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Masters Theses Student Theses and Dissertations

1920

The preparation and physical properties of benzene- and toluene-The preparation and physical properties of benzene- and toluene-

sulphonamides sulphonamides

Karl K. Kershner

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Recommended Citation Recommended Citation Kershner, Karl K., "The preparation and physical properties of benzene- and toluene-sulphonamides" (1920). Masters Theses. 4669. https://scholarsmine.mst.edu/masters_theses/4669

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THE PREPARATION i\ND PHYSIC.L·~ PROPEHTIgS OF BENZENE­

AND TOLUENE- SULPHONAUIDES.

BY

K. K. Kershner

A

THESIS

submitted to the faculty of the

SCHOOL OF MINES AND METALLURGY OF THE UNIVERSI~Y OF MISSOURI

in partial fulfillment of the work required for the

Degree of

MASTER OF SCIENCE IN CHEMICAL ENGINEERING

Rolla, Mo.

10aO.

23045

TADT-IE OF CONTEHTS.

Introduct ion •.....•..... ........ ,. . . .. ..... . . . . General ConsiderELtions ... . . . . ............ . 4-5

Procedure ...... . .. . .. . . . . . . . . . . . .. . ........ . 0-15

Solubilities •. . . . . . . .. . ................... . 16-18

Curves of Solubili ties c),nd Inpuritles •. . . 10-30

General Conclusions •• . . . . . . . . . . . . . . . . . . . . 31-33

Bi b1iosraphy ••. . . . . . . . . . . .... 34-38

Intlex •......... . .... ., . . . . . ...

INTRODUCTION.

The formation of sulphonamide derivativeo is

often of distinct importance. These substances are eas-

ily purified and give sharp ucptins pOints w"hich make them

of value for identification phases of resea.rch worlc. Also

the Y tl.re of vt~lue comr.lercially as in the production of

saccharin and other siwl1ar compounds. The purpose of this

inveDtigatlon is to necure infornnt1on on the cooparative

production and yiel[l of oulphonamides, and intermediate

products, formetl from their respective ring hyul'locn.rbons,

as benzene and toluene. Careful melting points [ll?e taken

on purified products and solubility curves developed for

different solvents. The latter give an interesting basis

for conparison.

It 1s the hope of 'the author to secure later, -

sim1lar [lata on other sulphonnnicle deri vc.ti vee.

It 1s also the wish of the uuthor to exprens

h1.s sincere appreciation for kindly asnistance and sugges-

tiona given by Dr. vr. D. Turner and prof. II. L. Dunlap

during the courBe of the work.

-3-

GENERAL CONSIDERATIONS.

The methods employed in synthetic production

lluve been drawn from various sources such as are aVail­

able from the publications listed in the bibliography,

page 34, of this work. 1m effort has been made to make

the uethods of procedure as sim.ple as possible.

The benzene and toluene, from which the nul­

phonic acids were formed, were dehydrated, purified and

freshly distilled. The theoretical amount of 7 per cent

fuming sulphuric acid necessary to sulphonate the quanti­

ty of benzene or toluene taken was used in each sulphon­

atlon, and the agitation and temperature controlled by

means of an electrically-driven, steam-jacketed nulphon­

ator.

The per cent yield ·on suI phonations was cal­

culated from the ruaount of benzene or toluene actually

sulphonated, th~s avoiding the necessity of deter~inlng

the quantity of free acid present in the 8ulphonates.

No attempts were mnde at solven·t extraction of ·the sul­

phonates.

A DeIDlotinsky thermostat, in which constant

tempernture control to within one-tenth of a degree Oen-

tigrade was possible, was employed in solubility work.

In the determination of melting points of

different compounds a therm.ometer standardized by the

German Bureau of Standards was employed and full correctldns

made. All. sanplen vrerethorouGhly dried before making a

deterrrtlna·tion.

PROCEDURE.

Production of Benzene Sulphonic Acid.

Benzene (3,520 grams) and 7 per cent fuming

sulphuric acid (4,372 grams) were placed in a sulphon­

ator and stirred for three hours. The acid was added

in a steady streacr during the first half hour •. The temp­

erature for the fi~st hour was ~eld at 40°C., for the

second hour at 45°C., and for the third hour at 50°C.

