THE STRUCTURE OF THE MERCURY 
 DERIVATIVES OF THE OLEFINES 
 
 BT 
 
 WARREN M.RON SPERRY 
 
 B. Chern., Corneil University, 1921 
 
 THESIS 
 
 SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS 
 FOR THE DEGREE OF MASTER OF SCIENCE IN CHEMISTRY 
 IN THE GRADUATE SCHOOL OF THE UNIVERSITY 
 OF ILLINOIS. 1922 
 
 l.’RBANA. ILLINOIS 
 
!2^SpZ2 -i ^ P 
 
 /922 
 Sf> 3 7 
 
 UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 . July 29 ^192 2 
 
 I HEREBY RECOMMEN13 THAI' THE THESIS PREPARED UNDER MY 
 
 SUPERVISION BY_ WARREN MYRON SPERRY 
 
 ENTITLED THE STRUCTURE OF THE MERCURY-DERIVATIVES 
 
 OF ^THE OLEFINES . 
 
 BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
 THE DEGREE OF MASTER OF SCIENCE 
 
 Recommendation concurred in* 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 Required for doctor’s degree but not for master's 
 
Digitized by the Internet Archive 
 in 2016 
 
 https://archive.org/details/structureofmercuOOsper 
 
ACKNOWLEDGMENT 
 
 The author wishes to acknowledge his Indebtedness to 
 Professor Roger Adams for suggesting the subject of this 
 research and for his many helpful suggestions throu^out 
 the work* 
 
 
CONTENTS 
 
 Page 
 
 I. INTRODUCTION 1 
 
 II. HISTORICAL AND THEORETICAL 2 
 
 A. The Structiiral Theory of Sand 2 
 
 1. Arguments Against 3 
 
 2. Arguments in Favor 4 
 
 B. cx-Mercurochloro Methyl Coumarane 4 
 
 1. Significance of Structure 4 
 
 2. Proof of Struct\u ?0 5 
 
 a. Analysis 5 
 
 b. Poi*mation in Absolute Alcohol 5 
 
 c. Action with Sodium Amalgam 6 
 
 d. Rate of Decomposition 6 
 
 III. EXPERIMENTAL 8 
 
 A# o-Allyl Phenol 8 
 
 B. c?c -Mercurochloro Methyl Coumarane 8 
 
 1. Formation in Water 8 
 
 2. Analysis for Mercury.... 9 
 
 3. Formation in Absolute Ethyl A.lcohol 11 
 
 4* Formation in Butyl Alcohol 13 
 
 C. OC -MercTiroiode Methyl Coumarane 13 
 
 D. Mercuric Acetate Derivative of o-Allyl Anisole . . 14 
 
 E. Mercuric Chloride Derivative of o-Allyl 18 
 
 Anisole 
 
 P. The Time of Decomposition 19 
 
 IV. CONCLUSION 21 
 
 V. SUMMARY 22 
 
 VI. BIBLIOGRAPHY 23 
 
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1 
 
 THE STRUCTURE OP THE MERCURY DERIVATIVES 
 OF THE OLEFINES. 
 
 I. INTRODUCTION. 
 
 It has been well-known for over twenty years that Inorganic mer- 
 cury salts react with ethylene, and, as far as is known, v/ith all of 
 the olefines of the ethylene type, usually in alkaline solution, to 
 form compounds of the type RHgXOH or (RH^)20. Although most of 
 these compounds are very well crystallized, easily formed, and easy 
 to handle, and although they have been quite thoroughly investigated, 
 there is still considerable question as to their correct structxu?e. 
 
 This work was taken up with the idea that a study of the mercury 
 derivative, analogous to the types mentioned above, of such compounds 
 as o-allyl phenol might shed light on the correct structure. The 
 reasons for arriving at this conclusion will appear under the dis- 
 cussion of theory. 
 

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 II. HISTORICAL AND THEORETICAL. 
 
 It was first discovered by Deniges^ that the olefines generally, 
 with the exception of ethylene, combine with merc\iric sulphate in 
 acid solution and yield yellow compounds of the type (SO^Hg, HgO)sR, 
 in which R is an olefine. He found that these compounds dissolve 
 readily in HCl with effervescence of the particular olefine gas from 
 which the compound was derived. 
 
