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 https://archive.org/details/hydrolysisofaromOOIewi 
 
H?.\ 
 
 UNIVERSITY OF ILLINOIS 
 
 May . ..24 198I- 
 
 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY 
 
 Alden. . Geo rge, . . .Lewi 3 
 
 entitled -The. ..Hy.&r.olys ia... of... Aromatic... Sulphonic. -Ac-ids- 
 
 IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE 
 DEGREE OF.. Ba.chelo.r*...oT..Sc.lence-in.....Cheinlat-r.y.. 
 
 <a±L 
 
 Instructor in Charge 
 
 Approved : 
 
 
 
 HEAD OF DEPARTMENT OF. 
 
 
 -Li C •Ljs 'CJ 1 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
ACKNOWLEDGEMENT. 
 
 The author wishes to express his appreciation 
 to Dr. C.S. Marvel under whose supervision this work was 
 carried on, for the helpful suggestions made during the 
 course of this investigation and in the writing of this 
 thesis. 
 
TABLE OF CONTENTS 
 
 page. 
 
 I 
 
 Introduction. 
 
 1 
 
 II 
 
 History. 
 
 2 
 
 III 
 
 Theoretical Part. 
 
 5 
 
 IV 
 
 Experimental Part. 
 
 10 
 
 
 Apparatus . 
 
 10 
 
 
 Prep, of Compounds. 
 
 10 
 
 
 Data. 
 
 19 
 
 V 
 
 Summary. 
 
 21 
 
 VI 
 
 Bibliography. 
 
 23 
 
1 
 
 The Hydrolysis of the Aromatic Sulphonic Acids. 
 
 I. Introduction 
 
 Altho the problem of hydrolyzing aromatic sulphonic 
 acids to the hydrocarbons is not a new one, nevertheless, it 
 has never been studied in a systematic manner. The author's 
 work was mainly to study the effect of the number of groups 
 in the ring, position, kind of groups and catalyzers on the 
 amount and rate of hydrolysis. Along the same line of work 
 the various temperatures of hydrolysis were determined which 
 suggests the possibility of a separation of various aromatic 
 compounds by fractional hydrolysis of their sulphonic acids. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
71 
 
 II History. 
 
 Freund (l) in 1861 found that on dry distilling 
 benzene sulphonic acid he obtained a product that had a 
 strong odor and a large refractive index. This compound 
 he called benzene. He believed either one of two things 
 happened. 
 
 Later in 1855 Beilstien (2) used a method of dry 
 distillation for the recovery of xylene from its sulphonic 
 acid and later in 1878 Jacobson (3) used a similar method 
 to recover metaxylene from its sulphonic acid. 
 
 Armstrong (4) in 1878 separated mesitylene and 
 pseudocumene by heating their sulphonic acids at 100°with 
 muriatic acid whereby the mesitylene sulphonic acid is alone 
 hydrolyzed; the pseud omene is recovered by heating at 
 
 o o 
 
 130 - 140. It was long known that mesitylene could be 
 separated from its sulphonic acid by mere steam distillation. 
 The same author in 1883 applied these methods to the tetra- 
 methyl benzenes. 
 
 Miller and Armstrong (5) did the first real work 
 on the subject and used the method that was used in this 
 work. The method consisted in passing the steam thru a hot 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 ' •. ,* n ; 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
concentrated acid solution until hydrolysis takes place. 
 
 They stated that the rate of hydrolysis does not depend on 
 the excess of sulphuric acid but that the sulphuric acid 
 is necessary to obtain a high temperature. They experienced 
 no difficulty in separating calcium and barium salts by 
 their methods. They stated that the sources of error are: 
 
 (a) Thru dissolution of a small quantity 
 
 in water. 
 
 (b) Thru incomplete separation of hydrocarbon. 
 
 (c) Thru evaporation of hydrocarbon. 
 
 They tabulated the hydrolysis points of benzene. 
 
 toluene, ortho, meta and paraxylenes sulphonic acids, etc., 
 and suggested the possibility of separating various hydro- 
 carbons by fractional hydrolysis of their sulphonic acids 
 but state that this is almost impossible because hydrolysis 
 is generally carried out at a temperature higher than the 
 critical hydrolysis temperature. They also did considerable 
 work with the hydrolysis of sulphonic acids in sealed tubes 
 and found that the temperatures of hydrolysis were very 
 different under these conditions. 
 
