V 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
THE CATALYTIC PREPARATION OF DIPHENYL ETHER 
 MIXED DIALKYL MERCURY COMPOUNDS 
 
 BY 
 
 JOHN BLACKWELL DAVIS 
 B. S. Beloit 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 
 1922 
 
Digitized by the Internet Archive 
 in 2016 
 
 https://archive.org/details/catalyticpreparaOOdavi 
 

 UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 January 16 _ \ 92 A 
 
 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY 
 SUPERVISION BY_ _ John-B. Davis 
 
 ENTITLED The Catalytic Preparation of D iphenyl Eth er 
 
 (a.ni ) M ixed D ialkvl Me r cury C omp ounds 
 
 BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
 THE DEGREE OF Master of Science 
 
 In Charge of Thesis 
 
 Head oi Department 
 
 Recommendation concurred in* 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 *Required for doctor’s degree but not for master’s 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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ACKNOWLEDGMENT . 
 
 The writer wishes to express his sincere thanks 
 and appreciation for Dr. Marvel’s many helpful 
 suggestions and criticisms received in the 
 course of this work. 
 
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TAELE OF CONTENTS. 
 
 
 The Catalytic Preparation of Diphenyl Ether, 
 
 
 Introductory 
 
 page 1 
 
 Historical 
 
 2 
 
 Theoretical 
 
 4 
 
 Experimental 
 
 
 l) Elecrtic Furnace 
 
 6 
 
 2) Catalyst 
 
 9 
 
 3) Effect of Aluminum Oxide on 
 
 
 Phenol at High Temperatures 
 
 9 
 
 4) Effect of Aluminum Sulfate on 
 
 
 Phenol at High Temperatures 
 
 11 
 
 Summary 
 
 13 
 
 Mixed Eialkvl Mercury Compounds. 
 
 
 Introduction 
 
 13 
 
 Historical 
 
 14 
 
 Theoretical 
 
 15 
 
 Experimental 
 
 
 l) The Preparation of 
 
 
 Benzyl Mercury Chloride 
 
 17 
 
 3) The Preparation of 
 
 
 Methyl Mercury Iodide 
 
 18 
 
 3) reaction of Methyl Magnesium Iodide 
 
 
 on Benzyl Mercury Chloride 
 
 19 
 
 4) Reaction of Ethyl Magnesium Bromide 
 
 
 on Methyl Mercury Iodide 
 
 20 
 
 Summary 
 
 21 
 

 
 
 
 
I 
 
 Par t I. 
 
 The Catalytic Preparation of Diphenyl Ether. 
 
- 1 - 
 
 INTRODUCTORY. 
 
 In a recent paper by A. Maihle and F. de Gordon 1 on the 
 study of the catalytic preparation of ethers, it was shown 
 that all the ethers of the primary aliphatic alcohols- up 
 to the fifth member of the series- could be prepared by 
 catalytic methods. These workers, using a Jena combustion 
 tube and combustion fmrnace, , obtained pure products at 
 fairly low temperatures (200-230 degrees). 
 
 Similar methods were tried by Maihle in the preparation of 
 
 3 
 
 some aromatic ethers, using thorium oxide as a catalyst . 
 
 3 
 
 Likewise mixed ethers have been prepared catalytically . 
 Attempts have been made to use other catalysts such as 
 titanium oxide and zirconium oxide in the preparation of 
 ethers and of thiophenols, none of which was as satisfactory 
 as thorium oxide. 
 
 This work was undertaken in an attempt to develop a cheap 
 
 method for the preparation of diphenyl ether. Aluminum oxide 
 
 was chosen as a catalyst since it is known that aluminum 
 
 phenolate, upon heating, will decompose to yield diphenyl 
 4 5 
 
 ether.' Also, aluminum oxide is very cheap, while thorium 
 oxide is comparatively expensive. An electric furnace was 
 used, since this permitted better temperature control. 
 
