PREPARATION OF 
 
 ORTHO AND PARA CHLORTOLUENE 
 PHEN LY ACETALDEHYDE 
 DIPHENYL 
 
 BY 
 
 JESSE RAY JOHNS 
 
 THESIS 
 
 FOR THE 
 
 DEGREE OF BACHELOR OF SCIENCE 
 
 IN 
 
 CHEMISTRY 
 
 COLLEGE OF LIBERAL ARTS AND SCIENCES 
 UNIVERSITY OF ILLINOIS 
 
 1921 
 
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ACKNOWLSDG-EI.IENT . 
 
 The author wishes to express his thanks and 
 appreciation to Dr, ROG-ER ADAMS thni whose helpful 
 suggestions and criticisms this work has been made possible. 
 
Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/details/preparationofortOOjohn 
 
PS 
 
 CONTENTS 
 
 I Introduction, 
 
 II History and Theory, 
 
 A, Phenylacetaldehyde, I 
 
 B Ghlortoluene, 9 
 
 C , Diphenyl 1 2 
 
 III Experimental, 
 
 A, Phenylacetaldehyde. 4 
 
 B , Diphenyl . 1 3 
 
 IV Discussion, 
 
 A, Phenylacetaldehyde, 7 
 
 B, Diphenyl. 19 
 
 C , Ohio r t o ill en e . 11 
 
 V Conclusions. 
 
 A, Phenylacetaldehyde, 8 
 
 B, Diphenyl, 20 
 
 VI Bibliography, 21 
 
INTRODUCTION 
 
 The work of the semester was divided between three 
 different subjects. The first subject investigated was the 
 preparation of phenylacetaldehyde. This aldehyde has a 
 very distinct hyacinth odor and is used a great deal as a 
 perfume. The ordinary '^aethods of preparing this aldehyde 
 are very expensive. It v/as with the idea of trying a 
 comparatively cheap catalytic reduction method that this 
 v/ork was attempted. 
 
 Two test runs of aa process for the preparation of 
 ortho and para chlortoluene were made. The directions do 
 not appear in printed form but were furnished by Dr, 
 
 Adams , 
 
 Diphenyl has been made by ineffective catalytic 
 methods ever since it was discovered, A new catalytic 
 method has been described by Dr. James'' that appears to 
 be very effective. This work on diphenyl has been 
 limited to improvements on the method described by 
 Dr. James, 
 
1 . 
 
 THE SYNTHESIS OF piraYLACETALNEHYDE. 
 
 I. THEORETICAL DISCUSSION. 
 
 Phenylacetaldehyde has a distinct hyacinth odor that 
 makes it valuable in perfumes. It appears on the market 
 in a solution of benzylbenzoate as "jacinth". This aldehyde 
 is a syntheyic product and does not appear in the natural 
 hyacinth perfume, 
 
 Phenylacetaldehyde can be made by three distinct 
 methods. First, the reduction of phenylaceticacid; second, 
 the G-rignard reaction; third, the decomposition of hydroxy 
 
 acids . 
 
 The classical method of preparing aldehydes is to 
 heat the calcium salt of the acid with calcium lorniate. 
 
 The acid is reduced to the aldehyde and calcium carbonate 
 is formed according to the reaction. 
 
 This reaction is not clean cut and the yield of aldehydes 
 
 of high molecular weight is very unsatisfactory, So^uibb 
 2 
 
 and Ipatief tried to improve this reaction by using the 
 salts of different metals than calcium. Instead of forming 
 the salts first and then heating them they passed the 
 mixture of acids thru a heated tube partially filled with 
 
 the metallic carbonate or oxide. They found that the 
 
 foiTTiic acid decomposed at a temperature belov/ onat 
 required for the reduction of the acid so that their 
 results v;ere unsatisfactory. Later Sabatier and Senders 
 
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 while working on the catalytic preparation of aldehydes 
 
 found that the use of titanium oxide would allow the 
 
 acid to be reduced at a low enough temperature so that 
 
 the formic acid could be used. In a later paper they 
 
 suggested the use of manganous oxide^ as an imprivement 
 
 over the use of titanium oxide or any other metallic 
 
 oxide that could be used. This oxide was claimed to reduce 
 
 acids of high molecular weight very readily, 
 
 Ph eny lac etaldehyde can also be prepared by means of 
 
 the G-rignard reaction. The benzyl magnesium halide compound 
 
 7 
 
 can be treated either with formic acid and decomposj^ 
 
 .fir 
 
 vd' tL T/-at ei to fcrr. phenylac etaldehyde. 
 