 Kelbe (6) in 1886 improved the Miller and Armstrong 
 
 method .somewhat by passing steam thru a heated copper tube 
 before passing it thru the solution. The advantages are 
 that a large excess of sulphuric acid is avoided and also 
 that ortho brom toluene and ortho brom xylene prepared by 
 
 this method seemed to be more stable toward oxidizing agents 
 than those prepared by other methods. 
 

 
 ■ 
 
 ' 
 
 
 
 
 ><' 
 
4 
 
 Jacobson (7) in 1887 found that when sodium 
 pentamethylbenzenesulphonate is shaken with concentrated 
 sulphuric acid and light petroleum, hydrolysis occurs and 
 the hydrocarbon is obtained on evaporation showing the 
 effect of a number of groups in the ring on hydrolysis. 
 
 Later Friedel and Craft (8) used aluminum chloride 
 and phosphoric acid to bring about the hydrolysis of the 
 aromatic sulphonic acids and obtained good results; the 
 yields in the relatively few cases tried were greater than 
 those with sulphuric acid. In the present work it was 
 found that almost invariably with phosphoric acid the yield 
 is about the same or greater than the yield with sulphuric 
 acid as a catalyst. 
 
 Fournier (9) in 1892 used Friedel and Craft methods 
 to obtain diethyl benzene from diethyl benzene sulphonic 
 acid with almost theoretical results. 
 
 Later in 1901 J.M. Craft (IQ) studied the rate 
 of hydrolysis of sulphonates; chiefly metaxylene sulphonate 
 for 10 - 35/£ of hydrochloric acid heated in sealed tubes 
 
 o 
 
 at 100. The amount of hydrolysis was noted for different 
 amounts of hydrochloric acid and the velocity of reaction 
 was found to be proportional to the concentration of the 
 catalytic agent. With an increase of 6 % in concentration 
 there is a velocity four times as great. Craft does not 
 fully understand the reason for this phenomena. 
 
 

 
 
 
 
 
 
 
 
 ' 
 
 
 
 
 
 
 
 
 
5 
 
 III Theoretical 
 
 Most of the previous writers have mentioned the 
 fact that benzene sulphonie acid can be hydrolyzed almast 
 quantitatively but these results could not be duplicated. 
 
 When we introduce an (OH) group in the benzene 
 ring the ortho and para hydrogens are greatly activated 
 and hydrolysis seems to take place easier. Thus para phenol 
 sulphonie acid hydrolyzes very easily; the rate being 
 greater with phosphoric acid as a catalyzer than with sul- 
 phuric acid as a catalyzer. 
 
 They yield of napthalene from alpha and beta 
 napthalene sulphonie acids are almost theoretical using 
 sulphuric acid a3 a catalyzer. With phosphoric acid as a 
 catalyzer the rate of hydrolysis is faster and the yield 
 is about the same. The alpha napthalene sulphonie acid 
 comes over fcapidly at first and suddenly stops which seems 
 to indicate that the sulphonie acid group is split off and 
 
 r^S UT phrvrm t.pg in t.Viia ‘h<a+.a nnalt.lnn 
 
 The yield with phosphoric acid is greater with 
 the alpha than with the beta napthalene sulphonie acid. 
 
 When the (OH) group is introduced into the napthalene 
 
 rings in the beta position the hydrolysis is decreased. 
 
 Bender (11) found a method of preparing napthol (1) sulphonie 
 acid (2) and stated that it hydrolyzed readily with sulphuric 
 

 
 
 
 
 
 
 
 
 
 
 
 I 
 
 ■ 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 * ■ 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
m 
 
 6 
 
 acid with theoretical results. From this we would believe 
 that when the sulphonic acid group is in the alpha position 
 it splits off and rearranges itself in the beta position 
 before hydrolyzing. This is almost impossible because of 
 the fact that the (OH) group is in the beta position and 
 therefore the hydrolysis would be low. In the case where 
 the sulphonic acid group is in the beta position hydrolysis 
 is rapid. 
 
 H 
 
 w KaJ 
 
 N&f\tholfe) Solfihon/r /\ciq/0) N&/ithol(lJ Sulphonic /\ci(jfc) 
 
 The amount of hydrolsis of napthol (2) sulphonic acid (1) 
 with sulphuric acid and phosphoric acid as catalyzers is 
 about the same. 
 