 1. Bui] . Soc. chim. 25,565(1901) 27,131(1902) 
 
 2. Comp. rend. 151,492(1910) 155, 261 (1913) 
 
 3. Comp. rend. 155 . 261(1912) 
 
 4. Ber. 15, 359TT6S3) 
 
 5. J. Chem. Soc. 41,8 (1882) 
 
V 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
HISTORICAL. 
 
 Diphenyl ether has been prepared by the use of a number 
 of chemical reactions. Hoffmeister in 1871 first prepared 
 this compound by the condensation of benzene diazonium sulfate 
 with phenol.^ It has been prepared by distilling a mixture of 
 equal molecular amounts of sodium phenolate and sodium 
 metaphosphate; by the condensation of potassium phenolate 
 
 rz A 
 
 and brombenzene; > by the use of flourbenzene and potassium 
 5 
 
 phenolate; by the decomposition of the ammonium salt of 
 
 g 
 
 phenyl salicylic acid; by the distillation of aluminum 
 
 7 
 
 phenolate. 
 
 A method which involves the dehydration of phenol is the 
 
 action of three parts of zinc chloride on one part of phenol, 
 
 which is heated in a bomb for eight hours at a temperature 
 
 8 
 
 of 350 degrees. J The yield in this case was only 5-6$ of 
 the weight of the phenol. None of the above methods gave 
 good yields and in almost every case numerous by-products 
 were obtained. 
 
 Catalytic methods for the preparation of diphenyl ether, 
 as well as numerous other aliphatic and aromatic ethers, have 
 been studied quite extensively by A. Maihle. 
 
 1. Ann. 159,181 (1871) 
 
 5. Ann. 343, 230 (1888) 
 
 6. Ann. 257, 78 (1890) 
 
 2. Ber. 15, 1124 (1882) 
 
 3. Ber. 38, 2311 (1905) 
 
 4. Ann. 350, 85 (1906) 
 
 7. J. Chem.Soc. 41, 8 (1882) 
 
 8. Ber. 14, 189 TT881) 
 
 

 
 
 
 
 
 
 
 
 
 
 
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 A catalytic method was described in which thorium oxide 
 was used as a cata^st; 1 2 titanium oxide and zirconium oxide 
 were both tried as catalysts by these workers, but the best 
 results were obtained by the use of thorium oxide. 
 
 Aluminum oxide has been used in the preparation of aliphatic 
 ethers but no record was found of its having been used 
 in the preparation of diphenyl ether nor of any of the other 
 aromatic ethers. 
 
 1. Comp. rend. 151 . 493 (1910) 
 
 2. Comp. rend. 6, 329 (1920) 
 

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-4- 
 
 THEORETICAL. 
 
 Since aluminum oxide has been successfully used for the 
 preparation of aliphatic ethers, 1 2 3 4 5 it was thought that it 
 might prove a good catalyst in the preparation of the 
 aromatic ethers. This was chosen, also, for the reason that 
 Gladstone and Tribe obtained a fair percentage of diphenyl 
 
 o 
 
 ether by the decomposition of aluminum phenolate. J They 
 
 heated 469 grs. of the material and obtained 268 grs. of 
 
 distillate- of this amount, over 60 $ was found to be diphenyl 
 
 ether. Likewise, Maihle and F.de Gordon obtained, by the use 
 
 of aluminum oxide as a catalyst, diethyl ether in as high 
 . 3 
 
 as 71 $ yields. Dipropyl ether was prepared by the same workers 
 with yields up to 54$. The preparation of certain mixed ali- 
 
 4 
 
 phatic ethers is also described in the literature, which 
 
 compounds the author claims have been prepared heretofor only 
 
 by "purely chemical" methods. 
 
 The theory of the mechanism of the dehydration action is 
 
 described as being analagous to the action of sulfuric acid 
 
 on primary alcohols. 0 
 
 Ohf -t- > /-/* O + ^ H 
 
 -S C v H < C /, -h Ch M-zh+i (d* O + i 
 
 ^ A/ C-Ai y-/ ♦ C A, "t d) dy. ff ^ 
 
 Thus the sulfuric acid is regenerated at the temperature 
 necessary for the formation of the ether. 
 
