Decreasing the concentration of acceptor by a factor of two had no effect on the rate constant and the tine required was halved. The hydrogenation of phenol can thus be considered to be independent of the concentration of acid used, proportional to the mount of catalyst used, independent of the concentration of the acceptor, and first order with respect to hydrogen pressure . 1.. effects of changing the conditions in the hydrogenation of cyclohexenene follow the sue pattern as with phenol except in the case where the initial hydrogen pressure was halved as shown in Table VIII. An increase in the tine required for the initial thirty per cent of 29 hydrogenation was noted but the increase was considerably less than a factor of two as was found in the case of phenol. Since cyclohenanone did not follow first order kinetics during the hydrogenation, this deviation is not surprising. It should be noted that all the data for the hydrogenation of the phenolic conpounds represents the composite effects of the two stages of hydrogenation taking place sinultaneously. Variations in the data fron what would be predicted for a single step hydrogenation which follows first order kinetics nay be attributed to this fact . 30 1. Specific reaction rate constants have been deternined for the high pressure hydrogenation of phenol and the three isoneric crosols using platinun oxide catalyst. 2. The tine required for the initial thirty per cent of hydrogenation of phenol, cyclohexanone, the three isoneric crosols, and their corresponding nethylcyclohexanones have been deternined . 3. The hydrogenation products of o-cresol and 2-nethy1cyclohennone were shown to have the sue ratio of cis-2-netmlcyclohoxanol to trans-Z-nethylcyclohexanol. In both cases the Ivdrogenation products contained seventy-five per cent of the cis isoner. h . Ii'he presence of an internediate ketone in the hydrogenation of phenol and the three isoneric crosols was confirned by the prepara- tion and isolation of solid derivatives of the corresponding ketones in each case. In addition, the concentration of the ketone throuuzout the hdrogenations was deternined quantitatively. The hydrogenation of the phenolic conpounds investigated were thus shown to undergo hydrogenation in a step-wise nanner. 5 . It was concluded that the ketone internediates did not follow first- order kinetics under the hydrogenation conditions investigated. 31 6. The deviation fra first-order kinetics for the phenolic conpounds investigated as hydrogenation progressed was explained on the basis of a higher concentration of ketone than of phenolic conpound in the reaction nixture in the final phase of hydrogenation. WIVES CITE 32 LEW CITED ven H. Bebus, Ann., E, 200 (1863). 