 It 0 
 
 or formic ester and deconpose!-' v/ith water to form the 
 
 G 
 
 aldehyde. This reaction besides being expensive gives 
 very poor yields^ 
 
 The great bulk of the work on the preparation of 
 
 phenylace b^?,dehyde has been done on the preparation and 
 
 decomposition of oxy acids to form the aldehyde, 
 
 9 
 
 In 1884 Glazer while working with Erlenmeyer 
 distilled a solution of phenyl- lactic acid in potassium 
 hydroxide. An oil came over that Bayer identified as 
 
 pheny lac etaldehyde. Very soon after this Lipp^^and 
 
 1 1 
 
 Hamburger took up the study of this reaction as a 
 means of preparing the aldehyde. Phenyl- lactic acid 
 itself was not used but its chlor derivative or 
 
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its hydroxy derivative, phenyl glucidic acid was used. 
 
 The starting point for the preparation of these tv/o 
 acids v;as cinnamic acid in all cases. 
 
 Cinnamic acid when treated with hypochlorous acid 
 unites directly with it. The double bond in the cinnamic 
 acid becomes saturated to form a chlor lactic acid, thus: 
 
 If the chlor lactic acid is treated with a strong alkali 
 
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 phenylglycidic asid salts ai*e formed. 
 
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 If this salt is acidified and boiled v^ith water the 
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 and the aldehyde, thus: ^ C 
 
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 in producing hypochlorous acid free from chlorine. The 
 free chlorine in the hypochlorous acid used attacked the 
 benzene ring and produced chlor derivatives of the 
 aldehy de, Bamburgerl 1 freed his hypochlorous acid by 
 treating a solution of sodium hypochlorite ¥^ith boric 
 
 acid, Glazer used carbon dioxide. None of the 
 
 12 
 
 methods produced an aldehyde free from chlorine, 
 
 13 
 
 In 1910 Erdmann patented a process in which he claimed 
 to have proauced a lactone of propionic acid by the 
 
 14 
 
 action of hypobromic acid an cinnamic acid, Diekmann, 
 however, proved that the lactone is nothing other than 
 the potassium salt of phenylglycidic acid. 
 
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4 
 
 EXPERIIv^ENTAL PART. 
 
 1 "5 
 
 Erdmann's process for the preparation of phenyl- 
 glycidic acid was used as the representative reaction 
 for the preparation of the oxy acid used in the 
 preparation of phenylacetaldehyde. 50 gms. of 
 cinnamic acid v/as added to 'J>G gms, of 50/^ KOK and 500 
 gms. of water. This v/as evaporated to 160 c.c. and 
 allowed to cool, 100 gms, of 50^ KOH was mixed with 70 
 gms. of ice and cooled. 73 gms. of bromine were nin into 
 the cooled gOH solution. After all the gromine was aaaed 
 10 gms. of KOH solution was added to remove as much 
 free broiiiine a,s possible. 
 
 The cooled potassium cinnamate solution was then 
 mixed with 500 gm*s , of ice and the potassium hypobromite 
 liquor added. After stirring the mixture well 70 gms. of 
 boric acid was added to free the HBrO, The reaction is 
 complete in an hour. At that time the mixture was made 
 alkaline to precipitate out the potassium salt of 
 phenylglycidic acid, 4o gms, of the potassium salt was 
 formed. On acidifying this potassium salt and distilling 
 the resulting solution 13 gms. of phenylacetaldehyde 
 was formed. Yield 26^, 
 
 Most of the work of the semester was centered on 
 the reduction of phenylacetic acid to phenylacetaledhyde. 
 Manganous oxide was used as a catalyzer, A furnace of 
 
 15 
 
 the type described by Rogers, Marvel, and Kamm for 
 the preparation of amylene. The temperature of the 
 

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 reaction carried on in the furnace did not rise above 
 350 C at any time so that careful Insulation was not 
 necessary. 
 
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 two inch iron pipe wound with 50 turns of #16 ni chrome 
 wire and insulated with asbestos. Over the resistence 
 wire winding was placed a section of asbestos steam 
 pipe covering. The temperature of the furnace was 
 regulated by the use of a pyrometer. 
 
