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NEW REACTIONS OF AROMATIC ARSINES 
 
 BY 
 
 lOSEPH LOWE HALL 
 
 B. S. University of Illinois, 1919 
 M. S. University of Illinois, 1921 
 
 • THESIS 
 
 SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS 
 FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CHEMISTRY 
 IN THE GRADUATE SCHOOL OF THE UNIVERSITY 
 OF ILLINOIS, 1922. 
 
 URBANA, ILLINOIS 
 

 
 
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 UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 l!a^— IO l,- ^ 1 922l 
 
 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY 
 
 SUPERVISION BY Tosg- ph Lo w e - H al l 
 
 ENTITLED ppA"' V Tr>TO nv ApnUA ttp a pc timer 
 
 BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
 THE DEGREE OF D oc t o r o f PLl 
 
 Recommendation concurred in* 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 ^Required for doctor’s degree but not for master’s 
 
CONTENTS 
 
 A c ImoY/ le dginen t 
 
 Introduction 1 
 
 Historical 3 
 
 Theoretical 10 
 
 Experimental. . 16 
 
 A. Preparation of Phenylarsine 16 
 
 B. Reactions with Phenylarsine 21 
 
 C. Reactions v/ith Phenylarsine-Grignard Complex 26 
 
 Summary , 38 
 
 Bibliography. . 39 
 
 Vita 40 
 
I 
 
 'll-'" 
 
 
 
ACEMOWLEDG!/lSNT 
 
 This investigation has been carried out under the direction 
 and supervision of Professor Roger Adams, to whom the writer 
 v/ishes to express sincere gratitude for his genereus and 
 capable assistance. 
 
Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/details/newreactionsofarOOhall 
 
INTRODUCTION 
 
 1 
 
 Investigation of arsenic compounds has recently been stimulated 
 by a government appropriation for university fellowships to be 
 awarded and supervised by the United States Interdepartmental 
 Social Hygiene Board, The purpose of the investigational v/ork 
 has been to develop new types of compounds of arsenic in the hope 
 of finding substances of therapeutic value in combatting venereal 
 diseases. Various kinds of arsenical drugs have been developed 
 and used since 1902, when Bechamp's compound "atoxyl" began to 
 be tried in therapeutics. Tv/o of the most successful and most 
 widely used of these compounds are "Salvarsan" and "Neosalvarsan" , 
 which is the sodium methylene -sulfinate of salvarsan. Both of 
 these compounds v/ere discovered by Ehrlich, who did a vast amount 
 of research in arsenical drugs. Compounds containing arsenic in 
 an available state for proper assimilation in the body appear to 
 exert a specific reaction against diseases of protozoal origin. 
 
 One of the serious problems is, of course, to reduce the toxicity 
 of the arsenic so that its use will not be dangerous. 
 
 The purpose of this investigation has been to carry out re- 
 actions with phenyl-arsine which might be analogous to those of 
 its nitrogen analogue, aniline. The arsines form a series of 
 compounds v/hich is very complete in its analogy with the amines 
 as far as structure is concerned“-prima 2 ->y , secondary, tertiary, 
 aliphatic, and aromatic types — but the chemical analogy is not 
 so close. C, S. Palmer (1) found that phenyl arsine condenses 
 with benzaldehyde and butyraldehyde v;ith the formation of 
 compounds corresponding somewhat to aldehyde ammonias, except that. 
 
 
2 
 
 whereas only one hydrogen on the nitrogen reacts in the formation 
 
 of aldehyde ammonia, both hydrogens on the arsenic react each 
 
 v/ith one mol of the aldehyde; a compound of the type CHOII) i^sR 
 
 6 5 2 ' 
 
 is formed. 
 
 The present investigation has been concerned with the further 
 study of reactions which are typical of the amines in their 
 application to the arsines, particularly reactions with acid 
 chlorides, anhydrides, and esters, nitroso compounds, and C-rig- 
 nard reactions. 
 
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 II. HISTORICAL 
 
 The discovery of the first organic compound of arsenic is 
 accredited to Cadet, who in 1760 obtained on distilling arsenic 
 trioxide with potassium acetate, a heavy, fuming liquid easily 
 inflammable in the air and of a very offensive odor. The arsenic 
 compomids which are thus formed are cacodyl and cacodyl oxide, 
 cacodyl being spontaneously inflammable. 
 
 Palmer (2) prepared the first secondary arsine by the reduction 
 of cacodyl chloride by means of platinized zinc and hydrochloric 
 acid in alcoholic solution. Lehn and V/ilcox (3), however, 
 found that it v;as unnecessary to prepare cacodyl chloride from 
 cacodyl oxide and mercuric chloride for this reduction; they 
 found that the direct reduction of cacodyl and cacodyl oxide took 
 place as well as that of the chloride, and therefore used for 
 this purpose the above-mentioned "Cadet's fuming arsenical liquid." 
 
 Palmer and Dehn also prepared the first primary arsine, mono- 
 methylarsine , by reducing methyldichlorlrsine ; they found the 
 reduction of methylarsonic acid, hov/ever, to be much more con- 
 venient. These investigators encountered difficulties because 
 of the extreme volatility of the product and its gr^eat avidity 
 for o:cygen. In the same communication they announce the dis- 
 covery of the first aromatic primary arsine, phenylarsine . 
 
 (Various reactions of this compound are the basis of the author's 
 present investigation). Palmer prepared phenylarsine by the 
 reduction of calcium phenylarsonate with amalgamated zinc dust 
 and hydrochloric acid. The reduction v/as earried on in a flask 
 equipped with a reflux condenser, in the top of which was fitted 
 
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 a dropping funnel and a bent tube dipping into mercury to serve 
 as an air trap in allowing the escape of the excess hydrogen. 
 Hydrochloric acid v/as slowly admitted througli the dropping funnel. 
 The reaction mixture was covered with a layer of ether to take 
 up the phenylarsine as it v;as formed, it being very insoluble in 
 v/ater. Essentially this same method is yet employed in this 
 laboratory, using, however, the free phenylar sonic acid. Palmer 
 mentions tv/o ways in V7hich the phenylarsonic acid maybe prepared: 
 First, that of La Coate and Michaelis (5) in v/hich the phenyl- 
 arsine dichloride is prepared from mercury diphenyl according to 
 the equation: 
 
 'Hg(CgH5)2 t 2 AsCl^ = 2 CgllgAsClg HgClg 
 
 The conversion of this product to phenylarsonic acid is evident 
 from the equations: 
 
 CgH5AsCl2 t Clg = CgHgAsCl^ 
 
 CgH5AsCl4 t 3 H2O = CgH5As0(0H)2-J- 4 HCl^ 
 
 The second and better m.ethod was that of I-.ichaelis and Loesner (6) 
 in ViThich the phenylarsine dichloride v/as prepared according to 
 the following equations: 
 
 AsClj t 3 CgHgCl t 6 Ha s {CQE^)^ks ‘ 6 HaCl 
 
 ^^6^5^ 3“^® t 2 AsClj (heat in closed tube) = 3 C0HgAsCl2 
 
 The m.ethod now used in this laboratory for the preparation 
 of phenylarsonic acid is that described by Norris (7) which will 
 be discussed under the experimental part. 
 
 According to Dehn (8) the methyl and ethyl amines are 10,000 
 to 15,000 times more soluble in water than the analogous arsines, 
 v/hich are only about one part soluble in ten thousand parts of 
 

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 v/afer’ at 25°. The s.olnbill 1 -y Increases with the increase of 
 basicity. Dehn observed that the odor of dilute phenylars3.ne 
 resembles that of hyacinths. The author, however, fails to re- 
 cognize any such reseirb lance and is inclined to believe that if 
 such existed, florists would find a market for hyacinths only 
 to those with either a perverted sense of smell, or none at all. 
 
 Phenylarsine is a transparent, colorless, highly refractive, 
 heavy oil, which boils at 148° at 760 mm., 93° at 70 mm., 84® at 
 55 mm., and 77 at 33 mm. -^t is insoluble in water, soluble in 
 alcohol, ether, and carbon disT-ilfide. In air it ¥/arms rapidly 
 and changes to a light yellov/, plastic mass. Three products 
 result from the oxidation as indicated by the follov\ring equations: 
 C0H5ASH2 -!■ O2 = C0H5ASO t H2O 
 C 0 K 5 ASH 2 t 3 0 = C 0 H 5 AsO(OE )2 
 2 CgH^AsHg t O 2 = CgHgAsiAsCgHg * 2 H20^ 
 
 Phenylarsine reacts with nitric acid v^ith explosive violence 
 to yield products as indicated by the equations: 
 
 C 0 H 5 ASH 2 t 6 HNO 3 = C 0 H 5 AsO(OH )2 t 3 H 2 O t 6 NO 2 
 2 CgH^AsHg t 4 HlIO^ = CgH^As :AsCgH^ t 4 HgO t 4 NOg 
 2 CgH^AsHg t 14 HNO 3 = 2 CgHgNOg t AsgO^ t 9 HgO t 12 NOg 
 
 Phenylarsine reacts with bromine in various steps as shown 
 by the equations: 
 
 CgH^AsHg t Brg z CgH^AsHBr .HBr 
 
 CgHgAsHBr t Br 2 = CgH^AsBrg.HBr 
 
 C0H5AsBr2 t Br2 =: C0H5Br t AsBr^ 
 
 Similar reactions with iodine occur: 
 
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 Dehn also finds (9) that phenylarsine is unchanged when 
 heated two hours in a sealed tube at 180°, but after heating 
 three hours at 510^ decomposition takes place according to the 
 equation: 
 
 3 C0H5ASH2 r (C0li0)2As t 2 As t 3 Hg 
 
 This reaction demonstrates the unstable linkage of the hydrogen 
 to the arsenic and explains in a measure the tendency of phenyl- 
 arsine to act as a reducing agent wherever possible rather than 
 to condense in a manner analogous to aniline. This tendency will 
 be discussed in the experim.ental part. 
 