2. . Translation by E. E. Reid, Catalgsis in Organic Chuistg, Van e, 2 loatrand Co., New Iork, N. I R. Ad‘s, V. Voorhees, and R. 1.. Minor, Organic gatheses, Collective Vol. I, p. 1152, John 1Wiley and Sons, New Iork, N. 1., 1932. V. N. Ipatieff, CatalQic Reactions at Rig Pressures and Tapere- tures, Hacnillan, ew ork, . ., . %. 1'.)Arnstrong and T. P. Hilditch, Proc. Roy. Soc., 100A, 2110 1921 . a. Adan and J. a. Marshall, J. Al. on... Soc., 29, 1970 (1928). a. A. sum, n. n. Aldernan, and r. w. Nadig, gag” g1, 272 (191:5). a. A. sum and a. r. H. Pennekasp, 9g” 3’31, 276 (19145). . H. A. saith and s. r. H. Penneknp, gay}... 91, 279 (191:5). R. a. Baloer and a. n. Schuets, 3:39., Q, 1250 (191.7). a. A. c. Bough, H. Hunter, and J. Ieryon, J. Chen. Soc., 1123, 2052. L. 14. Jackson, A. x. Macbeth, and J. A. 11111:, gig” £232, 171?. K. Innoto, J. Chem. Soc. Japan, fig, 1151 (1939). o. Vavon, A. Perlin, and A. Korean, Bull. soc. em.” 5;, 6m. (1932). A. sum, H. Hauber, and R. Schonfelder, Ann., 52;, 1 (1923). a. w. Van Dolah and w. a. Erode, Ind. Eng. Chen., 2, 1157 (19117). A. I. Macbeth and J. A. 11111:, J. Chen. Soc., 709 (1916). L. P. Fieser, $grinents in Organic Chemistry, Part II, Heath and Co., New York, . ., , p. 3 8. 33 19. L. T. Sandhorn, Organic mtheses, Collective Vol. I, Second Edition, 3110, John Viley and Sons, New ork, N. I., 19111. 20. N. A. Lange, Handbook of Chuistlz, Handbook Publishers, Sandusky, Ohio , Seventh ition, 9. 21. P. Angiani and R. Cornubert, Bull. soc. chin., 13, 359 (1915). 22. P. Ansiani and a. Cornubert, Coupt. Rend., £12, 71 (191.11). 23. N. D.'Cheronis and J. B. Eniriksn, Seninicro Qualitative Or anic Analysis, Thonas I. Crowell 00., New: York, N. 1". ,"I§Ii7"."" '5' "' 211. I. H. Heilbron, H. H. Bunbury, and V. E. Jones, Dieti§n£¥ of Organic Conpounds, Vol. II, Oxford University Press, ew ork, N. I., 25. x. N. c-pben and B. x. Calpbell, Chen. Revs., 21, 77 (191.2). 26. K. a. Stone, Determination of Organic Compounds, p. 95, unpuhlished nanuscript. 27. A. A. Pavlic and a. Adkins, J.'A-. Chen. Soc., 29.» 11171 (19116). 28. A. A. Balandin, Acta Phys. Chin., 3g, 81 (191.7). APPENDIX 3h on 9: ~.o 83 3.3.0 30.0 a. K n. a a. o omn 2.3. o 836 9.: we ~.o 82 $36 33.0 hm fins «.o 83 83.0 886 1.13 in do 82 3.36 28.0 .3: had «6 89 3.3.0 236 333% «on 133 A73 a .38”: 33 3:3 fin}: tan-note nor. H83.— toe n35: dofifiefi n 73.6 «o :B non-.6»: wanna do tars no Bean 5 2.: maHaHonu mum. wand» me 985 E48 364 Brand aging : 2H Ennis; 4 m4 nefm can: 86m ODE—”:4 Rho» .9: H6: 4 HH 9% .3 iguana—saga 50 an HEB. ASHEHH mun ah awn—”Dad an. a: 9.54.3200 ”94m non—“92mm CHE—”g Ea.“ 35 «. a u. o coma mane. 0 $8. 