THE CATALYTIC REDUCTION OF 
 PARA DIMETHYLAMINOPHENOL 
 
 BY 
 
 HERMANN CONRAD NIES HECKEL 
 
 B.S. University of Illinois, 1921 
 
 THESIS 
 
 SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS 
 FOR THE DEGREE OF MASTER OF SCIENCE IN CHEMISTRY 
 IN THE GRADUATE SCHOOL OF THE UNIVERSITY 
 OF ILLINOIS, 1922 
 
 URBANA, ILLINOIS 
 
UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 May 27 192^. 
 
 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY 
 
 s u PERVI SION BY Hermann 0 oni^cL Hies Eec^ksl 
 
 ENTITLED „ JLe__(^tal3ry,c ReMati p-JDimatliylaininoplienol . 
 
 BE ACCEPTED AS EULFILLING THIS PART OF THE REQUIREMENTS FOR 
 
 THE DEGREE OF 
 
 in Chemistry 
 
 Recommendation concurred in* 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 ^Required for doctor’s degree but not for master’s 
 
 ^:990f>-3 
 
i 
 
 
 aiuc 
 
 Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/details/catalyticreductiOOheck 
 
I wish to express my sincere thanks and 
 appreciation to Professor Roger Adams for the sug- 
 gestion of this problem and for the interest shown 
 therein. 
 
TABLE OF CONTENTS 
 
 ■ 
 
 Page 
 
 I. INTRODUCTION 1 
 
 II. HISTORICAL PART 1 
 
 III. THEORETICAL PART 5 
 
 IV. EXPEREJEI^’TAL PART 8 
 
 A. Preparation of Catalysts 8 
 
 I. Colloidal Platinum 8 
 
 II. Platinum Black 9 
 
 a. Method of Feulgen 9 
 
 b. Sodium Nitrate Fusion 9 
 
 B. Preparation of p-Dimethylamino phenol and Hydrochloride 10 
 
 C. Preparation of Acetyl-p-dimethylaminophonol 10 
 
 D. Reduction Experiments 10 
 
 I. With p-Dimethylamino phenol 10 
 
 a. Colloidal Platinum 10 
 
 b. Platinum Black 11 
 
 II. With p-Dimethylaminophenol Hydrochloride 11 
 
 a. Colloidal Platinum 11 
 
 b. Platinum Black 12 
 
 E. Description of Products 12 
 
 I. Dimethylamino cyclohexane 12 
 
 II. p-Dimethylaminocyclohexanol 13 
 
 V. SUIvmRY 14 
 
 VI. BIBLlOGRilPHY 15 
 
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 The object of this investigation was to develop a suitable method 
 for the preparation of dialkylaminocyclohexanols. 
 
 The plan ?;as to prepare these alcohols and then condense them with 
 acid chlorides to give the esters of benzoic and p-aniinobenzoic acids. These 
 aminoalcohols, being aliphatic in nature, should produce esters v/hich possess 
 local anaesthetic properties, due to the similarity in structure v;ith cocaine 
 and novocaine. 
 
 This report, hov/ever, v;ill deal only with a study of the preparation ofp- 
 dimethylaminocyclohexanol by the catalytic reduction of p-dinethylaminophenol . 
 This aminoalcohol has not been prepared before, so that it is of interest to 
 learn its physical constants. 
 
 L. Brunei (l) prepared o-diethylaminocyclohexanol by the action of diethylamine 
 on the oxide of o-cyclohexanediol, the reaction proceeding as follow’s: 
 
 It is hoped that within the next year the ortho, meta and para 
 
 dimethylaminocyclohexanols as v;ell as the diethyl derivatives will be prepared. 
 
 II. HISTORICAL PART 
 
 To date, only one dialkylamino cyclohexane 1 has been prepared. 
 
 By similar reactions he also prepared o- amino cyclohexanol and o-ethylamino- 
 
 cyclohexanol, using respectively, ammonia and ethylamine. 
 
1 . 
 
