DERIVATIVES OF O-TOLYL ARSINE 
 
 BY 
 
 JOHN STANTON PIERCE 
 B. S., Georgetown College, 1920 
 
 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 
 
 1921 
 

 
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UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 July -EB 1 92X 
 
 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY 
 
 jr' SUPERVISION BY John Stant on Pierce 
 
 ENTITLED „ __ _ _I)aiL iy . at .i v e_s_,.Ql n-Xo.Iylarsine 
 
 BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
 THE DEGREE OF Laster oX.^nleuGO 
 
 Recommendation concurred in* 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 ^Required for doctor’s degree but not for master’s 
 
 476972 
 
Digitized by the Internet Archive 
 
 in 2016 
 
 
 https://archive.org/details/derivativesofotoOOpier 
 
TABLE OF GOIITELTS 
 
 I. 
 
 II. 
 
 III. 
 
 IV. 
 
 V. 
 
 VI. 
 
 page 
 
 Ac knowl e d geme nt 
 
 Historical 2 
 
 Theoretical 3 
 
 Experimental 5 
 
 Preparation of o-tolylarsinic acid 
 Preparation and properties of o-tolylarsine 
 Condensation of o-tolylarsine with benzal- 
 dehyde; properties of condensation product 
 Condensation of o-tolylarsine with paraldehyde; 
 properties of condensation product. 
 
 Suinmary 10 
 
 Bibliography 11 
 
 CO I — I 
 

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 The v/riter wishes to exT^ress his 
 appreciation for the helpful sus;gestions 
 from Professor Roger Adams, imder whose 
 supervision this work was carried out. 
 
 

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2 
 
 Derivatives of o-Tolylarsine . 
 
 I. 
 
 Historical 
 
 For almost a century the study of organic arsenical compounds 
 
 has been of great interest to chemists, fhis interest v/as heisht- 
 
 1 
 
 ened by the introduction of atoxyl into therapeutics about 1902. 
 
 The synthesis of salvarsan by Ehrlich in 1909 stimulated to a high- 
 er degree the search for organic arsenical compounds of therapeutic 
 value. In this quest of new arsenical compounds, the preparation 
 aJid reactions of organic arsines have been studied extensively. 
 

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 II. 
 
 Theoretical 
 
 Phen;ylarsine , the first primary aromatic arsine to he isolated, 
 v/as prepared in 1901 hy Palmer and Dehn. Previous attempts to is- 
 olate primary arsines had proven unsuccessful due to their great 
 ease of oxidation. The method employed hy Palmer and Dehn, the re- 
 duction of an arsinic acid with amalgamated zinc dust and hydro- 
 chloric acid in an inert atmosphere, is of almost universal appli- 
 cation for the preparation of primary arsines. 
 
 Oxidizing agents on primary arsines give a variety of products, 
 the relative amounts of each depending mainly on the strength of 
 
 the oxidizing agent, although other factors, such as solvent and 
 
 o 
 
 concentration, have some effect. Strong oxidizing agents, as po- 
 tassium permanganate, take the arsines all the way to the correspon- 
 
 4 
 
 ding arsinic acids. Milder oxidizing agents, as ferric chloride, 
 
 5 
 
 oxidize these arsines to the corresponding arsinious oxide. With 
 
 atmospheric oxygen, phenyl arsine gives a m.ixture of phenyl-arsinic 
 
 6 
 
 acid, phenyl arsenious oxide and arseno benzene. As the arsines 
 
 are so easily oxidized, all v/ork ^vith them must be done in an inert 
 
 atmosphere. Halogens, with the primary arsines, also give a great 
 
 variety of products, among which are arsenious halides, the corres- 
 
 7 
 
 ponding arsinic acid and arsenious oxide. 
 
 The primary aromatic arsines form a num.ber of condensation pro- 
 ducts with a variety of different reagents. Thus, they react with 
 
 Q 
 
 aryl arsenious chlorides, and aryl stibinous chlorides, arseno and 
 arseno stibino compounds respectively being formed. Similarly, v/ith 
 
 arsenious oxides, arseno compounds are formed.^ Some substituted 
 
 primary aromatic arsines, with salts of silver, copper, gold and 
 
 10 
 
 platinum form addition products. With the chlorides of arsenic. 
 