At the conclusion of the third hour the product was drawn

off, allowed to stand, cool and separate into layers.

The l~yers were then separated. There was found to be

5231 grams of benzene sulphonio acid, 1300 grams of sul­

phuric acid and 1144 grams of benzene present. A loss

of 3 per cent occurred due to evaporation and mechanical

manipulation. The actual yield was 68 per cent of the

theoretical.

A similar synthesis gave a yield of 66 per cent

and~a loss of 3 per cent.

Production of Ortho- and Para-toluene Sulphonic Acids.

Toluene (3,480 grams) and 7 per cent fu~ing

sulphuric acid (3,552 gr[~1s) were placed in a sulphona­

tor and stirred at a temperature of 75-80°C., for three

hours. The acid was added in a sterLdy stream during the

first half hour. After the three hours had elapsed the

products were drawn fro!!'} the nulphonator, allowed to stand,

and cool and separate into layers. The lower layer of

sulphonate wns dark brown in color and very viscous at

20°0. There was found to be 6542 grams of ortho- and

para-toluene sulphonic acid, 355 grams of sulphuric [lcid,

and 322 grams of toluene present. There was a loss of

three per cent due to evaporation and mechanical manipu­

lation. The actual yield was 90 per cent of the theoretic­

al. (See General Conclusions, page vi, with regard to

this yield.

Formation of the Sodiuo SQlt of Benzene Sulphonic

Acid..

An excess of saturnted sodiwJ chloride solu-

tion was added to ·the sulphonic acid and the mixture

stirred thoroughly and permitted to stand. No crystal

formation was evident. A small quantity of the liquid

showed no crystals after s'tanding at roor:! temperature

for two weeks. Accordingly the entire mixture was plac­

ed in a large porcelain evaporating dish and concentrnt-

ed till a test showed crystal formation upon cooling.

The whole solution was then cooled, the crystals of

sodium benzene sulphonate filtered off, centrifuged,

and dried. The liquor obtained from centrifuging was

added to the filtrate. This process was continued till

only a small amount of mother liquor remained. The

dried sodium benzene sulphonate was recrystallized from

absolute alcohol in order to remove any sodium chlorlde,

sodium sulphate, or other impurity present. This was

accomplished by placing a quantity of impure crystals

in a round-bottom flask, adding absolute alcohol, heat­

ing the alcohol to its boiling point, and filtering by

suction through a filter paper in a glass funnel contain­

ing a porcelain cone. The filtrate was chilled and •

the crystals formed were filtered off, centrifuged, and

dried. These dried crystals were again put into 801u-

-8-

'tion in hot absolute alcohol, the solution filtered and

cooled, and the resulting crystals filtered off, centr~l-"

fuge(l [uHl dried.. A pure produ.ct of sodiumbenzenesulphon­

nte was thus obtained. Tests were made 'to determine

the complete absence from the crystals of such impuri­

ties as sodiull1 chloride [,l,nd sodium sulphate. A yield

of npproximntely 81 per cent was secured. A part of the

19 per cent loss was due to mechanical m~~nipulntion,

unsulphona'ted benzene present in the sulphonate, (See

General Conclusions, page 31.), and to the final bit of

mother liquor that was not brought to dryness and the cry­

stals purified.

Extrac'tions were run on each crystallization

of the sodium salt from the mother liquor. A weighed

amount of the dri ed sodium salt was placed in an extrac"­

tion thimble and extracted 3 hours with absolute alcohol.

The 10s8 in weight at the conclusion of the extraction

gave the amount of pure sodiumsulphobenzoate present as

the insoluble sodium chloride, sodium sulphate and other

impurities remained in the thimble. The extraction solu­

tion of alcohol was evaporated to dryness and a check

run on the amount of sodiumbenzenesulphonate present.

The sodiumbenzenesulphonate obtained from the extraction

solution was also tested to determine if any sodium chlor-

lde, sodium sulphate or other impurities were present.

It was founcl that the extraction gave only pure sodlum­

benzenesulphonate. The crystals of sodium suIt were

thoroughly dried before the extrnction was started in

order to remove all water present, especially from the

sodium sulphate. Sadiuu sulphate containing water of

crystt:vliization is sO::llevlh(~ t soluble in absolute alcohol.