 1. Coup. rend. 170, 329 (1920) 
 
 2. J. Chem. Soc. j41, 8 (1882) 
 
 3. Bull. soc. chim. 25, 565 (1901); 27, 121 (1902) 
 
 4. Bull. soc. chim. 27 . 328 (1902) 
 
 5. Comp. rend. 150 , 823 (1910) 
 

 
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 Similar reactions are supposed to take place when such a 
 catalyst as thorium oxide is used. The thorate and water is 
 first formed by the action of the phenol on the oxide and 
 the thorate in turn decomposed into the ether and the original 
 oxide. 1 r 
 
 z(c* -OH) y Z5 4, —* 77, o (oCh Hzh+i) z + HiO 
 77, o (ocr, y Zh-OH --*• 2 (r<- O C7 y 7f,o(o/t)^ 
 
 71 o C °R)x » 77, + 74 a. O 
 
 Titanium oxide and zirconium oxide behave similarly. The 
 
 theory of the mechanism in the preparation of diphenyl ether 
 
 by the use of thorium oxide as a catalyst was similarly 
 3 
 
 described. , v f \ 
 
 £ fc b //s oHj + 7J>0* + 7 ?ofo - 6^ 
 
 7Z O (oCo > Th + (it 
 
 In working with aluminum oxide it was expected that a 
 
 similar reaction might take place. 
 
 6 ((tZ/rw; * v3/4 o +- z (Z£(ou // 0 J 3 
 
 2 aJ, (oc b Hs) 3 * t ^3^-3 fa fa)*. ° 
 
 This method, however, was not found useful because at the 
 temperature required for the formation of diphenyl ether, a 
 secondary reaction occurs and the diphenyl ether is converted 
 into diphenylene oxide and hydrogen. 
 
 
 \ 
 
 V 
 
 o 
 
 
 
 > 
 
 / 
 
 c 
 
 o 
 
 H: 
 
 1. Comp rend. 151 . 359 (1910) 
 3. Comp rend. 151, 493 (1910) 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
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-6 
 
 EXPERIMENTAL. 
 
 Electric Furnace. 
 
 A piece of ordinary one inch iron pipe was cut to a length 
 of (Potty inches. One end, at "A”, was fitted with a pipe "T" 
 and about eight inchee of pipe fitted into this at right angles 
 to the long pipe. The opposite end, at "B", was filed smooth 
 and a condenser later fitted on. The pipe was covered with a 
 layer of alundum cement about one-quarter of an inch in 
 thickness, extending from the "T" to within an inch or two of 
 the opposite end. The cement was allowed to dry thoroughly 
 and then forty or fifty feet of #14 chromel "C" resistance 
 wife was wound on this layer. Care was taken to have the coils 
 of wire so placed as not to make contact; also, although the 
 wire was wound tightly, it must not be wound tight enough to 
 cut through the cement layer and thereby make contact with 
 the metal. The coil was tied to the pipe firmly, leaving 
 enough wire at both ends to make connections. Over this coil 
 was plastered another layer of cement, of sufficient thick- 
 ness to completely cover the wire. This layer was allowed to 
 dry for about twenty-four hours and then thoroughly baked on 
 by passing a current through the wire for an hour or so. 
 
 After this treatment, there resulted a hard, firm cement 
 layer and the pipe could be handled readily without danger of 
 the cement falling off. 
 
 The bottoms were removed from five or six ordinary tin 
 cans and these then fitted together so as to form a jacket, 
 the length of which could be regulated. Holes were cut in 
 

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the center of two of the covers- just large enough to fit over 
 the pipe and cement layer, these to serve as ends for the 
 jacket. Two smaller holes were punched in one of the covers to 
 hold small porcelain tubes, an inch or two long- made from 
 broken porcelain triangles, to serve as insulators for the ends 
 of the heating coil which are to be terminated outside of the 
 jacket on suitable binding posts. This cover was fitted down 
 over the pipe and cement layer to the pipe "T" at "A" and 
 securely fastened there. Both ends of the nichrome wire were 
 cleaned and spliced to separate pieces of #16 copper wire. 
 