 In all cases the phenylacetic acid was dissolved 
 in the formic acid and introduced into the furnace 
 thru a dropping funnel. The ratio of three parts of 
 formic acid and one part of phenylacetic acid was 
 decided on at* giving the best results. The catalyst in 
 all cases was manganous oxide. Pieces of pumice stone 
 were coated with wet manganous carbonate and introduced 
 into the furnace in sufficient amount to fill the pipe 
 loosely. The furnace temperature was then raised to 300 
 and methyl alcohol was passed in to form the oxide. 
 
 In no case was a satisfactory yield of phenyl- 
 acetaldehyde formed by the use of this furnace. The 
 temperature of 300-325 C suggested by Sabatier was found 
 to be the only one that gave any results at all. 
 
 The fomic acid used in these experiments varied from 
 50^ acid to 90^. The use of the 50^ acid gave only a 
 very high boiling oil and no aldehyde. The 90 ^ acid 
 gave n ot more than a 9^0 yield as a maximum. As the 
 
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 store room the pure acid was not used. 
 
 3 
 
 Sabatier and Senders also claimed that this catalytic 
 reaction is also very satisfactory for the preparation of 
 esters. Using 1 mol of amyl alcohol and 2 mols of glacial 
 acetic acid a 70^ yield of amyl acetate was produced 
 in a test run. 
 
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7 
 
 DISCUSSION. 
 
 The reaction as carried on by the author v;as not 
 at all satisfactory at any time. The failure of the 
 reaction was not due to any known cause. Reactions 
 with different purities of the formic acid seemed to 
 indicate that the amount of water in the reaction had 
 something to do with the yield of the aldehyde but not 
 enough to account for the greater part of the impurities 
 formed in the reaction. 
 
 The liquid coming from the furnace did not contain 
 any free formic acid and only traces of phenylacetic acid. 
 The great bulk of the acid was decomposed to form a 
 sticky very high boiling oil of varying boiling point. 
 
 As this reaction was carried on in the original 
 experiments in a glass tube and the formic acid and 
 phenylacetic acid passed into the tube in vapor form 
 sej^arately the method might be differer.t enough to 
 cause all the change in yield. 
 
 No means of carrying the original experiment out 
 wa.3 available otherwise a comparison of results would 
 have been made. 
 
 The easy preparation of amyl acetate, however, 
 showed that the apparatus as set up might be a very good 
 method of making esters. 
 

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8 
 
 CONCLUSION 
 
 The results obtained in the attempted catalytic 
 method for the preparation of phenylacetaldehyde show 
 that the method used cannot be made practical without 
 some very great improvements. 
 
 The author believes the failure of the reaction was 
 due to the following reasons . 
 
 (a) Impure acid, 
 
 (b) Incorrect preparation of the catalyst. 
 

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9 
 
 SYNTHESIS OP ORTHO iUID PARA CHLORTOLUENE. 
 THEORETICAL DISCUSSION. 
 
 There are only two methods for the prepa.'Xtion of 
 the chlortoluene. Chlorine v/ill act on toluene to form 
 ortho and para chlortoluene according to the reaction 
 
 unless very dilute solutions are used when the yield of 
 
 The direct chlorination of toluene is very greatly 
 
 The separation of the o and p- chlortoluene formed by 
 the direct action of chlorine can be separated by 
 completely sulfonating both chlortoluenes and fractionally 
 crystallizing the sodium or barium salts. Or by 
 sulfonating out the o- chlortoluene and separating the 
 
 two by this method, 
 
 A test run on the direct chlorination of toluene 
 was made in the following manner; 
 
 In a 5 liter flask fitted with a good reflux condenser 
 and mechanical stirrer was placed 1650 gms, toluene and 
 18 gms. of powdered iron. Chlorine was passed into the 
 toluene until the specific grayity reached 1,o6, The 
 time of chlorination was about 8 hours. After chlorination 
 the liquid was fractionated direct. The part coming over 
 
 1 f\ 
 
 The diazo reaction is also used' but the yield is poor 
 
 accelerated by the use of iron or other metals 
 
 19 
 
4 • 
 
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10 
 
 below was considered unchlorinated toluene and amounted to 
 300 c,c. The fraction coming over between 150- 160 C was 
 a mixture of the monochlortoluenes , This fraction had a 
 volume of 1600 c.c. The fraction above 160 consisted of 
 dichiortoluene and had a volueme of 125 c.c. 
 