 Dehn (3) observes that aliphatic secondary arsines have 
 greater affinity for oxygen than primary arsines, the affinity 
 increasing with the number of alkyl groups introduced; the se- 
 condary and tertiary arsines are spontaneously inflammable. 
 
 Dime thy lar sine reacts easily with halogens, halogen a elds , and 
 their heavy metal salts, v/ith oxygen and sulfur, oxides and 
 sulfides, and with oxygenated acids and salts. Reactions with 
 halogens, halogen acids, and alkyl halides begin with a direct 
 addition forming a pentavalent arsenic, followed by a molecular 
 cleavage leaving a trivalent arsenic. Dime thy lar s ine gives a 
 wide variety of products on oxidation with pure or atmospheric 
 oxygen, as shown by the equations: 
 
 1. 6 (CH2)gAsH t 3 Og ~ ( CHgA s ) ^A s gOg ^ 4 ^2^6 ^ ^ ^2^ 
 
 2. 4 (CH3)2 AsH t Og : 4 (CHjAs)^ t 2 CgHg <• 2 HgO 
 
 3. 4 (CH3)2 AsH O 2 : AS2 t 4 C2H0 t 2 H2O 
 
7 
 
 4. 2 (CH5)2AsH t 9 Og z t 4 COg t 7 HgO 
 
 5. 4 (CH2)gAsH t Og = 2 ((CH2)As)g t 2 HgO 
 
 6 . 2 (CH2)gAsE t Og = ((CH2)As)gO t HgO 
 
 7. (CH3)2AsH t Og z (CH3)2As00H 
 
 The aromatic secondary arsines are obtained by reduction of 
 the corresponding arsinic acids with apparently the same ease 
 as the aliphatic secondary arsines, Dehn's method (3) of prepar 
 ing diphenyl arsinic acid is designed to obviate the use of mer- 
 cury diphenyl in the method of La Coste and Michaelis with its 
 inconvenience and poor yields. The procedure is sim.ply an 
 adaptation of the method of Michaelis and Loesner with the 
 addition of an ingenious operation for the isolation of the 
 desired product. The reactions are carried out according to 
 the equations; (the first being nedrly quantitative) 
 
 3 CgHgCl t AsCl^ t 6 Ka = (CgHg)3As t 6 NaCl 
 
 2 (CgHg^^s t ASCI 3 (30 hours at 22Q<=>) z 3 (CgH 5 ) 2 AsCl 
 
 Water is added to the reaction mixture and chlorine is passed 
 into it, whereupon the following reactions take place vifith the 
 various constituents present; 
 
 1. ASCI3 r 4 H2O t CI2 = H3ASO4 r 5 HCl 
 
 2. CgH^AsClg t 3 HgO t Clg = CgH^AsO^Hg t 4 HCl 
 
 3. (CgHg)gAsCl t 2 HgO t Clg = (CgHg)gAsOOH t 3 HCl 
 
 4. (CgH^)3As . HgO » Clg = t 2 HCl 
 
 The product of the fourth reaction is insoluble in v^ater and 
 may be filtered from the hot solution, in which the others are 
 soluble. On the addition of magnesia mixture in the cold, the 
 
8 
 
 product of the first reaction readily comes down, and on boiling 
 likev/ise the product of the second reaction precipitates, but 
 not the third, which may then be separated by filtration. 
 
 7,'hen the filtrate is acidified the diphenylarsinic acid is pre- 
 cipitated, as it is very sli^tly soluble in v;ater at room temi- 
 perature . Dehn used a system of this sort for analysis to de- 
 termine the degree of substitution in arsines and their d.erivatives 
 He also found an application of the Volhard titration for halo- 
 gens quite applicable to halogen substituted arsines such as 
 phenylarsine dichloride, tetraethyl arsonium iodide, etc. The 
 product was boiled up v/ith standard silver nitrate, and the 
 excess titrated with potassium thiocyanate, using ferric alum as 
 an indicator. The preparation of diphenylarsinic acid, hov/ever, 
 was developed much more efficiently , in Germany during the war 
 (Morris), as it v/as an intermediate in the mianTifacture of di- 
 phenyl chlorarsine (blue cross). The preparation v;as carried 
 out according to the equations: 
 
 CgHgNgCl ^ Na^AsOj s C0H^AsOgNa2 ^ NaCl * Ng 
 
 CgH^AsOjNag t 2 HCl = CgH^AsO^Hg t 2 NaCl 
 C0H0AsOgH2 t ^ ^^2^ ” * ^2^^4 
 
 C0HgAsOgNa2 t C0H^N2C1 = { CgHg)2As0gNa t NaCl t Ng 
 
 Numerous German patents have appeared in the last ten years 
 involving reactions of aromatic arsines. Primary arsines v;ere 
 found to react (10) with arsenoxides or chlorides vjith the 
 splitting out of a molecule of water or tv/o molecules of hydro- 
 chloric acid. Thus it is possible to make asymmetric substi- 
 tuted arsenobenzenes of the general type, R’AsrAsR". Pro- 
 
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 cesses for the production of this type of coiiipounds are covered 
 by other patents (11) (12) (13) which involve methods for the 
 simltane ous reduction of arsonic acids or oxides of tv/o different 
 types. For instance upon the rediiction of two arsonic acids 
 together in equimolecular amounts, R’As 0 ( 0 H )2 ahd R”As 0 ( 0 iI) 2 ^ an 
 unsymnietrical arsenobenzene derivative is obtained, R’As:AsR'*, 
 
 It has been fomid (14) that compounds containing arsenic 
 linked to phosphorus, arsenic, antimony, tellurium, and selenium 
 could be obtained by passing the hj^^’drides, phosphine, arsine, 
 stibine, etc. into aromatic arsine -dichlorides , or aromatic ar- 
 sine oxides (15). Arsenostibene compounds of the type X’AsrSbX" 
 have been made (16) in which X may be either organic or inorganic 
 radicals, by the reaction of antimony trihalides, phenylstibine- 
 dichloride, etc. on aromatic arsines. Similarly such c ompounds 
 have been made (17) by the reaction of stibine oxides and aro- 
 matic arsines. Corresponding reactions of compounds containing 
 bismuth (IS) instead of antimony vdth aromatic arsines have 
 yielded arseno-bismutliene compounds. However, no compounds 
 containing the linkage -As;H- have been reported. Such a com- 
 poimd v/ould -be interesting, since all of the above-mentioned 
 analogous types containing phosphorus, antimony, etc. are of 
 therapeutic value. 
 

10 
 
 ITT. THEORETICAL 
 
 Since aniline is readily acetylated and, benzoylated, it seemed 
 possible that analogous products might be obtained from phenyl- 
 arsine; CgHgAsIICOCngj CgH^AsHCOCglig; or that possibly tv/o 
 
 acyl radicals might attach to the arsenic. Attempts to prepare 
 any such compounds were unsuccessful, with practically no reaction 
 occurring at all, and that only inizolving the formation of a 
 little arsenobenzene by the reducing action of phenylarsine . 
 
 Palmer’s (1) aldehyde condensations led to the investigation 
 of possible similar reactions with a ketone capable of enolizing, 
 as in aceto-acetic ester. Of course a reaction analogous to 
 the Claisen reaction with the ester group is possible. Evidences 
 of water splitting out as an intermediate step v/ere observed, 
 but the final product was arsenobenzene. 
 
 In an attempt to prepare a compound containing the linlcage 
 -As:N“, similar to compounds containing phosphorus, antimony, 
 bismuth, etc., in place of nitrogen, the following reaction w’as 
 thought to be a possibility: 
 
 CgHgAsHg t ON-CgH^-lUCH^)^ = CgH^As ;N-CgH^N( CH3)2 t HgO. 
 
 No such compound was isolated, only arsenobenzene and complex 
 oxidation-reduction products coming from the reaction, 
 
 A v/hite, cr:/stalline product was isolated v/hich analyzes 
 closely for (^20^24*^5^2^*® 2* dissolves readily in v/ater, the 
 
 solution gradually becoming pink and turning blue on heating. 
 
 It cannot be recrystallized from water or extracted from it with 
 immiscible solvents. It reacts acid in aqueous solution, and 
 on titration, using phenolphthalein, gave a neutral equivalent of 
 
 in excess 10/^ NaOH. and the solution 
 

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11 
 
 is colorless. On acidifying in presence of litmus paper the 
 solution tiorns rose pink at the neutral point, hut becomes color- 
 less in very slight excess of acid. Magnesia mixture v;as added; 
 no precipitate appeared until heating, indicating the presence 
 of phenylarsonic acid (3). These observations lead to the con- 
 clusion that the compound probably consists of an amino salt of 
 phenylarsonic acid and some amphoteric substance. It seems 
 possible 'and logical to assume that the nitroso group v/as reduced 
 to a hydroxylamine group by phenylar sine , and that water split 
 out from this hydroxyl group and a hydrogen on phenylars ine ; 
 
 2 (CH3)2N-CgH4 -NO t 2 CgH^AsHg s 2 ( CH^) gN-CgH^NHOH 
 
 ^ CgHgA s 1 A s CgHg . ! 
 