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- 2 - 
 
 Osterberg and Kendall (2) also prepared o-diethylaminocyclohexanol. 
 They, however, dehydrated cyclohexanol and obtained tetrahydrobenzene. To 
 this they added hypo chlorous acid giving o-chloro cyclohexanol, v/hich was then 
 condensed v/ith diethylamine to give the desired compound. 
 
 In 1894 Moyes and Ballard (3) studied the action of nitrous acid 
 on alkylarcines. From 1.4 diamino cyclohexane they obtained p-amino cyclohexanol. 
 
 Skita and Rolfes (4), by means of colloidal platinum, reduced 
 acetanilide, phenacetin and the acetotoluides to the corresponding acetylcyclo- 
 hexyloniines. Anisidine and phenetidine in the presence of hydrochloric acid 
 gave both cyclohexylamine and dicyclohexylamine, the ethereal group being 
 readily removed. 
 
 These authors also reduced the three aminophenols in the presence 
 of acetic and hydrochloric acids. From the meta and para compounds they ob- 
 tained both the mono- and dicyclohexylamines . With the ortho isomer, however, 
 they also obtained dodekahydrophenoxazine, which probably results from the 
 condensation of tv;o molecules of o-tuninophenol and the subsequent reduction 
 
 of the condensation product. 
 
 
 
 
 
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 These investigators did not attempt to stop at the aminoalcohol stage, but 
 continued the reduction until the theoretical amount of hydrogen, necessary 
 to carry the reduction to the cyclohexylamine stage, had been absorbed. 
 
 In a previous paper, Skita (5) observed that in reducing aniline 
 by nesjis of colloidal platinum in acetic acid solution, he could control to 
 some extent the formation of the mono- and dicyclohexylamines, thru the ad- 
 dition of hydrochloric acid. The yield of mono cyclohexylamine is thereby 
 
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 increased. 
 
 As regards the hydrogenation of phenols by means of platinum to 
 the cyclohexaiiol derivatives, not much work has been done. Vavon and Detrie 
 (6) reduced phenol in glacial acetic acid solution using platinum black as 
 the catalyst. They found that the reduction proceeded very readily. Hovirever, 
 only a sixty-six percent yield of cyclohexanol was obtained, the remainder 
 being further reduced to cyclohexane. These investigators further observed 
 that the masking of the phenolic group, 8,s for example, the formation of ^ 
 ether, exerted a restraining influence upon the speed of the reduction. Ex- 
 periments in this laboratory have shown that by means of platinum black, pre- 
 pared by the fusion of chlorplatinic acid with sodium nitrate (15), phenol 
 could be hydrogenated in alcoholic solution to give a theoretical yield of 
 cyclohexanol, the hydrogen being absorbed very readily. 
 
 Further literature on the reduction of the benzene nucleus is very 
 meager. In 1^12 V/illstatter and Hatt (7), using platinum black, reduced ben- 
 zene, toluene and durol to the hexahydro derivatives. They also reduced phenol, 
 obtaining results which are comparable to those of Vavon and Detrie, mentioned 
 above. With aniline, Willstat ter obtained a mixture of the mono- and dicyclo- 
 hexylamines. 
 
 Skita and Meyer (8) reduced the benzene nucleus in benzene, toluene 
 and benzoic acid thru the use of colloidal platinum. In reducing aromatic 
 aldehydes, Skita and Brunner (9) observed that the reduction did not stop at 
 the alcohol stage, but continued to the saturated hydrocarbon, the benzene 
 nucleus being reduced as v/ell as the alcohol group. Thus cinnamyl aldehyde 
 gives both cyclohejcylpropane and cyclohexylpropyl alcohol. 
 
 Willstatter and Jaquet (10) in I 9 I 8 , published a paper concerning 
 the hydrogenation of aromatic compounds by means of platinum containing oxygen. 
 

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 They observed that in reducing phthalic and naphthalic anhydrides by the use 
 of platinum black, the absorption of hydrogen stops after only a short time. 
 