 The monochlor fraction was then treated with an 
 equal weight of concentrated sulf'.ric acid, After stirring 
 the sulfuric acid mixture for 8 hours on a water bath the 
 sulfuric acid layer was drawn off and an eo_uai weight of fre 
 fresh acid was added. This process was repeated three times. 
 
 The sulfuric acid now contains all the ortho chlortoluene. 
 
 The unsulfonated layer was washed with dilute sodium carbonate 
 and then with fresh vtrater and distilled. The fraction 
 boiling at158-6o was p-chlortoluene. The yield v/as 56o 
 gms . 
 
 The sulfuric acid layer was diluted with an equal 
 volume of water and heated. At 200 the mixture Vfas rapidly 
 steam distilled. The sulfonic acid became decomposed and 
 the ortho chlortoluene regenerated, 544 gms, of o-chlor- 
 toluene were produced. 
 
It 
 
 CONCLUSION. 
 
 The results were quite comparable with those 
 given by the authors (Clarke and Ogden), The 
 percent of o-chlortoluene recovered was less than 
 that given by them but this was due probably due to 
 a slov/er saponofication of the sulfonated mixture 
 and therefore a greater percent of decomposition 
 of the o-chlortoluene. 
 
V;'' 
 
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 ^ V - .. , - 4 , .;,:iv4,#^- 
 
 
 
 
 r*^-aw=— jtsrse^ / ■> 
 
12 
 
 PREPARATION OF DIPHENYL 
 THEORETICAL DISCUSSION. 
 
 Diphenyl is made commercially by passing benzene 
 
 vapors thru a red hot iron tube. This is the method used 
 
 by Bertholet^ original decomposition 
 
 3 
 
 products of benzene. Before this time, however Fittig 
 
 prepared diphenyl by treating brombenzene with metallic 
 
 5 
 
 sodium. Grant and James found that by passing the vapors 
 of benzene over a heated ni chrome wire better results 
 could be obtained than by Bertholet's method or by Fittig' 
 method. These three methods are the only ones that are 
 of any practical importance at all. 
 
 The catalytic preparation of diphenyl is Just a 
 simple splitting out of hydrogen between two benzenes 
 
 is too expensive in comparison to the cheaper catylitic 
 methods, Lilce all the other methods of preparation of 
 
 diphenyl considerable amounts of high boiling products 
 
 3 
 
 are formed and therefore the product formed is no purer 
 than that formed by any other method. 
 
 
 n i m i ■■ ■ ifTT^ 
 
13 
 
 EKPERIICTTAL PART. 
 
 5 
 
 The apparatus described by Grant and Janies was 
 first used. It consisted of a loop of resistence wire so 
 supported in a refluxing apparatus that the v;ire could 
 be heated with an electric current. Fig. 1 v;ill better 
 illustrate this. As the ni chrome wire described by Grant 
 and James was not available number 18 B&S gague wire was 
 used instead. With a current sufficient to bum out ten 
 ampere fuses no reaction took place after refluxing the 
 benzene one hour. The wire was not heated above a dull red 
 heat, A small quantity of free carbon was deposited on the 
 wire. Both alternating and direct currents gave negative 
 results . 
 
 A section of number 28 v^ire was v^ound in a three 
 millimeter sporal and heated electrically as before, Yfnen 
 the wire v;as heated to bright redness witha 110 volt 
 direct current a reaction occurred. This was shovn by the 
 elimination of a white smoke from the top of the condenser 
 and the condensation of drops of a brown liquid on the sides 
 of the flask. After three hours the excess benzene was 
 distilled away and 46 grams of a tarry residue remained. 
 
 On fractionation this tar gave 12 grams of a solid 
 boiling at 24C-250 , This solid was diphenyl. 
 
I 
 
 ' *T 
 
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14 
 
 The results of four runs are tabulated below. 
 
 l(7t , tar 
 
 Wt, diphenyl. 
 
 foyleld. 
 
 48 
 
 12 
 
 25 
 
 51 
 
 15 
 
 29 
 
 50 
 
 14 
 
 28 
 
 55 
 
 17 
 
 31 
 
 Sixty cycle alt 
 
 emating currents gave 
 
 practically 
 
 results , 
 
 
 
 \7t , tar 
 
 Wt, diphenyl 
 
 ^yield 
 
 45 
 
 10 
 
 22,5 
 
 42 
 
 9 
 
 21,4 
 
 47 
 
 10 
 
 21,3 
 
 44 
 
 1 1 
 
 25 . 
 