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 11 
 
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 12 
 
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 13 
 
 Recently, it v/as found that primary arsines condense with aldehyde. 
 As part of a series of experiments to see whether or not this reac- 
 tion is general, condensation products were m.ade of o-tolylarsine 
 with benzaldehyde and paraldehyde. 
 

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 Experimental 
 o-Tolylarsinic acid. 
 
 14 
 
 This acid was prepared hy Bart's method. 321 g. of o-tolui- 
 dine was dissolved in a mixture of 3 liters of v/ater and 740 g. of 
 concentrated hydrochloric acid. After cooling to 5° a solution of 
 207 g. of sodium nitrite was added slov/ly and the excess acid neu- 
 tralized with sodium carbonate. This mixture v;as then run slowly 
 into a sodium arsenite solution made by dissolving 716 g. of sodium 
 carbonate and 445 g. of arsenic trioxide in 3 liters of v/ater. A- 
 bout 50 g. of copper sulphate was used as a catalyst. During the 
 addition, and for about three hours after, the mixture was vigor- 
 ously stirred. Then it wa.s filtered from tar, acidified, and the 
 o-tolylarsinic acid separated from the solution by filtration. The 
 yield was 260 grams, v/hich is 57% of theoretical. Its m:elting point 
 was 159! An attempt was made to increase the yield by evaporation 
 of the m.other liquor but so much sodium chloride and so little o- 
 tolylarsinic acid that the extraction of the acid would not have 
 been worth the tim.e and reagents required. 
 
 o-Tolyl Arsine. 
 
 In the reduction of o-tolylarsinic acid to the corresponding 
 arsine, runs of 75 grams of acid were made. This v;as v;ell mixed 
 with 300 grams of amalgamated zinc dust. The reduction was carried 
 out in a 2 liter, round bottom flashy containing the above mixture, 
 and about 500 cc of ether. It v/as fitted with a dropping funnel and 
 upright condenser with mercury seal to permit hydrogen to escape yet 
 to prevent the entrance of atmospheric oxygen. Concentrated hydro- 
 chloric acid was introduced at the rate of seven or eight drops a 
 
6 . 
 
 minute till practically all of the zinc had reacted. Then the ether 
 v/hich was lost hy evaporation v;as replaced and the ether layer si- 
 phoned off into a flask, and dried with calcium chloride. The ether 
 solution of the reduction product v/as then sucked up into a Claisen, 
 through which carhon dioxide v;as passed slowly, and the ether dis- 
 tilled off. The linuid left, boiled, with slight decomposition at 
 12 1'^ 93mm and 133” 131mm. 
 
 It v/as found more convenient, part of the time, to distill the 
 reduction product without drying it v/ith calcium chloride. In these 
 cases, the distillate, on standing, separated into tv;o well defined 
 layers, the layer of water on top serving as a protection against 
 atmospheric oxygen, which sometime leaked into the apparatus. 
 
 An attempt was m.ade to distill some of the reduction product 
 at atmospheric pressure, 742 mm., but it practically all decomposed, 
 giving off a fairly heavy cloud of smoke. The boiling point is a- 
 bove 152'’, for at this tem.perature , som.e of it condensed on the bulb 
 of the thermometer. 
 
 V/hen the hydrochloric acid was added at the rate indicated a- 
 bove, yields of about 32 grams or 52f^ of theoretical were obtained, 
 r/hen the acid v/as added faster, likely hydrogen was evolved faster 
 than it could be used in the nascent state to reduce the o-tolylar- 
 sinic acid. In the longer runs, likely the arsine formed ?;as oxi- 
 dized to a certain extent by atmospheric oxygen leaking into the ap- 
 paratus . 
 
 The reduction product analyzed for o-tolylarsine by Robertson's 
 
 15 
 
 method for the estimation of arsenic in organic compounds. 
 