 The piece of copper wire at "A" need only be about sixteen 
 inches long. The piece spliced to the resistance wire at "3" 
 should be long enough to reach back to "A rt . This length is 
 conducted back to "A” through a piece of capillary glass 
 tubing, out through the porcelain insulator and fastened to 
 a suitable binding post. The binding posts were bolted to a 
 strip of wood which was wired to the upright piece of pipe. 
 
 The shorter piece of copper wire was conducted out through the 
 other insulator and fastened to the other binding post. The 
 copper wire is more convenient to use on the outside of the 
 jacket, since it does not heat up to any degree while the 
 furnace is in operation. Care was taken to so bend those 
 parts of the wires which were to be enclosed in the jacket, 
 so that they would not make contact upon a slight jarring of 
 the apparatus. 
 
 The jacket was slipped down over the pipe and fitted snugly 
 to the cover at "A". This jacket was then filled with a 
 quantity of "Sil-Q-Cel" as a heat insulator and the cover 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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 plaoed on at M B '* . The open end of the pipe "T" waa fitted with 
 a one by ^tree-quarter inch bushing, carrying a well of 
 sufficient length to extend about half way into the furnace, 
 and sealed at that end. This smaller pipe was used to hold the 
 pyrometer or thermometer. The jacket surrounding the furnace 
 was covered with one thickness of ordinary steam-pipe covering 
 and this fastened in place with metal bands. 
 
 When the furnace was wound for the first time, two coils 
 of about #17 wire were used; arranged so that one was wound 
 between the coils of the other. It was hoped that this 
 arrangment might afford better temperature control, since one 
 might pass current through one or both coils. In actual use, 
 however, the furnace burned out twice with this arrangment - 
 probably due to the fact that the coils were necessarily wound 
 too close together, since about sixty feet of wire was used. 
 About three feet of 13 mm. glass tubing was fastened to the 
 pipe at ”3” to serve as an air condenser. 
 
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-C>_ 
 
 <y 
 
 Cat alyst . 
 
 Sufficient pumice was ground to about pea size to fill 
 the furnace to within an inch or two of the end. This was 
 thoroughly soaked in water for 1-3 hours and then, while moist, 
 rolled in 10-15 gr3. of powdered aluminum oxide (c.p. ) until 
 the pieces were well coated with the catalyst. Ths furnace was 
 then filled to within a few inches of the end, with this 
 material. The smaller pieces were dropped in first so as to 
 have that part surrounding the"well "filled with the material. 
 
 In one or two runs, aluminum sulfate was used as a catalyst. 
 Ths proceedure in this case was to boil the finely divided 
 pumice with a saturated solution of aluminum sulfate for about 
 one hour. It was then allowed to dry and used as in the case 
 of the oxide. 
 
 -The Effect of Alumi n um Oxide on Phenol at High Temper atures. 
 
 In the first run the temperature of the furnace was 
 190-300 degrees. lOOgrs. of phenol was weighed into an 
 ordinary distilling flask and distilled into the furnace thru 
 the upright iron pipe. In this and the next two or three runs, 
 a dark brown liquid distilled over - the color of which was 
 probably due to the reduction o£ a quantity of rust in the 
 pipe and the formation of oxidation products of phenol. Dense 
 white fumes accompanied the liquid, which condensed only upon 
 standing for an hour or so. The liquid distillate was shaken 
 with strong NaOH solution. The entire distillate was soluble, 
 and when again acidified and distilled, pure crystals of phenol 
 were obtained, leaving a small amount of a black tarry substance 
 

 
 
 
 
 
 
 
 
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- 10 - 
 
 in the distilling flask. About 35 minutes were required in this 
 run for the distillation of the phenol into the furnace. 
 