 Hofman and Sand^ studied this general reaction in more detail 
 and found that the following types of compounds were formed by the 
 action of ethylene on solutions of mercuric salts: (1) Ethanol mer- 
 cury salts of the form OH - CHg - CHg - HgJC; (2) ethyl ether mercury 
 salts of the form 0(CH2 - CHa*H^) 2 . They explained the formation 
 of these compounds on the supposition that the mercury salt HgXa 
 splits into the ions HgpC and X which then combine with the ethylene, 
 converting it into the saturated compound XHg - CHa - CHa - X which 
 then undergoes hydrolysis to form the ethanol mercury compound. 
 Compounds of the second type migjit result from the following reac- 
 tion, XHg - CHa - CHa - - CHg - HgX = 0(CHa.CHa.HgX)a 
 
 + HX. These investigators also reported compounds of the type 
 CHa = CH - HgX and (CaHaHgX)^^ but they seem to have later abandoned 
 the view that such compounds existed. It is now knoAvn that the com- 
 pounds studied and reported to be these were identical with the 
 ethanol compounds. 
 
 Later investigators, particularly Manchot® doubt the structure I 
 of these compounds as proposed by Hofman and Sand. He bases his dls- 
 
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agreeraent on the fact that practically all of these compounds are 
 very easily and rapidly decomposed by HCl* Sand^ explains this re- 
 action by assuming that it occurs in the following steps: (1) Re- 
 placement of the hydroxyl group by Cl, and (2) the splitting out of 
 HgCla* Manchot® says that this mechamism is untenable because no 
 case is known of an alcoholic hydroxyl being so easily and readily 
 replaced by a Cl, and, moreover, no case is known of a Cl splitting 
 out of the group -CHaCl without difficulty. But these compounds de- 
 compose almost instantly; so rapidly in fact that from the ethylene 
 addition compounds, ethylene is evolved with almost the speed with 
 which CO 2 is evolved from a carbonate upon the addition of acid. 
 
 Sand® also proposed another possible explanation of the mechan- 
 ism of this decomposition. This depends on the possibility of two 
 tautomeric forms. 
 
 I II 
 
 CHa - CHa ^ XHgCHa - CHaOH 
 
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 According to this theory the effect of acid is to drive the 
 above reaction to the left with the formation of form I from which 
 ethylene is readily split off. Manchot considers this theory to be 
 untenable because (1) it is \inthinkable that full valence will 
 change to a partial valence, (2) it is difficult to conceive of an 
 hydroxyl group leaving the stable alcohol grouping and migrating to 
 a mercury atom merely on the addition of weak HCl, and (3) this 
 theory does not explain the action on compounds of the type 
 (XHg - CHa - CHa)20. 
 

 
 
 
 
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 The question then is whether these compounds have a definite 
 structural form, or whether they are merely molecular addition com- 
 pounds without definite structural formulas* The argximents in favor 
 of the structural formulas are as follows: (1) The ethanol mercuric 
 iodide reacts with iodine dissolved in potassium iodide to give 
 ethylene iodohydrine and under the same conditions the diethyl ether 
 dlmercuric iodide gives (S (3 diiodo - diethyl ether; (2) many of 
 these compounds when treated with sulphides yield the corresponding 
 alcohols according this general reaction 
 
 OH - C - C - + HaS HO - S - fi - H + HgS + HX 
 
 As an example may he given the reaction with the derivatives of cin- 
 namic acid’’’* 
 
 CqHs - CH - OH - COgR^ + NH3 + HaS ^ CeHg - GH - CHg - COgR^ 
 
 Such reactions as these it is almost impossible to explain on the 
 basis of a molecular structure* 
 
 This work was taken up in an endeavor to furnish further evi- 
 dence in favor of the theory of the structure of these compounds as 
 proposed by Sand. It was thought that a study of the structure of 
 the mercury addition product of o-allyl phenol migjit furnish such 
 evidence because if the Sand theory is true, the compound as first 
 formed would have this struct\ire 
 
 and it would be very likely that water would split out from the ad- 
 
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Jacent hydroxyl groups to give a coumarane derivative* 
 
 In case such a compound should be formed, it would be an almost in- 
 contestable proof that at least this particular addition product conJ 
 formed to Sand's theory* 
 
 The mercuric chloride addition product of o-allyl phenol was 
 made and it was found that it was, as predicted, a coumarane deriva- 
 
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 tive of the structure indicated above* This structvire was proved by 
 the following points: (a) The analysis of three constituents checked 
 the theoretical for this structure; (b) the compound was made in ab- 
 solute ethyl and absolute butyl alcohol solutions; (c) upon treatment 
 with sodium amalgam a compound was formed which gave a correct analy- 
 sis for this structure®; 
 
 (d) this compound formed readily in acid solution and was not rapidly 
 decomposed by HCl* j 
 
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 The fact that a compound was obtained in absolute alcohol solu- 
 tion identical with the one obtained from water solution is almost a 
 final proof of the ring structure since in all other olefine addition 
 compounds an -OR compound is formed where ROH is the alcohol em- 
 ployed as solvent* 
 
 CHa = CHg + HgCla + ROH ^ RO - CHa - CHa - HgCl + HCl 
 
 The only possible explanation of this reaction is the following: 
 
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The action of sodium amalgam in forming RgHg compounds is fairly 
 general. 
 