 The ortho, raeta and para toluene sulphonic acids 
 were then studied in order to give us an idea as to the 
 effect of position in the ring relative to the time and 
 amount of hydrolysis. With sulphuric acid as a catalyzer 
 we found that the ortho toluene sulphonic acid hydrolyzes 
 and that the meta and para toluene sulphonic acids do not 
 showing that position In the ring does have an effect. 
 
 With phosphoric acid as a catalyzer we found that the para 
 toluene sulphonic acid hydrolyzes easier than the ortho 
 toluene sulphonic acid so we can see that the catalyzer has 
 
 an effect on the rate of hydrolysis as well as the position 
 of the ring has an effect on the rate of hydrolysis. If 
 conclusions are to be drawn from a series of experiments of 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 f 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . ' 
 
 
 
 
 
 
 » 
 
 
 
 
 
 
 
 
 
 
 
 
 
this nature the same catalyzers must be used through out. 
 
 The para chloro, para bromo and para iodo benzene 
 sulphonic acids were next studied with a view of seeing 
 whether or not the weight of the group in the ring had 
 anything to do with the amount and time of hydrolysis. 
 
 With sulphuric acid as a catalyzer we have for chloro 
 benzene sulphonic acid 12 % hydrolysis, for bromo benzene 
 sulphonic acid 37 % hydrolysis and for iodo benzene sulphonic 
 acid 56 % hydrolysis showing that as the molecular weight 
 increases the amount of hydrolysis increases. With phos- 
 phoric acid as a catalyzer this is also true but the rate 
 and amount of hydrolysis are considerably greater. In the 
 case of chloro benzene sulphonic acid the hydrolysis is 
 just four times as great and the time of hydrolysis is 
 shorter. In each case phosphoric acid is a better catalyzer 
 of the two. This may be because with an excess of sulphuric 
 acid there is a greater tendency to resulphonate. In all 
 the causes mentioned we can see that the kind of group has 
 an effect on hydrolysis and also that with increasing mole- 
 cular weight the amount is greater. 
 
 The sodium meta nitro benzene sulphonate was 
 found to act very differently from other sulphonates studied. 
 The distillate from the hydrolysis with sulphuric acid was 
 of a yellow color and the residue in the flask was mainly 
 carbon showing that the molecule was destroyed. The distillate 
 contained no nitro benzene and did not give a test for nitric 
 acid. Phosphoric acid was tried with no better results. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
8 
 
 Evidently the nitro compounds decompose very differently from 
 the other sulphonic acids studied. 
 
 Jacob 3 on (7) found that the pent a methyl benzene 
 sulphonic acid decomposed on mere shaking with sulphuric 
 acid. With these facts in mind it was thought that increas- 
 ing the weight of an aliphatic side chain might have an 
 analogous effect. With these compounds however the increase 
 of hydrolysis does not exactly follow the rule. We notice 
 that the para toluene sulphonic acid does not hydrolyze 
 with sulphuric acid as a catalyzer. The ethyl benzene and 
 
 secondary butyl benzene sulphonic acids do hydrolyze showing 
 that an increase in the weight of the molecule increases 
 the amount of hydrolysis. With the use of phosphoric acid 
 as a catalyzer the yields are practically doubled showing 
 that phosphoric acid is a better catalyzer. 
 
 With lauryl benzene sulphonic acid the heat 
 generated, by the addition of sulphuric acid to the water 
 solution was sufficient to hydrolyze the sulphonic acid. 
 
 ^e can see from this the effect of the weight of the 
 
 group or groups in the ring on the amount and time of 
 hydrolysis. Sodium |>ara chloro benzene sulphonate was 
 then hydrolyzed and the introduction of another group in 
 the ring had a marked effect on the amount of hydrolysis, 
 the hydrolysis with both sulphuric acid and phosphoric 
 acid as catalyzers being about Q0%, 
 
 With the use of sodium ortho dichloro benzene 
 sulphonate we have a similar reaction, the hydrolysis with 
 

 
 
 
 . 
 