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7 
 
 Calculated for GH 5 C 6 H 4 ASH 2 % arsenic 
 
 44.60 
 
 ,2716 gram substance reduced 65.60 ac.of io- 
 dine solution (lc.c.= ,001792. g. arsenic) 43.28 
 
 .3182 gram substance reduced 77,67 c.c, of io- 
 dine solution 43.74 
 
 ,2526 gram substance reduced 61.69 c.c. of io- 
 dine solution 43.76 
 
 o-l'olylaraine , colorless liq_uid with garlic like odor, v/as ra- 
 pidly oxidised by atmospheric oxygen. Y/hite, yellov/, and red sub- 
 stances were present in the oxidation product. The v/hite product 
 was o-tolylarsinic acid, as was shov.ii by its melting point, fhe yel- 
 low compound, v/hich melted at 205 - 208" probably was o-arsenotoluerfi. 
 The sample for analysis was recrystallized from benzene. 
 
 arsenic 
 
 Calculated for GHgCgH 4 As= AsCgH/GHrz; 45.14 
 
 .1530 gram of substance reduced 20.18 c.c. 
 of iodine solution (1 c.c. -003515 g. 
 
 arseiiic ) 4^,36 I 
 
 o-Tolylarsine and Benzaldehyde . 
 
 To 15 grams of o-tolylarsine kept in an atm.o sphere of carbon 
 dioxide v/ere added about eight drops of concentrated hydrochloric 
 acid and 18 gram.s of benzaldehyde , in small portions. The reduction 
 mixture soon became quite v/arm and after a short period of time, 
 partially solidified. Although condensation took place in a few minr 
 utes, apparently the reaction vvas more complete when the mixture 
 was allowed to stand a few days in an inert atmosphere. After sev- 
 eral days the excess benaaldohyde was filtered off with suction, and 
 the solid left on the filter paper extracted v/ith ether. White, 
 needle-like crystals, which melted at 140"were obtained. The sample 
 for analysis was recrystallized from ether. 
 

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8 
 
 > arsenic 
 
 Calculated for CH'^CgHaAsHoI C 5H5CHO )s 19.71 
 
 .1507 gram of sulstance reduced 8.03 c.c. of 
 
 iodine solution (1 c.c. **.003515 g. arsenic) 18.73 
 
 .1391 gram of substance reduced 7.45 c.c. of io- 
 dine solution 18.82 
 
 T’he above product evidently was a condensation of one mole 
 
 of o-tolylarsine and two moles of benzaldehyde . fhe following for- 
 
 mula : 
 
 is a possible and probable one. This condensation product is hydro- 
 lyzed by cold, concentrated, hydrochloric acid and slightly by boil- 
 ing dilute hydrochloric. It is not hydrolyzed by boiling five mxin- 
 utes with 30% sodium hydroxide solution. 
 
 o-Tolyl Arsine and Paraldehyde. 
 
 A similar experi^ient v/as carried out to determine the action of 
 paraldehyde on o-tolylarsine . To about 25 grams of the arsine a few 
 drops of concentrated hydrochloric acid and about 35 grams of paral- 
 dehyde v/ere added. The mixture became slightly warm but not so warm I 
 as in the previous experiment. V/hen the reaction had ceased, the 
 flask was sealed and set aside. After a fev; days the mixture con- 
 tained a white solid and v/as rather turbid. The excess paraldehyde, 
 about 18 gramSjWas distilled off at 180 mm pressure, leaving a clear 
 yellow solution. An attempt was made to distill this at the sarnie 
 pressure, but it decomposed, turning red. At 23 mm. it boiled at 
 165°. On second distillation, about 18 gram.s of product, slightly 
 
9 
 
 turbid, v;as obtained. In neither case was all of the product dis- 
 tilled, as it charred slightly on getting to a lov/ volume. On stand- 
 ing a few days a 'vvliite solid settled out. fhe liquid was decanted 
 from the solid and on distillation, a clear product, boiling at 
 
