PREPARATION OF ORGANIC ALUMINIUM 
 COMPOUNDS BY THE GRIGNARD 
 REACTION 
 
 liV 
 
 RALPH WALDO POOLER 
 
 B.S. University of Illinois, 1921 
 
 THESIS 
 
 SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS 
 FOR THE DEGREE OF MASTER OF SCIENCE IN CHEMISTRY 
 IN THE GRADUATE SCHOOL OF THE UNIVERSITY 
 OF ILLINOIS, 1922 
 
 URBANA, ILLINOIS 
 
Digitized by the Internet Archive 
 in 2016 
 
 https://archive.org/detaiis/preparationoforgOOfogi 
 
A, 
 
 UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 -1922— 
 
 1 HEREBY RECOMMEND THAI' THE THESIS PREPARED UNDER MA' 
 
 SUPERVISION BY Ha34)±L-''laLdo Fnglep 
 
 ENTITLEDPr_eT)arajtion of— Qi»gan1.C- 
 
 Gr_ignand EeacM on . 
 
 BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
 
 THE DEGREE OF Idaater o f So lenna- 
 
 CcX/vi?. jj. 
 
 In Charge of Thesis 
 
 ^ Head of Department 
 
 Recommendation concurred in* 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 Retjuired for doctor’s degree but not for master’s 
 

 
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CONTENTS 
 
 Pages 
 
 ACKNOWLEDCTvIENT 
 
 I INTRODUCTION 1 
 
 Purpose of Research 1 
 
 Methods of Separating Rare Earths nov/ in Use 1 
 
 Application to Priedel and Crafts’ Reaction 2 
 
 II HISTORICAL AND THEORETICAL 3 
 
 History of Priedel and Crafts’ Reaction 3 
 
 Applications 3 
 
 Theories Advajiced for Mechanism Envolved 3 
 
 Theory of Formation of Phenyl Aluminium Chloride 7 
 
 III EXPERIMENTAL 9 
 
 Apparatus 9 
 
 Preparation of Reagents 10 
 
 Propyl Magnesium Bromide 10 
 
 Phenyl Magnesium Bromide 10 
 
 Dry Petroelum Ether 11 
 
 Aluminiimi Bromide 11 
 
 IV CONCLUSION 25 
 
 V BIBLIOGRAPHY 26 
 
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ACKNOWLEDGMENT 
 
 This problem was suggested by Dr.C. S. Marvel 
 The writer wishes to thank him for his many sug 
 gestions and untiring assistance. 
 
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1 
 
 I 
 
 I 
 
 INTRODUCTION 
 
 The study of the action of Grignard reagent, RM^, on aluminium 
 chloride and bromide was suggested by the fact that an analogous re- 
 action using mercuric halides had been carried out very successfully 
 in this laboratory by other workers* 
 
 It was noticeable that in all cases the dialkyl mercury com- 
 pounds were all liquids* Also by reference to the literature it was 
 found that the aryl and alkyl aluminium compounds were also liquids. 
 It mi^t be stated here that the alkyl and aryl aluminium compounds 
 in themselves have little interest but throu^ the study of these 
 compounds, one ?/ould be able to study the rare earth alkyls* In 
 other words the original idea of this research was to find a means of 
 separating the rare earths from each other by fractional distillation 
 of the alkyl or aryl rare earth compounds, prepared by the action of 
 Grignard ’s reagent on their chlorides* 
 
 I Since aluminium is in the same group in the periodic table and 
 
 j 
 
 I there is no great difference in the properties of these elements, 
 
 i 
 
 I and due to the abundance of alwninium and its compounds, it was used 
 
 las a starting point for this investigation. 
 
 I 
 
 i The methods^most commonly used for the separation of the rare 
 
 I earth elements from one another are of tv/o general kinds: (1) Those 
 
 I depending on the difference in solubility of the various salts; (2) 
 
 1 
 
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2 
 
 and those based upon the difference on the basicity of elements* 
 
 The above mentioned methods are both wasteful and tedious. So it 
 was thought that fractional distillation would be quicker and easier 
 if a method could be worked out. 
 
 The chlorides and bromides of the rare earths are easily pre- 
 pared in anhydrous state and this point tends to favor the use of 
 the Grignard reagent in preparation of alkyl derivatives. These 
 ilkyl rare earths then in turn could be fractional distilled and the 
 desired fractions collected, 
 
 ?/ith this aim in view investigation was started and it was at 
 once noticed that the reaction do not go to give the trialkyl com- 
 poimd but appeared to form a compound of the RAlClg type. This 
 proved to be interesting because of the fact it could be used to study 
 the mechanism of the Friedel and Grafts’ reaction. Therefore, the 
 work shifted to the study of the mechanism of the Friedel and Crafts’ 
 reaction and the greater portion of the v/ork was devoted to this line 
 