 The fact that the reduction begins at all seems to be due to the presence of 
 oxygen in the fresh catalyst. Their experiments indicate that the tv;o cata- 
 lysts; namely, platinum containing oxygen and the same free from oxygon, are 
 possessed of widely different characteristics. Thus, by the frequent loading 
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 naphthalic anhydride and phthalimide v/ith ease. 
 
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 hours, they were unable to reduce even such easily reduced compounds as the 
 olefines. Hov/ever, the need of oxygen in reductions seems to be dependent 
 upon the ease of reduction of the substance in question. Thus, for the reduc- 
 tion of an olefine, the catalyst need not possess nearly so much oxygen as 
 in the reduction of a benzene nucleus, due to the fact that the latter is so 
 difficultly reduced. With such difficultly reduced substances, the oxygen 
 content of the catalyst is very quickly depleted, 
 
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 tion as due to the formation of a peroxide with the metal bivalent and then a 
 combined hydride and peroxide with the metal quadrivalent, thereby effecting 
 the transfer of the hydrogen. The following equations show the probable re- 
 lations; 
 
 As the hydrogen is split off, some oxygen is also removed in the form of v;ater, 
 thus accounting for the v;ell knov/n fact that the catalyst slov/ly becomes in- 
 
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 Skita (12) doubts the above mechanism due to the fact that in 
 hydrogenating aromatic compounds by means of colloidal platinum, oxygen was 
 found to be unnecessary. This investigator shook colloidal platinum in an 
 atmosphere of hydrogen for thirty hours, as V/illstatter had done v;ith platinum 
 black. Whereas Willstatter found his preparation was inactive, Skita observed 
 that his v;ould reduce phenol to cyclohexanol, Willstatter also observed that 
 his active catalyst would set iodine free from iodides due to its oxidative 
 properties. Skita, thereupon, added potassium iodide to a preparation of col- 
 loidal platinum, thus being assured of an oxygen free catalyst. At ordinary 
 temperatures this catalyst proved inactive, but upon heating to 50-60° C, the 
 reduction proceeded, but only one-eighth as fast as normally. These facts led 
 Skita to believe the possibility of some other mechanism than the one mentioned 
 above. He does not, however, claim to have proven that the above mechanism 
 does not hold. 
 
 III. THEORETICAL PART 
 
 The only method v/hich seemed at all promising for the preparation 
 of this series of dialky lamino alcohols, especially as regards the preparation 
 of the meta and para derivatives, vras the catalytic reduction of the corre- 
 sponding dialky laminopheno Is thru the use of the platinum metals. 
 
 The only reported reduction of aminophenols led to the formation 
 of mono- and dicyclohexylamine and in addition, in the case of the ortho isomer, 
 dodekahydrophenoxazine. It was thus thought possible that the above reduction 
 might be stopped at the alcohol stage after the theoretical absorption of 
 hydrogen. Furthermore, since Skita observed that the addition of a small 
 amount of hydrochloric acid hindered the splitting off of the amino residue, 
 
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 and since the addition of the acid would raake the base v;ater soluble, it seemed 
 
 advisable to v/ork with the hydrochloride of the free base. 
 
 However, before the reduction of the hydrochloride was attempted, 
 
 it seemed worth while to attempt the reduction of the free base. Thus, it v/as 
 attempted to reduce p-dimethylaminophenol, both in aqueous suspension and in 
 alcoholic solution. In the former case both colloidal platinum and platinum 
 black were tried and in the latter case, platinum black alone was tried. In 
 no instance, however, was the reduction successful. 
 
 As regards the reduction of the hydrochloride, it v/as found that 
 the addition of the theoretical amount of hydrochloric acid to the free base 
 was not effective, either with colloidal platinum, prepared by the method of 
 Skita and Meyer (I3) or v/ith the black, prepared by the method of Feulgen (14) 
 or by sodium nitrate fusion (15) • 
 
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 cipitation of the base from dry ether by meajis of dry hydrochloric acid gas, 
 the reduction did proceed, but only very slov/ly. With colloidal platinum the 
 main product is dimethylamino cyclohexane, only a trace of p-dimethylaminocyclo- 
 hexanol being obtained. 
 