 165° 21mm. , v;as obtained. The index of refraction is 
 30 
 
 (n) 1.5573 % arsenic 
 
 Calculated for C%G6H4AsH2( CH.-xCHO ) 2 29.25 
 
 .0974 gram substance reduced 7.67 c.c. of 
 
 iodine solution ( Ic .c .-.003528 gram ar- 
 senic) 27.78 
 
 .1527 gram, substance reduced 12.04 c.c, of 
 
 iodine solution 27.82 
 
 fhis substance possibly has the structure: 
 
 H 
 
 OH 
 
 similar to the one suggested for the condensation product ofxbenzal 
 dehyde and o-tolylarsine . ' 
 
 The paraldehyde condensation product mentioned above was hy- 
 drolyzed by cold, concentrated hydrochloric acid, giving a strong 
 odor of paraldehyde and yellov; and red solids. These likely were 
 oxidation products of the o-tolylarsine which was form.ed by the hy- 
 drolysis. Boiling dilute hydrochloric hydrolyzes the condensation 
 product slightly. It is not hydrolyzed v/ith boiling dilute or cold 
 30h alkali, but on boiling v/ith 30;^ sodium hydroxide, it is hydro- 
 
 lyzed. 
 
0 
 
 
 
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10 
 
 Summary . 
 
 1. Condensation products were made "by the action of o-tolyl- 
 arsine on bensaldehyde and paraldehyde. 
 
 2. C?he condensation products are stable in cold dilute acid 
 and alkali but are hydrolyzed by boiling dilute acid. Both 
 are hydrolyzed by cold, concentrated hydrochloric acid. In 
 the presence of cold alkali, the bensaldehyde product is more 
 stable than the paraldehyde condensation product. 
 

 
 i'> ;'; ■■;'i. ■ ; '‘'i' ?, 'KV', 1 | ''^;‘ ; 
 
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 t- 
 
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 ‘a.- <' . 
 
 ' j 
 
 lU , ‘J 
 
 S' ‘ ^ • •u ■ > \V){^ ivl B^ffi frr'iL ,'■ ^ 
 
 ■i^f : , jr: ;,S'- 
 
 m ^' / : ' vKS ,, .; ii^,, 
 
 -V ;■ s.'V': 'I ' '-x. X & -S'S 
 
 • > .'• * ' <’v‘-^-- ' i-> if ' A '\ •-' x:' ■•^•' ‘*v '.'"^'•’"i,' ' ’■/■ 
 
 ■ i 
 
 •■ rJ 
 
 ''h ■ 
 
 . -' . / . X-? ' . "1 'Tfe!*4| 
 
 ' i-«# , » . ‘>^ »C: ' . : .'4 ♦ . V'* ' .• 
 
 
 '’ll ► 
 
 *) s 
 
 
 
 ;' '.•X9/A* 
 
 
 iN- • , V 
 
 V't ; 
 
 . < V' 
 
 J ' ‘ 
 
 
 / '• 
 
 
 Mi.; ■-‘. . ■■ : » ■■. , , . .'^„ M : ., " ■.'* ,1 
 
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 Vil 
 
11 
 
 ±5iblio,3raphy. 
 
 1. Morgan, Organic eompounds of Arsenic and imtimony, XVI. 
 
 E. Palmer and Pehn, Ber., 1901, 34, 35,93. 
 
 3. Morgan, Organic Compounds of Arsenic and Antimony, 89; Pehn, 
 Primary Arsines, 51. 
 
 4. Pehn, Am.Ch. J., 40, 105, 1908. 
 
 5. Pehn and Wilcox, Am. Oh. J., 35,35, 1906. 
 
 6. Pehn, Primary Arsines, 51. 
 
 7. Morgan, Organic Compounds of Arsenic and Antimony, 89; 
 
 Pelm, Primary Arsines, 28, 53. 
 
 8. P.R.P. 254187, 269743. 
 
 9. P.R.P. 251571. 
 
 10. P.R.P. 275216. 
 
 11. P.R.P. 269745,269743. 
 
 12. Palmer and Pehn, Am. Ch. J., 47, 54, 1912. 
 
 13. Adams and Palmer, J. A. G. S., 42, 2575, 1920. 
 
 14. P.R.P. 250264. 
 
 15. Robertson, J. A. C. 3. 43, 182, 1921.