 2 RHgX + sodium amalgam RgHg + HgXa 
 
 Therefore, when a compound is obtained which gives the correct 
 analysis for the one vs^ich would be obtained if the coumarane struc- 
 ture is correct and the general reaction occurs, it is fairly good 
 evidence in favor of the coumarane structure. Moreover, it is very 
 difficult to find a molecular formula which will satisfy the analy- 
 sis of the compound. 
 
 A fairly extended study of the speed of solution of this corapo\ind 
 in various strengths of HCl and HC2H3O3 was made since its behavior 
 in this connection appeared to be very significant. Sand^ directs 
 that these olefl.ne derivatives be made in a weakly alkaline solution. 
 They do not form in acid solution because acid decomposes them as 
 fast as they are formed. The equilibrium may be expressed as fol- 
 lows: 
 
 CHg = CHs + HgCla ClCHg - CHa - HgCl 
 
 n 
 
 OH - CHa - CHa - HgCl + HCl 
 
 Assuming as we must that these are reversible reactions the presence 
 of an excess of HCl would force them both to the left to give ethy- 
 lene and mercuric chloride. 
 
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 It was found, however, that the mercuric chloride derivative of 
 o-allyl phenol formed almost instantly in the cold with fairly high 
 yields in acid solution while the mercuric chloride derivative of 
 o-allyl anisole did not form at all in acid solution and only very 
 slowly if at all in alkaline solution* 
 
 The time of decomposition of the mercuric chloride derivative of 
 o-allyl phenol was taken for various concentrations of acid as given 
 in the table under experimental. This table shows clearly that the 
 decomposition is relatively slow. In the case of practically all of 
 these olefine mercury compounds it is almost instantaneous. The mer- 
 curic acetate derivative of o-allyl anisole was made and although it 
 is a syrupy compound very difficult to purify, it was observed that 
 it decomposed almost Instantly with strong HCl to give o-allyl ani- 
 sole and mercuric salts. 
 
 These phenonoma may be explained by a series of equilibria as 
 follows: 
 
 ( 2 ) 
 
 H (1) Cl +H 2 O JM jpHj 
 
 CH8-CH=CH2+HgCl2 ^\-CH2-CH-CH2-HgCl \,CH2-CH-CH2-HgCl 
 
 1 |( 3 ) 
 
 I^^^^CH^CH-CHa-HgCl+HzO 
 
 Equilibria (1) and (2) are the general equilibria for all these com- 
 pounds; but equilibria (3) tends to throw the whole reaction to the 
 right and counteract the reversing action of the HCl. This equili- 
 brium probably tends to go rather strongly to the right and so the 
 compound is formed in acid solution and acid dissolves it slowly* 
 

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8 
 
 III. EXPERIMENTAL. 
 
 0 - Allyl Phenol . 
 
 I 
 
 This compound was made by the rearrangement of allyl phenyl 
 ether, according to the general directions of Claisen® with the modi- 
 fications given by Adams and Rlndfusz^®. 
 
 oc- Mercurochloro Methyl Coumarane . 
 
 To a sli^tly acid solution of 22 g. mercuric chloride in 250 cc. 
 of water were added slowly with vigorous stirring 10 g. of o-allyl 
 phenol. A white solid commenced to precipitate at once. The mix- 
 ture was allowed to stand over ni^t and was then filtered and 
 
 o 
 
 washed well with water. It was dried and recrystallized from 95 
 
 ethyl alcohol. The melting point of the recrystallized product was 
 
 e 
 
 137.5 • A small amount was recrystallized from fresh alcohol and 
 the same melting point was obtained, so the compound was taken as 
 pure. The recrystallized compound is formed in beautiful, shiny, 
 
 flaky crystals. The yield of the recrystallized product (without 
 
 o 
 
 concentration of mother liquors) was 18.5 g. this being a 67.3 /® 
 yield. This yield ml^t have been increased by using a larger ex- 
 cess of mercuric chloride and by the slower addition of the phenol. 1 
 At any rate it is a largo yield for a mercury addition in acid solu- [ 
 tion. A theoretical yield would not be expected because there is 
 undoubtedly an equilibrium set up as is shown by the solubility 
 