 The next attempt was with platinum black prepared according to the 
 method of Feulgen and it, too, proved a failure. In this case the reduction 
 did not proceed at all. V/hen platinum black, prepared by the sodium nitrate 
 fusion method was used, the reduction was effected, but only very slowly. The 
 platinum black at first seemed to form a colloidal suspension which was de- 
 stroyed after the entrance of approximately one-half the theoretical amount of 
 hydrogen. From this point on, no hydrogen was absorbed. The coagulation 
 without doubt results from the cyclohexanol formed in the reduction. It was 
 attempted to overcome this difficulty by using both 95 percent alcohol and 
 50 percent alcohol instead of water as the solvent. However, the attempts with 
 
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 these two modifications proved no better than that in which v;ater alone v;as 
 used. The yield in all three cases was practically the same, consisting of 
 approximately 20 percent p-dicethylaminocyclohexanol, 25 percent dimethylamino- 
 cyclohexane, and approximately 2 percent of cyclohexanol. 
 
 As stated above, the reduction proceeds very slowly. The probable 
 cause for this is that p-dimethylaminophenol is very easily oxidized, its sol- 
 ution turning black even on standing in the air. The same applies to the 
 hydrochloride. Since the aninophenol is so easily oxidized, the oxygen content 
 of the platinum is very quickly depleted, thus causing the catalyst to lose 
 its activity. This is substantiated to some extent by the fact that if fresh 
 platinum black is added to a colorless solution of the hydrochloride in water, 
 the latter being kept in an atmosphere of hydrogen, the solution will turn 
 brown in the immediate vicinity of the catalyst. This indicates that an oxi- 
 dation is taking place and seems to corroborate V/illstatter ' s conclusions 
 regarding the necessity of oxygen in active platinum. The platinum black in 
 this case cannot be revivified by shaking vdth air as in the case of the reduc- 
 tion of many other organic compounds. The same explanation applies here; 
 namely, the oxygen is taken from the platinum as fast as the latter absorbs it 
 from the air. This seems to be substantiated by the fact that v;hen the color- 
 less solution emd inactive catalyst are shaken v.dth air the former quickly turns 
 black. 
 
 That the amino group might exert a poisoning effect on the cata- 
 lyst is very improbable, especially since in the above case it has been covered 
 in the form of a hydrochloride. Certainly the phenolic group does not exert 
 an undesirable effect, since phenol reduces v/ith great ease. 
 
 The probable reason why the platinum black, prepared by sodium 
 nitrate fusion, will effect the reduction, whereas that prepared by the method 
 
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 of r’eulgen will not, is because the former undoubtedly possesses much more 
 oxygen. This explanation is supported by the fact that the former will reduce 
 salicylaldehyde about twenty times as fast as the latter and will retain its 
 activity much longer. 
 
 Since the alcohol group is reduced off to an extent of 50 percent, 
 it seemed advisable to cover this group by some means, such that the free 
 hydroxyl group could be easily regenerated. For this purpose the acetyl de- 
 rivative of p-dimethylciminophenol was prepared. An attempt to reduce this 
 substance in alcoholic solution, using the more active platinum black, pre- 
 pared by sodium nitrate fusion, proved unsuccessful. 
 
 Thus, the only satisfa.ctory method for reducing p-dimethylamino- 
 phenol seems to be the hydrogenation of the isolated hydrochloride in aqueous 
 solution by means of platinum black prepared by the sodium nitrate fusion 
 method. This study will be continued thru the coming year, and it is hoped 
 that the method v/ill be improved. This will probably be accomplished by the 
 choice of a better solvent, since the latter seems to exert a strong influence 
 upon the reduction. 
 