II 
 
 3 
 
 HISTORICAL AND THEORETICAL 
 
 The Priedel and Crafts' reaction, a reaction which has had an 
 extremely wide and varied application, was discovered in 1877 by 
 C* Priedel and J, M* Crafts®* It is connected more particularly witli 
 synthesis of aromatic hydrocarbons but is also used in synthesizing 
 a variety of other organic compounds such as, acid chlorides, ketones 
 aldehydes and acids* I^droxyl and amino groups, if present in the 
 nucleus must be protected by converting the former into an ether and 
 the latter into an acetyl derivative* Nitro compounds do not react* 
 The reaction may also be used to produce internal condensations * 
 
 Due to the dehydrating action of anhydrous aluminium chloride under 
 some conditions it may also prodixje decomposition. Pinally it may 
 accomplish a transfer of carbons from one carbon atom to another 
 within the benzene nucleus* The active agent in the reaction is 
 aluminium chloride. Perric chloride and zinc chloride have been 
 used to a lesser extent* 
 
 Several theories have been advanced to explain the various 
 changes produced by aluminium chloride* The first publications® in 
 1877, offered a theory of the reaction based upon analogies with the 
 properties of organo-me tallic bodies. It was supposed that all the 
 observed effects might be explained by the existence, even in small 
 proportions of an organo-me tallic chloride, CO-Als, Clg, which 
 being constantly decomposed according to the equation and constantly 
 
 + RCL 
 

 
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 renewed, would explain the contact action of aluminium chloride. 
 
 This theory was kept in view throughout subsequent work and was 
 strengthened by many new facts and paj?ticularly by those relating to 
 the readiness with which oxygen-, carbon dioxide®, sulphur dioxide 
 and cyanogen are absorbed by the benzene compound with aluminium 
 chloride, giving respectively phenol, benzoic acid, phenyl mercaptans 
 and diphenyl sulphide, phenyl sulfonic acid, and phenyl cyanide. The 
 smll quantity of each of these products obtained may be ascribed to 
 the insolubility of the gases in benzene. These results may be easi- 
 ly understood if we admit the products of the organo-metallic com- 
 pound alluded too. For example in case of phenol, the CH>-Al2Cl5 
 combines v/ith oxygen to form the phenate of AlgClg, which is decom- 
 posed by water v/ith liberation of phenol, thusi- 
 
 So it is evident here that aluminium chloride does not induce 
 the reaction by its mere presence. The connection betv/een the hydro- 
 carbon and the chlorine compound as made by one giving up the h^'^dro- 
 gen and the other giving up its chlorine with formation of hydro- 
 chloric acid similar to this is the reaction of Grignard reagent 
 with oxygen. 
 
 The action of the compound d^-AlgClg should be analogous to 
 that of triphenyl aluminium®. The la.tter v/as prepared by action of 
 alufninium on diphenyl mercury and gives with benzyl chloride, di- 
 
 ' phenyl methane; with oxygen, phenol; and with sulphur, phenyl mer- 
 I captan; but has no action on halogen substituted in benzene ring. 
 
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 as aluminium chloride and benzene* 
 
 Zinc ethyl is known to break up by heating into ethylene and 
 ethane. Here again the analogy holds good; for hydrocarbons heated 
 with aluminium chloride break up into single saturated compoimds, 
 which are easily isolated, and into complex unsaturated compounds# 
 
 No conclusive proof of the intermediate compound was advanced al- 
 though certain experiments carried out in the course of the research 
 seemed to indicate its formation in small quantities. The evidence 
 is scanty and inconclusive# 
 
 The equation representing the formation of an aromatic hydrocar- 
 bon would represent aluminium chloride as a true catalyst. In prac- 
 tise, however, this is not found to be the case in preparing deriva- 
 tives containing oxygen. For in certain reactions it is foimd that 
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 the action of aluminium chloride as a catalyst, providing it can be 
 
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 i shown that it forms a stable compound with the products of the re- 
 ; action. The observation of Gustavson® and other seem to point in 
 ’ this direction. A niimber of definite products have been isolated 
 
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 which seem to act as catalyst for example; Al2Cl66(CeH0 ) and ethyl 
 chloride gives AlgCleCeHs ( )3 6 
 
 Steele concluded that the action of alimiinium chloride in induc- 
 ing the Friedel and Crafts* reaction differs from many cases of a 
 true catalyst only in accident that these reagents combine with cer- 
 tain substances produced during the reaction and are thus removed 
 from the system. 
 
 In rather recent research carried out under supervision of Dr. 
 Oliver Kamm® it was found that v/hen benzene was refluxed with alu- 
 minium chloride very little hydrochloric acid is given off. 
 
 a 
 
 A^AICIs 
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 -Cl 
 
 = ^AlCl; 
 
 + HCl 
 
 They assume that aluminiuia chloride adds to a double bond in the 
 
 ^CH 
 
 benzene ring to form CH. 7 pAlClg , and this compound then 
 
 ^CH CH ^ 
 
 breaks down to give •d>AlCla and hydrochloric acid. Further evi- 
 dence in support of this theory may be cited by production of phenol 
 by passing oxygen or air into a mixture of aluminium chloride and 
 benzene . 
 
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 The fact that some chlorination products are actually obtained 
 as evidence in favor of the above mechanism. In all of these reac- 
 

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 fcions it was found that the yields vrene proportional to the amount of 
 aluminium chloride used in proportion to the other reagents. 
 