 
 
 
 
 
 
 ' 
 
 » 
 
 b 
 
 
9 
 
 sulphuric acid being about 65$. In this case the hydrolysis 
 with sulphuric acid is greater than with phosphoric acid 
 as a catalyzer. Similarly with ortho xylene sulphonic acid 
 we have tho same effect of additional groups in the ring 
 although the yield is not the 3ame as the yield with the 
 sodium ortho dichloro benzene sulphonate. 
 
 It has long been known that camphor when steam 
 distilled in the presence of a dehydrating agent gave 
 cymene. It was found that in a similar manner camphor 
 
 sulphonic acid breaks dov/n to cymene very readily. 
 
 Sodium benzyl sulphonate was studied to see what 
 effect hydrolysis would have on an aliphatic hydrocarbon 
 in comparison with an aromatic hydrocarbon. Sulphuric acid 
 and phosphoric acid were both used as catalyzers but with 
 negative results. 
 
 In the preparation of lauryl benzene by the 
 Friedel and Craft reaction an intermediate compound 
 perhaps dodecylene, was isolated. It gave the bromine test 
 for unsaturation and its boiling point and specific gravity 
 was like that of dodecylene. This may be evidence in 
 
 favor of the theory that the first steps in the ordinary 
 Friedel and Craft reaction is a splitting out of the 
 halogen acid from the alkyl halide. 
 

 
 . 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 fei 
 
 
 
 
 
 
 
 
 
 
 
IV Experimental. 
 
 in 
 
 Apparatus . 
 
 The apparatus used was a simple steam distillation 
 apparatus. The distilling flask was connected to an air 
 
 condenser which in turn was connected to a water condenser. 
 
 All the connections leading into the flask were made of 
 pyrex tubing and because of the high temperatures of hydrolysis 
 the thermometer was incased in a pyrex tub? which was filled 
 with cotton seed oil. This precaution was taken to prevent 
 the thermometer from being broken and to prevent the numbers 
 on the thermometer from being effaced. 
 
 Preparation of Compounds. 
 
 The following compounds were already prepared 
 
 and therefore there is no need of discussing their methods 
 of preparation: sodium benzene sulphonate, sodium beta 
 
 napthalene sulphonate, sodium para brom benzene sulphonate, 
 sodium meta nitro benzene sulphonate, sodium para chlor 
 toluene sulphonate, sodium ortho dichloro benzene sulphonate, 
 sodium ortho xylene sulphonate, methyl ether of carvocrol 
 sulphonic acid and camphor sulphonic acid. 
 
 Sodium alpha napthalene sulphonate:- This com- 
 pound was prepared affic&rding to the method of Barnett (12) 
 which will not be described here. It was found that when 
 the alpha napthalene sulphonic acid was boiled with water 
 

 
 * 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
11 
 
 to remove the napthalene that a considerable amount was 
 hydrolyzed and it was almost impossible to obtain a product 
 uncontaminated with napthalene. Sodium carbonate was added 
 to the solution and it was found that the sodium salt was 
 relatively stable to boiling with water so that in this 
 manner the compound could be easily purified. 
 
 Para phenol sul phonic acid:- This compound was 
 prepared according to Vanino (21). Two hundred (200) grams 
 of phenol was melted at 35° - 40° , 100 grams of fuming 
 
 sulphuric acid was added care being taken that the temp- 
 erature does not rise too high. This mixture was heated 
 slightly and allowed to stand for about twenty-four hours. 
 The two layers gradually disappeared and on standing the 
 sulphonic acid crystallised out. The slight excess of 
 sulphuric acid was not removed because it was not necessary 
 for the experiment. 
 
 Sodium napthol (2) sulphonate (l):- To about 
 40 grams of b-napthol about 100 c.c. of sulphuric acid 
 (mixture of * 1 % fuming sulphuric acid and concentrated 
 sulphuric acid) was added and the whole mass heated on 
 an oil bath to 160° until the two layers disappeared. 
 
 The excessof sulphuric acid was neutralized with barium 
 hydroxide, the barium sulphate filtered off and the filtrate 
 added to a saturated sodium chloride solution. The yield 
 was poor, about 9 grams. 
 
 Sodium ortho toluene sulphonate:— Several methods 
 were tried in the preparation of sodium ortho toluene sul- 
 

 
 
 
 
 
phonate. The amide of 0 -toluene sul phonic acid was refluxed 
 for several hours with a sodium carbonate solution but with 
 little success. 
 