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 air 
 
 (CH3)2N-CgH4-NH-AsH-CgH5 Og « ( CH3) gN-CgH^-NH-AsOOH-CgHg I 
 
 The latter compound is p- dimethyl amino anilide of phenylarsonic I 
 acid. Phenylarsonic acid (formed along with arsenobenzene by the i 
 oxidizing action of the nitroso group) may form a salt with the 
 dimethylamino group giving the compound, 
 
 CgH5As0{0H)0NH(CH3)2-CgH4NH-As0(0H)GgHg. | 
 
 The anilide compound, being amphoteric, would be soluble in both 
 acid and alkali, and because of the amphoteric nature , a neutral 
 equivalent determination would not be of any value. The air 
 oxidation of the arsenic coupled to the nitrogen wouild explain 
 why considerable length of tlm.e (12 hours) was required ..before 
 the material appeared in the acetone or benzene solution after 
 the reaction had gone to completion. After filtering and v^ithout 
 concentrating, frequently a second crop of crystals would be 
 obtained on standing. This compound, being a salt of a very weak 
 
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 12 
 
 base and a weak acid, Vi^ on Id be almost completely hydrolyzed in 
 aqueous solution, and the amphoteric nature of the anilide com- 
 pound would interfere with its extraction w ith immiscible solvents 
 as was observed. The para-diamino structure, being s omev/hat 
 unstable and subject to oxidation, may account for its decomposition 
 with heat and its color play v/ ith ferric chloride and silver ni- 
 trate . 
 
 iiuch of this assumption can be substantiated if phenylarsine 
 can be shown to c ondense with hydroxylamine s directly. This j 
 
 investigation will be taken up at a later date. I 
 
 A. J. <,iuick found in this laboratory that phenylarsine re- | 
 
 acting mth two mols of an alkyl Grignard reagent liberated I 
 
 quantitatively two mols of the corresponding hydrocarbon, in 
 accordance with the follov;ing equation; I 
 
 CgH5AsH2 t 2 RMgX s GgH5As(MgX)2 t 2 RE I 
 
 This phenylarsine -Grignard complex seemed to afford a means of j 
 
 attaching various halogenated substances to the arsenic as follows: 
 
 CgH5As(MgX)2 t 2 RX = C0H5ASR2 t 2 MgX2 
 Or it might be possible to limit the reaction to the formation i 
 
 of s econdary a rsines ; ! 
 
 CgH5As(MgX)2 ^ RX a CgH5AsR(MgX) t MgX2 
 
 CgH^AsR(MgX) t HCl = CgH^AsRH MgXCl. 
 
 The application of this method to the formation of secondary 
 arsines, and the formation of tertiary arsines containing three 
 different groups has not yet been undertaken, but will be studied 
 later. ^'Nevertheless it was found that in certain cases, e.g. 
 benzyl chloride, only one group entered, even in presence of 
 

 
 fHi^ft'i^P’XW'^'' "X >tr^y^a hlmr, ,Mdo 
 
 r e " '■ ■ *’ '■■ = 1 - • ) ‘ 0 ‘p7‘ ^ 
 
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 ■ ^ \ sjM '^'? >■• 
 
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 «l ; '&4’i,’ ■ 
 
 ; '.-oi; al- ^ ' . J . ■ay?' ;;/= t'l^v. 
 
 j ■ . ’ . t ' , ■ , i'A :' /' y/flr,' '. , 
 
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 .;v t « aetp,* 
 
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 l; ^ '’ i’ '■ -'/■ ' •■., ;,{V...,,,.!^.. ..^i2'l''?i«p*''A . ■ ^W'. 
 
 wtj- oi^v :.'¥i ‘ * ^ f ;'}^; 4 ^ 
 
 ■ , ‘>w , ,:■ ' ,4.. f- ^ 
 
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13 
 
 large excess of benzyl chloride, presumably on account of steric 
 hindrance. 
 
 By this method attempts to prepare acetylated and benzoylated 
 phenylarsine by the use of acyl clilorides again proved futile. 
 Tertiary arsines, hov/ever, were successfully prepared by the use 
 of ethyl, propyl, and butyl bromides or iodides. 
 
 An attempt to make Palmer’s (1) benzaldehyde condensation 
 product was attended by no reaction at all, the phenylarsine 
 being as^ain liberated on adding ice and dilute HgSO^. 
 
 Chloracetic aster did not couple v/ith the phenylarsine -Grignard 
 complex as one might expect its active halogen to lead it to do. 
 
 On the other hand it oxidized the phenylarsine to arsenobenzene , 
 as did the acetoacetic ester previously mentioned, presumably at 
 the expense of the carboxyl group. 
 
 Attempts to form ring structures including arsemic by the 
 reaction of dihalo’genated substances on the phenylarsine -Grignard 
 complex all were unsuccessful. The preparation of a piperazine 
 analogue of arsenic seemed possible through the following reaction: 
 
 CeHsAs: 
 
 J’i X B: h CHo-GHo -|Sr XMg 
 
 A A 
 
 ' Bil -CHo-CHo- iBr ' xE 
 
 ^AsCgHg = 
 
 CgHgAs 
 
 CHq-CHq. 
 
 ^..sCgHg t 4 MgBrX 
 CHg-CHg^ 
 
 It was also hoped that dichloroethyl ether might yield a morpholine 
 analogue as follows: 
 
 CgHgAs 
 
 
 ‘iS 
 
 CiCHp-CHp 
 
 > = C^HcAs^ 
 
 CHg-CHg. 
 
 CHo-CIL 
 
 
 0 t 2 MgClX 
 
 Likewise pent ame thy lene bromide was expected to yield a piperidine 
 

 
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14 
 
 analogue, arsepedine (20) by the reaction, 
 
 B I CHo-CHo.^ 
 
 1 X 
 
 CeHgAs 
 
 * B: h Hn-CHo^ 
 
 CHg-CHg 
 
 CHg r CgHgAs^ ^ MgBrX. 
 
 ’CHo-CH. 
 
 No substitution was found with the ethylene bromide and dichloro- 
 ethyl ether, only arsenobenzene appearing in the reaction mixture, 
 probably from the behavior of the Grignard complex as an alkaline 
 condensing agent. Principally arsenobenzene resulted from 
 the reaction with pent ame thy lene bromide, but another soluble 
 fraction V/ as distilled, and the distillate on standing yielded 
 crystals of phenyl brompent ame thy lene arsinic acid. 
 
 
 BrCH2CH2CH2CH2CIi2 
 
 'AsO(OH) 
 
 
 which indicated that a secondary arsine had been formed, phenyl 
 brorapentarne thy lene arsine. 
 
 
 ErCHgC HgCIIgCH ^ Hg- 
 
 AsH. 
 
 Tith benzyl chloride in the theoretical amount (2 mols) only 
 one seemed to enter, as evidenced by the subsequent air oxidation 
 to phenylbenzyl arsinic acid. \"/ith twice the theoretical amount, 
 however, some tertiary arsine probably formed, but combined with 
 more benzyl chloride to yield phenyl tribenzylarsonium chloride. 
 
 No coupling could be induced with aromatic halogens, even the 
 active halogen in p-chloronit robenzene . 
 
 It v;as foimd impossible to make the p he nylar sine -Grignard 
 complex by the action of magnesium on phenylarsine dichloride, 
 v;hich might be expected to take place as follov\Ts: 
 
 CgKgAsClg t 2 Mg = CQH5As(MgCl)2^ 
 
a la.’l 
 
 
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15 
 
 Thus it is seen that phenylarsine shows a very strong ten- 
 dency to act as a reducing agent on oxygenated substances (even 
 carboxyl groups)^ and dihalogenat eu substances, itself being ox 
 idized principally to arse nobenzene . Consequently reactions 
 which iruj^ht be predicted by analogy to reactions of the amines, 
 in the case of phenylarsine very frequently occur instead as 
 oxidation-reduct ion reactions Vvhenever the opportunity presents 
 itse If. 
 
. . V I 
 
 TJ 
 
 
 ’ -r\;i 
 
 '^vi ;.’ : , 'C'l 
 
 ^ ^ ‘ ■■" ;’’V< ^ 
 
16 
 
 IV. EXPElRIJffiNTAL 
 A. Preparation of Phenylarsine . 
 
 Phenylarsonic acid, from v/hich phenylar sine was t o be prepared 
 by reduction was made by the method desdribed by Norris (7). 
 
 For this purpose tv;o deep cylindrical copper cans, each holding 
 25 liters, v/ere used. In each can v/ as mixed one kilo of arsenic 
 trioxide and two kilos of sodium carbonate to which v/as added 
 six liters of v/ater. Live steam, was conducted into the mixture 
 v:ith stirring for about 15 minutes when practically all the ar- 
 senic had gone into solution. This step v/as found materially to 
 Increase the yield, as the arsenic trioside does not enter very 
 readily into solution in sodium carbonate at ordinary temperature, 
 and b e ing heavy is likely to settle into a compact mass in the 
 bottom during the diazot ization even though stirring is employed. 
 Then 45 gram.s of copper sulfate dissolved in water was added and 
 stirred in. The tv;o cans were placed side by side in a deep 
 wooden tub and surrounded by w"ater to which was added a little ice 
 occasionally as needed to maintain the reaction mixture at 15°. 
 
 For each of the twn batches four charges of diazo solution were 
 made up as needed, each charge containing 
 186 grams {182 cc.) aniline 
 400 cc . concentrated HCl 
 
 1 liter water and ice to make up 5 liters. 
 