 So far tv/o theories have been advanced to explain how aluminium 
 chloride induces the Friede?, ejid Crafts* reaction and have been dis- 
 cussed in proceeding pages. It v/as first maintained that the action 
 cf aluminium chloride was that of a catalyst and second it is clairaed 
 bhat the aluminium chloride takes part in the reaction and is used 
 proportionally. 
 
 Experimental facts favor the view that <I>Al2Cl^ or <H>AlCl2 
 Is formed in case of the hydrocarbon derivatives as v/ell as in the 
 
 oxygen derivatives. If benzene and aluminium chloride a.re treated 
 
 nrith ethylene the resulting product is ethyl benzene^®, 
 
 A H H HCl 
 
 f )^A1 C = = /V- C - C - Aids = ) ) 
 
 ^C1 Ij H H V +AlCls 
 
 Ulso it has been shown by Gustavs on^^ that normal propyl bromide with 
 oenzene in the presence of aluminium chloride gives isopropyl benzene, 
 Ikewlse isopropyl bromide with benzene presence of aluminium chloride 
 Srield isopropyl benzene. The reaction may be explained by the fact 
 hat if either Isopropyl bromide or normal propyl bromide is tree.ted 
 vith aluminium chloride the same unsaturated propyl compound v/ill be 
 cbtained. The double bond breaks and the phenyl aluminium chloride 
 
 H H 
 
 adds in according to Markonnikoff s rule, -C-^-AlCl 
 
 A ^ 
 
 /y-AlCla + CHa - C = 
 
 H 
 
 H _ 
 
 H 
 
 HCl 
 
 ■ — CHa 
 \GHa 
 
 Likewise isobutyl chloride and benzene in presence of aluminium 
 chloride give tertiary butyl benzene. 
 
8 
 
 In case of the oxygen derivatives the similar addition to the 
 double bond takes place# If phenyl aluminium chloride is treated 
 with acetyl chloride the corresponding ketone can be obtained by 
 splitting down v/ith v/ater# 
 
 In order to test out the above hypothesis an attempt to prepare 
 a compound of this natiire, CgHsAlCla v/as carried out in the following 
 manner. One mole of aluminium chloride or bromide v/as treated with 
 one mole of phenyl magnesium bromide under certain conditions speci- 
 fied in the experimental part. Since chlorbenzene will not react with 
 magnesium In anhydrous ether it was necessary to use the phenyl 
 bromide. Then it was necessary to prepare aluminium bromide in order 
 to have the compound contain one halogen instead of a mixture of 
 halogens. The product obtained from the reaction of phenyl magnesium 
 bromide and aluminium bromide xms treated with acetyl chloride and 
 then decomposed with water and the resulting compound was aceto- 
 phenone, which is evidence in favor of the above mechanism. This is 
 as far as the reactions were carried, on accoimt of the fact that 
 the time was limited and the compounds were very unstable and diffi- 
 cult to isolate and pui‘ify. 
 
 Cl 
 
Ill 
 
 9 
 
 EXPERIMENTAL 
 
 1. Apparatus . 
 
 The setup of the apparatus in case of preparing the organic 
 aluminium compounds was identical in all cases# A three neck flask 
 was fitted v/ith a mercury sealed glass stirrer placed in the mouth of 
 the flask. One of the necks was fitted vdth a long condenser and the 
 other neck of flask was fitted with a separating funnel and a tube 
 for passing nitrogen into the flask# Figure I shows the setup com- 
 plete • 
 
 The setup for the preparation of aluminium bromide consists of 
 a romd bottom flask connected with a reflux condenser and a sepatory 
 funnel# The top of the inverted condenser is fitted with a cork and 
 glass tubing which leads into a flat bottom wide mouthed bottle, 
 which also contains an inverted condenser with the upper end closed 
 with a calcium chloride tube# Figure II shows the setup as it was 
 used# 
 
 The products were dried in an atmosphere of nitrogen# The ap- 
 paratus used consisted of a tall cylindrical can, in the centre of 
 which v/as cut a large hole# A large rubber stopper fitted with a 
 large hard glass test tube was fitted in the hole and made water 
 tight# The test tube was fitted v/ith a tv/o hole rubber stopper# In 
 
 one hole a tube was placed v/hich was connected to the vacuum; in the 
 
 nigrogen tank 
 
 other hole a stopcock was placed v/hich v/as connected up v/ith and 
 the desired temperature was maintained by use of a flame# The tem- 
 perature was regulated by a theroraeter placed on top of the water 
 bath. 
 
I 
 
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10 
 
 A vacuiHn filter was set up which cnonsisted of a filter flask 
 with a large round glass funnel placed in the neck of the flask* In- 
 side of the funnel, a Buchner funnel was held tight by means of a 
 cork. The top of the round glass funnel was covered by the top of a 
 desiccator which had an opening in the center, th_rough which the pro- 
 duct and the nitrogen could be admitted. 
 