 The method of hydrolysis described in Winther (13) 
 which uses chlorsulphonic acid was tried. This method 
 
 consists in heating the amide with chlorsulphonic acid for 
 
 several hours at 130 - 150^ extracting with ether and 
 
 hydrolyzing with sodiu$ carbonate. The reaction did not 
 
 work. 
 
 Finally a mixture of ortho and para toluene 
 sulphonyl chlorides were separated by vacuum distillation 
 as used by Majert and Ebers (14). About thirty parts in 
 a hundred were distilled over giving us the ortho compound 
 and by a series of vacuum distillations the ortho compound 
 was obtained pure. This sulphonyl chloride was hydrolyzed 
 by refluxing with a saturated sodium carbonate solution 
 with almost theoretical results. 
 
 Sodium meta toluene sul phonate:- This compound 
 was prepared according to the method of Metcalf (15) and 
 
 Griffin (16). To 100 grams of para toluidine was added 
 200 grams of 7 % fuming sulphuric acid. This mass was 
 
 heated until fumes of sulphur dioxide came off and the 
 mixture kept at 180 for an hour. After cooling the mixture 
 was Poured into twice its volume of water and a dark pasty 
 mass resulted consisting mainly of the meta and ortho 
 sul phonic acids of para toluidine. The remaining sulphuric 
 acid was precipitated by an excess of barium hydroxide, 
 the solution boiled to remove any unchanged toluidine and 
 

 
 
 
 . . ' ■> --*?** If 
 
 
 
 
 
 
 
 
 
 
 
 
 
13 
 
 the barium sulphate filtered off. On cooling the long sulphur 
 yellow needles crystallized out. This was filtered off and 
 the ortho and meta sul phonic acids we re separated by difference 
 of solubility ina potassium hydroxide solution. The para 
 toluidine meta sulphonic acid is insoluble while the para 
 toluidine ortho sulphonic acid is soluble in the potassium 
 hydroxide solution. 
 
 Twenty-five (25) grams of the potassium para 
 toluidine meta sulphonate was suspended in a 150 G,c. of a 
 92 %> solution of alcohol to which hydrochloric acid had been 
 added. This was placedin an ice bath and when the temp- 
 erature was at 0° sodium nitrite was added and the temperature 
 
 O 
 
 gradually allowed to rise up to 46 until the reaction was 
 complete, which requires about 30 minutes. The pinkish 
 white crystals were filtered off by a filter pump and washed 
 with alcohol. 
 
 Twenty (20) grams of this diazo compound was 
 decomposed in 200 c.c. of absolute methyl alcohol to which 
 
 9 grams of dried sodium carbonate had been added. This 
 
 0 
 
 reaction was carried on at 0 and the solution gradually 
 
 O 
 
 warmed to 30. This solution was allowed to stand over 
 night and then heated to 35. The alcohol was distilled 
 off and the resulting mixture was so contaminated with 
 sodium chloride that it was almost impossible to obtain a 
 pure product. 
 
 Instead of sodium nitrite, amyl nitrite was used 
 with better results, because a sodium salt was not formed. 
 

 
 
 
 
 ...... 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
14 
 
 This method is practically the same except that the diazo 
 
 compound was prepared and decomposed in the same alcoholic 
 
 from 
 
 suspension. The yield was poor M i about 25 grams of the 
 potassium para toluidine meta sulphonate only 6 grams of 
 the dark impure potassium meta toluene sulphonate resulted. 
 
 Sodium para toluene sulphonate:- This compound 
 was prepared by refluxing para toluene sulphonyl chloride 
 with a saturated sodium carbonate solution for about an 
 hour. The reaction goes very easily and the yield is 
 almost quantitative. 
 
 Sodium para chi or benzene sulphonate:- This 
 compound was prepared by the same method as used by 
 Langmuir (17) in preparing sodium para iodo benzene sul- 
 phonate. 60 c.c. of chlor benzene was heated with 120 c.c. 
 of an equal mixture of 7 % fuming sulphuric acid and 
 concentrated sulphuric acid on an oil bath for several 
 hours or until the two layers had disappeared. This 
 solution was added to the same amount of water and finally 
 when cooled poured into a saturated sodium chloride sol- 
 ution. The sodium para chlor benzene sulphonate was 
 filtered off by suction. The yield was good, about 70 grams. 
 