 140 grams NaN02» 
 
 For the diaao sollition two large bottles v;ith side vents at 
 the bottom were used from which the s-olution was donducted by 
 a tube provided with an adjustable pinch-cock. The aniline and. 
 

 
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 ' ‘“jt ;• ' S..vii ' '' >■■■•■' ». ‘J 
 
 
 ■I 
 
 ., i 1 /Ai^ 
 
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 St f .t- N/i; ri . V . /aSS§i»jKrH 
 
 ^ ■ V • -^5 "■T*.'i’ *'iM •'■ J 'v*‘-' 'U 
 
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 7 T.t;-’* • u n'i’ 4 Vrr, ^ 
 
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 n 
 
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 t‘^'*- lt>W 
 
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 1 1 * 
 
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 s» 
 
 .'(fw. ‘r -00 n ♦.'-/ 
 
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 ■ \ . ■ 
 
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 .;:p' 
 
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 ..^ , . . :■ . gi /':;i 
 
 ' ‘^i<4 i, - JnX*‘- w M 
 
 t ■ :t it , M awv,* l. .vl‘*^*/.w 
 
 4 ' ■" ' 'M ■ :i 
 
 l» 
 
 i 
 
 ■* 
 
 .« . I *i * \ \ 
 
 j- 
 
 • # ' ' ' ' '■ ' ' ’’ ' M 
 
 a - ■ iK'-jo 
 
 .> -i?w 
 
 ■k*. 
 
 , "'- '.'jfiW'fS ,l(i* ■ • OillB ':;^; kj 
 
 'J* *J«. • * jJ'il! ,. J . ,1 mYASj# 
 
 4 ' 
 
 :drii?.fu;:’ I 
 
 ‘'Ir 
 
 r;'\'^'. '"■■'■ .;■*■■' 'vV-'" ',' .■ X /J 
 
 * 1 i~^ii‘ r tfli >iih ii ni i -Jt ^ > ■^itiMlir"i‘> r>ini imiPii i#d ^/^rMBHBifiliiiilH 
 
 
 
17 
 
 water were put in these bottles, and to it v;as added the HCl. 
 
 Ice was added to make up to three liters (previously marked on 
 the bottle), and the sodium nitrite dissolved in as little v/ater 
 as possibly was added s lov/ly with stirring. The sodium arsenite 
 solution v/as efficiently, though not vigorously, stirred with 
 motor driven stirrers, and the diazo solution was ru.n in slowly 
 in a stream about the size of the lead in a pencil. At this 
 rate the ice is sufficient to keep the solution cold until it 
 is all run in. Considerable frothing occuirs because of the 
 evolution of carbon dioxide, but the occasional addition of a 
 little benzene is effective in contbrolling it. 
 
 The m.ixtujT-e is stirred for an hour after all the diazo 
 solution has been run in, and then allowed to stand over night 
 in order to allow tarry matter to settle out. After filtering, 
 the solution is concentrated in large evaporating dished on 
 steam cones to about five liters for each batch. At this point 
 the addition of 100--200 cc . of concentrated HCl ¥/ill precipitate 
 considerable tarry matter withoiit throwing dov/n any of the acid. 
 It should then b e filtered and cooled. The combined batches 
 (about 10 liters) Vi/ere put in a four gallon stone Jar Vi/hich was 
 set in a sink and cooled v;ith running v/ater. Concentrated HCl 
 v;as added with stirring until the reaction to litmus paper was 
 decidedly and promptly acid. The phenylarsonic acid separated 
 out until the contents of the Jar were almost solid. After 
 standing over night the acid v/as filtered and sucked dry as 
 possible and washed with a little distilled Virater. The nearly 
 white product Vvas spread out to dry. The filtrate was neutra- 
 lized vjith ammonia, and a solution of ferric chloride added as 
 

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 ^ i I i. ^ I ^ iJ ^ 
 
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 y i -j. 
 
 -• ■ , _ A. J 
 
 W<i 
 
 
 
 
 , «f \ 
 
 
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 r I r,, I ••( , 1 r ■ -I j!'.; 9 'f‘"ll.' ' ; e .ilPjH: M' ji» 
 
 I • J^PK 
 
 { M - .ta ^ .i ft 
 
 
 ^ r« o'*' ' 'V ■■ •!■(.!. ••MU yv'&jffi 
 
 IA' • - •:i:jr^!-^ -V \a.‘/-s 
 
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 ' ' ■ , '■' ■■ <*' ' I'^J^'' r^H'' I 
 
 
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 t». '-K** 
 
 or . y ‘iJt'Jl ^*'(^ t,- 
 
 
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 ' ' . ‘ I ! r/ if/ 
 
18 
 
 precipitation continued., it being necessary to add more ammonia 
 from, t ime to time to maintain a neutral solution. The ferric 
 salt formed is very insoluble (the filtrate gave no reaction v; ith 
 potassium ferrocyanide ) ; it is v;hite and very fine, settling 
 slowly and filtering with difficiilty. This product is of course 
 very’' impure since tv/enty per cent excess AsgO^ v;as used at the 
 start and v/illbe precipitated as ferric arsenite. Neverthe- 
 less it serves equally as v;ell for rediiction as the free acid. 
 
 Its content of phenylarsonic acid depends of course on the com- 
 pleteness of the precipitation of the free acid, v;hich varies , 
 Thirty per cent yields of phenylarsine were obtained from the 
 iron salt, vi/hereas the yields on the free acid average betv/een 
 forty and sixty percent, A yield of 93 percent phenylarsonic 
 acid based on the aniline was obtained by this method. 
 
 For the preparation of phenyrlarsine the pheny^lar s onic acid 
 was reduced with amalgamated zinc dust and hydrochloric acid: 
 CgH^AsO^Hg t 6 H = CgHgAsHg t 3 HgO 
 
 Batches of 200 grams (1 mol) v/ere reduced using 400 grams zinc 
 dust (6 m.ols, or twice the theoretical amount) and one liter of 
 concentrated HCl. About 25 grams of mercuric chloride v/as 
 dissolved in a liter of water in a 5 liter round -bottom IPlask. 
 
 The zinc dust was added and shal?:en up several minutes to insure 
 even amalgamation. The phenylarsonic acid v/as then ad.ded and 
 the v/hole mixture v/ell shaken. The flask v;as fitted with a two- 
 hole rubber stopper, one hole for the condenser, and the other 
 (v/hich is plugged during the reduction) for a delivery tube to 
 draw off the ether layer after reduction. In the top of the 
 condenser was fitted a 500 cc. dropping funnel and a vent tube for 
 

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19 
 
 the escaping hydrogen TCJhich dipped into a test tube containing 
 ir.ercury to serve as a trap to prevent entrance of air into the 
 apparatus. A half liter of ether v;as admitted through the 
 dropping funnel and was replenished occasionally as it v;as car- 
 ried out with the escaping hydrogen. The apparatus was placed 
 in a sink and the condenser v/ater allowed to run dovm over the 
 flask in order to minimize the loss of ether. The hydrochloric 
 acid was admitted slowly through the dropping funnel in batches 
 of 250 cc . per day and the m.ixture allowed to stand a day or 
 two after all the acid had been added. If the process is hurried 
 a considerable amount of zinc is 1^'ft unattacked in the flask and 
 a low yield of phenylarsine is obtained. 
 
 The plug is rem.oved from the stopper in the flask and the 
 delivery tube inserted Vvhich runs into a liter separatory funnel 
 supported on a ring stand from the floor. Ftised calcium chloride 
 is placed in the funnel and COg conducted into it. It was found 
 that placing a v; ad of glass wool in the bottom of the funnel 
 prevented much annoyance from the stop-cock sticking. Water 
 v;as admitted through the dropping funnel until the ether layer 
 arose and was forced out through the delivery tube into the se- 
 paratory funnel, v;hich w’as then stoppered and allov;ed to stand for 
 about an hour. The dried ether solut ion vi?as then run into a 
 
 distilling apparatus consisting of a 500 cc . distilling flask 
 and a 250 cc. receiver from vi/hich the air had been displaced by 
 COg. A small tube extending to the bottom of the distilling 
 flask conducting dry COg, its flow being regulated by an ad- 
 justable pinch- cock, v;as used to prevent bumping and oxidation 
 during distillation. The ether was evaporated off over a steam 
 
T 4. 
 
 i. 
 
 rt 
 
 
 • c 
 
 : 'a;- ' . ’ I 
 
 
 ( 
 
 e 
 
 I 
 
 <■ . . o :t ^ i/"* 
 
 t r r > n 
 
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 r.f 
 
20 
 
 jet and allowed to pass on through the uncooled condenser. An 
 
 aspirator was connected (with a three-way stop-cock and a manometer 
 
 in the train) to the condenser and e vacuat ion started, restricting 
 » 
 
 the flow of CO2 hy the pinch-cock so that its rate of bubbling 
 through the drying tube was somiewhat less than before, insuring 
 no admission of air into the train betv/een the flask and the CO2 
 tank. ?/hen the phenylarsine began to distil, the condenser 
 was cooled v;ith running water. After completion of the distil- 
 lation, the three-way stop-cock in the aspirator train was closed 
 and COg rapidly admitted to fill the apparatus. For preserving 
 the phenylarsine test tubes were draw^n out to a narrow neck, 
 filled with CO2J stoppered, labelled, weighed, and the weight 
 marked on the label. The receiver v/as removed and immediately 
 stoppered v/ith a rubber stopper lihrough which passed a small tube 
 conducting ^^02 • The phenylarsine was then carefully poured 
 out through the sidearm of the receiver into the test tiibes 
 which were then immediately stoppered. The steady stream, of 
 CO2 prevents any oxidation whatsoever. The tubes were sealed 
 off at the neck and Vveighed, each with its corresponding stopper 
 and sealed-off piece. This weight is entered on the label, and 
 by difference is obtained the v/eight of the phenylarsine in each 
 tube. This method is much more satisfactory than attempting to 
 weigh up a sample for each experiment. Portions of 15 — 20 grams 
 were pit up in each tube. The capillary tip can be snapped 
 off the tube and its contents transferred to a reaction apparatus 
 with practically no loss from oxidation. 
 