A curve, page 19, was plotted with the per cent of im­

purity present in the product of each crystallization

agninst the serial number of the crystallization. The

only variable vIas that no definite per cent of water

was volatilized before each cooling to crystal formation.

The crystallizntion was governed by frequent testing of

small portions of the mother liquor to find if cryntnls

separated upon cooling.

-10-

Formation of the SodiuEl SuIt of Ortho- and Para­

Toluene Sulphonic Acids.

The mixtUl'ae of ortho- and para-toluene sul­

phonic acids nnll free sulphuric t'locid was treated with

an excess of a saturnted. solution of sodiuLl chloride.

After standing i'or n period of 18 hours a slight form.a­

tion of crystals was notlceable. The mixture was now

placed in Cl In,ree porcelain evapornting dish a.nd frac­

tionally crystallized til,l only a snull amount of mother

lIquor rerJluined. The crystallization product of ortho­

and para-sodiumsulphotoluate was purified and tested

in-the same manner as described under "Formation of the

Sodium Sn,It of Benzene Sulphonic ACid t', page 8, A yield

of approximately?? per cent was secured and some loss

was due to mechanical manipulation, unaulphonated toluene

present in the sulphonate, (See General ConcluBions, page

31.), and unused mother liquor. A curve was plotted,

page 20, with 'the per cent inpuritles against the serial

number of the crystallization, similar 'to the one plotted

for the crystallizations of the sodiumsulphobe~zoute,

page 10, and subject to the same va.riable.

ConverGion of Sod1umoulphobenzoate to

Benzenesulphonchloride.

A quantity of sodiumbenzenesulphonate was

placed in n porcelnin evapornting dish, treated with

an excess of phosphorus pen'tachloride and warmed on [l

water-bath till the nction wus complete. This reaction

should be carried on in a hood and care taken to avoid

inhaling the tunes or permitting them to attack the

eyes. Cold water was now slowly added and the liquid

contents of the tlWaporatlng dish transferr~d to a suit­

able separatory funnel. The lower oily layer of ben­

zenesulphonchloride was drawn off and washed "....veral

times with water. The spec1fic gravity was found to

be 1.385. A yield of 76 per cent of the theoretical

was secured. Three duplicate conversions gave yields

of 70, 78, and 75 per cent of the theoretical.

Conversion of Ortho- nnd Pnra-nodiumnulphontoluate

to Ortho- and Pnrn-toluenesulphonchloride.

A quanti ty of ortho- and pur,a-sodlumsulpho­

tolunte was treated with an excess of phosphorus penta-

chloride, warmed and set in a hood till the reaction

Vias cOMplete. Cold water was slowly added and the

solid paratoluenesulphonchloride filtered from the

water and liquid ort:hotoluenesulphonchloride by suction.

The para compound was wn.shed with water, centrifuged

to remove the last traces of orthotoluenesulphonchlor-

ide, again washed with water,and then dried by vacuum.

The melting point of the product of ,paratoluenesulphon­

chloride was found to be 69.3·C·. A yteld of 79 per

cent of the theoretical was secured. A 'duplicate syn­

thesis gave a yield of·78 per cent of the theoretical.

-1.3-

Synthesis of Benzenesulphonchloride to Benzene­

sulphonamide.

To n quantity of benzenesulphonchloride

a slight excess of concentrated ammonia was added over

the amount theoretlcally required to complete the re-

action- Upon completion of the reaction the resulting

clear nolution was boiled till only a slight test for

ammonia gas could be detected in the vapors. The solu­

tion was now chilled, the crystnls of benzenesulphon­

amide filtered off, washed with a smnll amount of water,

and dried. These crystals were in turn recrystalliz-

ed from concentrated ammonia and from alcohol before

they were considered of sufficient purity for solubil­

ity work. The melting point of the finnl benzenesul­

phonamide was found to be 151.1°0. A yield of 81

per cent of the theoretical was secured. A duplicate

synthesis gave a yield of 82 per cent.

Synthesis of paratoluenenulphonchloride to :Rara­

toluenesulphonamide.

