Title: Meta Toluene Sulphonic Acid and Related Compounds
Author: Allen, Charles Francis Hitchcock
Language: English
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  BOSTON UNIVERSITY
  GRADUATE SCHOOL
  THESIS
  META TOLUENE SULPHONIC ACID and RELATED COMPOUNDS

  Submitted by
  Charles Francis Hitchcock Allen
  (A.B., Boston University, 1919)

  In partial fulfilment of requirements for
  the degree of Master of Arts
  1920



  TABLE OF CONTENTS.


  META TOLUENE SULPHONIC ACID and RELATED COMPOUNDS
  THEORETICAL DISCUSSION
  SULPHONATION OF ORTHO TOLUIDINE
  SULPHONATION OF PARA TOLUIDINE
  DIAZOTIZATION OF ORTHO TOLUIDINE SULPHONIC ACID.
  PHYSICAL PROPERTIES OF THE DIAZO COMPOUND
  DECOMPOSITION OF THE DIAZO COMPOUND
  A STUDY OF THE SOLUTION OBTAINED BY THE DECOMPOSITION
     OF THE DIAZO COMPOUND
  CONCLUSION
  BIBLIOGRAPHY



META TOLUENE SULPHONIC ACID and RELATED COMPOUNDS


Theoretically toluene should yield three isomeric mono sulphonic acids,
in which the entering sulphonic acid group occupies the positions
ortho, meta, or para to the methyl group.

The action of sulphuric acid on toluene was first investigated by
Jaworsky, (Ztschr. Chem. 1,272), who described one toluene sulphonic
acid as the resulting compound. In 1869 Engelhardt and Latschinoff
(Ibid. 617), heated toluene with sulphuric acid and made and studied
the potassium salt of the resulting acid. They obtained two forms, and
identified them by fusion with caustic potash which converted them into
the ortho and para cresols, showing that sulphonation had taken place
in the positions ortho and para to the methyl group.

Barth (Ann. chem. (Liebig) 152,91), working similarly but fusing under
different conditions which also caused oxidation of the methyl group to
a carboxyl group obtained para hydroxy benzoic acid and salicylic acid
(ortho hydroxy benzoic acid.) This also proved that the sulphonic acid
group had entered in the ortho and para positions.

Anna Wolkow (Ztschr. Chem (1870) 321), confirmed this work but ascribed
the meta position to the sulphonic acid that passed into salicylic
acid. She also made two acid chlorides and amides and recorded their
melting points.

Fittig and Ramsay (Ann. chem. (Liebig) 168,242) studied this result
of Anna Wolkow, and to determine and settle the constitutions of the
sulphonic acids, carefully prepared and purified their sulphonic
acids; they proved definitely that no meta acid was formed, and that
the products were only the ortho and para toluene sulphonic acids.

Hubner and Post (Ann. chem. (Liebig) 169,47) worked on pure para brom
toluene, and obtained two para brom toluene mono-sulphonic acids, one
of which they proved to be the ortho acid by removal of the bromine by
metallic sodium, and oxidation to salicylic acid. By exclusion they
decided that the other acid must be one containing the sulphonic acid
group in meta position to the methyl group.

F.C.G. Müller (same as Hubner and Post) made the barium salt of ortho
brom toluene sulphonic acid, and then removed the bromine by treatment
with sodium amalgam. The excess of alkali was removed by sulphuric
acid, the sodium sulphate removed by evaporation and crystallization,
and the residue dried. On treatment with phosphorus pentachloride
an oily toluene sulphonchloride was obtained; this was decomposed
by heating with water, the hydrochloric acid removed by repeated
evaporations, and the syrup thus obtained evaporated to a crystalline
condition. Several salts were made and studied. His amide melted at
90-91. Because this acid differed in properties from the two previously
mentioned, Müller considered it to be the meta toluene sulphonic acid.

About this time F. Gervor (Ann. chem. (Liebig) 169,383), made ortho
diazo toluene sulphonic acid by subjecting ortho toluidine sulphonic
acid to nitrous fumes. This was decomposed with alcohol under
pressure, and a sodium salt of the acid obtained; this was converted
into the chloride and an amide which melted at 148, differing in this
and other properties from the amides of the ortho and para toluene
sulphonic acids previously known.

In 1874 Pechmann (Ibid., 173,195) obtained a quantity of para toluidine
meta sulphonic acid by heating para toluidine with sulphuric acid,
and crystallizing out the para toluidine ortho sulphonic acid and
disulphonic acids, leaving the meta acid in solution because of its
greater solubility. The diazo compound was made by treatment of the
acid in alcoholic suspension with nitrous fumes, and decomposed with
alcohol under pressure. Various salts of the resulting sulphonic
acid were made and studied, also the chloride and amide which melted
"somewhere below 100".

In 1875 Pagel (Ann. chem. (Liebig) 176,297) working on ortho toluidine
sulphonic acid, made a toluene sulphonic acid which resembled Muller’s.
His amide melted at 104.