 Sodium para iodo benzene sulphonate:- This 
 compound was prepared by the previous mentioned method of 
 Langmuir. From 50 grams of iodo benzene, 35 grams of the 
 sodium para iodo benzene sulphonate was obtained. 
 
 Sodium para ethyl benzene sulphonate:- To 50 c.c. 
 of ethyl benzene 100 c.c. of a mixture of 7 % fuming sulphuric 
 

 
 
 
 
 
 
 * 
 
 
 
 
 ' 
 
 
 
 
 
 . 
 
 
 
 
 
 
15 
 
 acid, and concentrated sulphuric acid was added and the 
 mixture heated gently on a steam cone until the two layers 
 mixed; allowed to stand several hours and added to 100 c.c. 
 of water. The excess of acid was neutralized with sodium 
 carbonate and then the mass was added to a saturated 
 sodium chloride solution. The sodium salt crystallized 
 out in beautiful leaflets; yield about 35 grams. 
 
 Secondary Butyl benzene:- Two runs were made 
 in the preparation of this compound. In the first run 
 45 c.c. of normal butyl bromide and 140 c.c. of benzene 
 were dried over calcium chloride and then refluxed with 
 20 grams of aluminum chloride for about three-fourths of 
 an hour. The mass was then poured into water. The two 
 layers were separated and the benzene extraction dried 
 over calcium chloride for about four hours. The benzene 
 was distilled off and the remainder was fractionated; 
 the fraction boiling at 172°- 176° at atmospheric pressure. 
 The yield was 34 grams. 
 
 In the second run 50 c.c. of normal butyl bromide, 
 200 c.c. of benzene and 20 grams of aluminum chloride were 
 used. The yield was 35 grams. 
 
 This reaction according to Schram (18) who used 
 normal butyl chloride instead of normal butyl bromide . gives 
 the secondary butyl benzene. The boiling point of the 
 
 Q O 
 
 compound (173 - 175) and the specific gravity (0.865) found, 
 corresponded to that for secondary butyl benzene. 
 
 Sodium secondary butyl benzene sulphonate:- 
 

 
 
 
 
 
 
 
 
 • 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 ‘ 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 - . . 
 
 _ 
 
16 
 
 34 grams of secondary butyl benzene, 50 c.c. sf concentrated 
 sulphuric acid and 20 c.c. of 7$ fuming sulphuric acid were 
 allowed to stand dor several hours in the cold but there 
 was no reaction. The mass was then heated on a steam cone 
 for several hours until the two layers disappeared. The 
 excess of acid was neutralized with sodium carbonate and 
 the resulting mixture added to a saturated sodium chloride 
 solution. The yield of the sodium salt was 15 grams. 
 
 Lauryl bromide:- This compound was prepared 
 according to the method of Kamm and Marvel (19). In a 
 250 c.c. round bottom flask 40 grams of lauryl alcohol, 
 
 85 grams of hydrobromic acid (34$) and 42 c.c. of sulphuric 
 acid were refluxed for about three hours. The solution 
 was diluted with water, the bromide separated by difference 
 of specific gravities and then washed with sulphuric acid, 
 water and dilute sodium carbonate solution successively. 
 
 The bromide was extracted with ether. The ether was then 
 evaporated off and the product distilled under a vacuum 
 
 O o 
 
 of about 40 mm., the bromide coming over at 196 - 200. 
 
 The yield was 30 grams or about 55$ of the theory. 
 Undoubtedly the low yield is due to the fact that a 34$ 
 solution of hydrobromic acid was used while the directions 
 call for a 48$ solution. 
 
 Lauryl benzene:- The reaction of Priedel and 
 Craft was used in the preparation of this compound. 
 
 29 grams of lauryl bromide, 250 c.c. of benzene and 25 grams 
 of aluminum chloride were refluxed for four hours. The 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
 ' 
 
 
 
 
 
 
 
 
 
 
 1 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
17 
 
 resulting solution was poured into water and the two layers 
 separated. The benzene lawyer was dried over calcium chloride 
 over night, benzene was distilled off and the remainder 
 distilled under a vacuum of 46 mm. Two fractions were 
 collected, the boiling point of the first fraction was 
 
 o © 
 
 100 - 110 and the yield was 8.50 grams, while the second 
 was 190°- 197° and the yield Was 10 grams. The first fraction 
 is perhaps dodecylene because is gave a positive test for 
 unsaturation and the specific gravity was almost that of 
 dodecylene, while the second fraction is undoubtedly lauryl 
 benzene. The specific gravity of lauryl benzene was found 
 to be 0.9225 at 20° and its boiling point 190°- 197°at 46 mm. 
 pressure. In odor and general appearance lauryl benzene 
 resembles the higher aliphatic hydrocarbons. 
 