 2. Preparation of Reagents . 
 
 PROPYL MAGNESIUM BROMIDE 
 
 Place in a one liter flask one mole of magnesium scrap, add a 
 crystal of iodine and 450 cc. of anhydrous ether. Fit the mouth of 
 the flask with a tv/o hole stopper. Through one hole place the end 
 of a condenser in a vertical condition and through the other hole a 
 separatory funnel is placed. Then add one mole of propyl bromide 
 drop by drop by means of a separatory funnel. If the reaction fails 
 to start, place a small amount of the above mentioned constituents in 
 a test tube and heat until reaction has started and then pour in the 
 one liter fla.sk. If the reaction becomes too vigorous it may be 
 slowed by applying a pan of ice to the bottom of the flask. After 
 all the propyl bromide has been added and the reaction ceases, re- 
 flux for one hour and then allow to cool. If magnesium propyl bro- 
 mide separates, add more dry ether in sufficient amount to keep it 
 in solution. Moisted air can be kept from coming in contact with 
 Grignard reagent by placing a calciLim chloride tube on top of the 
 condenser during the reaction. 
 
 PHENYL M AGNES lUl^ BROMIDE 
 
 Phenyl magnesium bromide is prepared by exactly the sam.e manner 
 

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11 
 
 as propyl magnesiiim bromide, brom-benzene being substituted for 
 propyl bromide, while the other constituents are the same. This re- 
 action is a little harder to get started but this may be accomplished 
 with ease if the ether in the flask is kept boiling for ten or fif- 
 teen minutes while the phenyl bromide is being added, 
 
 DRY PSTROLEim ETHER 
 
 o 
 
 Petroleum ether v/as distilled and the 70-80 boiling fraction 
 was collected. This fraction was placed in a separatory funnel and 
 shaken well with concentrated sulph-uric acid. After shaking the 
 liquid was allowed to stand and the concentrated sulph-uric acid was 
 drawn off. This v/ashing was repeated several times. In this way 
 the unsaturated hydrocarbons can be removed. The petroleum ether 
 was next shaken vdth water to remove all acid and the water was re- 
 moved by allowing the petroleum ether to stand for twenty four hours 
 with Gael 2 . The liquid was then poured off the CaClg into a distil- 
 ling flask containing sodium, which removed the last traces of water. 
 The liquid was then distilled and the collected in a bottle, 
 
 ALUI^INIUM BROMIDE 
 
 The preparation of aluminium bromide proved to be rather diffi- 
 cult and many attempts were made before a successful means of obtain- 
 ing it v/as found, 
 
 A distilling flask was placed on an oil bath and connected to a 
 combustion tube which was drav/n out at the end nearest the flask and 
 slightly bent at the other end. In the top of the distilling bulb a 
 dropping funnel was placed and filled with bromine. The aluminium 
 
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12 
 
 strips which were previously washed with alkali, water, alcohol and 
 ether were placed in the combustion tube and the tube heated to al- 
 most red heat. Then bromine was dropped into the empty hot flask 
 and in this way the bromine was vaporized and passed over the alumini- 
 um. The alumini\im bromide vapors were condensed in a flask at the 
 other end which was water cooled and which had an outlet for excess 
 bromine vapors. 
 
 If bromine was added to the flask slowly the vapors were not 
 forced over into the combustion tube and if it was added fast enough 
 to cause the vapors to pass over, the reaction was too violent and 
 the prod-uct could not be condensed. So in order to carry the bromine 
 over and still have a slow reaction it was necessary to have a gas 
 passing through the system to carry bromine over. Anything which con- 
 tains oxygen could not be used so nitrogen was tried. This did not 
 
 prove successful because at the temperature to which the aluminium 
 
 it 
 
 must be heated in order to make it react with bromine, was also high 
 enough to cause it to unite with nitrogen to form nitride.^ 
 
 The next step to simplify the process was to insert a stop-cock 
 in betv/een the flask and combustion tube and in this manner allow the 
 bromine to pass over only when desired. The flask was protected with 
 a safety valve so that when the pressure became too great in the flask 
 the cork would come out, in this way reduce the pressure. This scheme 
 worked better than any previously tried but it was too difficult to 
 regulate the temperature in the laboratory by means of flames. It 
 probably would have been satisfactory method in an electric furnace, 
 where a constant temper atin^e could be maintained. 
 
13 
 
 The next attempt to make alumini-um bromide was by bromination of 
 aluminium strips in the presence of carbon tetrachloride. This did 
 not prove to be satisfactory and also using ether as a solvent did 
 lot help# 
 
 Finally aluminium was placed in dry ether and dry hydrobromic 
 acid was allowed to pass through the solvent. After the solvent be- 
 came saturated the hydrobromic acid began to eat up the aluminium and 
 lydrogen was evolved. The aluminium as it passed into solution formed 
 a heavy oily liquid which separated from the ether. The dry hydro- 
 Dromic acid was made by placing benzene and ion fillings in the flask 
 in Figure II and dropping bromine into it. 
 