A quantity of para'toluenesulphonchloride

was treated with concentrated ammonia till the conver­

sion to the D~ide was complete. The resulting clear

solution was bo11edttll only ft .slight excess of n.rD.r.lonia

remainefl. and thpn t.he oolution was cooled, and the

crystnls purified in the s~, .. me i1anner as d.escribed for

benzenesulphonnmide c!"'yotnls under Synthenis of Ben­

zel1.esulphonchloricl p, to Bcnzenenulphonamide on page 14.

The finn.l pro(!uct of parutoluenesulphonnmide gave a

melting point of 137.7°0. A yield 6f 71 per cent of the

theoretica.l was secured. A duplicate synthesis gave

a yield of 75 per cent.

-15-

SOLUBILITIES.

Solvents and Solutes.

The solvents used were alsolute alcohol and

pure water. The alcohol was made absolute by dlBtll1a~

tion from lime followed by a second distillation from

anhydrous copper sulphate and by D. final standing over

metallic calcium. The water was freshly distilled and

tested for purity_

The compounds whose solubilities were deter~­

Ined were those prepared by methods outlined under If Pro­

cedure ft, page 6.

Solubilities were determined at 15, 30, 45,

and 80" C •. All compounds were thorouGhly dried before

starting a determination.

Method for Determination of Solubilities.

Solute D.nd sol vent were placed in 250 c. c.

glass bottles f1 tted wi th ground-glass stoppers, hec:tt-

ed to the degree of temperature at which they were to be

subjected, and the stoppers tightly fastened. This pre­

heating Served to counteract subsequent pressure which

might be developed and as a guide to the approximate propor~-

-16-

tiona of solute to solvent. The bottles were tested for

leakage, placed~ in a constant-temperature DeKhotinslcy

thermostat, and rotated continuously for 10 hours. At

tIle conclusion of this 10 hour rotation the bottles

were removed from the rotator and, after loonening the

stoppers, left standing in the thermostat for a short

time to ~nrmit the solute to settle. With pipettes,

heated in an electric oven to a temperature slightly

higher than the temperature of the thermostat, a small

amount of the solvent containing the'solute in solution

was placed in tared, glass-stoppered weighing bottles. "

The reason for the use of heated pipettes was to pre~

vent the crystall1zatlon of the solute from the warm

solvent. The weighing bottles were cooled in a deslca­

tor, weighed, transferred to the electric oven, and the

solvent evaporated at about 10°0., below its boiling

point. After complete drying the weighing bottles and

contents were cooled in a deslcator, weighed, and the

grams solute in 100 grams,solvent calculated. These

calculations were not taken for final in curve plotting

till they were checked in triplicate to the second deci­

mal place from different determinations. The amount of

solvent containing solute in solution that was placed in

the tared weighing bottles depended upon the solubility of

the solute. The greater the solubility of the solute

-11-

the more cl1fflcul't it wan to obtain a thorough evapora­

tion and drying. The pipettes were inverted to permit

of faster transference of liquid and a short piece of

rubber tubing attached to prevent burning the lips.

Curves.

CurveD were Illotted which show the solubil­

ity of sodiumbenzenesulphonate, ortho- and para-toluene-

sulphonate, benzene~ulphonamide and paratolueneaulphon­

amide in pure water and ~bsolute water a~ various temp­

eratures. Two sheets of comparative curves were also

drawn. A complete list of these curves can be found

in the index, page \11.

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PAGE"

1\: ISSOlJRI SCHOOI~ Ol~ ~IINl~S Solubility Curve for Sodiuillsulphobenzoute in Absolute

Al cohol.

o ... 0 o o _W Ttfi­'( 0

Form E~-&m-·9- .17-·-· D.1'. C() . Temperature in Degrees Centigrade.

... 21::-.0.

P A G E"._ ... . 18_t.L... __ ~I.lSS()[!RI SCI-I 00 l .. 01; ~IINl~S

o 10 20 30 40 50 60 ?O Form :B:;-5m--·9~17-B. P.Co. T~mperature in Degrees Centigrade.

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10 20

~IISS.O(JRI SCHOOI~ O~~ MINES

i+

30 40 5 0 60

Form E-5m-9-17--- B. P.Co. Tem!)erature in Degrees Centicracle.

