The preparation and physical properties of benzene- and ...
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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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0 , o
-l T
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.
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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-