 A second run was made, again using 100 grs. of phenol and 
 distilling it into the furnace at a temperature of 190-200 deg. 
 The time required for distillation, however, was about 1^ hours. 
 The distillate was again shaken with strong sodium hydroxide 
 solution, acidified and the phenol recovered. The entire amount 
 of distillate was soluble in the alkali and an amount of 
 tar was again left upon recovery of the phenol. 
 
 Two other runs were made at this temperature, but with a 
 lengthening of the time required to distill the phenol into 
 the furnace. The longest time required was 2g hours. In each 
 case practically all of the phenol was recovered, unchanged. 
 
 The furnace was then filled with a new supply of the catalyst. 
 This time, however, the pumice was boiled for 1-2 hours with 
 a thin paste of the aluminum oxide, then allowed to dry. This 
 was done in hopes that the pores of the carrier might become 
 impregnated with the catalyst, and the catalytic action thus 
 be increased. The time required for this run was S-Sj hours. 
 
 Six subsequent runs were made at the following temperatures : - 
 200-210°; 240-260°; 280-300°; 330-350°; 365-375°; 400-425? 
 
 In no case, however, was any product other than phenol obtained. 
 
 Another method was tried- using 100 grs. of phenol and at 
 a temperature of 460-490°. This consisted in inserting the 
 end of the air condenser into a stopper and fitting this into 
 a vacuum filter flask. Also, the pumice was packed into the 
 furnaae more tightly and a slight suction applied during the 
 
 run. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
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 In this way the rate of distillation of the phenol could be 
 easily controlled. Three runs were made requiring about three 
 hours each. In one case, upon the addition of the strong alkaline 
 solution to the distillate, there separated out a small quantify 
 of a brown precipitate* This was filtered off and a melting 
 point taken. It melted at 30-33°; and burned leaving a black 
 residue. A. Maihle describes the formation of diphenylene oxide 
 by the action of thorium oxide on phenol at 475? which 
 compound melted at 83? This therefore, was concluded to be 
 diphenylene oxide- although there was only enough formed to 
 take a melting point. The other two runs yielded only alkali 
 soluble material and phenol was recovered from this in each 
 case. 
 
 The action of al uminum sul fate pJienol .high, .hemps ratnre.3. 
 
 Two runs were made using aluminum sulfate as a catalyst. 
 
 100 grs. of phenol was distilled into the furnace at 510-530° 
 in three hours, a slight suction also being used. The products 
 in both cases were alkali soluble and phenol was recovered. 
 
 Two runs were made using a dropping funnel. The phenol was 
 dissolved in a small amount of benzene and dropped into the 
 furnace slowly- instead of distilling it in. The temperature in 
 this case was 450-460° and the time of the run was about ij hrs. 
 This method of introducing the phenol was not very satisfactory, 
 since the speed with which the mixture was introduced into 
 the furnace could not be so readily controlled. The products 
 were alkali soluble in both cases. 
 
 When working with temperatures below 350° a thermometer 
 
- 12 - 
 
 was used. In all cases where the temperature was above 350°, a 
 pyrometer was made use of. 
 
 SUMMARY. 
 
 Several attempts have been made to prepare diphenyl ether 
 catalytically, in an electric furnace, using aluminum oxide and 
 aluminum sulfate as catalysts. Temperatures varying from 
 200°to 500° have been used. In no case wa3 any diphenyl ether 
 obtained. At 490°, aluminum oxide converts some phenol into 
 diphenylene oxide. This seems to indicate that the catalytic 
 formation of diphenyl ether is not possible- using aluminum oxide 
 as a catalyst- since it decomposes into diphenylene oxide with 
 a loss of hydrogen at any temperature high enough to cause the 
 dehydration of the phenol. 
 

 
 
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Part IT 
 
 Mixed Dialkyl Mercury Compounds. 
 
-13- 
 
 INTRO DUC TORY. 
 