 The oily layer which contains the aluminiimi bromide was subjected 
 to a current of dry air \mtil all the hydrobromic acid had been ex- 
 pelled and then washed with anhydrous ether and evaporated to dry- 
 ness, three or four times and in this v/ay a nice solid product was 
 obtained. The yield of pure anhydrous aluminium bromide is 95 per 
 cent, 
 
 3, Ac ti on of Grignard’s Reagent on Aluminium Chloride and Bromide , 
 PROPYL MAGNESIUM BROMIDE AND ALUMINIUM! CHLORIDE 
 
 My first attempt was to prepare tripropyl aluminium. Three moles 
 of propyl magnesium bromide were placed in the flask shown in Figure I 
 and a little of the aluminium chloride added slowly to it, through the 
 neck of the flask. Nitrogen was also allowed to pass slowly through 
 the solution in the flask in order to have an inert atmosphere. The 
 stirrer v/as then started and the rest of the mole of aluminium chlor- 
 
v.>- - •• -• 
 
 ', *lo f ■' 
 
 \, 
 
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14 
 
 ide was added slowly. A violent reaction took place with the forma- 
 tion of a solid mass in the bottom of the flask. The heat of reac- 
 tion was so great that most all the ether was lost and a gray clay 
 like mass was left in the bottom. This solid was not deccxnposed by 
 water but acid decomposed it very rapidly. 
 
 In the next run the aluminium chloride was added more slowly and 
 at the same time the flask was kept in an ice bath after the reaction 
 had ceased it was refluxed for fifteen to twenty hours and at the 
 
 end of this time it v/as distilled under pressiu’e of 190 mm., but no- 
 
 o 
 
 thing came over above 55 . The reaction expected was as follov/s: 
 
 /Br 
 
 3 CgH,^ MgBr + AlClg = (GgH 7 )Al + 3 Mg 
 
 Cl 
 
 In case of alkyl mercury com.pounds it has been found that it re- 
 quired a much higher temperature and a longer time to attach the sec- 
 ond alkyl group to mercury than it does the first alkyl group. So it 
 seemed logical it would apply likewise to aluminium compounds of this 
 nature. And since the alkyl groups must be linked to aluminium dis- 
 placing three chlorine atoms it seemed as thou^ it v/ould require a 
 longer time and a much higher temperature to place the second and 
 
 third alkyl groups onto aluminium. So a higher boiling substance was 
 
 o 
 
 used in place of dry ethyl ether. Dry petroleum ether, b.p. 70-80 , 
 were used. The propyl magnesium bromide was made in exactly the same 
 way as described for propyl magnesium bromide. In this case the 
 Grignard reagent was not soluble in dry petroleum ether and dimethyl 
 aniline was used as catalyst instead of iodine. 
 
 The propyl magnesium bromide suspended in petroleum ether solu- 
 tion was treated in the same manner as described in the first run. 
 
15 
 
 After all the aluminiijm chloride had been added it was allowed to re- 
 flux for thirty- six hours and then cooled, transferred to distilling 
 flask and distilled. The petroleum ether was driven off and as the 
 temperature was increased the dark brown oily liquid began to decom- 
 pose, A solid similar to the one in the first case was found in the 
 bottom of the flask. 
 
 In order to get around the formation of the undesirable mass in 
 the bottom of the flask a new method of procedure was tried. This 
 time the aluminium chloride was dissolved in dry ether and placed on 
 the 3-neck round bottom flask. The stirrer was started and nitrogen 
 was passed through several minutes to expell all the air. Then 3 
 moles of propyl magnesium bromide was added slov/ly to the one mole of 
 alimninium chloride, dissolved in the dry ether. After the reaction 
 had stopped the stirring was continued and the liquid v/as refluxed 
 for thirty minutes, A solid was formed on the bottom of the fld'sk 
 which contained light brov/n crystals and also some propyl magnesium 
 bromide • 
 
 In similar manner the above reaction was run and instead of 3 
 moles of CgHfj-MgBr one mole was used. The time of reflux this time 
 was increased to thirty-six hours. A nice li^t yellow crystalline 
 solid separated out in the bottom of the flask. This was filtered 
 by means of the filter described in the first part of this article 
 and sealed in a glass stoppered bottle. 
 
 The compound then obtained burned readily and the residue con- 
 tained aluminium. It was easily decomposed by moisture. By blo?/ing 
 one’s breath upon the compound hydrolsis would take place. On adding 
 

 
 'i-K € 
 
 hoi.i-H rxt- 1 ^' .'•' .fCv-i'"’ 
 
 Cl , 
 
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 di;">Xod*: --oX; jXf'A vXXT/v. ■: oX^c-s ircfVT;:. X •.*? .To tt - '-T -’j- 
 
 frf iXoe. ■‘XT '.X ’ j o /lov- 
 
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16 
 
 water to a little to it in a test tube a gas was given off which 
 burned readily, 
 
 A ,2000 gram sample was heated v/ith water and the gas collected. 
 The number of cc, given off by this sample was 36, which indicated 
 that one propyl group had replaced a chlorine group in the alu:-iiiniura 
 chloride , 
 