 Sodium lauryl benzene sulphonate :- To 7 grams 
 of lauryl benzene 20 c.c. of concentrated sulphuric acid 
 and 10 c.c. of 7 % fuming sulphuric acid were added. 
 
 This mixture was occasionally shaken and sulphonated very 
 readily in the cold. It was poured in a similar amount 
 of water, the excess of acid neutralized the sodium car- 
 bonate and finally added to a saturated sodium chloride 
 solution where the sodium salt crystallized out. The yield 
 was very poor; about 2 grams. This poop yield may be 
 explained by the fact that hydrolysis took place when it 
 was poured into water. 
 
 Sodium benzyl sulphonate:- The potassium salt 
 of this compound was first prepared by Bflhler (20), by 
 

 
 
 
 
 
 V 
 
 
 i 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
' 
 
 refluxing benzyl chloride with potassium sulfite. To 100 grams 
 of benzyl chloride a solution containing 125 grams of sodium 
 sulfite was added and this mixture refluxed for about five 
 hours. When the reaction was finished there remained an oil 
 which had a boiling point of 190° and ifc evidently benzyl 
 
 alcohol. On cooling the solution the sodium benzyl sulphonate 
 crystallized out in beautiful leaflets. The yield is 85 
 
 grams or about 45^ of theory. The yield of benzyl alcohol 
 
 was 40 c.c. 
 
 In figuring the yields in the following data 
 the author in each case endeavoured to prepare the mono 
 
 sulphonic acid and all the yields are figured approximately 
 on this basis. 
 

 

 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 I ' 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 . 
 
 
 
 
 
 . 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
DATA (Continued) 
 
 Sodium para 
 
 
 
 
 
 
 
 secondary buty! 
 
 5 
 
 50 c.c. H a S0 4 
 
 170-195 
 
 °l/3 
 
 0.64 
 
 23 
 
 benzene sul- 
 
 10 
 
 " fl h 3 pq, 
 
 170-210 
 
 1/2 
 
 2.58 
 
 47 
 
 phonate. 
 
 
 
 
 
 
 
 Sodium lauryl 
 
 Hydro 
 
 lyzes almost quar 
 
 titativ 
 
 ely on 
 
 additl 
 
 on 
 
 benzene sul- 
 
 
 of sulphuric 
 
 acid. 
 
 
 
 
 phonate . 
 
 
 
 
 
 
 
 Sodium para 
 
 10 
 
 35 c.c. H, S0„ 
 
 200-220 
 
 i W 
 
 4.81 
 
 87 
 
 chlor toluene 
 
 10 
 
 It tt ^ TT ^ 
 
 TI II 
 
 2.14 
 
 40 
 
 sulphonate. 
 
 10 
 
 50 " H 3 P0 y 
 
 240-280 
 
 3/4 
 
 4.23 
 
 77 
 
 Sodium ortho 
 
 10 
 
 25 c.c. H d S0 v 
 
 240-280 
 
 3/4 
 
 4.00 
 
 66 
 
 dichloro ben- 
 
 10 
 
 ti n ti 
 
 TI fl 
 
 ti 
 
 ti 
 
 it 
 
 zene sul phonal 
 
 e 10 
 
 " M H 3 P0, 
 
 260-320 
 
 35 mir 
 
 .3.30 
 
 55 
 
 Sodium ortho 
 
 10 
 
 25 c.c. H, S0 V 
 
 160-130 
 
 1 , 
 
 1.88 
 
 45 
 
 xylene sulphon- 
 
 10 
 
 Tt If tl 
 
 150-180 
 
 3/4 
 
 1.54 
 
 35 
 
 ate . 
 
 
 
 
 
 
 
 Methyl ether of 
 
 10 
 
 25 c n c. H §0, 
 
 IfiO-lJJO 
 
 25 mir 
 
 . 3.86 
 
 50 
 
 carvocrol sul- 
 
 6 
 
 
 ti 
 
 2.18 
 
 52 
 
 phonic acid. 
 