 In a recent article, Jones and Werner described some work 
 on aromatic mercury compounds, 1 from which they formulated a 
 theory concerning the electronic structure of dialkyl and di- 
 aryl mercury compounds. Their assumption is that one of the 
 valences functions positively and the other negatively. Thus, 
 according to this, we may have compounds of the type:- 
 
 — ~j< 
 
 t * 
 
 — + _ + f 
 
 K — *3 — * 
 
 This work was undertaken in an attempt to prepare some mixed 
 dialkyl mercury compounds, keeping in mind the possibility of 
 the utilization 6f these as a proof of the types of valence 
 on mercury in organic compounds. 
 
 1. J. Am. Chem. Soc . 40, 1257 (1918) 
 

 
 
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-14- 
 
 HISTORTCAL. 
 
 Hilpert and Gruttner,in 1915, described the preparation of 
 
 a number of dialkyl mercury compounds and, among them, benzyl 
 
 ethyl mercury, which is the first mixed dialkyl mercury 
 
 1 m 
 
 compound to be described. This compound was prepared from:- 
 C_ ^ Hs /&r- -4- cp C. //j OJL - — > < p c //*_ // j C »- Ms fj 
 
 In the same paper, the following mixed alkyl-aryl compounds 
 
 were described:- benzyl mercury phenyl, benzyl mercury ethyl, 
 
 ethyl mercury phenyl and benzyl mercury o-tolyl. 
 
 A number of simple diaryl and dialkyl mercury compounds 
 
 have been prepared. Duppa and Frankland describe the preparation 
 
 2 
 
 of mercury diethyl and mercury dimethyl. Wolff has prepared 
 
 3 
 
 diphenyl mercury; Pope and Gibson describe the preparation of 
 
 4 
 
 dibenzyl mercury. However with the exception of the work of 
 Hilpert and Gruttner, very little is known concerning the 
 mixed organic mercury compounds. 
 
 1. Ber. 48, 906 (1915) 
 
 3. Ann. 130, 105 (1865) 
 
 3. Ber. 48, 64 (1915) 
 
 4. J. Chem. Soc. 101, 735 (1912) 
 

 
 
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-3 5- 
 
 THEORETICAL. 
 
 If mercury in organic compounds really has one positive 
 and one negative valence, a compound such as benzyl mercury 
 methyl, upon treatment with hydrochloric acid, should hydrolyze 
 in two different ways:- 
 
 (V G&s- Q & *■ CM* 
 
 t l 
 
 fij CiHsC-Z/t — C/J 3 ' ^ ' * V ^ 3C 
 
 In studying the reaction of the Grignard reagent on 
 
 mercuric chloride, it hat been found that one of the atoms 
 
 of chlorine is much mors easily replaced by an alkyl group 
 
 than is the second atom, - " It was thought that, by making use 
 
 of this fact and preparing mixed dialkyl mercury compounds 
 
 step-wise, the electronic isomers in this series might possibly 
 
 be obtained. Thus, benzyl methyl mercury prepared in the 
 
 following way might exist in two isomeric forms. 
 
 0) <p /y^ CJZ v- OP- //j » <&> c /-/j CJ2 •*- 
 
 Hj at -*• c//_3 sgjS —+ 5 ^°^ c//y + 
 
 (zj C/6^ S + cs-Mj-e* c // 3 /£} ^ 
 
 C // 3 MyS + cj? <?> ^ 
 
 If the products obtained from these two series of reactions 
 break down differently upon treatment with hydrochloric acid, 
 or, if the products behave in the same way, but still give all 
 of the decomposition products mentioned above ( a,b), then the 
 evidence furnished by these experiments would favor the theory 
 of Jones and We*ner. 
 
 1. Marvel and Gould- J. Am. Chem. Soc . January 1933. 
 

 
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-16- 
 
 However, if the products obtained, from the above reactions 
 behave in the same way toward acids and yield only one set 
 of deconiposi tion products, the evidence would not be so 
 favorable to this theory. 
 
 After this work had been started, there appeared a paper 
 by Kharasch and Jacobsohn,' 1 ' in which the theory of Jones and 
 Werner was more or less conclusively disproved. 
 