PAGE'. 2r:J: ....

70

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:.

M.lSSOURI SCIIOOI~ OF ~fIN:ES Solubility Curve for Pa ratoluenesulphona nide in Pure ~ater.

j<~Ol'm l:!~·-5m-9-17-D.P.Co. Temperature in Degrees Centigrade.

~IISSO[)RI SCIIOOl. OF l\I :. ~ES Solubility Curve for in Absolute

.-0 ~O 20 30 40 Form E-5m-9-17-RP.Co. Temperature in Degrees Centigrade.

t: -:-' " + f- i-I+ ' ~ i-~ .,

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2'0 JO 40 )0 6

GEHERAL CONCLUSIONS.

Benzene Gulphonn,terl with the theoretical a.mount

of 7 per cent fuminc~ Bulllhuric iJ.cid and agitated for :3

hours at a temperature of 40~50~C., gave a yield of 67

per cent of the theoretical and (1 loss of 3 per cent due

to evaporation, and mechani cal manipulatlon.

Toluene sulphonated with the theoretical a­

mount of 7 per cent fuming sulphuric acid and agitated

for 3 hours at a temperature of 75-88 0 0., gave a yield

of gO per cent of the theoretical and a.losB of !5 per

C6-11t due to evaporation and mechanical manipulation.

However it in very probable that this gO per cent yield

1s too hi~h since some of the toluene must have been

contained in the viscous sulphonate. (See ltGenernl Con­

siderations tf ~ page 4, as to the calculation of yields.)'

It would be necessary to extract the nulphonlc acids

to get quantitative data on the flElOunt of benzene or

toluene present.

A COElpclriBon of the two curves, page 19-20,

show the ortho- and para-aodiumtoluenesulphonn'te is

more insoluble in a hot, acid" solution of its mO.ther

liquor than the sodiumbenzenesulphonate under similar

conditions. The bulk n~ the formereomes off in the

-31-

first? crystallizations with less thn,n 4 per cent of

impuri ty, while the lat'ter largely COfJ8S off in the fir8t

9 crystallizations with Blightly more than 27 per cent

of iml)Url ty.

The chlorination of 8odiumbenzf~nesulphonate

gave a yield of 77 per cent of the theoretical for ben-

zeneBulphonchloricle.

The chlorination of ortho- antI para"sodium­

toluenesulphonnte gave a yield of 79 per cent of the

theoretical for the chIaro-derivative. This was entire-

ly puratoluenesulphonchloride for the ortho isomer was

discarded at t"his point. The ortho isomer was of only

slight amount.

In the formation of benzenesulphonamide and

paratoluenesulphon<..uriide from benzenesulphonchloride and

parato!uenesulphonchloride the yie~d was 81 per cent

-and 73 per cent respectively of the theoretical yield.

The mel ting pOints of pure cO!1pounds were

found to be!

paratoluenesulphonchloride-------50.3°C. Benzenesulphonamide----------- ---151.1° C. Paratoluenesulphonamide---------137.7°C.

The specific gravity of benzenesulphonchlorlde

was found to be 1.385 at 20°C.

Sodlumsulphobenzoate and ortho- and para-sod­

ium.toluenesulphonate were motle soluble in pure water

than their corresponding sulphonamide derivatives. Ben­

-3a~

zenesulphonamide and paratoluenesulphonamide were more

soluble in absolute alcohol than the sod1um salts of

benzene- nnd toluene-sulphonlc acids. Ortho- and para­

sodiumtolueneBulphonate \Vas more soluble 1n pure water

and absolute r~,lcohol than was sodlwn benzenesulphonate:.,

However below 259 C., the reverse was true but above the

temperature of 25°0., the genera! statement holds true.

BenzeneaulDhonurnlde VIas raore Boluble in pure water than

paratoluenesulphonamlde but 1n absolut'e alcohol the para.­

toluenesulphonamide was the more soluble.

BIBLIOGRAPHY.

Downs, C. R., Sulphonating benzene and sir:ll1ar hydro­

carbons: U. S. Put. 1,279,205. Sept. 17,

1918.

Dermis, L. H., Aromatic sulphonlc acids and their salts:

Can. Pat. 177,138. May 28, 1017.