 
 
 
 
 
 
 Camphor sulphon- 
 
 10 
 
 25 c.c. H a S0 4 
 
 160-170 
 
 1/2 
 
 2.40 
 
 25 
 
 ic acid. 
 
 10 
 
 50 " H 3 P0 4 
 
 160-180 
 
 it 
 
 3.90 
 
 40 
 
 Sodium benzyl 
 
 10 
 
 25 c.c. H a SO w 
 
 160-210 
 
 1 
 
 
 __ 
 
 sulphonate. 
 
 10 
 
 40 ” H 3 PO v 
 
 it ti 
 
 it 
 
 — 
 
 - 
 
 Sodium para 
 
 10 
 
 25 c.c. H.SOu 
 
 200-210 
 
 1 
 
 2.98 
 
 45 
 
 bromo benzene 
 
 10 
 
 25 " 
 
 200-240 
 
 1 
 
 3.72 
 
 57 
 
 sulphonate . 
 
 10 
 
 25 c.c. H 3 P0* 
 
 220-240 
 
 1/4 
 
 4.10 
 
 62 
 

 
 
 
 
 ' 
 
 
 
 
 
 
21 
 
 V SUMMARY. 
 
 I The following compounds were prepared and the amount, tine 
 
 and temperatures of hydrolysis studied: Sodium benzene 
 
 sulphonate, Fara phenol sulphonic acid, Sodium beta 
 napthalene sulphonate, Sodium alpha napthalene sul- 
 phonate, Sodium napthol (2) sulphonate (1), Sodium 
 ortho toluene sulphonate, Sodium meta toluene sulphon- 
 ate, Sodium para toluene sulphonate, Sodium para 
 chloro benzene sulphonate, Sodium para bromo benzene 
 sulphonate, Sodium para iodo benzene sulphonate, 
 
 Sodium meta nitro benzene sulphonate, Sodium para 
 ethyl benzene sulphonate. Sodium para secondary 
 butyl benzene sulphonate, Sodium lauryl benzene 
 sulphonate, Sodium para chlor toluene sulphonate, 
 
 Sodium ortho dichloro benzene sulphonate, Sodium 
 ortho xylene sulphonate, Methyl ether of* carvocrol 
 sulphonic acid. Camphor sulphonic acid, and Sodium 
 benzyl sulphonate. 
 
 II It has been shown that the time and amount of hydrolysis 
 
 of aromatic sulphonic acids depends on: 
 
 (a) Kind of groups in ring. 
 
 (b) Number of groups in ring. 
 
 (c) Position of groups in ring. 
 
 III Phosphoric acid was used as a catalyzer and in many 
 
 cases was superior to sulphuric acid as a catalyzer. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
22 
 
 IV Sodium benzyl suLphonate was found to act very differently 
 
 from the other compounds studied showing the charact- 
 eristics of the aliphatic compounds. 
 
 V Lauryl benzene has been prepared and its physical 
 
 constants determined. It was shown that it sulphon- 
 ates very readily but that the sulphonic acid was 
 relatively unstable. 
 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 , 
 
 
 
 
 
 
23 
 
 VI BIBLIOGRAPHY. 
 
 1. Annalen 120:80 (1861) 
 
 2. " 133:36 (1865* 
 
 3. Ber. 11:19 (1878) 
 
 4. Ber. 11:1697 (1878) 
 
 5. J. Chem. Soe. 45:148 (1884) 
 
 6. Ber. 19:92 (1886) 
 
 7. Ber. 20:900 (1387) 
 
 3. Comptes Rendus 109:95 (1909) 
 
 9. Bulletin de la Societie Chemie (3) 7:652 (1892) 
 
 10. Ber. 34:1350 (1901) 
 
 11. Ber. 22:994 (1889) 
 
 12. Barnett "Preparation of Organic Compounds” 232 (1912) 
 
 13. D. R. P. 105870 
 
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 15. J. Chem. Soc. 15:301 (1893) 
 
 16. " " n 19:183 (1897) 
 
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 18. Monatsheft 9:620 (1898) 
 
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 20. Annalen 154:50 (1870) 
 
 21. Vanino "Organic Chemistry" p. 611 (1914)