^ >■ 
 
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21 
 
 B. Reactions with Phenylars ine . 
 
 With Acetic Anhydride , 
 
 Phenylars ine (17 g) was added to 3 mols of acetic anhydride 
 in an atmosphere of CO 2 . No discernible evolntidn of heat nor 
 evidence of any reaction was observed. The mixture v/as refluxed 
 over night and vacuum distilled, all passing over in the neighbor- 
 hodd of 85° at 50 mm. pressure, Phenylarsine boild at 84° at 
 55 mm. The effect of a few drops of Concentrated H 2 S 04 was tried: 
 it sputtered as it was added but no change was observed except 
 the remainder of a small am.ount of tarry matter on distillation. 
 
 With Acetyl Chloride^ 
 
 Three mols of acetyl chloride were added to the distillate 
 containing the phenylarsine and acetic anhydride and refluxed 
 several hours. No solid product appeared. On distillation 
 considerable dark tarry substance remained in the flask under 
 90° at 45 mm. On attempting to take up this material in benzene 
 the m.ass loosened up and partially went into solution. The 
 part insoluble in benzene v/as taken up in alcohol, decolorized 
 v/ith bone-black, and evaporated in an attempt to crystallize, 
 but practically nothing remained. Apparently the material, 
 which v/as very dark brov/n, remiained with the bone-black. 
 
 The reddish-brov/n benzene solution was evaporated on a steam 
 bath to dryness, leaving a sticky transparent residue; this was 
 taken up in alcohol and decolorized with bone-black. On con- 
 centrating, a little sticky, transparent, pale yellov/ residue 
 was left which v/as recrystallized from benzene and identified by 
 mixed mielting point as arsenobenzene , It seems likely that a 
 little phenylarsine remained with the tar and oxidized on expo- 
 
'V* 
 
 I 
 
 [» » . 
 
 
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 ' ■' > * '* 't 'JL 
 
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 . ' ,. 
 
 '{‘r^r . v-vr^uj(.^l P^rJr Jiflw .- ■q.c/’ ^CO'JI^ .t'liiiSiT'lw^' ’ 
 
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 ■ ' * ' .'■ ’ ■*> . '■ 'tirtfti;: !’ ' 
 
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 - J . ' ' ~ < ' . 
 
 tXi . ' * 4 ^ 
 
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 , f 1 * 4 ‘»^'t' ^ji/jf.ti< x~- ■ .r 1 8 
 
 1.^- jjjl • -’.j -^'‘' ■ 
 
 iff-'ilff-'-jiv-'f J. .* i, ‘V - ' ’ ' 
 
 / ''KSl . ' . ■ . , 
 
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 ... ^ . ■* ll J..:' .. i . '!• 
 
 9 
 
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 . , ". ‘ ■' f . . ■*.' •: • ’« I.'-*- !' ' W •jJiv'i^' 
 
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 q .1 ■ \ \ 
 
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 -r-,j^f> '■•f- •■■?»•.? '.I,' '.rr 
 
 vsci'scs^r^ft* cs«^i; 
 
22 
 
 sure to the air to arsenobenzene . Apparently no clearly defined 
 reaction occurred. 
 
 With Benzoyl Chloride , 
 
 Phenylarsine (16 g) was sealed up v/lth three mols of benzoyl 
 chloride and a small excess of CaO in a bomb tube. No heat was 
 evolved, and no change was apparent after several hours. The 
 tube was left in a steam bath over night; the contents turned red 
 and on cooling solidified. Considerable pressure was evident on 
 opening the tube. The mass was extracted tvirice with ether and 
 the residue treated with hot benzene. 
 
 The ether extract was shaken out 6 --8 times with dilute NaOH 
 to rem.ove benzoic acid and benzoyl chloride. The ether was 
 evaporated off, leaving a pale yellov; oil which solidified on 
 exposure to the air for a short time. It would not then 
 redissolve in ether. Before solidifying phenylarsine was 
 apparent from its odor and blistering action on the skin. The 
 solid was purified and identified as arsenobenzene by mdxed mel- 
 ting point. Arsenobenzene was also found in the benzene extract 
 from the original product. No evidence of a benzoylated phenyl- 
 arsine was found. 
 
 With Acetoacetic Ester . 
 
 Phenylarsine (6.8 g) with two mols of acetoacetic ester and 
 three drops of concentrated HCl were sealed up in a bomb tube. 
 
 There was no noticeable evolution of heat, but the mixture became 
 immediately tiu’bid and colorless globules gradually separated 
 and rose to the surface forming a layer corresponding approximately 
 to the theoretical volume of water splitting out mol for mol v/ith 
 the phejiylars ine . This layer gradually disappeared, and the 
 
-.TMjLp.r 
 
 5;'’- ‘ .‘-M T4, 7 (?: 14,.^ 
 
 } :■'■•"• ■ "■ii 
 
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 , -Wni 
 
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 , Sj;/; 
 
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 i ’0 ‘ ■,'^?-. 
 
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 n: 
 
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 . f 
 
 
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 ^ I - : -hed '3 l> ^ j ’ X ■ ^ .♦•Ai 
 
 m 
 
 texiro Q»j' ‘ 
 
 / Vi= .'f • -■ c 
 
 
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 1^^- ‘Jr^r^-’'''f f- ‘^•' ; L wr. • Cico , fi . l)»’ ' 
 
 idioD V/'' '•- 
 
 
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 • '■ / '• - t:^ / .■’ .J' •» '■' ‘'7j¥ 
 
23 
 
 mixture turned slightly yerllow. After warming gently for a fev; 
 hours and cooling, a very small amount of crystalline material 
 appeared. It was heated over night on a steam bath, v/hereon a 
 mass of large, nearly white needles had formed to a depth of 
 about one -fourth of the liquid. On continued heating the mdxture 
 became a solid mass of crystals, and a little liquid condensed 
 on cooling the tube. Very high pressure viras observed on opening 
 the tube. The released gas had a pleasant ester-like odor. 
 
 The crystalline solid v/as found to be almost pure arsenobenzene . 
 
 On recrystallization from benzene it showed no depression in a 
 mixed melting point v/ith pure arsenobenzene, 
 
 VJith p-Nitrosodimethylaniline . 
 
 Phenylarsine (16.6 g) dissolved in dry petroleum ether was 
 slowly admitted to one mol of p-nitrosodimethylaniline in petro- 
 leum ether. Since the amine is spai'ingly soluble in the ether, 
 the m.ixture was shaken during the reaction, which proceeded 
 vigorously, but was subdued on cooling v;ith ice. After the 
 reaction a black tar-like material insoluble in the ether remained; 
 it was washed with petroleum ether and treated w ith b enzene , in 
 which it was largely soluble. The residue was found to be sol- 
 uble in alcohol and v/ater, imparting to each a deep blue color. 
 
 The deep red, almost opaque benzene solution v/as found to contain 
 a small amount of the unused p-nitrosodimethylaniline; on con- 
 centration several crops of brown soft crystalline material were 
 obtained, which were evidently contamdnated by the blue substance. 
 It v/as found practically impossible to separate the blue material 
 from the rest. Even the first few crops of cryttals, v/hich v/ere 
 nearly free from it, after several recrystallizations from chloro- 
 

 
 ’•’K i?nv> 
 
 
 tJH .,. ..' 1 .' J 
 
 .l0''tliq>li J, 
 
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 i >■. .]:■ v'.' 7 v‘,'. . . i .: 1 K "'* 77 +., 3 t . 
 
 1 
 
 . .:d 
 
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 ’♦•'Pi - ■ 'v ^ 
 
 
 '. > ■ i 
 
 l' 5 » 
 
 
 
 
 .•^ -;X rr: i‘ .‘V* 
 
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 ■* • ‘ V,.- \'i- 
 
 .. -jr. r - 1 ‘;t' i 2 .‘K%«^''f.' 4 Jt^*' 
 
 ' /=Vr, *A- , 4 *. 
 
 ■ '* " ' ' 
 
 f'fC t jt .T 1 
 
 i' ...>*v* 
 
 
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 f 
 
 V. 
 
 y- tAL££4l‘ 
 
 
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 vs M 
 
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 l»r‘. 3 '-’ 
 
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 ‘ • ’ 4|iSl.<%;xW 
 
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 I ,rr .vrowA^^W; : 
 
 :•; pg^' 'i ' ■■ '^'4/ '/ ■ -41 
 
 %■: im s^ar-: ^atfcVJ ; -• jwr ,: 
 
 li! xo-v:-/ ,Va .>-6; n^t-vs^*'' , .■ - 
 
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24 
 
 form showed traces of it. 
 