 IV. EXPERUmiTKL PA.RT 
 A. Preparation of Catalysts 
 I. Colloidal Platinum 
 
 The colloidal platinum was prepared according to Skita and Meyer 
 ( 13 ). One-half gram of gum arabic v/as dissolved in water by grinding in a 
 mortar and adding from time to time a small amount of water. Then the desired 
 amount of 10 percent chlorplatinic acid solution v/as added and the solution 
 diluted to the desired volume. The resulting solution was inoculated by add- 
 ing a small amount of colloidal platinum, prepared by reducing 0.5 to 1 cc. 
 
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 of chlorplatinic acid in an alkaline solution v/ith hydrazine hydrochloride or 
 sulfate. This solution \ms shaken with hydrogen, v/hereupon the platinum v/as 
 reduced, giving a colloidal solution. The substance to be reduced v/as then 
 added. 
 
 II. Preparation of Platinum Black. 
 
 (a) Method of Feulgen (14) 
 
 Five grams of chlorplatinic acid v/as dissolved in 5 cc. of v/ater, 
 and to this v/as added 7 cc. of 40 percent formaldehyde solution. The latter 
 v/as then cooled in an ice bath and a solution of 5 gr. of sodium hydroxide 
 in 10 cc. of v/ater v;as added drop by drop v/ith vigorous stirring. Care should 
 be exercised here as the reaction becomes vigorous find foams excessively upon 
 too rapid an addition. The reaction mixture v/as allov/ed to stand for one-half 
 hour at room temperature. The temperature was then raised to 55° C. and kept 
 there for one-quarter hour, whereupon it was diluted v/ith 250 cc. water. The 
 Bother liquor was decanted and more water added, the latter being acidified 
 with acetic acid to prevent the formation of a colloidal suspension. The plat- 
 inum black was finally filtered off and dried in vacuo over sulfuric acid. 
 
 (b) Sodium Ilitrate Fusion Method (15) 
 
 Five grams of chlorplatinic acid was dissolved in IOO-I 5 O cc. of 
 v/ater and to this v/as added approximately 50 gr. of sodium nitrate. The solu- 
 tion was evapora.ted to dryness and then fused. It v/as kept at this tempera- 
 ture until the vigorous evolution of gas ceased. The melt was cooled and ex- 
 tracted Y/ith hot water. The platinum black v/as then filtered off, thoroughly 
 v/ashed and finally dried in vacuo over sulfuric acid. The final product is 
 of a brown color and when shaken v/ith hydrogen in an aqueous or alcoholic 
 solution produces a colloidal suspension which v/ill again coagulate upon shak- 
 ing v/ith air. 
 
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- 10 - 
 
 B. Preparation of p-Diinethylaminophenol £ind its Hydrochloride 
 
 To prepare the above the free base \ms first isolated from the 
 oxalate salt which is obtained as a by-product in the manufacture of p-methyl- 
 aminophenol, which is used as a developer. 
 
 To 182 gr. (0.5 ^nol.) of p-dlmethylaminophenol oxalate was added 
 enough water to make stirring easy. Forty gr. (1 mol.) of sodiin hydroxide, 
 dissolved in approximately 100 cc. of water, v/as added T/ith vigorous stirring 
 to prevent clumping. This mixture was extracted with benzene and then filtered. 
 The benzene layer \?as separated and distilled in vacuo, the i^ree base distill- 
 ing over at 125° C. at about 7*8 imn. pressure. The distillate should be 
 rapidly cooled as it oxidizes very readily upon exposure to air. 
 
 To prepare the hydrochloride the free base was dissolved in dry 
 ether cooled in ice and diT’ hydrochloric acid gas passed in. At first the hydro- 
 chloride came down as a sticky mass which became crystalline as an excess of 
 acid was passed in. The product was then filtered, washed vath dry ether and 
 finally dried in the air, 
 
 C. Preparation of Acetyl-p-dimothylsmiinophenol 
 
 The acetyl derivative of p-dimethylaminophenol v/as prepared by 
 mixing together 30 gr. of the free base with 35 gr. of acetic anliydride and 
 heating on the steam bath for one hour. The reaction mixture was then cooled 
 and poured into a small amount of ice water. The product was filtered off, 
 thoroughly washed \d.th water and finally recrystallized from butyl alcohol, 
 giving pretty pink crystals melting at 78° C. 
 