 
 
 table below 
 
9 
 
 The compound was analyzed for carbon by the peroxide bomb method 
 with the following results: 
 
 II 
 
 III 
 
 Wt. of sample 
 ( grams ) 
 
 .5355 
 
 • • • • 
 
 .6243 
 
 7794 
 
 Vol. of Cla 
 (cc. ) 
 
 344.8 
 
 # • • • 
 
 396.2 
 
 493.8 
 
 Barometer 
 (mm. of Hg) 
 
 743 
 
 • • « • 
 
 743 
 
 .... 743 
 
 Temperature 
 
 30® 
 
 • # « • 
 
 28® 
 
 .... 26.2® 
 
 o 
 
 o 
 
 o 
 
 29.10 
 
 • • • • 
 
 29.01 
 
 .... 29 . 23 
 
 Theoretical for 
 
 
 ■GHg^^CH 
 
 - CHs - 
 
 HgCl 29.26 
 
 The compound was 
 
 analyzed for chlorine by 
 
 the Carius meth< 
 
 following results 
 
 • 
 
 • 
 
 
 
 
 
 I 
 
 
 II 
 
 
 Wt . of sample 
 
 .2853 
 
 • • # • 
 
 .3231 
 
 
 Wt. AgCl 
 
 .1116 
 
 # « • • 
 
 .1268 
 
 
 “/o Cl 
 
 9.68 
 
 • « • e 
 
 9.708 
 
 
 Theoretical forf^^cST^H-CHs-HgCl 9.62 
 
 Considerable difficulty was encountered in the analysis for mer- 
 cury. The following set of directions was finally worked out and 
 used in the analyses. 
 
 A sample of about .5 g. is welded into a 200 cc. round bottom 
 flask which is fitted with a tight stopper carrying a dropping 
 funnel and a bent glass tube leading to a Plllgot tube. This appa- 
 ratus is described by Bauer in his description of a somewhat slmi- 
 
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10 
 
 lar method of analysis. It might be stated that Bauers* method was 
 tried and might have worked had the hydrogen peroxide used been 
 strong enough. At any rate check results could not be obtained 
 using this method. To the sample are added 3 cc. concentrated HCl 
 throu^ the dropping funnel and the mixture is boiled until complete 
 solution has taken place. It is then diluted to 100 cc. and in the 
 same flask the mercury is precipitated as the sulphide. This is 
 filtered and well washed and the filter paper containing the sul- 
 phide is transferred to the same flask and connected to the same ap- 
 paratus described above. The Pillgot tube v/hich contains any mer- 
 cury which may have distilled out during the solution process is not 
 disturbed during the precipitation or filtration processes. The 
 sulphide is now dissolved in about 3-4 cc. of aqua regia and after 
 dilution the solution is filtered to remove paper and sulphur and 
 then made ammoniacal. To this ansnoniacal solution are added 5 cc. 
 of 10®/® potassium iodide solution and then 1 cc. of a standard sil- 
 ver nitrate solution. This gives a white precipitate of Agl. 
 Standard potassium cyanide solution is then added until the precipi- 
 tate just dissolves. In usual procedure as the end-point is some- 
 what hard to detect at the first trial it is best to back-tltrate 
 adding more silver nitrate from a burette and finally subtracting 
 the silver nitrate \ised in the terms of its equivalent in potassium 
 cyanide. This method of titration was the same as that used by 
 Bauer except for the fact that it was found better to use more in- 
 dicator than he used. Some trouble was encountered from the fact 
 that a deep yellow color usually appeared, when the solution was 
 made ammoniacal, which interfered somewhat with the end-point. With 
 
i; 0 
 
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 >•. 
 
11 
 
 practice a good end-point may be obtained, however, in the presence 
 of this color. A black background is best for this end-point. It 
 was fo\ind best to use fairly weak solutions (.02-. 03 N) because with 
 the more concentrated solutions, which were used at first, so little 
 solution was used for the sample, taken that no checks could be ob- 
 tained. The silver nitrate solution was standardized by the silver 
 chloride gravimetric method using Gooch crucible. The potassium 
 cyanide solution was standardized by running the ratio with the sil- 
 ver nitrate by the same titration method used in the analysis. The 
 
 following data were 
 
 obtained from the 
 
 analyses. 
 