 In all probability the differences in the percentage of 
 diphenyl formed was due to differences in temperature of 
 the wire and not to any differences in electrical effects 
 of direct and alternating currents. 
 
 After the benzene vapors passed over the heated 
 ni chrome wire they were so hot that they decomposed the 
 cork in the neck of the flask. The condensed benzene and 
 diphenyl rtinning down over the sides of the hot flask 
 also caused considerable trouble by cracking the glass. 
 
 It was also apparent after the preliminary runs that the 
 diphenyl percentage in tar was too low for the amounts of 
 tar produced. The apparatus in Fig, 2 was devised to 
 improve some of these difficulties. 
 
 The hot wire was suspended in a tube free from 
 the flask and so arranged so that the condensed benzene 
 
.r 
 
 
 
 'OftUwO V. Jv.q/.*'. '.':r 
 
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 •7 
 
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15 
 
 returns to the flask thru a separate tube. The wire v/as 
 suspended as far from the cork as possible to eliminate 
 the decomposition of the cork as much as possible. The 
 connection between the flask for refluxing the benzene and 
 the tube containing the hot wire served also as a 
 fractionating column to keep as much of the diphenyl 
 already formed from again coming in contact with the 
 catalyzer. Trial runs showed that this apparatus was 
 a great improvement over the first apparatus, 
 
 Wt. t ar Wt, diphenyl ^yield 
 
 48 25 52 
 
 55 51 56 
 
 The disintegration of the cork was not prevented, however, 
 and the tar from the cork proved very objectionable. The 
 diphenyl fractionated from this tar kept the odor of the 
 burned cork even after a second fractionation and 
 crystallization from alcohol, 
 
 G-reat difficulty was experienced with the resistence 
 wire used. It was necessary to heat the wire almost to 
 its melting point to cause the condensation of the benzene 
 At this temperature a great deal of sagging takes place 
 and there is much magnetic attraction betvmen the sides 
 of the loop so that the wires are drawn together and short 
 circuting takes place. When the hot wire is cooled below 
 the temperature of condensation of benzene excessive 
 carbonization of the wire takes place. This phenomenon 
 

 * I ^7. • 
 
 
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16 
 
 occurs if the hot wire comes in contact with a cold 
 support or the outside of the tube. The wire tends to be 
 covered with soot at the cooled portion and tends to 
 spread over the wire. It is therefore impossible to 
 support the heated loop at its mid portions to keep the 
 loop compact . 
 
 To overcome the difficulty given by the cork and to 
 add a larger fractionating column to the apparatus to 
 keep the diphenyl down the apparatus in Fig. 5 was 
 devised. The entire apparatus was made of pyrex glass 
 by Dr. Anders. 
 
 In experimenting with this apparatus large amounts 
 of of diphenyl were not desired. The lengths of the runs 
 
 were cut to about two hours . 
 
 There are definite limits of temperature for the 
 best preparation of diphenyl. At apxjroximate cherry redness 
 the Wire is quite rapidly coated with carbon and ceases to 
 be active as a catalyzer. If the temperature is raised 
 carbon does not co3.lect on the wire and there is a slight 
 smoke given off thru the condenser. At still higher 
 temperatures much smoke is formed ana the wire is 
 rapidly decomposed. The data below shows the effects 
 of different temperatures. (At the lowest temperature) 
 
 Benzene used &ms . tar Gms. diphenyl ^'^penzeSe . 
 
 56 16 11.5 72.5 28.6 
 
”1. ; 
 
 < » y 
 
 ■'■■'.fS. '.Ui- 
 
 ^:*S i >ar?-6fTT^itTaiw 
 
17 
 
 At decomposition temperaU..-e of v/ire. 
 
 Benzene used. Ut.tar Wt. diphenyl, ^diphenyl jJdiphenyl 
 
 DSnZt Gli0 
 
 65 13 7 54 11 
 
 This data shows quite conclusively that the best 
 temperature for the reaction is the lowest possible 
 temperature to carry on the reaction or sliglitly above 
 that necessary to keep the wire free from carbon. At this 
 temperature practically no smoke is formed and the solids 
 are quite free from large amounts of free carbon. 
 
 Even at the best temperature for the reaction the 
 wire becomes coated v;ith a black shell that resembles 
 oxide and Is probably a carbide of nickel. This coating 
 does not seem to interfere in any way with the speed of 
 
 the reastion. 
 