 D. Reduction Experiments 
 
 I. With p-Dimethylaminophenol 
 (a) Colloidal Platinum 
 
 To a preparation of colloidal platinum as described above and con- 
 
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- 11 - 
 
 taining 0.5 gr. platinvm, 5 gi*- of p-dlmethylaminophenol Viras added and the 
 voliune of liquid increased to approximately 50 cc. Hydrogen was then passed in 
 under a pressure of 30-35 Ihs., but none was absorbed. 
 
 (b) Platinum black 
 
 To a suspension of 5 gr. of the free base in 50 cc. water was added 0.5 
 gr. platinum black, prepared by the sodium nitrate fusion method. The reaction 
 mixture v;as then shaken for one hour v;ith hydrogen under a pressure of 30-35 
 lbs. as above but no absorption took place. The same was repeated using 50 cc. 
 of alcohol in place of the water, but with no better results. 
 
 Another series of experiments on the free base was tried. Here the 
 theoretical amount of hydrochloric acid was added to take the base into solu- 
 tion, These attempts proved unsuccessful v/ith colloidal platinum and the two 
 platinum blacks. 
 
 The reduction of the acetyl derivative of p-dimeth3'-lamino phenol was at- 
 tempted, using platinum black, prepared by the sodium nitrate fusion method 
 and alcohol as the solvent. It likewise proved unsuccessful. 
 
 II. With p-Dimethylaminophenol Hydrochloride 
 (a) Colloidal Platinum 
 
 To a preparation of colloidal platinum, containing 0.5 gr. plati- 
 num, 12 gr. of free hydrochloride was added and the solution diluted to about 
 60 cc. This was then shaken with hydrogen under a pressure of 30-35 lbs. When 
 approximately one-half the theoretical amount of hydrogen had been absorbed, 
 the reaction stopped. The colloidal platinum vra.s precipitated by acidifying 
 strongly with hydrochloric acid and heating to boiling. The platinum was fil- 
 tered off and the filtrate evaporated to 25-30 cc. in vacuo. Solid sodium 
 hydroxide was then added to saturation and the basic layer extracted with ether 
 or benzene. The extract was then distilled in vacuo, 5 gr. of dimethylamino- 
 

 
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- 12 - 
 
 cyclohexane, 7;ith a small amount of the desired alcohol, being obtained. The 
 former distilled over at 52-54-° C. at 17 mm. and the latter at 125° C. 
 
 (b) Platinum Black 
 
 To a solution of 12 gr. of the hydrochloride in 60 cc. of water 
 was added 0.5 gr. of platinum black, prepared according to Feulgen. Hydrogen 
 was then passed in under a pressure of 30“35 lbs., but no absorption took 
 place. 
 
 The same was repeated, using 42 gr. of the hydrochloride in 120 cc. 
 of water and 2 gr. of platinum black, prepared by the sodium nitrate fusion 
 method. The reduction proceeded, but only very slowly. As v/ith colloidal 
 platinum, the absorption stopped in midreaction. To attain this stage re- 
 quired from 10 - 14 hrs. At this point the platinum black, which at first 
 assumed a colloidal state, flocked out. Upon working up the reaction mixture 
 as before 11 gr. of dimethylamino cyclohexane, 3 gr. of cyclohexanol and 8 gr. 
 of p-dimethylamino cyclohexanol were obtained. The cyclohexanol steam distilled 
 over upon evaporating the solution in vacuo. The p-diraethylaminocyclohexanol 
 distilled over at 99.5 " 100° a-'t 7 pressure. 
 
 Similar runs virere made using 95 percent and 50 percent alcohol as 
 the solvents. The results were practically the same as those obtained above. 
 