Arowatic sulphonates: Jap. Pat. Feb. 22,

1917.

Separating sulphonic acid d.erivatives

of aromatic hydrocarbons from their nixtures

with sulphuric acid and converting ther.l into

salts: Fr. Pat. 483,716. Aug. 2, 1917.

Sulphonic acid; sulphuric acid: Brit.

Pat. 109,709. Dec. 7, 1916.

Separating an aromatic sulphonic acid

:from sulphuric acid: Swiss Pat. 75,550. Jan.

2, 1918.

Aromatic sulphonic [lcid: U. S. Pat. 1,211,D23.

Veley, V. H., The affinity constants of lUllino-carbox­

ylic and aninosulphonic acida us determin-

er: by the aid of rJethyl orange: Pre Chern.

Soc., 22, p. 313.

-34-

Jljinnky, M" Gp. Pat. 847,078. Chern. Abo. 1, p. 1337.

Bull, H., U. S. Pat. 1,84'(, 400. Nov. 20,1018.

"i.-- to'""""'er .t.l.cl. _ 0."-:'" , J. R., Fr. Pat. 12,783. Chern. Abe. 1, p. 1401 •

Beltzer, A., Ind. chim. flin. met. 4, P. 37~-3, 1017.

Seyewetz, A., and Block, Tne productlon of aromatic

sulphamates and sulpl10nanines by the action

of sodlu!!l tlilosu19h [l"te on the nitro'tlerlva-

tives: Bull. soc. chima 4, P. 320-27.

Dreyfus, e., Brit. Pat. 13,056. June 5, 1~06.

Brit. Pat. 13, 054. June 5, 1906.

Uhlmann, P. W., Gr. Pat. 24,826. Nov. 5, 1£106.

Ley, H., and Erler, P., Formation of sir.lple and cOIIlplex

salts of organic hyclroxy ncidD: Z. anorg.

Chern., 56, p. 401-21.

Miersch, W., Gr. Pat. 19£),959. Jan. 3, 1906.

Gr. Pat. 200,015. Sept. 21, iDe7.

Gr. Put. 2,565~ Feb. 1, 1007.

Gr. Pat. 201,g71. Jan. 3, 1007.

Kastle, J. H., Preparation of certain oulphonic acids

in the free state: Am. Chem. Journ., 44,

p. 483-7.

Fechter, F., and Tamm, \"1., Electrolytic re~1.uction of

aromatic sulphonic chlorides: Ber., 4~,

p. 3032-38 •.

-35-

Holleman, A. H., and Polak, cT. cT., Simultaneous forma­

tion of isomeric substitution products of

benzene. Quantitntive study of the sulphona­

tion of benzenesulphonlc acid; Rec. trav.

chim. 29, p. 416-45.

Brit. Pat • .8tt,7~O. Dec. 21, 1t1iO. Chern. Abs. £, p. 1500.

Schmid't, 0:" U. S. Pat. 1,027,908. Hay 28, 1010. Chern.

Abs. 8, p. 1057.

Holleman, A. H., and Caland, P., Quantitative investi­

gations of the sulphonation of toluene:. Ber.

44, p. 2504-2.8.

Voswinkel, A., Ger. Pat. 22g,814. Jan. 19, 1000. Chern.

Abs. 5, p. 2608.

Uhlmann, P. W., Gr. Pat. 22{),537. Nov.?, 1905. Chern.

Aba. 5, p. 2535.

Langkammerer, H., and Heldu8chka, A., Para- and ortho­

toluenesulphinic acids: Journ. Prakt. Chern.

88, p. 425-42.

Gr. Pat. 287,932. Jan. 16, 1014. ' Chem. Abs. 10, p. 2500.

Gr. Pat. .286,712. Jan .• 29 , 1013. Chern. Abo. 10, p. 1012.

ElliS, C. , Aromatic sadiuo sulphonaten and phenol: U. s. Pat. 1,179,415.

Brit. Pat. 22,854. Oct. 0, 1013. Chern. Abs. £4, p. 055.

-38-

Stoddard, W. B., A further study of the prod.ucts formed

by the Gction of heat on parasulphamidoben-

zoic acid.: Am. Chern •. Journ. 47, p. 3, 1012.