0 on «.0 one name... 386 on” «.o 82 2.36 385 o... «.0 82 8.36 Rand a.» do 8...." mama... 386 o. a N. o 82 man o. o 58. o confinement»: 32 0.334 Affiadv 23an «com oncogene—Homo «R 3.55 .3 13.5 no :3 again H333 no 28.5 .8 San: 1 .3..an 5 E 558 ES BER 3§2§E .2 E .6542... a we .3." can: 93 8B5 fies :5 an; 4 2H unanEnSBo .8 8:45; mZOHaanoo E can—Hab .3 BEE 50 E HEB aha—AH mum. mon— aag EB and. man—mac NE non—”Boa nun-Hahn HHH> H.349 36 TABLE II Cyclehenne High Pressure 0.0391; Holes 0.1000 3. no, ' 0.5 ll. of acetic acid Tins Temperaxure Pressure Log (Minutes) (Degrees c.) (p.s.1.) Po/p 0.0 23 1300 .. 1.0 23 1135 -- 1.5 2h * 1115 .. 3.3 2h 1095 -- 20.6 23 985 -- h7.5 23 980 - 62.3 23 980 -- TABLE I Phenol High Pressure 0.0228 Holes 0.1175 g. M, 0.2 .1. of acetic acid, 0.8 ll. of ethyl alcohol Holes (So-pd. Log “rile Temperature Pressure (Minutes) (Degrcss c.) (p.s.i.) Hydrogenated Po/P 0.0 so 1300 .0000 .000 2 .8 so 1255 .0018 .015 7 .1 51 1195 .00h2 .037 10.2 50 1155 .0058 .050 1h.8 50 1095 .0081 .075 17.8 51 1055 .0097 .091 21.1 51 975 .0120 .116 35 .S 50 855 .0176 .182 as .3 50 795 .0199 .211: 52 .2 50 775 .0207 .225 38 TABLE II Cyclohexsnone High Pressure 0 .0197 H0]... 0 .0995 x. m. 0.2 ml. of acetic acid, 0.8 :1. of ethyl alcohol Tile Temperature Pressure Holes Colpd. Log (Minutes) (nap-«s c.) " (p.s.i.) Hydrogenated Po/P ‘ 0.0 so ‘ 1300 * .0000 .000 1.6 50 1285 .0018 .005 3.0 so .1275 .0029 _ .008 6.9 so 1255 .0052 .015 11.6 50 1235 .0075 .022 16.1 50 1215 .0099 .029 23 .6 50 1195 .0122 .037 33.2 50 1175 .0185 .0111; 57.5 50 1155 .0168 .050 39 TABLE III o-Oresol High Pressure 0.01917 Holes 0.1000 g. PtO, 0.2 ll. of acetic acid, 0.8 ll. of acetic acid I“ 613‘...) {$333) {:33 3:313:33. :77 o .o % so 1300 .0000 .000 1 .9 50 1275 .0010 . .008 9 .2 51 1195 .0011 .037 11: .7 50 1135 .0061: .059 23 .6 50 1th .0098 .095 28.7 50 990 .0113 .112 36.6 50 965 .0129 .129 82 .8 1.9 985 .0137 .138 1.6 .0 50 935 .0180 .183 52.0 50 915 .01116 .153 60 .8 50 895 .0156 .162 116.5 - 50 815 .0187 .203 TABLE XIII ho ‘ M Sfié‘z’fifimm“ 28.373. 0.2 ll. of acetic acid, 0.8 ll. of etml alcohol Tine T-psrature Pressure Holes (So-pd. Log (Hinttes) (Degrees 0.) (13.8.1 .) Hydrogenated Po/P 0.0 50 1300 .OCDO .000 1.0 50 1295 .0006 .002 2 .h 119 12 85 .0017 .005 5.5 50 1275 .0028 .008 8 .6 SO 1265 .0080 .012 13 .8 50 1255 .0051 .015 18 .3 50 12145 .m62 .019 31 .h 50 1225 .GJBS .026 172 .0 50 1215 .016) .029 58.8 50 1205 .0107 .033 TABLE XIV I-Cresol High Pressure 0.0191 Holes 0.0985 3. no. 0.2 ll. of acetic acid, 0.8 ll. of ethyl alcohol 031:1.) €3.33?) 533:3 3:63.523; 32% 0.3 50 1 I 1m I .0000 .000 1.3 50 1285 .0006 .005 5.3 50 1235 .0025 .022 10 .1 51 ‘ 1175 .0011? .0171; 17 .0 50 , 1095 .0078 .075 26 . 8 50 985 .0123 .121 30.1 50 955 .0131 .1313 35.0 50 915 .01h6 .153 39 .0 50 895 .0153 .162 H; .6 £9 875 .0161 .172 TABLE“ 3-Hetlv1cyclohexanone High Pressure 0.0159 Moles 0.0819 :. P002 0.2 :1. of acetic acid, 0.8 .1. of ethyl alcohol (23:...) $3353?) 