 
 Wt. of sample 
 
 I 
 
 . 5203 .... 
 
 II 
 
 . 4298 .... 
 
 III 
 
 .5940 
 
 Vol. NaCN sol. 
 equivalent to 
 the mercury 
 
 51.19 .... 
 
 45 . 50 .... 
 
 58.32 
 
 Normality fac- 
 tor of NaCN 
 sol. 
 
 .02757 .... 
 
 .02757 .... 
 
 .02757 
 
 ®/^ Mercury 
 
 54 . 42 .... 
 
 54 . 07 .... 
 
 54.30 
 
 Theoretical for 
 
 CH - 
 
 CHs - HgCl 
 
 54.27 
 
 This compound was also analyzed for mercury by Professor Whit- 
 more, of Northwestern University, by his gold crucible method^® and 
 the results agreed very closely with those obtained above. 
 
 Reaction of Mercxxric Chloride and o-Allyl Phenol 
 in Absolute Alcohol . 
 
 To a solution of 13.5 g. mercuric chloride in 43 cc. absolute 
 alcohol were added 6 g. o-allyl phenol. A white precipitate com- 
 menced to form as soon as stirring was started. At the end of 
 

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12 
 
 twenty minutes stirring this was filtered and dried. The melting 
 point was 136® and the yield 4.5 g. On recrystallization from 
 110 cc. 95®/o alcohol 3.8 g. of product melting at 137.5® were ob- 
 tained . 
 
 Fifteen grams of mercuric chloride were added to the filtrate 
 slowly (as fast as it dissolved). A white precipitate commenced to 
 form and a large amount came down. This was filtered and melted at 
 134® and the yield was 15 g. On recrystallization from 250 cc. al- 
 cohol 5.5 g. melting at 137.5® were obtained. 
 
 The solution was again saturated with mercuric chloride and al- 
 lowed to stand over night. A small amount of precipitate had formed 
 and was filtered but did not melt up to 145® and so was discarded. 
 
 The alcohol resid^aes from the recrystallizations were concen- 
 trated and on the addition of water a white silvery precipitate of 
 the appearance of calomel appeared. This was filtered but did not 
 melt. There was tendancy for these solutions to become red in color. 
 
 Some of the recrystallized product obtained above was mixed with 
 cx: -mercurochloro methyl coumarane sind the same melting point 137.5® 
 was obtained. Prom this we may conclude that a 56®/o yield of pure 
 oc -mercurochloro methyl coumarane is obtained in a saturated abso- 
 lute alcohol solution of merc\iric chloride and that there is some 
 evidence of the partial oxidation of the phenol with the formation 
 of calomel. 
 

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13 
 
 Reaction of Mercuric Chloride with 
 o-Allyl Phenol In Butyl Alcohol Solution. 
 
 To a solution of 9 g. mercuric chloride in 41 g. absolute n-buty] 
 alcohol were added 4.3 g. o-allyl phenol. In about five minutes a 
 white precipitate commenced to form and came down in fairly large 
 amounts. This was filtered and recrystallized giving a yield of 
 2.3 g. of a white, crystalline product melting at 137.5® and giving 
 the same melting point when mixed with c?c -mercurochloro methyl 
 coumarane . 
 
 cac "Merciaroiodo Methyl Coumarane . 
 
 To a solution of 10 g. of potassium iodide in 200 cc. of water 
 were added 10 g. oc -mercurochloro methyl coumarane. This mixtxire 
 was vigorously stirred and heated. At about 80® the crystals ap- 
 peared to become more amorphous. The heating was continued just to 
 the boiling point and stirring was continued until the mixture cooled 
 The solid was filtered and washed well with water and dried. The 
 yield at this point was 13.4 g. of crystals melting at 115®-116®. 
 
 The theoretical yield is only 12.5 g. and probably the excess yield 
 was due to occlusion of water or error in the balance. This product 
 was recrystallized using 250 cc. of 95®/^ alcohol. This time 10 g. 
 of shiny white plates were obtained which became grayish on standing. 
 The melting point was 115. 5®- 116. 5® . On a second recrystallization 
 using 170 cc. of alcohol 8 g. of beautiful, white, shiny crystals 
 were obtained melting at 116®-116.5®. 
 