Roul11er, A. C., Reaction between carboxylic acids and

benzenesulphonanicle at high temperatures:

Am. Chem. Journ. 47, P. 475, 1912.

Barge, ~., and Givandan, L., Separation of toluene 0-

and p-sulphonanides: D. R. P. 154,656.

D. R. P., 124,407, Toluene-o-sulphonic chloride and the

o-sulphonic chlorides of the ethereal benzoat~8.

Krafft, F., and Wilke, W., Isolation of sulphonlc acid

by vacuum distillation: Ber. 33, p. 3207-3209,

1900.

Moale, P. R'., Decomposi tion of paradiazo-orthotoluene­

sulphonlc acid with absolute m§thylic alco-

hoI in presence of other substances: Am.

Chern. Journ. 20, p. 2QS-30a, 1898.

Halsslg, F. A., paratoluenesulphinlc acid: J. pre chern.

56, p. 213-241, 1ag7 • .

Norton, rea H., Derivatives of benzenesulphonic acid:

Journ. Am. Chem. Soc. 19, p. 835-838, 1877.

Zassh:1, K., Utl11 zat..:L mn:. of p-toluenesulphonyl chloride:

Journ. Pharm. Soc. No. 437, p. 551-555, 1018.

-37-

Noyes, 11. A., and Wallter, e., ITetutoluenenulphonamide:

Am. Chern. Journ. 8, p. 185-190.

INDEX.

Bi bli ogrr:1phy ........................................... . Page

34

Comparison of Solubility Curves •....•.....• 2~-30

Conversion of Ortho- and Para-sodiwn-

8ulphotoluate to Ortho- and

Parutoluenesulphonchloride...... ~3

Conversion of Sodiumsulphobenzoate to

Benzenesulphonchloride" ......... " • 12

Curves. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. • 18

Curve for the Crystallization of O~tho-

and Para-sodiurnsulphotoluute.... HO

Curve for the Crystallization of

Sodiumsulphobenzoate............ 19

Formation of the Sodiura Salt of Ortho-

and Para-toluenesulphonic Acids.. ~1

Formation of the Sodium Salt of Ben-

zenesulphonic Acid.............. 8

General Conclusionn................................ 31

General Considerations... ..............•... 4

In t ro due t i on • • • • • .. • " • . .. .. .. • .. .. • • .. • • • • • • • • .. • .. • 3-

Melting Points •..•..•..•..................• 5, 32

Method for the Determination of

Solubilities.................... 15

-39-

Page Production of Benzene Sulphonic Acid........ 6

Production of Ortho- and Parn-toluene-

Sulphonic Acids'...................... ?

Solubility Curve for Benzenesulphon-

in Absolute Alcohol •.•••.•

Solubility Curve for Benzenesulnhon-

nraide in pu re ',Vo. t er • • .. .. • • . .. . .. • .. • 25

SolubilIty Curve for Ortho- and Para-

Rodi~~sulphotoluate in

Absolute Alcohol.................... 24

Sol u1Jility Curve for OrtlJ.o - ('.l1C:' ?[~rci..-

S oeli uf:lsulphot.olu,'; te in

Pu 1"1 e \Va t e r. . .. .. .. .. .. . . .. . .. .. . .. .. .. .. .. .. . . 23

Solubility Curve for Paratoluenesulphon-

arJ.lde in Absolute Alcohol............ 28

Solubility Curve for Pnratolueuesulphon-

Solubility' Curve for Sodiu~-lSulphobGnzoate

in A1)soIute Alcohol.................... 22

Solubill ty Curve" for Sodiurlsuiphobenzoate

in Pure Water.. . . . . . . .. . . .. . . . . . . • 21

Solvents and Solutes......................... 16

-40-

PUGe Synthesis of Benze:ner;ulphonchloride to

Benzenesulphonunide... ... ..•.... 14

Synthesis of P~rntolueneGulphonchloride

to ?ara'toluencsulphonaLlide...... 15

Table of Contents. ..••.. .... .•.••••..•..... 2

T i"t 1 e .............................. II .. .. • • • • • .. • 1

2:~()45

-41-