 For this reason the entire reaction was repeated in benzene 
 in vi/hich the amine v;as first completely dissolved. In this case 
 no blue substance v;as formed, and no odor of phenylarsine v/as 
 evident after the reaction. The solution as before v/as deep 
 red. On concentrating and after standing about 12 hours the 
 material crystallized out as in the first case, and was recrystal- 
 lized from chloroform: m.p, 140° (darkens between 130° and 155^) . 
 
 The reaction was similarly carried out in acetone v/ith much 
 the same results, except that a cleaner product, and a somewhat 
 better yield was obtained directly on concentration of the re- 
 action mixtur-e; 6,8 grams of unre crystallized, nearly white 
 product was obtained from 14 grams of phenylarsine. IfJhen the 
 acetone solution was concentrated to a very small volume, a 
 crop of crystals v/as obtained rich orange in color and insoluble 
 in water, but soluble in dilute acid to a deep red color. It 
 was consequently -purified by dissolving in dilute E 2 ^ 0 ^, filter- 
 ing to remove arsenobenzene (considerable of v/hichv/as present), 
 precipitating with dilute ITaOH solution, and filtering with 
 suction. It v/as recrystallized from acetone : m.p. 266--267°. 
 
 4,4 ’ -dime thy lamino -azobenzene , ( CH|^) 2 N-C 0 H^-N:N-CgH^N ( CH ^) 2 
 melts at 265° (Richter^. The remaining acetone solution con- 
 tained a black, tarry material, 
 
 BecaxTse of the formation of considerable arsenobenzene and 
 azo compound, it v/as considered that the oxidation might be less- 
 ened by greater dilution v/ ith acetone and by running the nitroso 
 compound into the phenylarsine. Consequently the phenylarsine 
 (14.7 g) v/as dissolved in 400 cc. of acetone and the nitroso- 
 
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 • : nrAyi t /,♦ /!i,^:U , t 
 
 f -i. ...^ 
 
 7 • 
 
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 b. . 
 
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25 
 
 dlmethylaniline (1 mol) in 300 cc. of acetone was added dropwise 
 m'ith stirring caused by bubbling COg through the phenylarsine . 
 
 The deep green nitroso solution ;vas decolorized as it promptly 
 reacted, even though the solution v/as cooled with ice, until 
 about one-third of it had been added, then the reaction mixture 
 became green. After standing over night a sm.all amount of cry- 
 stalline material had appeared. Four crops of crystals were 
 obtained by successive concentrations, the last being alrmst to 
 a syrup and requiring much washing with acetone to remove the tar. 
 Hov/ever none of the p-di( dine thy lamino)azobenzene appeared as 
 in the previous modification at this stage. The yield was 
 also somewhat higher, am.ounting to 7.6 grams of crude product. 
 Even better yields and more satisfactory resu.lts were obtained by 
 adding the nitroso solution at once v/ith vigorous shaking in the 
 cold. 
 
 The white product crystallized from chloroform in fine white 
 fluffy needles. It v/as almost instantaneously soluble in ¥\rater 
 but could not be recovered from it either by concentration on a 
 steam b ath or extracting with iiranlscible solvents. On concen- 
 tration it turned blue and on coming to dryness appeared as a 
 dark blue residue, probably the same as obtained in the earlier 
 reactions. The aqueous solution gave vivid color reactions 
 viTith silver nitrate and ferric chloride solutions. 
 
 Subs., 0.1487: COg, 0.2512 
 
 Calc, for Cg^Hg^O^NgAsg: C, 46.00^. Found 46,10^ 
 
 Subs., 0.1284: 18.27 cc. Iodine, 1 cc . r 0.002 g. As. 
 
 Calc.: As, 28.75^L Found 28.44,^ 
 
i > 
 
 A 
 
26 
 
 Subs,, 0.3984: 19.7 cc . N at 28*^ and 740.5 mm. 
 
 Calc.: N, 5.37^. Found 5.35^ 
 
 The arsenic was determined by Robertson’s method (19). 
 Analyses v/ere made on pure arsenobenzene in an attempt to apply 
 the Parr peroxide bomb. The fusion was acidified v;ith HCl and 
 boiled to decompose the H 2 O 2 ; the arsenic was precipitated in 
 strong HCl in the cold as the pentasulfide and weighed in a Gooch 
 crucible (Treadvjell-Hall, vol. II, p. 205) . Good results were 
 obtained, but the method proved unsatisfactory with the compound 
 containing nitrogen, probably because of the formation of oxides 
 of nitrogen in the fusion and the subsequent liberation of free 
 sulphur in the precipitation v/ith H 2 S. Attempts to extract the 
 free sulphur v/ith CS 2 according to Treadwell-Hall, vol. II, pp. 
 169--170 were unsuccessful because of the tight, compact nature 
 of the precipitate. 
 
 With ^ Ketone Gri.gnard Compound . 
 
 To ethyl magnesiixm b romide (2 mols) lo/as added two mols of 
 dry acetone. After the reaction v;as complete, 17.7 grams of 
 phenylarsine (1 mol) v/as added. No reaction was apparent and 
 the mixture v/as refluxed with stirring for several hours. Ice 
 and dilute H2S0^ v;ere added and the ether layer separated. The 
 odor of phenylarsine 'was apparent in the ether, and considerable 
 arsenobenzene crystallized out, v>fhich v/as identified by mixed 
 melting point. Evidently no reaction took place, 
 
 C. Reactions with Phenylars ine-Grignard Complex. 
 
 Phenylarsine was dissolved in anhydrous ether and to it was 
 
I 
 
 
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27 
 
 slowly added two raols of an alkyl magnesiiim halide in e then 
 (ethyl bromide was used for making the Grignard reagent; methyl 
 iodide was tried but trouble v^as encountered from iodine being 
 liberated on decomposing the Grignard with dilute HgSO^j which 
 combines readily w/ith substituted arsines) . A voluminous evo- 
 lution of gaseous hydrocarbon occurred, and the reaction mixture 
 needed to b e cooled ocasionally. The reaction was carried out 
 in an atmosphere of dry nitrogen; as it proceeded, a layer of 
 heavy, greenish oil separated beneath the ether layer. An 
 attempt was made to isolate some of the product; the ether v;as 
 distilled off under vacuum in a water bath which v; as gradually 
 raised to 60° where it was maintained for over an hour. Nitro- 
 gen v/as then admitted and the muss cooled dov/n; it remained 
 soft and transparent like a heavy syrup. A portion removed on 
 a glass rod oxidized readily in the air and smelled strongly of 
 phenylarsine . Since the product v;ould not crystallize, no 
 attempt was m.ade to analyze it. 
 
 T/ith Acetyl Chloride . 
 
 Phenylarsine (15 g) v;as converted to the Grignard complex 
 and to it v;as added two mols of acetyl chloride dropv/ise; the 
 reaction flask v;as surrounded by ice, yet the reaction was ex- 
 ceedingly violent until about half the acetyl chloride had been 
 added. At this point a light yellow solid began to separate. 
 
 By the time all the m.aterial had been added a heavy, semi-solid, 
 oil-like material separated which soon solidified; after standing 
 stoppered for an hour the mass v/as nearly solid except for a little 
 ether yet present. The odor of acetyl chloride was still strongly 
 apparent . 
 
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28 
 
 Water v/as added and the mixture extracted w ith ether. The 
 solid material v^as washed with water to remove the magnesiujn salt, 
 recrystallized from benzene and identified as arsenobenzene , 
 
 The ether extract v;as vacuum distilled, but v/as exceedingly 
 small, only about 2 cc. of distillate being obtained boiling at 
 206° at 44 mm. with partial decomposition. 
 
 With Benzoyl Chloride . 
 
 The prededing experiment was duplicated using benzoyl chloride 
 in place of acetyl chloride. Results were practically the same, 
 though the reaction was not nearly so vigorous. The reaction 
 mixture was solid by the time all the material had been added, 
 and was orange color. The solid material after extracting w ith 
 v;ater was found to consist mostly of arsenobenzene. The ether 
 solution yielded a very small high boiling fraction Vihich on 
 cooling partially solidified. 
 
 With Eth:~ 1 Iodide and Bromide . 
 
 Phenylarsine (17 g) was converted to the Grisnard complex 
 and two m.ols of ethyl iodide were added to it. A lively reaction 
 occurred causing the ether to boil. When the mixture had cooled, 
 it was a homogeneous, nearly colorless solution. Ice and dilute 
 H 2 S 04 v/ere added to the mixture: no solid appeared and no odor 
 
 of phenylarsine was apparent. The ether layer was separated 
 and the aqueous fraction v;ashed once v/ith ether, v/hich became 
 dark from iodine liberated from decomposing HI, This color 
 disappeared on c ombining with the original ether fraction. The 
 ether was evaporated under vacuur.i leaving a colorless, mobile 
 liquid which distilled with considerable decomposition over a 
 wide range, 220 --260°. 
 
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29 
 
 The iodine was thought responsible for this conduct in having 
 added to form a pentavalent arsenic compound. Hence the entire 
 experiment was repeated using ethyl bromide instead of iodide. 
 