_r 
 
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14 
 
 This compound was analyzed by Professor ¥/hitmore for mercury and 
 the results obtained checked closely with the theoretical for 
 
 ^.CHa^CH - CHg - Hgl 
 
 o-Allyl Anlsole . 
 
 o-Allyl anisole was made by the directions given by Adams and 
 Rindfusz^® . 
 
 The Mercuric Acetate Derivative of 
 0 "Allyl Anisole » 
 
 13 
 
 Following the directions given by Balbiano and Paolini for 
 making the mercuric acetate derivative of aplol, an attempt was made 
 to make the corresponding derivative of o-allyl anisole* To a solu- 
 tion of 3.18 g* HgCCgHaOg) in 12.5 cc. water were added 1.5 g. 
 o-allyl phenol with stirring. It was noted that in about fifteen 
 minutes the oil which floated at first was commencing to settle to 
 the bottom and become very syrupy and stringy. Some of this syrup 
 was washed as well as possible with water and then boiled a short 
 time with concentrated HCl. o-Allyl anisole and a solution from 
 which mercuric sulphide was precipitated in large quantities by HgS, 
 were obtained. The o-allyl anisole was identified by extraction 
 with ether and determination of the boiling point. It checked that 
 of o-allyl anisole. This seemed to show conclusively that the com- 
 pound was the one desired and so the work was directed to a study of 
 this syrup with the Intention of causing it to crystallize if possi- 
 ble or of making a crystalline derivative. 
 
15 
 
 An attempt was made to carry out the reaction in the presence of 
 benzene but the only effect seemed to be that of forming an emulsion. 
 
 It was next found that the reaction was more rapid when alkali 
 was added in accordance with the general facts concerning these addi- 
 tion compounds. The method followed in making this syrup in most of j 
 the subsequent runs was to put together in a container the substances 
 in molecular quantities as noted in the first experiment and then to j 
 add a 10®/© NaOH solution in small portions waiting each time until 
 the basic mercuric acetate had disappeared before adding another 
 portion. This was continued until no precipitate appeared on the 
 addition of more alkali and the heavy syrup had settled to the bot- 
 tom of the container. 
 
 It was found that the syrup solidified when chilled with ice but 
 melted again when warmed. This fact was used in most of the experi- 
 ments to separata the reaction mixture from the syrup. It was 
 chilled and then the water solution was poured off. 
 
 The next efforts were directed toward the formation of a crystal- 
 line iodide or nitrate from this syrupy acetate. Some of the acetate 
 which had been made as above was treated with a concentrated solution 
 of KI. After standing two days a yellow oil had separated on top of 
 the solution. This was separated and washed with water. Then to 
 1/2 cc. of this oil were added 3 cc. of concentrated HGl and upon 
 gentle heating a red compound formed which was soluble in excess KI 
 solution and gave a large amount of HgS when treated with HgS. 
 o-Allyl anlsole was also obtained. It would seem from this experi- 
 ment that the iodide derivative was also oily since the red compound 
 
16 
 
 must have been merc\iric iodide and the oil obtained must have been 
 the mercuric iodide derivative* 
 
 An attempt was made to make the nitrate but oxidation appeared 
 to take place and only a very gxirnmy, tarry mass was obtained. 
 
 It was found that this syrup was slightly soluble in ether but 
 insoluble in petroleum ether. Consequently tlie following method of 
 purification was carried out. The syrup made as above was stirred 
 with fairly large amounts of ether several times until most of the 
 syrup had dissolved. The ether solution was then dried over sodium 
 sulphate suid the ether was then distilled off leaving the syrup. 
 This was then shaken well with boiling petroleum ether to remove 
 any o-allyl anlsole and then the syrup was again taken up in ether, 
 dried, and the ether was distilled. This left a small amount of a 
 heavy, viscous oil, of about the appearance of glycerine. This oil 
 dissolved almost Instantly in concentrated HCl to give a mercury 
 solution and o-allyl anisole. 
 
 It was thou^t that this product would be soluble in alcohol but 
 on the addition of this solvent to some of the syrup which had not 
 been purified by ether extraction, a large amount of a white pre- 
 cipitate separated at once. This was filtered and was found to be 
 insoluble in hot concentrated HCl. It melted at 160®-170® with de- 
 composition, and burned with a smoky flame when heated in a porce- 
 lain dish and ignited. The nature of this substance was not deter- 
 
 ^ It was later found that sodium sulphate had a strong tendency to 
 
 absorb the syrup 
 
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 mined, V/ere it not for its insolubility in HCl, it might be an 
 isomeric product and the syrup rai^t be a mixture of two substances 
 such as are obtained with safrol and methyl cavicrol^®. Its insolu- 
 bility in HCl makes this hard to believe and probably the white com- 
 pound is a basic mercuric acetate. 
 