32:23 333.5338 :52 0 .0 50 1300 I .0000 .000 0 .9 SO 1295 .0006 .002 2 .2 50 ‘ 1285 .0017 .005 8.2 50 1275 .0029 .008 6.3 50 1265 .0010 .012 12.6 50 121.5 .0063 .019 19.0 50 1225 .0085 .026 27 .8 1.9 1205 .0108 .033 30.0 SO 1195 .0119 .037 03 TABLE XVI p-Cresol 1119 Pressure 0.0192 Holes 0.0939 8. PW; 0.2 ll. of acetic acid, 0.8 ll. of ethyl alcohol Tile Tesperature Pressure Moles 00-pd. Leg (Minutes) (Degrees C.) (p.a.i.) Hydrogenated Po/P 0.0 50 1300 .0000 .000 3.6 51 1255 .0017 .015 6.9 50 » 1215 .0033 .029 15.1 50 1115 .0071 .067 22.3 h9 1035 .0102 .099 32.6 50 935 .0180 .1h3 39.8 50 895 .0156 .162 86.1 50 875 .0163 .172 50.2 h? 865 .0167 .177 58.0 50 855 .0171 .182 TABLE XVII h-Hetfilcyclohexanone High Pressure 0 011.9 H0108 0.0771 g. 280, O .2 ll. of acetic acid, 0 .8 11.0! ethyl alcohol Tine Tuperature Pressure Moles COIpd. Lo (Minutes) (Degrees C .) (p .s.i.) Hydrogenation P07? 0.0 50 1300 .0000 .000 0.9 50 1295 .0006 .002 2 .1 50 1285 .0018 .005 11.7 50 1275 0030 .008 7.6 50 1265 .OOhZ .012 11.1. 50 1255 0051 .015 13.1: 179 121.5 0066 .019 19 .3 50 1235 0076 .022 28.1 50 1225 .0089 .026 29 .2 50 1215 0101 .029 36.8 50 1205 .0113 .033 hS o. N m. 1. H. 5 flow N. am .33 a. 3 1.. Q. o. s o. OOH Awoos. Soc. mm 8. .38. $8. 2.8. 3.8. 83. 38. mag. .15. GE ~43 6.4m «.3 «.3 .19” mg. m.n 0.6 o.- .n. R a. R 4.2 m.mn lawn «.mm 0? 9m 0.0 2. 8 om 9.. on om S O H0025 H0005 Hoaonoaoho Hoasxgoapho econsngoaeho econ-Honoacho neavcdouoavhm «0 000003 me 050: no accouem mo neaox no 950.3.” me «one: £3000..." HHE H.349 146 9m «.88. 9% $8. 8.5 .38. 8 a. n ««8. N. «m «do. o. R 88. 8 BA #8. «.3 88. «.R «:8. 2. «.3 «moo. p. R 38. a. o: 88. 8 «.8 2.8. n.«« 28. «.3 88. cm a. S «moo. m. m." onoo. H. R «poo. 3 m. 8 E8. «.3 28. «.~.« $8. on «.2. 28. «.8 «H8. 8.8 28. o« o. 8 88. p. H «80. «. «H .38. S c.8H .38. o. o 88. 0.8 88. o H3955 H3805 Hogonoaoho Hoanonotho 30:50:08th onoaonoapho noupanowonchm .3 p805 no 88: Abaoz.« Absozu« -8332 -«P»o¥« 8588 no .2393.“ no nado: no .5023 Ho :82 H—H 5mg. h? m. p 38. 4.3 88. as 28. o. R 4 o. «a £8. m.8 58. 8.2. 38. o.8 n. ma mnoo. m. 3 «30. H. mm 38. o. 2. 3: $8. «.3 £8. m. um 88. o.8 9% 2.8. .33 38. QR $8. 0.8 m. om R 8. o. «a 28. a. on G8. o. 3 n. we 33. n. ma $8. . m. «N 28. o. on m.i. 33. fig :8. mda «moo. o. 8 a. mm .68. n. N :08. h. .9 38. o. 3 o. 2: R8. o. a 080. o. o 08. o. c ‘ H395:- Houonous Hog-noaoho agonoaoho onouuHonoduho ongonoaoho noawunowohfim go 283m mo 8?: 4.3»..ng -13»me Ahapozum cafiaomun 3.88 no 9523 ma «0?: , no .2825" «0 undo: NH Handy. h8 we 38. m.8 88. 0.3 $8. 8 m . «H :8. e. 3 :30. a. «m .38. 8 m. 2” R8. a. 3 :80. a. an 88. 2. m. cm mmoo. 0. sm «So. a. an .38. 8 9.3 2.8. .3m 88. 0.8 .38. om o. «m 88. a. mm 38. a. fi 38. 2 H43 88. Sh #8. «.3 $8. on 0.2. .33. 9m 38. fima $8. 8 o. S $8. a. a m8o. a. o 38. 3 o. 02 «So. o.o 88. . o.o 88. o acaohoum Hononuun 8333.63 Hogxonoaoho 23530."th «nan-Honogho aoapunomguhm mo 2.9:; 8 3?: $332.: 45.2.: Assisi 432?: 3.28 no 430.8." Ho no.8: no £80qu no nado: E Han. h? TABLE XIII Phone]. . High Pressure 0.0228 H0108 0.1175 g. PtO, 0.1 .1. of antic acid, 0.9 I1. 