 Br 
 
 CsH^MgBr + Aids > C 3 H 7 AICI 2 + Mg ^ 
 
 Cl 
 2O 
 
 GqEq + AlClgOH 
 
 This compound was not analyzed because of the mixture of alumini- 
 um halogens which would naturally be present in the molecule. Also 
 no solvent could be found which would dissolve it and therefore 
 could not be purified, 
 
 ACTION OP PHENYL MAGNSSIUJ/i BROMIDE ON ALUMINIIB'I CHLORIDE 
 
 Phenyl magnesium brom-ide was prepared by the method previously 
 described. Then aluminium chloride was dissolved in an excess of an- 
 hydrous ether and poured into the three neck flask. The stirrer was 
 started and the phenyl magnesium bromide was added slowly with con- 
 tinuous stirring. The reaction was fast and a great deal of heat was 
 evolved as a steady stream of ether ran back from the condenser. 
 
 After the three moles of phenyl magnesium bromide had been added the 
 liquid was allowed to reflux for fifteen to sixteen ho\irs v/ith a 
 stream of nitrogen bubbling through the constantly stirred mixture. 
 The nitrogen was previously dried by passing it through sulphuric 
 acid. 
 
17 
 
 After refluxing, the flask v/as allowed to cool and the contents 
 of the flask were placed in a vacuum desiccator and ether allowed to 
 evaporate off. There remained in the dish after evaporation a dark 
 brown solid covered with a oily brovm liquid which could not be evap- 
 orated by means of the vacuum and which also decomposed on heating. 
 The contents of the dish was placed in the vacuum filter and dried as 
 completely as possible in this manner. 
 
 Qualitative tests were then performed on the solid. It burned 
 readily when placed on the end of a spatula and subjected to the 
 flame, giving a sooty black flame. A little was next fused with so- 
 dium. and tested with silver nitrate for halogens and it gave a test 
 for both bromine and chlorine. 
 
 The next step was to find a solvent so that it might be recrys- 
 tallized and purified. On adding water or acids it was foimd that 
 hydrolysis took place very rapidly in the cold. On the top of the 
 water was a yellow layer which had an odor like benzene. The yellow 
 layer was separated from the water and aluminium hydroxide and a meta 
 dinitro derivative was made by treating the liquid with a mixture of 
 nitric acid and sulphuric acid. A white solid was precipitated out 
 and this v/as allov/ed to dry and a melting point taken. It corre- 
 sponded to the melting point for meta dinitro benzene given in the 
 
 o 
 
 literature ra.p, 90 /o. A.lcohol also failed as a solvent because hy- 
 drolysis again took place but this time more slowly. On trying ether 
 as a solvent the only layer was produced and this therefore could not 
 be used to an advantage as a solvent. The product was also insoluble 
 in carbon tetrachloride, ligroin, acetone, toluene, chloroform. 
 
18 
 
 anisol and only very slightly soluble in benzene. Carbon bisulphide 
 also failed to have any dissolving action on the product, so a good 
 solvent for the compound could not be found. Benzene proved to be 
 the best solvent. By several extractions with boiling benzene, some 
 of the product could be obtained but it was not pure. 
 
 A few reactions were tried with the brown crystalline product. A 
 little of the compound was placed in a flask and refluxed with excess 
 of ethyl bromide for three hours. The object was to test the theory 
 and see if any ethyl benzene could be produced. But on examination 
 
 of the contents of the flask there was no ethyl benzene formed* ?/hen 
 this run was mad.e no hydrochloric acid gas was passed into the solu- 
 tion while the mixture was refluxing and this may account for the 
 failure to obtain the ethyl benzene, because when ethyl benzene is 
 made by using ethyl bromide, benzene, and aluminium chloride by the 
 Friedel and Grafts’ reaction an atmosphere of hydrochloric acid gas 
 is present. 
 
 Another portion of the product v/as treated with acetyl chloride 
 and the reaction was very vigorous. A solid product was found in the 
 bottom of the flask. The solid product was readily hydrolyzed by 
 water in the cold with the formation of a yellow layer on the 
 top of the water, v/hich had the characteristic odor of acetophenone. 
 The layer was drawn off and treated with phenyl hydrazine. A white 
 
 precipitate was produced which melted at 104 . The melting point of 
 
 o 
 

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19 
 
 o 
 
 the phenyl hydrazine of acetophenone given in the literature as 103 • 
 In similar manner the compound was treated with benzoyl chloride and 
 then with water. It gave a very characteristic odor of benzophenone , 
 
 A quantitative analysis was not run on this compound because of the 
 fact that it could not be obtained pure and also because a mixture of 
 halogen was present and a true analysis could not be obtained. Either 
 of the compounds shown in the equation might be present or even a 
 mixture of the two. So the next step necessary in order to have a 
 
 . Br 
 
 ■MgBr 
 
 Ether 
 
 + AICI3 
 
 0 “ 
 
 \ 
 
 Cl 
 
 Al-Cl 
 
 \ 
 
 Cl 
 
 uniform compound was to use aluminium bromide instead of aluminium 
 chloride. Since aromatic chlorine compounds will not react with 
 magnesium in dry ether, 
 