 The ether layer was v/ashed with v;ater and dilute NaOH to remove 
 magnesium salts and HE.r, dried with CaCl 2 ^ and distilled as be- 
 fore, ^n this case much closer boiling range was observed, the 
 maximum, being 220--230° v/ith by far the greater part of it going 
 over at 223--225*^; yield 12.5 grams. The distillate v/as added 
 to 1.5 mols of ethyl iodide in a pressure tube and heated on a 
 steam bath several hours. Vi'hen first mixed the solution Vi/as 
 clear, colorless, and homogeneous, but became turbid in a minute 
 or so. After heating for an hour on the steam bath, half the 
 contents of the tube were solid; in another hour it was nearly 
 all solid. The solid product was found to be too soluble for 
 satisfactory recrystallization from v;ater, alcohol, chloroform, 
 ether, and butyl alcohol. It was found, however, to crystallize 
 well from a mixture of 2 parts of benzene to 1 of acetone, from 
 which it v;as obtained in beautiful hard, granular, v/hite crystals 
 of prism formation. It melted sharply at 104°, 
 
 Subs., 0.2826, 0.2394: 27.80, 23.60 cc. Iodine 
 
 (Icc, r 0.001963 g. As) 
 
 Calc, for CgH 5 As(C 2 l%) 3 l; As, 20.49^o 
 Calc, for CgH3As(C2Hg)3l.H20: As, 19.53^ 
 
 Found, 19.31, 19.35^ 
 
 With n- Propyl Bromide . 
 
 Phenylarsine (16 g) v/as converted to the Grignard complex 
 and to it v;as added 26 grams of n-propyl bromide (2 mols) . The 
 reaction went smoothly, the m.ixture v/arming up appreciably. 
 
30 
 
 The mixture was decomposed v/ith ice and dilute H2S0^ as before. 
 
 The ether fraction was vacuum distilled, boiling at 138--140°/25 mm 
 A yield of 10 g. phenyl -dipropyl arsine was obtained. A portion 
 of it (5 g) was mixed with 5 g. n-propyl iodide and heated in a 
 pressure tube on a steam bath for 3 hours. It had changed to 
 a heavy darjc colored oil v/hich solidified on cooling to a soft 
 mass of crystals. This material was found to crystallize well 
 from the benzene acetone mixture used before, and appeared 
 similar to the analogous ethyl compound: m.p. 168°. 
 
 Subs. 0.3182, 0.2750: Iodine 29,54, 25.51 
 
 (1 cc. iodine = 0.001963 g. As) 
 
 Calc, for GQll^As{C^Er^)^l: As, 18.38^ 
 
 Found, 18.22, 18.21^^ 
 
 With n- Butyl Iodide . 
 
 Phenylarsine (16 g) was converted to the Grignard complex and 
 to it was added two mols of n-butyl iodide. No reaction was 
 apparent, the heavy dark layer below the ether remaining unchanged 
 in appearance. The mixture was refluxed over steam for half an 
 hour and allowed to cool; the liquid appeared to be homogeneous, 
 but after standing for some time tv/o layers v/ere apparent. 
 
 They were nearly the same color, light amber yellow, in contrast 
 with the almost opaque greenish layer of Grignard complex. 
 
 After treatment as before the ether fraction was vacuum distilled; 
 b.p. 173--175°/38 ram. Yield 15 g., 55^. 
 
 A portion of the distillate (5 g) V\ras mixed vath 5 g. of n- 
 butyl iodide in a pressure tube. After heating two hours in a 
 steam bath a little heavy dark oil appeared in the bottom of the 
 

 .n 
 
 r 
 
 ro 
 
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 V ’ - -■*. 
 
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 '! ■; N ^ .. 
 
 •‘ '. '.» w ' l.ii} 
 
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 ^ /•' ^* - .rXc '? *- ': i'- 
 
 ‘ ix <'M ,f o t 
 
 ^ . I , I Ij.f t' 
 
 '4 
 
 K* 
 
 . 7 ' 
 
 .’ -‘ r ■. *'■ ■ ' I 
 
 \ V 
 
 • dr-u. 
 
 • i'. 
 
31 
 
 mixtiAre . Heating 24 hours more converted the entire mixture to 
 the dark oil, which on cooling solidified into a mass of soft 
 crystals. The material v;as twice crystallized from benzene, 
 from which it separated in white, thin flakes resembling benzoic 
 acid; m.p. 140°, yield 4.5 g. 
 
 Subs., 0.2492: Iodine 20.97 (lc5?. = 0.001963 g. As) 
 
 Calc, for CgHgAs(C^Hg)2l: As, 16.67. Found 16.52 
 
 An attempt was made to analyse these three arsoniiim iodides 
 for iodine boiling up with an excess of standard AgNO^ and 
 titrating w ith iTH^CNS, using ferric alum as an indicator as 
 suggested by Behn (3). But the method v/as found impractical 
 because of coloration difficulties which masked the end-point 
 completely. In one instance the first addition of thiocyanate 
 produced a deep violet coloration. 
 
 With Benz aldehyde . 
 
 Phenylarsine (17 g) was converted to the G-rignard complex 
 and to it v;as added two mo Is of benzaldehyde dissolved in anhy- 
 drous ether. A decided evolution of heat occurred and the solu- 
 tion became heavily turbid. The heavy oily layer under the 
 ether did not change in appearance, however, even after prolonged 
 and vigorous shaking. Ice and dilute were added and the 
 
 ether layer separated. A yellow crystalline material soon 
 began to separate from the ether and continued coming out for a 
 couple of days. It was identified as arsenobenzene by mixed 
 melting point. Evidently the phenylarsine had not reacted. 
 
 With Chloracetic Ester. 
 
 Phenylarsine (16 g) was converted to the Grignard complex 
 
1 
 
32 
 
 and to it v/as added two mols of chloracetic ester. The reaction 
 v/as vigorous and required to be cooled with ice. Solid light 
 yellow, material separated from the mixture. On decomposing w ith 
 ice and dilute HgSO^ considerable of the solid was present and 
 v;as filtered out. Several crops v/ere similarly obtained before 
 no more finally appeared. The material v/as identified as arseno- 
 benzene by mixed melting point. 
 
 Phenylarsine (10.5 g) was converted to the Orignard complex 
 and to it v/as added 15.7 g. (1 mol) of ethylene bromide. Little 
 heat was evolved, and a light colored solid appeared. The 
 appearance of the mixture v/as not noticeably changed after re- 
 fluxing for an hour. -^fter decomposition v/ith ice and dilute 
 
 Practically nothing was left after evaporating off the ether. 
 
 The solid v/as identified as arsenobenzene by mixed melting point. 
 
 Phenylarsine (11.4 g) v/as converted to the Grignard complex 
 and to it v/as added 10. 6 g. (1 mol) of dichloroethyl et?ner. 
 Shortly a reaction began causing the ether to boil. A pale 
 yellow solid appeared in the mixture and on standing considerable 
 more appeared. After adding ice and dilute HgSO^ the solid v/as 
 filtered out. On standing more solid appeared in the ether 
 fraction and v/as filtered oiit . It v/as identified as arsenoben- 
 zene by m.ixed melting point. 
 
 ■’’.^ith Pent amethylene Bromide . 
 
 Phenylarsine (14.6 g) was converted to the Grignard complex 
 
 P/ith Ethylene Bromide . 
 
 ^s'^^4 solid was' filtered out and the ether layer separated. 
 
 and to it v/as added 21.8 g. (1 mol) of pentamethylene bromide. 
 
33 
 
 The reaction proceeded vigoroiisly. After decomposing with ice 
 and dilute the ether fraction v;as vacuum distilled. A 
 
 small amount of material (about 4 grams) passed over at 160-- 
 170°/30mm, A mercuric chloride derivative prepared in alcoholic 
 solution m.elted over considerable range even after several re- 
 crystallizations from alcohol, and 15--20 degrees lower than the 
 mercuric chloride derivative of arsepedine (20). 
 
 The reaction was repeated in the cold with stirring, using 
 15,1 g. of phenylarsine . The ether extract distilled over con- 
 siderable range and amounted to about 10 gram.s of impure material 
 ( 150--200°/35--40 mm.). On standing, the distillate became half 
 solid withv/hite coarsely crystalline material, which was re- 
 crystallized from a mixture of acetone and benzene; transparent, 
 granular cubes and prisms, m.p. 161--162^. The m.aterial w^as 
 readily sol’ble in v/ater, giving a distinct acid reaction to lit- 
 mus paper, 
 
 Tubs. 0,2071, 0.2403: Iodine 25.09, 29.10 
 
 (1 cc . iodine - 0.001965 g. As) 
 
 Calc, for (CgH5)Br(CH2)5As0(0H) ; As 23.51?^ 
 
 Found, 23.78, 23.77f^ 
 
 The STibstance gave a decided test for halogen by the copper 
 v.'ire miethod, 
 
 With Allyl Bromide . 
 
 Phenylarsine (21.9 g) was converted to the 3-rlgnard complex 
 and to it was added 34.4 g. (2 m.ols) allyl bromide. The reaction 
 was carried on in a two-necked flask provided w ith a stirrer and 
 a reflux condenser. The flask was surrounded with salt and ice 
 and the allyl bromide was added dropv/ise through the condenser. 
 
34 
 
 Considerable light yellow solid appeared during the reaction 
 which was identified as ar s e nob en zone by mixed melting point. 
 
 The ether layer yielded about 1 cc, of heavy oil after evaporating 
 off the ether, v/hich, distilled v/ith decorapos.it ion. 
 
 VJith Benzyl Chloride . 
 
 Phenylarsine (20.5 g) v/as converted to the Grignard complex 
 and to it was added 34 g. ( 2 mols) of benzyl chloride in the f 
 
 cold v;ith stirring. After adding ice and water and separating 
 the ether layer, a white, finely crystalline materia 1 b egan to 
 separate from the ether solution. This white solid continued 
 to form for several days, when the ether solution remained clear 
 on filtering. 
 