0! “.le alcohol (23.2.3...) 'fmfi?) 8°35? 3335335.. 337!» 0 .0 50 13m .0000 .000 1.2 so 1285 .0006 .005 3.0 50 1255 .0018 .015 1.. 3 51 12 35 .0026 .022 7.0 51 1195 .oohz .037 10.0 50 1155 .0058 .090 13 .5 50 1115 .0073 .067 16.7 50 1075 .0089 .083 19 .8 1:9 1035 .0105 .099 23.0 50 995 .0120 .116 28 .5 _ 50 935 .01).). .110 35.6 so 875 .0167 .172 TABLE XXIII Phenol High Pressure 0.0228 m1.- 0.2350 3. 200. 0.2 :1. of uotic acid, 0.8 ll. of 01;th alcohol Tine Imam-afar. Pram H0100 COIPd. Log Camus) (nap-cos c.) (p.a.i.) Hydrogontt’ad Po/P 0.0 so 1300 .0000 .000 0.9 50 1285 .0006 .005 1.9 50 1255 .0018 .015 2.7 50 1235 .0026 .022 5.1 51 1195 .0002 .037 7.8 SO 1155 .0058 .050 10.7 50 1115 .0073 .067 13.8 50 1075 .0089 .083 16.8 50 1035 .0105 .099 19.7 50 995 .0120 .116 2h.5 50 935 .01“: .110 29.5 SO 275 .0167 .172 TABLE HIV Phenol . High Prccalrc 0.0228 HOIOI 0.0588 3. 21.0, 0.2 :1. of acetic acid, 0.8 ll. of cthyl dcohol 02.28.) {fig-”3‘53 3°37? 1333:3338 :79 0.0 50 1300 .0000 .000 1.1 50 1285 .0006 .005 3.3 50 1255 .0018 .015 5.0 50 1235 .0026 .022 8.0 51 1195 .0002 .037 12.2 50 1155 .0058 .050 15.9 50 1115 0073 .067 19.2 50 1075 .0089 .083 23.9 50 1035 .0105 .099 31.7 50 955 .0136 .131. 38.3 50 895 .0160 .162 52 TABLE :17 31.13328 Holes gffigz'm, 0.2 :1. of acetic acid, 0.8 :1. or ethyl alcohol (xi-.13..) {333333) {:33 $35351 11137: O .0 50 650 .0000 .000 h .2 50 615 .0011. .021: 6 .h 50 595 .0021 .038 9.7 50 575 .0029 .053 12 .3 h9 555 .0037 .069 15 .7 50 535 .0005 .085 19 .0 50 515 .0052 .101 23.1 50 895 .0060 .118 30$ 50 1155 .0075 .155 82 .1 50 395 .0099 .216 TABLE nu Ph0ncl High Pressure 0.0111. Holea ~ 0.1175 ;. PtO. 0.2 :1. of acetic acid, 0.8 nl. of ethyl alcohol £33..) 8:213:85?) ““6333?” $353381 3:}. 0 .0 50 1300 .0000 .000 1 .6 50 127 5 .0010 .003 1.1 so 1235 .oozs .022 6.0 50 I 1215 .0033 .029 8 .9 50 1175 .0003 .0“! 11.7 so 1135 .0051. .059 15 .1 119 1095 .0079 .075 17 .0 SO 1075 .0037 .083 19 .5 5° 1055 .0095 .091 TABLE nvu Cyclohexanone High Pressure 0.0197 H0108 0.0995 7:. P10. 0.1 ll. of acetic acid, 0.9 .1. of etiql alcohol (1:21.) €519.33?) ‘°“2:1..‘.’if3"““ 38:25:22.; it}. 0.0 50 1300 .0000 .000 1.7 50 1285 .0018 .005 3.1 51 1275 .0029 .008 7 .2 51 1255 .0052 .015 11 .8 SO 1235 .0075 .022 16.1: so 1215 , .0099 .029 211.0 50 1195 .0122 .03? 3h .1 50 1175 .01h5 .0111: 119.3 50 1155 .0168 .050 TABLE m1 Cyclchenncns High Pressure 0.0197 Holes 0.1990 3. PW. 0.2 .1. acetic acid,-O.8 I1. of ethyl alcohol Actual Pressure Holes Comd . (11:11:00 $353?) (11.: .1.) Hydrogenated :79 0.0 50 1300 .0000 .000 1.2 50 1285 .0018 .005 1.7 50 1275 .0029 .008 3.11 50 1255 .0052 .015 5 .6 50 1235 .0075 .022 9 .1 SO 1215 .0099 .029 13.7 50 1195 .0122 .037 18.7 50 1175 .0105 .0“; 25.2 50 1155 .0168 .050 56 .0105 TABLE mx Cyclchexanene High Pressure 0.0197 Holes 0.01198 3. H0. 