 E. Description of Products 
 
 I. Dimethylamino cyclohexane 
 
 This compound has already been prepared but its physical constants 
 do not agree closely with those reported in the literature. Therefore, it 
 seemed of value to determine the following constants: 
 
 (1) Boiling Point l60® C. 
 
 (2) Specific Gravity 0.84? 
 
 (3) Index of Refraction 1.4528 
 
 250 
 
I 
 
“13- 
 
 The hydrochloride upon recrystallization fron butyl alcohol melted at 238° C. 
 Analysis; ,Subs. O.3O93 gr., 17.00 cc. O.IO96K AgllO^ 
 
 Calc, .for CqH^^N.HCI: 01,21.69^;, Found: 21.36;'i 
 
 Subs. 0.4793 gr., 43.71 cc. O.O843N acid, 
 
 Calc, for CgH^^N; N, 11.02^, Found; 10.76/% 
 
 II. p-Dimethylaminocyclohexanol 
 
 As stated above, this substance has never been prepared before. It 
 is a colorless and very viscous liquid possessing the following physical con- 
 
 stants: 
 
 (1) Boiling Point 228° C. 
 
 (2) Specific Gravity O.983 
 
 (3) Index of Refraction ) 1.4859 
 
 The hydrochloride is very hygroscopic. Indeed, it absorbs moisture 
 from the atmosphere so fast that it is impossible to get the substance into 
 a melting point tube. After careful drying in a vacuum oven at 100° C. it was 
 analy zed, Analy sis: 
 
 Subs. 0,2844 gr., 14.53 cc, 0,1096 N AgNO^ 
 
 0.4702 gr., 34.3 cc. N2 (32° C., 739.4 mm.) 
 
 Calc, for C3H1.7ON.HCl: Cl, 19.85^; N, 7.80^, 
 
 Found: Cl, I9.76/0; N, 7.?2f» 
 
ry.sm 
 
- 14 - 
 
 V. smaiARY 
 
 The reduction of the hydrochloride of p-dinethylarninophenol was 
 effected catalytically by means of platinum black, prepared by the fusion of 
 chlorplatinic acid with sodixam nitrate. 
 
 The products of the above reduction in aqueous solution, consisted 
 of approximately equal ar*iounts of p-dimethylaminocyclohexanol and dimethyl- 
 amino cyclohexane. 
 
 The observations led to the conclusion that the slowness with 
 v/hich the reduction proceeds was due to the fact that the oxygen content of 
 the platinum was very quickly and seriously depleted by the easily oxidizable 
 p-dimethylaminophenol hydrochloride. 
 
 p-Dinethylaminocyclohexanol, which has not been previously de- 
 scribed, was obtained as a colorless, viscous liquid and its physical constants 
 
 were determined 
 

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-15- 
 
 VI. BIBLlOGPulPHY 
 
 1. Brunei - Ann. Chim. (8) 6,252 (1905) 
 
 2. Osterberg and Kendall - J. An. Chem. Soc, 43, 1370 (1921) 
 
 3. Noyes and Ballard - Ber. 27, 1450 (1894) 
 
 4. Skita and Rolfes - Ber, 53» 1242 (1920) 
 
 5. Skita and Berendt - Ber. 52, 15^9 (^919) 
 
 6. Vavon and Detrie - Compt, rend. 172, 1231 (1921) 
 
 7. Y/illstatter and Hatt - Ber. 45, 1471 (1912) 
 
 8. Skita and Meyer - Ber. 45, 3589 (1912) 
 
 9. Skita and Brunner - Ber, 48, 1685 (1915) 
 
 10. Willstatter and Jaquet - Ber. 51, 76? (1918) 
 
 11. Willstatter and ?/aldschmidt-Leitz - Ber. 54-, 113 (1921) 
 
 12. Skita - Ber. 55, 139 (1922) 
 
 13. Skita and Meyer - Ber. 45, 3579 (1912) 
 
 14. Feulgen - Ber. 54, 36O (I92I) 
 
 15. Adams and Voorhees - Thesis, University of Illinois (1922) 
 
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