 Due to the extremely harmful physiological action of these 
 mercury compounds, it was found necessary to discontinue the 
 work on this problem, before any conclusive results were 
 obtained. 
 
 . Am. Chem. Soc, _43, 1894 (1931) 
 
 1. J 
 

 
 
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-17- 
 
 EXPERIMENTAL. 
 
 Benz yl Mercury chloride . 
 
 a) Preparat ion of the Grignard reagent . 
 
 In a 500cc round bottom flask, fitted with a rdflux 
 condenser, is placed a mixture of 8 gre. of magnesium turnings 
 and 200 cc of anhydrous ether. A separatory funnel is used to 
 add, thru the condenser, 40 grs. of benzyl chloride- a crystal 
 of iodine is also added, as a catalyst. Upon the addition of a 
 few drops of the benzyl chloride and slight heating for a few 
 minutes, the reaction begins and runs smoothly. The benzyl 
 chloride is dropped in just fast enough to kepp the reaction 
 going. The mixture is refluxed for about an hour, after the 
 addition of the benzyl chloride. Any unchanged magnesium is 
 removed by rapid filtration thru glass wool. 
 
 b) Reaction of the Grignard with m ercuric chloride . 
 
 In a three-necked, three liter round bottom flask, 
 fitted with a condenser and a mercury-seal stirrer, is placed 
 a mixture of 80 grs. of dry, powdered mercuric chloride and 
 200 cc of dry ether. It was found advisable to add the mercuric 
 chloride to the ether with continual stirring, so that it would 
 not settle and form a cake at the bottom of the flask. The 
 Grignard prepared above was added to this mixture, drop by drop, 
 with continual stirring. The reaction mixture heats up during 
 the addition of the Grignard, which may be added just rapid 
 enough to keep the ether refluxing gently. After all the 
 Grignard has been added, the mixture is refluxed 0 $ the steam-bath 
 for 45 minutes. The flask is then cooled and 100-150 cc of 
 water added, to decpmpose any excess Grignard reagent. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-18- 
 
 The mass is then filtered with suction, washed with water and 
 a little dilute hydrochloric acid, sucked dry and recrystallized 
 from boiling alcohol, separating in 3hiny leaflets-m.p. 104° 
 
 The mother liquors from the filtration were concentrated, the 
 precipitate filtered off and treated as above. In all, 55 grs., 
 67$ of the theory were obtained. 
 
 Notes:- Two runs were made in which the ether was distilled 
 off from the final reaction mixture before any water 
 was added. In both cases the yield was very small, 
 seemingly due to a decomposition of the product 
 during the distillation of the ether. It was found 
 that prolonged refluxing after the addition of the 
 Grignard reagent did not increase the yields; but 
 the use of freshly prepared benzyl chloride, in 
 making the Grignard was found to be advantageous. 
 
 Methyl Mercury Iodide 
 
 a) Prep ration of the Grigna rd pe agent. 
 
 In a 500 cc round bottom flask, fitted with a reflux 
 condenser, is placed a mixture of 18 grs. of magnesium turnings 
 and 300 cc of dry ether-a crystal of iodine is added as a catalyst 
 Thru the condenser, by means of a separatory funnel, 73 grs. 
 of methyl iodide are gradually added. After the addition of a 
 small amount of the methyl iodide and alight heating, the 
 reaction runs smoothly and is finally completed by refluxing 
 for about an hour. Any unchanged magnesium l£ filtered off 
 rapidly through glass wool. 
 
 b) Reacti on of the Gri gnard. with mercuric chloride . 
 
 In a three-necked, three liter round bottom flask. 
 