0.2 .1. of acetic acid, 0.8 :1. of ethyl alcohol The Taperatnre Actual Pressure H01- Coupd. Log (Minutes) (Dsgress c.) (15.: .1.) Hydrogenated Po/P 0.0 50 1300 .00“) .000 1.? 50 1285 .0018 .005 3.3 50 * 1275 .0029 .008 ll .0 119 1255 .0052 .015 20.2 50 1235 .0075 .022 28 .8 SO 1215 .0099 .029 113.9 50 1195 .0122 .037 50.6 50 1185 .0133 .0110 58 .0 50 1175 .0011 57 TABLE III Cyclohexancne ‘ High Pressure 0.0197 1161.- 0.0995 g. 900, 0.2 ml. of acetic acid, 0.8 nl. of ethyl alcohol (132“) @5323?) “’“(Sfl’lfim' $33333; {-7375 0.0 SO 650 .0000 .000 A 1.h 50 635 .0017 .010 5.11 50 615 .0011 .021. 11.2 50 595 .0060 .038 17 .17 51 575 .0087 .053 25.2 50 555 .0110 .069 35 .1 50 535 .0131: .035 1411.5 50 515 .0156 .101 58 TABLE m1 Cyclohexancne High Pressure 0.0099 Moles 0.0995 8. P150, 0.2 :1. of acetic acid, 0.8 :1. of etlwl alcohol Tile Temperature Actual Pressure Holes Coupd. Log (Minutes) (Degrees c.) (p.s.1.) Hydrogenation Po/‘P 0.0 50 1300 .0000 .0“) 1J4 50 1285 0018 .005 14.5 50 1275 .0029 .008 7.5 51 1265 .00141 .012 12 .9 50 1255 0353 .015 18 .1 SO 1205 .0061; .019 26 .0 SO 1235 .007 6 .022 36.11 50 1225 .0087 .026 .9: magH I>n.;<_2n_orn%!$ezn 0 33A 3 £5.16“ 1|...» o_ .0 v£ wr cw A00 ~99“ Inlaoaazflfo: 0+. $70,021 0 ._m o ..e A. p._p 004 0 I. bu. o 0 33A ‘5 Es’hsllv o m R .3. Nb. (O .ouc .09: .2” ~__, 139. p Log fix“. E. tckuownawfiaz ca wugn+rin<\n4xsxes Weigh-f a{ DIE'H”R‘£C In grams ""9 F G B v.33: I+ €033: banana” 0..” Iekfifiwmxl+sv3 O 0 0m V303“: O f m o h v; n X C h :o. c Q. 0 tr 0 .T n c m 5 P O \Dmfimflan‘..\. t‘Q‘oUQJHXSS I. O v.0 £0 60 $0 u? N: 5 PCI'CCIH' OF Z'Mcffiy/Cyclohcxahone -—) thNN $2.21 .fi $313.- fitnbLXu-Zpoin 7+ <5..an Canaan O .. a— 0“ I‘lWOQQS'Ago! 0‘” o n.1nv \Ufifinnsl 0* I<&~.oon39.x~oz Illv m0 no #0 NO Na u: .N Percen-f 0F 3- Me'th/Icyclohexa none ---> .59 NM 3323. c.” «(31.211 fi “sQ.NN.I—H bdfinflS.‘ 0+. nogxuoanz‘d, a ’+ an*r4_nafl+74~nnxwzoxa w» 9711.qu V40 (Pa .nnp . d p o c u n e 7 .ouo n d Mr ... c n c n 0 a l x e A ’0 b o 0 CK I. .23 a u... by?! figs)” W a; D 4......AE p \p\ . .fivvF NH \ 0 Axfizflg R . Aliza E D fining I giving 41:80 ‘3 338.59. IIV fl h. ‘0 G. M0 VITA Nae: Arthur F. Miller Born: November 15, 1925 in Alhtabula, Ohio Acadenio Cat-«r: Anhtabnln High School, Aahtahula, Ohio, 19110-1910 Bowling Gram State University, Bowling Orton, Ohio, 19116-1950 Michigm State College, But Lansing, Michigan, 1950-1953 Degree: field: B. 3. Bowling Green State University, 1950 u; b‘ . - i . - Q J “I . '.. ma? r ‘« 9".rg-"v-‘zuk1s‘ .- .“1'J‘ " . ' 1 ‘- {4'5" ' . ' 5 0 fr, at: o " U :" ‘ l‘" ‘. . ' . r r .. _, .7 f r. "‘9 . ‘0 I ‘ if“ 3?. v A . Ar «If, _- 7‘s- ' «"5 "3* r o . e4 ‘ 5 'fi . 'Y — o i ‘ \- l I- ‘ :1 o‘l‘ . A v ‘ 5",‘1". ' NJ - I . . - ' ‘ - lllllllli‘ 32