 One portion of this alcohol solution was vacuum distilled until 
 the alcohol was removed, but as soon as it was heated in an attempt 
 to distill the syrup which remained, it decomposed giving metallic 
 mercury. This was carried out at 14 mm. 
 
 The alcohol was distilled from another portion and a syrup was 
 obtained similar in appearance to that obtained by ether extraction. 
 This was again dissolved in alcohol and a salt solution was added, 
 
 A white, flocculent precipitate came dovm at once and was filtered. 
 It gave no sharp melting point but commenced to soften at 65® and 
 melted at 70®, It was fo\md to be insoluble in all the common sol- 
 vents but dissolved in concentrated HCl almost immediately on addi- 
 tion and gave o-allyl anlsole and mercury in solution. This was 
 probably the mercuric chloride derivative of o-allyl anisole but be- 
 cause it could not be crystallized this could not be proved. It is 
 not known why this product would not dissolve in alcohol as analo- 
 gous products do. 
 
 The final experiment was an attempt to carry out the addition in 
 methyl alcohol solution. To a solution 32 g, mercxirlc acetate in 
 200 cc, methyl alcohol were added 13,3 g, o-allyl anlsole and the 
 solution was refluxed for ei^t hoiirs. There was a small amount of 
 a white residue (l/2 gra, ) and this was filtered off and the alcohol 
 
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18 
 
 was vacuum distilled leaving a heavy, syrupy oil very similar in ap- 
 pearance to the product obtained above -hen it had been purified by 
 ether extraction. Slightly more than a theoretical yield for the 
 compound was obtained 
 
 but this was probably due to an error in wei^t, since the whole 
 flask was weired, or to the occlusion of some alcohol. 
 
 About half this product was decomposed with concentrated HCl, 
 less than a minute being required, and then the diluted solution 
 was extracted with ether, the ether solution was dried over calciiam 
 chloride, and the boiling point of the residual oil was taken. It 
 boiled at 198® and this boiling point was checked with pure o-allyl 
 anisole in the same apparatus. 
 
 The results of this work are rather inconclusive, d\ae in large 
 part to the difficulty of working with these syrupy products. It 
 seems to be fairly clearly indicated, however, that mercuric acetate 
 reacts with o-allyl anisole to give a syrup which probably by analogy 
 has the structure 
 
 and that a similar product is formed in alcohol solution of the 
 probable structure 
 
 A satiirated solution of mercuric chloride containing a slight ex- 
 
 OCH3 
 
 CHs - GH - GHg - HgCaHoOa 
 
 OH 
 
 GHg - GH - CHa - HgCaHsOg 
 
 Mercuric Chloride and o-Allyl Anisole . 
 
19 
 
 cess of HCl was treated with a small amount of o-allyl anisole and 
 the mixture allowed to stand for several days with frequent shaking# 
 No reaction could he detected# 
 
 The same experiment was tried with the addition of alkali in 
 enou^ excess to precipitate basic merctoric chloride# This time 
 after a days standing the oil sank to the bottom and became syrupy 
 as in the case of the mercuric acetate indicating the probable for- 
 mation of a mercupochloro addition product# 
 
 Determination of the Time of Decomposition of 
 oc -Mercurochloro Methyl Coumarane by Acids # 
 
 In these experiments the strength of the acids used was deter- 
 mined by titration against a standard alkali# Fifty milligram 
 samples of -mercurochloro methyl coumarane were accurately weigh©<i 
 into small test tubes and in each case 2 cc# of the standard acid 
 was added and the tube was shaken well# As soon as the crystals ap- 
 peared to have changed to an oil the time was taken# However, the 
 decomposition was probably not complete because in each case it was 
 observed that on longer standing the oil became lighter and floated 
 to the top# 
 
20 
 
 Table* 
 
 Acid ®/ Composition Time for Decomposi- Remarks 
 
 ® tion in Cold (29®) 
 
 1. 
 
 HCl .... 
 
 33*46 
 
 • • • • 
 
 2 1/2 min* 
 
 
 1 
 
 2. 
 
 HCl .... 
 
 30*00 
 
 • • e e 
 
 4 1/2 min* 
 
 
 
 3* 
 
 HCl .... 
 