 ACTION OF PHENYL MAGNESIA BROMIDE ON ALUMINIIB! BROMIDE 
 
 One mole of aluminium bromide prepared as described previously 
 , containing 
 
 was placed in a three neck flask /\ anhydrous ether. Three moles of 
 phenyl magnesium bromide were added slowly to the aluminium bromide. 
 The phenylraagnesium bromide must be added slowly and with constant 
 
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20 
 
 stirring because the heat produced causes a constant stream of ether 
 to flow dovm the condenser and this will escape at the top if reac- 
 tion is allowed to run too fast. On adding the phenyl magnesium 
 bromide the color of the solution was first orange and then it chang- 
 ed to white and finally to a dark brown color. The mixture was re- 
 fluxed for fifteen hours after all the phenyl magnesium bromide had 
 been added and then cooled. The ether was next evaporated off and 
 the solid brown crystallized product v/as obtained which had the same 
 appearance as the one obtained when aluminium chloride was used. This 
 compound was as highly insoluble as the aluminium chloride compounds. 
 
 A little of the compound was placed in a beaker and benzene was 
 added and heated to boiling. The soluble portion was poured off and 
 more benzene added to the beaker and this was repeated until the ben- 
 zene was perfectly clear. The product thus obtained from the benzene 
 
 o 
 
 extract was dried at 100 in a vacuum drier. An analysis on the 
 compound was carried out. The carbon did not check with the theo- 
 retical percentage. However, an analysis showed the presence of 
 aluminium, magnesium and bromine 
 
 In the next run a different method of procedure was adapted. 
 
 One mole of aluminium bromide was placed in the flask and one mole 
 of phenyl m.agnesiura bromide was added slowly and after reaction had 
 ceased, the mixture was refluxed for five hours and then the second 
 mole of Grignard's reagent was added and likewise refluxed for five 
 hours. At the end of this time the third mole of Grignard's reagent 
 was added and refluxing continued for five hours longer. The flask 
 was then cooled and an excess of acetyl chloride was added slowly 
 

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21 
 
 with constant stirring. A beautiful orange precipitate settled down 
 to the bottom of the flask. This product was drav/n off, filtered by 
 means of vacuum filter, and dried in the vacuum drier# 
 
 An analysis was carried out on this sample for carbons, halogens, 
 
 and aluminium and the following results were obtained: 
 
 . o 
 
 .5000 grams of substance gave 148 cc. of COg at 28 and 
 748#6 mm. pressure 
 
 Calc, for C, H, Al, Halogen Oxygen C = 15.7 
 
 Pound C = 13.8 
 
 •5000 grams of substance required 50.53 cc . of AgNOs which 
 was 0981 normal. 
 
 cc . calculated = 50.9 
 
 cc. found =: 50.53 
 
 Aluminium was determined by heating .5000 grams of substance 
 in crucible in open air and the oxide was weired. 
 
 Calculated for aluminium = 9,1 
 
 Pound =10.8 
 
 In the calculation of the theoretical results the formation of 
 the following compound was used as bases: 
 
 This compound was readily hydrolyzed by water giving a small quantity 
 of acetophenone. 
 
 The final and best method of procedure which was found, was to 
 place one mole of aluminium bromide in the three neck flask connect 
 
 Cl 
 
C. -f.- ■ 'bX 
 
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22 
 
 up as indicated in Figure I and add slowly v/ith constant stirring 
 one mole of phenyl magnesium bromide and three portions to the flask 
 allowing the mixture to reflux for five hours each time before the 
 next portion was added. After the three portions had been added the 
 mixture refluxed for fifteen hours, the flask was cooled and an oily 
 clear layer v/as in the flask. The oily layer was drawn off and 
 placed in a flask fitted Y/ith a rubber stopper. This oily substance 
 was then shaken v/ith carbon disulphide and at once the oily layer 
 formed a solid mass of brown crystals in the bottom of the flask. 
 
 The solid was then shaken well v/ith carbon disulphide to remove all 
 of excess alimiinium bromide. After this treatment ether was added to 
 remove any excess phenyl magnesium bromide and then the solid v/as 
 finally treated with sjiisol to remove any magnesium bromide v/hich 
 might be present. After this treatment it was again heated to the 
 carbon bisulphide in order to obtain again a good crystalline product 
 The carbon bisulphide was removed by vacuum filter and then the prod- 
 uct was dried in a vacuum drier. 
 
 The product hydrolyzed very readily with v/ater giving benzene. 
 
 It reacted v/ith a.cetyl chloride giving acetophenone on ana.lysis it 
 showed the presence of carbon, aluminium and bromine. It melted be- 
 
 o 
 
 tv/een 280-285 • A quantitative analysis was run on the product and 
 
 o 
 
 it v/as found by the total carbon method that it contained 26,5 /o 
 carbon which Indicated a formula of the follov/ing structure dl> AlClg 
 H owever, on further analysis it v/as found that the percentage alu- 
 minium and bromine obtained experimentally did not check with this 
 formula. At this point it occurred to the writer that v/hen the com- 
 pound was hydrolyzed by water that ether was alv/ays given off. So 
 
23 
 
 from this it was concluded that one molecule of ether of crystalliza- 
 tion was present and v/hen this v/as taken into consideration the alu- 
 minium and bromine checked with the calculated amount, but the carbon 
 did not check as the results of analysis will show. 
 