-IP- 
 
 fitted with a reflux condenser and a mercury-oeal stirrer, is 
 
 placed a mixture of 140 grs. of mercuric chloride and 400 cc 
 
 of anhydrous ether- observing .the same precautions as in the 
 
 preparation of benzyl chloride. The Grignard reagent was slowly 
 
 added to this mixture, with continual stirring and after all of 
 
 it had been added, the reaction mixture refluxed for about an 
 
 taour. The flask was then cooled, and a small quantity of water 
 
 added (35-30 00 )". The ether was distilled off and the residue 
 
 * 
 
 shaken with a mixture of 300 cc of water and 5 - 10 cc of 
 hydrochloric acid. The mass wa.s then filtered, washed and sucked 
 dry on the Buchner funnel. The product contained an amount of 
 mercuric iodide and two crystallizations from hot alcohol were 
 necessary. The mother liquors yielded more product upon concen- 
 tration. The crystals were slightly yellow in color and melted 
 at 143-143? The yield was 73 $ of the theory. 
 
 Notes:- The presence of a trace of mercuric iodide causes a 
 slight red coloration; even upon recrystallization 
 the product seems to decompose upon standing with 
 the -formation of an unknown red decomposition product. 
 
 Reac tion of m ethyl magnes ium iodide on benzyl me rcury chl o ride . 
 
 a) Prepara tion of tfoe Grignard Reagent . 
 
 This was prepared in the usual way from 3j grs. of 
 magnesium turnings; 15 grs. of methyl iodide and 150 cc of dry 
 either and the reaction mixture filtered rapidly thru glass wool. 
 
 b ) reaction of the Grignard with b enzyl mercu ry chlo ride . 
 
 In a 500 cc round bottom flask fitten with a reflux 
 condenser, was placed 100 cc of dry ether and 29 grs. of benzyl 
 mercury chloride. To this mixture, the Grignard was slowly added. 
 
- 20 - 
 
 The reaction mixture was refluxed for 12 hours. At the ehd of 
 that time there was left a small amount of a white solid whifah 
 was entirely insoluble in the ether. Upon addition of water to 
 the solution there separated out a white crystalline substance, 
 which melted over a range of four degrees- from 72°-76? 
 
 Elementary analysis showed both iodine and chlorine to be 
 present. It was probably a mixture of benzyl chloride and iodide 
 and methyl chloride and iodide. 
 
 Notes:- Upon the addition of the Grignard reagent to the 
 
 ether solution, a vigorous reaction took place which 
 necessitated the cooling of the flask with ice. 
 
 Reac tioi of Ethyl Magnesiu m Bromide .on Methyl Mercury Io dide 
 
 a) Preparation of the Grignar d Reagent . 
 
 The reagent was prepared from 4 grs. of magnesium and 
 10.6 cc of ethyl bromide in 160 cc of dry ether, filtering the 
 product thru glass wool to remove any unchanged magnesium. 
 
 b) Reaction of the Grignard with methyl mercury iodide. 
 
 In a 500 cc round bottom flask fitted with a reflux 
 condenser, was placed a mixture of 43 grs. of methyl mercuric 
 iodide and 150 cc of anhydrous ether. The Grignard was added 
 slowly, through the condenser. There resulted a vigorous reaction 
 which necessitated the cooling of the mixture, during the 
 addition of the Grignard. It was then refluxed for three hours 
 and allowed to stand over night. A small amount of insoluble 
 material was left. 10-20 cc of water was added to the reaction 
 product and the layers separated. The solid in the ethereal 
 layer was filtered off and the filtrate distilled. A very small 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-31- 
 
 quantity of solid was left in the distillation flask, and at no 
 time did the temperature rise above 36? 
 
 The solid was dried and an elementary analysis showed bromine 
 and iodine to be present. It melted £rom 151°- 154° and was 
 probably a mixture of ethyl mercuric bromide and methyl mercuric 
 iodide . 
 
 No attempts were made to further identify the compounds 
 resulting from these condensations- beacuse of the physiological 
 action of them. 
 
 SUMARY. 
 
 The Grignard reagent has been used in the preparation of 
 alkyl mercury halides. However, the reaction between an alkyl 
 mercury halide and the Grignard does not seem to run smoothly 
 to gtve mixed mercury dialkyl compounds.