 The solid was found to be soluble in dilute alkali and pract- 
 ically insoluble inv/ater, hot or cold. It v/as therefore dissol- 
 ved in dilute NaOH, filtered (although it was almost entirely 
 dissolved), acidified, fi Itered v; ith suction, v/ashed v/ith water, 
 and sucked as dry as possible. It v;as found to crystallize 
 beautifully from hot alcohol, frora which it separated in fine, 
 white, glistening needles: m.p. 196--197‘^. 
 
 Subs. 0.3415: Iodine, 46.45 cc. ( 1 cc. = 0.001963 g. As) 
 
 Calc, for CgH 5 CH 2 (CgH 5 )AsOOH: As, 27.17^ 
 
 Found: As, 26.70^ 
 
 The experiment was repeated vrith 20.2 g. phenylarsine. 
 
 •Fwice the theoretical amount of benzyl chloride (66.5 g., 4 mols) 
 was added v/ith stirring at room temperature. On the addition of 
 ice and dilute HgSO^ a v^hite solid immediately precipitated and 
 v;as filtered out. It was fo\md to crystallize well from hot 
 water, coming down in fine white needles: m.p, 142--143'^. It 
 

35 
 
 did not appear any more soluble in weak alkali than in v/ater. 
 
 Subs. 0,2687: ^odine 21.85 (1 cc. = 0.001963 g. As) 
 
 Calc, for 0'gH5(Cgil5CH2)3AsCl: As, 16.29,^ 
 
 Found 15 . 96/j 
 
 A voluminous yield of phenylbenzylarsinic acid very slowly 
 separated from the ether solution as in the first case. 
 
 With Aromat Ic Halides : Brombenzene . 
 
 Phenylarsine (19.4 g) was converted to the Orignard c omples 
 and to it was added 2 mols of brombenzene. As no reaction y/as 
 apparent the mixture was refluxed several hours v;ith stirring. 
 After adding ice and dilute HgSO^ the ether layer v;as found to 
 contain the unreacted phenylarsine and brombenzene . For, after 
 allov;ing the phenylarsine to oxidize to arsenobenzene, filtering, 
 and distilling the ether extract, the boiling point was found to 
 coincide with that of brombenzene. 
 
 7/ith p-Chloronitrobenzene . 
 
 Phenylarsine (16.1 g) v/as converted to the Grignard c omplex 
 and to it v/as added two mols of p-ohloronitrobenzene dissolved in 
 dry ether. The mixture v/as cooled with ice and stirred. Con- 
 siderable arsenobenzene v/as formed diiring the reaction, and more 
 appeared in the ether solution after decomposing with ice and 
 
 dilute H2S0^ and separating the layers. No basic amino compound 
 was found;’ on making the aqueous fraction alkaline and shaking out 
 with ether. Consequently the nit ro group v/as not reduced to an 
 amino group. An ether soluble material (containing no arsenic) 
 was found in the ether fraction along v/ith unreacted p-chloro- 
 nitrobenzene , from which it v/as separated by several crystalli- 
 zations from alcohol; it was soft, orange colored material; 
 
36 
 
 softens and melts 170--176®. 4, 4 ’ -dichloroazobenzene melts at 
 
 163--184° (Richter). 
 
 Further Study of the Reaction with Ethyl Bromide . 
 
 An attempt was made to find optimum conditions for the for- 
 mation of the tertiary arsine by altering the factors of heat and 
 mass relationship. 
 
 (1) Phenylarsine (18.5 g) was converted to the Grignard 
 complex and to it v/as added 26.2 g. (2 mols) of ethyl bromide. 
 
 The reaction mixture v;as cooled v;ith ice and stirred for an hour 
 after the materials were mixed. Without allowing to warm up, 
 the mdxture was treated with dilute Il2S0^ as usual. The ether 
 v/as evaporated under vacuumi; on admission of air the contents of 
 the flask became warir^ and entirely solidified. Some of the 
 solid was recrystallized from benzene and identified as arseno- 
 benzene by a mixed melting point. 
 
 (2) Phenylarsine (17,5 g) v/as treated as above, except that 
 before adding ice and dilute H 2 S 0 ^ it was gently refluxed for 
 half an hour. The ether layer was allov/ed to stand for some time, 
 v/hereupoh yellov/ needles of arsenobenzene separated o\it. On 
 evaporating the ether, a small amount, perhaps 2 cc. of the ter- 
 tiary arsine remained. 
 
 (3) Phenylarsine (18.3 g) v/as similarly treated v/ithout 
 cooling or refluxing, and twice the theory (4 mols) of ethyl 
 bromide. Stirring was continued an hour after mdxing the ma- 
 terials. After the usual treatment the ether fraction v/as 
 evaporated under vacuum. The residual oil v/armed up somev/hat 
 on admission of air, but no solid appeared; it was vacuum dis- 
 tilled, and redistilled. A fraction was taken at 125--130°/25mm. 
 
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 and a small high boiling residue remained. The distillate 
 weighed 11 g, , 4:5% yield. 
 
 It is evident tt least that cooling hinders the reaction 
 almost completely, and that the best yield is obtained at room 
 temperature v;ith excess of ethyl bromide. 
 
 Attempt to make the G-rignard Complex of Phenylar s ine 
 from Phenylar sine Dichloride . 
 
 Phenylarsine dichloride (22 g) was dissolved in anh^^-drous 
 ether and t o it was added 2 mols of magnesium. Wo reaction took 
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38 
 
 V. SUMYARY 
 
 1. It v/as fo-ond impossible to prepare acetylated or benzoy- .• 
 lated derivatives of phenylarsine analogous to the anilides; 
 either no reaction occurred at all, or the phenylarsine was par- 
 tially oxidized to arsenobenzene . 
 
 2, An attempt to condense phenylarsine with an aromatic 
 nitroso compound, splitting out a molecule of water and forming 
 a linkage of the type -As:U- was unsuccessful. Evidence points 
 to the formtion of an anilide of an ar sonic acid, containing the 
 
 group: 
 
 0 
 
 -As-!'^H- 
 
 OH 
 
 3. The phenylarsine-Gr ignard complex formed by adding an 
 
 alkyl Grignard reagent to phenylarsine was found to offer a means 
 of attaching various groups to the arsenic through the use of 
 certain halogenated substances by a reaction of the type. 
 
 C 
 
 6H5AS 
 
 MgX 
 
 MgX 
 
 2 RX = CgllgAsRg t 2 MgXg. 
 
 4. Through the phenylarsine -Grignard complex both one and 
 tvi/o hydrocarbon groups were attached to the arsenic, forming 
 secondary and tertiary mixed arsines. 
 
 5. Attempts to form ring structures including the arsenic 
 by the use of dihalogenated compounds were unsuccessful. 
 
 6. Aromatic compounds containing the halogen in the benzene 
 nucleus would not react with the phenylarsine -Grignard complex. 
 
59 
 
 VI. BIBLIOGRAPHY 
 
 (1) The Reactions of the Arsines, Preliminary paper. Con- 
 
 densation of Primary Arsines with Aldehydes. Roger 
 
 Adams and C. S. Palmer. J. Am. Chem. Soc. 2375 
 
 (1920) 
 
 (2) Palmer, Ber. 1378 (1894) 
 
 (3) Dehn and Wilcox, Am. Chem. J., 1--54 (1906) 
 
 (4) Palmer and Dehn, Ber. M, 3594 (1901) 
 
 (5) La Coste and Michaelis, Ann. 201 , 203 (1880) 
 
 (6) Michaelis and Loesner, Ber. 27, 264 (1894) 
 
 (7) Norris, J, Ind. and Eng. Chem. IJ, 824 (1919) 
 
 (8) Dehn, Am. Chem. J., 101 (1905) 
 
 (9) Dehn, Am. Chem. J., 88 (1908) 
 
 (10) D.R.P, 254.187 
 
 (11) D.R.P. 251,104 
 
 (12) D.R.P. 253,226 
 
 (13) D.R.P. 270,254 
 
 (14) D.R.P. 269,699 
 
 (15) D.R.P. 269,700 
 
 (16) D.R.P. 269,743 
 
 (17) D.R.P. 269,744 
 
 (18) D.R.P. 269,745 
 
 (19) Estimation of Arsenic in Organic Compomds . G. R. Robertson. 
 
 J. Am. Chem. Soc., 43, 182 (1921) 
 
 (20) Organic Compounds of Arsenic and Mercury. G. T. Morgan. 
 
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VITA 
 
 40 
 
 The v/riter was horn in Sullivan, Illinois, January 3, 1893, 
 and obtained his early education at that place, graduating from 
 the Sullivan High School in 1912. The follov/ing year he took 
 post graduate v/ork in high school and filled the position of as- 
 sistant in the science department. He entered the University 
 of Illinois in 1914, choosing the course in Chemical Engineering, 
 and graduated in 1919. He received the degree of Master of 
 Science in Chemistry in 1921. 
 
 Appointments : 
 
 Scholarship, University of Illinois, 1919--20. 
 
 U. S. Interdepartmental Social Hygiene Board FelloVifship, 
 University of Illinois, 1920--21. 
 
 Fellowship, University of Illinois, 1921--22. 
 
 Fiiblications : 
 
 Transference Nurrbers of Sodium and Potassium in Mixed 
 Chloride Solutions. With S. A. Bra ley. J. Am. 
 Chem. Soc. 1770 (1920) 
 
 On the Electrical Properties of Illium. With Charles 
 T. linipp. The Physical Reviev/, 19, 283 (1922)