 ,5000 grams of substance gave 
 and 740 mm, pressure 
 
 cc, of COa at 30 
 
 -AlBr, 
 
 Calculated for carbon 
 Calculated for carbon O -AlBr 2 (C 2 H 5 )g 0 
 Experimental for carbon 
 
 = 27.7 
 
 = 35,5 
 = 26,3 
 
 ,5000 grams of substance gave ,1087 grams of AlgOg 
 
 o 
 
 Calculated for aluminium = 7,98 
 
 Pound for aluminium = 7,5 
 
 .5000 grams of substance required 35,35 cc , of ,0981 normal 
 silver nitrate 
 
 Calculated for bromine 
 Found for broraine 
 
 = 47.3 7, 
 
 = 47.89°/ 
 
 since the bombs v/hich were used for making fusions contained no 
 gasket ajfid also the fact that ether might be driven off before fusion 
 temperature was reached, it was thought that in this way the carbon 
 of the ether of crystallization was lost. For as it was stated be- 
 fore the carbon checked v/ith the formula assumed without the molecule 
 of ether of crystallization. The carbon and hydrogen was then deter- 
 mined by combustion. The results were as follows: 
 
 .2000 grams sample gave .2215 grams of COg 
 
 Calculated for carbon = 38.5 
 
 Found for carbon 
 
 =30.20 
 
24 
 
 2000 grams of substance gave .OVIV grams of HgO 
 Calculated for hydrogen 
 Found for hydrogen 
 
 = 4.5 / 
 
 ' o 
 
 = 4.04 /o 
 
 o 
 
 The carbon again did not check with the theoretical amount, 
 which may be due to the fact that in combustion the compound burned 
 so easily that the combustion ran to fast and some carbon dioxide 
 escaped before it could be dissolved and also some of carbon dioxide 
 might have been carried out by a stream of oxygen which was constant- 
 ly passed through during combustion. The experim.ental work was 
 closed at this point. 
 

 
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 t; 
 
 
IV 
 
 25 
 
 CONCLUSION 
 
 The Grlgnard’s reagent reacts with aluminium chloride and bromide 
 but the allcyl ra.dical do not replace all the chlorine to give the 
 tri alkyl compound* 
 
 Good evidence was obtained which indicated that phenyl aluminium 
 dibromide was formed when aluminium bromide v/as treated with phenyl 
 magnesium bromide* The phenyl aluminium dibromide was broken down 
 by water giving benzene j it reacted, with acetyl chloride, v/hich v/as 
 hyd.rolyzed by water to give acetophenone^ it gave on burning a char- 
 acteristic odor of phenol* 
 
 9-ryl aluminium dichlorides a.re solids which are readily 
 hydrolyzed by water, acids and alcohol and consequently are very un- 
 stable in presence of air* 
 
 The behavior of phenyl aluminium, dibromide toward acetyl chloride 
 furnishes good evidence that a similar compound is formed as an in- 
 termediate in the Friedel and Craft’s reaction in preparation of both 
 hydrocarbons and oxygen derivatives. 
 
 Anhydrous aluminium chloride or magnesium bromide may be easily 
 prepared by passing dry hydrobromic acid through dry ether containing 
 sm.all strips of these metals* 
 

 
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V 
 
 26 
 
 BIBLIOGRAPHY 
 
 1. B. S, Hopkins, General Chemistry of Rarer Elements. 
 
 2. Cohen. Vol.II, p.l95. 
 
 3. Corap. rend. 86, pp. 884-7; Comp, rend .86, pp. 1368-71. 
 
 4. J. Chera. Soc.M, 670 (1878). 
 
 5. J. Chem. Soc.M, 792 (1878). 
 
 6. J. Chern. Soc.77, 1006 (1900). 
 
 7. Steele. Trans. Chem. Soc.83, 1470 (1903). 
 
 8. Mayo. Study of Priedel and Crafts' Reaction. 
 
 9. Bull. Soc. Chera. 2, 31, 529; Bull. Soc. Chem, 2, 34, 322; Bull. 
 
 Soc. Chera,2, 42, 213-216, 
 
 10, Monatsh. fiir chemie 9, 613 (1898). 
 
 11, Ann, de chimie et de phys,(6) 449 (1884); Ann, de chimie et 
 
 de phys,(6) 1£, 411 (1887); Ann. de chimie et de phys.(6) 11, 
 263 (1887); Ann de chimie et de phys.(6) lA, 333 (1888), 
 
 12, Elbs synthetische darstellung methoden, Vol.II, p, 140-171. 
 
 13, Amer, Chem, J.^, 365 (1900). 
 
 14, Rec. Trans, chimie 19^, 19 (1900). 
 
 15, Ber.43,, 3627 (1908). 
 
 16, Annual reports of progress of chemistry for 1916, Vol.13, pp,98 
 
 99 .