 23*80 
 
 • • • • 
 
 9 min* 
 
 
 
 4* 
 
 HCl .... 
 
 14*20 
 
 • • • • 
 
 5 hours 
 
 
 
 5* 
 
 HCl .... 
 
 7*50 
 
 • ♦ • # 
 
 21 1/2 hours 
 
 
 
 6* 
 
 HCl ... * 
 
 2*50 
 
 • • • • 
 
 No solution) 
 
 • • a • 
 
 Dissolves 
 
 
 
 
 
 ) 
 
 • • • • 
 
 slowly 
 
 7* 
 
 HCl .... 
 
 1*30 
 
 • • • • 
 
 No solution) 
 
 • • • • 
 
 with heating 
 
 8* 
 
 Acetic .... 
 
 100 
 
 • • • • 
 
 No solution) 
 
 • • • • 
 • • • • 
 
 On boiling 
 
 
 
 
 
 ) 
 
 • • e • 
 
 solution oc- 
 
 9* 
 
 Acetic .... 
 
 80 
 
 e • • • 
 
 No solution) 
 
 • • • • 
 
 curred but 
 
 
 
 
 
 ) 
 
 0 • • • 
 
 on cooling 
 
 10* 
 
 Acetic .... 
 
 56 
 
 • • • • 
 
 No solution) 
 
 • • • # 
 
 -mercuro- 
 
 
 
 
 
 
 • • • • 
 
 chloro 
 
 methyl coiara- 
 arane pre- 
 cipitated. 
 
 As opposed to these figures the derivative of o-allyl anisole 
 
 was decomposed almost Instantly by concentrated HCl (o3.46®/ )• It 
 
 o 
 
 was decomposed by 7.5®/© HCl and gentle warming in five minutes 
 while under the same conditions cC -mercur-ochloro methyl coumarane 
 required ten minutes* 
 
 I 
 
r 
 
21 
 
 IV. CONCLUSION. 
 
 It is admitted that the decomposition of these olefine mercury 
 compounds by HCl is difficult to explain on the basis of a struc- 
 tural formula; but it is much more difficult to explain the other 
 reactions of these compounds and particularly the formation of 
 this coumarane derivative on the basis of a molecular formula. It 
 is conceivable that the mercury has some sort of a loosening action 
 on the hydroxyl group under the influence of acids because many 
 cases are now known of one group's affecting another in such a man- 
 ner. It may be concluded, therefore, that although we are not sure 
 just what the mechanism of the decomposition of these compounds by 
 HCl is, the structure as proposed by Sand is essentially correct. 
 
I* , « 
 
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22 
 
 V, SUMMARY. 
 
 1. The mercuric chloride derivative of o-allyl phenol has been 
 made and it has been shown that it is a coumarane derivative of the 
 structiire 
 
 ^ ^ CHg'^CH - CHa - HgCl 
 
 2. It has been shown that this compound is formed with fairly 
 large yields in acid solution and that it is decomposed with greater 
 difficulty by acids than other mercury olefine derivatives. 
 
 3. The mercuric acetate derivative of o-allyl anisole has been 
 made but its structure has not been proved due to its syrupy nature. 
 
 4. A new proof of the structure of the mercury derivatives of 
 the olefines as proposed by Sand has been given. 
 
•>* 
 
 r 
 
 
 K .J.T- :» i i . ^ . i * .V -....• •*■ 
 
 , • Ov .’< '•;• 7i :u: •: ’ -• ■ -y. " "u' .' 
 
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 tvv ■ V ‘‘f-:-. vt G.' 
 
 I f . . .1 , 1. ‘ 
 
 ( • '. 0>. ,'f f Ci'". ■- ■ « V 
 
VI. BIBLIOGRAPHY 
 
 1. Compt. rend. 126 , 1145-1148 (1898). 
 
 2. Ber.^, 1340-1353 (1900). 
 
 3. Ann. 420. 170-190 (1920). 
 
 4. Ber.M, 1387 (1901). 
 
 5. Ann. 329, 151 (1903). 
 
 6. Ber.M, 1385 (1901). 
 
 7. Ber.44, 1432 (1911). 
 
 8. Thesis by Roman (1922). 
 
 9. Ber.^, 3157 (1912); Ann. 401. 561 (1913). 
 
 10. J. Am. Chem. Soc .41, 648 (1919). 
 
 11. Ber.54, 2079 (1921). 
 
 12. Organic Compounds of Mercury, p.365. 
 
 13. Ber.36, 3575 (1903).