 It was found that the rate of formation of 
 diphenyl varied directly as the lengtl of the wire. A 
 foot section of ni chrome wire vfill produce about 15 
 grams of diphenyl per hour while a 4 foot section will 
 produce about 50 grams per hour. As the surface of the 
 Wire varies directly as the length the yield must 
 be dependent on the area of the wire exposed. 
 
 using the best conditions found up to this time 
 a series of three runs were made to determine the best 
 possible yield of diphenyl from the amount of benzene 
 
 used in the reaction. 
 
Vuw V r.. :*to iyp e^vof^v. M ir!t 
 
 V ^ ■ " ■"'• ‘ ' " ’■ 
 
 I 
 
 ■ . ' ' I ' . 
 
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18 
 
 Wt, benzene 
 
 tarCnot diphenyl) Wt. 
 
 diphenyl . 
 
 ^diphenyl 
 
 solids 
 
 56 
 
 6 
 
 16 
 
 72.5 
 
 40 
 
 1 1 
 
 42 
 
 81 
 
 40 
 
 2 
 
 Wt. diphenyl on 
 benzene used, 
 28,6 
 
 30 
 
 50 
 
 12 
 
 85 
 
 Glilor "benzene was used in one run in place of ben^ n , 
 the resultins product was not ohlordiphenyl but HCl split 
 off and diphenyl was formed. Toluene in the same apparatus 
 decomposed with the elimination of large amounts of soot 
 
 that quickly clogsed the apparatus. 
 
 Nickel wire was used in a fev; of the runs hut it 
 so soft When heated that it caused a great deal of trouble. 
 The results, however approximated those with niohrome wire. 
 Tungsten wire was used in one run but the wire became so 
 completely carbonized in a few minutes that it ceased to 
 have sufficient reslstence so that it coula be heated to 
 the proper temperature. 
 
V. 
 
19 
 
 DISCUSSION, 
 
 The foregoing experiments proved quite conclusively 
 that the method for the preparation of diphenyl studied 
 equals and probably surpasses any method in common use 
 for the preparation of diphenyl, A study of the data 
 shows that there is a very great loss of benzene in the 
 reaction. There is no smell of benzene in the gases given 
 off thru the condenser so the benzene must be decomposed 
 and given off as some decomposition products of benzene. 
 
 No attempt was made to analyze the gas and determine 
 what the decomposition products v;ere. If some other 
 catalyze^ can be found that will work at a lower temperature 
 the reaction can be much improved for in all probability 
 at a lower trmperature much less benzene v/ill be lost 
 by decomposition. 
 
 This reaction can be improved still further by 
 cut ting the time of contact of catalyzer and benzene 
 as short as possible. This can be done by passing the 
 vapors of benzene over the heated wire perpendicular 
 t o the wire and not along the wire as was done in 
 most of the experiments tried. The diphenyl will 
 be given less time to condense with itself and produce 
 the undesirable higher boiling fraction of the tar. 
 
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 CONCLUSION. 
 
 nth the apparatus used and a nickel Vvire as the 
 catalizer the yield is approximately at a maximum. 
 
 The 60/^ loss of benzene in the reaction cannot be 
 avoided unless soiAe new catalizer is used that will 
 cause the reaction to teke r)la,ce at a lower temjjS: nature. 
 The temperature necessary in using nickel as lizer 
 
 is so high that a great deal of decomposition of tlio 
 benzene takes place. 
 
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21 
 
 BIBLlOGRAPIiY 
 
 I Reference not found in original, 
 
 2, Ber. 62; 478, 
 
 3. Ann. Igl 363; Comp. Rend. 156:830 
 
 4 Z. f. C^. 1366, 707. 
 
 5 d.A.C.S, 954-35-139 
 
 6 154:561 Comp. Rend, 
 
 7 Hauben. Chem Zeit. 1905. 
 
 B G-er Pat #157,573 
 
 o Ber, 13: 457 Ber,. 13: 308 
 
 10 Ann, 219:179 
 
 I I Ann , 47:83. 
 
 12 Ann. 2l6;301 
 
 13 Ger Pat, #107,229 
 
 14 Ber, 43:1035-38, 
 
 15 Chemical Reagents. Illinois University Press. 
 
 16 Ber. 6 794 ( 1673) 
 
 17 Ann, ^ 145 kBs3) 
 
 If Ber. 8 1402 Clf75) 
 
 1 9 Ann . 237 151 ( 1 687 )