In 1877 Beckurts (Ber.d.che. Ges. 10, 943), seeking for a good method
of obtaining pure ortho toluene sulphonic acid, heated toluene and
sulphuric acid in the ordinary way, and made the potassium salts of the
resulting acids. By treatment with phosphorus pentachloride he obtained
the acid chlorides which he separated by cooling to -15, and filtering
off the solid para compound. The remaining liquid was transformed into
an amide and purified by fractional crystallization. Two compounds
were obtained with sharp melting points of 153 and 104. From this work
he concluded that the sulphonation of toluene yielded all the three
possible acids.

Fahlberg (Am. Chem. J. 1, 170), doubted Beckurts’ statement, because
although his acid showed different properties he neglected to prove
its constitution by converting it into the hydroxy benzoic acid. He
therefore repeated Beckurts’ work, and identified the amide melting at
154 as coming from ortho toluene sulphonic acid, by conversion into
salicylic acid. The other amide with a sharp, constant melting point
of 108 was oxidized, and the products separated and identified as para
sulphamine benzoic acid, anhydro ortho sulphamine benzoic acid, and
acid potassium ortho sulphobenzoate. These were the products one would
expect from an oxidation of a mixture of the ortho and para toluene
sulphonamides. Further proof that his acid was a mixture was obtained
by mixing amounts of pure ortho and para toluene sulphonic acids, and
by repeated crystallizations a form was obtained which melted at 108.

F.H.S. Muller (Ber. d. chem. Ges. 13, 1348), mentioned the formation of
meta toluene sulphonic acid by the action of sulphurous acid upon the
corresponding diazo compound, but gave no details except the melting
points of his amide, anilide, and toluide.

Claesson and Wallin in 1879 (Ibid. p. 1848), claimed that they had
obtained meta toluene sulphonic acid by the action of chlorsulphonic
acid upon toluene. They used very large quantities of materials. They
obtained three acids, and identified them as the ortho and para,
and called the third the meta acid, despite the fact that they had
knowledge of Fahlberg’s work.

The next step was undertaken by R. Otto (Ibid, 13, 1292), at the
request of Beckurts. He examined some of the latter’s supposed meta
toluene sulphonamide, and found it to be a mixture of the amides of the
ortho and para acids.

Nevile and Winther (Ibid. 13, 1940), while investigating the formation
of amino sulphonic acids, obtained a toluene sulphonic acid by heating
ortho diazo toluene sulphonic acid with alcohol under pressure, and
also by reducing brom toluene sulphonic acid with sodium amalgam. It
was converted into the chloride and amide,--the latter melting at
106.5-107.5.

In 1886, Valin (Ibid. 2952), convinced by the work of Otto that
Fahlberg’s views were correct, and that he and Klason had not obtained
meta toluene sulphonic acid, again attacked the problem; an acid was
made and salts described.

In 1891, Metcalf (Am. Che. J. 15,301) (Dissertation, 1892), proved
that decomposition of para diazo toluene meta sulphonic acid with
ethyl alcohol under pressure resulted in the formation of para ethoxy
meta toluene sulphonic acid in far greater quantity. Consequently the
toluene meta sulphonic acid could not have been obtained by either
Pechmann or Valin.

Griffin, (Dissertation, 1895), prepared what he thought was a solution
of the meta toluene sulphonic acid from the amide, and made and studied
several salts as well as the anilide and toluide. However he did not
investigate his solution to find out what it contained, but went ahead
on the assumption that he had a solution of this acid. It is on the
basis of his lack of investigation that I am working.

The derivatives of para toluene sulphonic acid have been made and
studied by Newell, (Dissertation, 1895), and are being investigated
further. He prepared para tolyl phenyl sulphone by the Friedal-Crafts
reaction, para phenyl sulphone benzoic acid by oxidation of the
sulphone with chromic acid, its salts, chloride, amide, and anilide,
and para benzoyl diphenyl sulphone from the acid by the Friedal-Crafts
reaction, and studied their reactions and properties.

The analogous derivatives of ortho toluene sulphonic acid were made
and studied by Canter, (Dissertation, 1900). He prepared ortho tolyl
phenyl sulphone by the Friedal-Crafts reaction, ortho phenyl sulphone
benzoic acid by oxidation of the sulphone by potassium permanganate,
its chloride, amide, and anilide, and ortho benzoyl diphenyl sulphone
from the acid by the Friedal-Crafts reaction.

The analogous derivatives of the meta toluene sulphonic acid with one
or two exceptions have not been made or studied, nor has the acid
itself been prepared in a form which could be recognized. The following
derivatives of meta toluene sulphonic acid have been made and studied;
the amide by Müller, Pechmann, Pagel, Beckurts, F.H.S. Muller, Nevile
and Winther, Chase Palmer, Klason, Valin, Noyes and Walker, Metcalf,
and Griffin; meta sulphamine benzoic acid by Limpricht and Uslar,
and Griffin; meta toluene sulphon anilide and toluide by Muller and
Wiesinger, (Ber. d. chem. Ges, 12,1348), and by Griffin; the latter
also made and studied several metallic salts.

The literature on the ortho and para toluene sulphonic acids and
their derivatives is voluminous, and covers a great many derivatives
which have been thoroughly studied and whose structure has been
determined. The literature on meta toluene sulphonic acid is very
meagre, comparatively, and all that could be found is mentioned in this
paper. This would seem to indicate that investigators have avoided
this series, and apparently the reason is due to the difficulties
encountered in isolating the free acid.



THEORETICAL DISCUSSION


The object of this paper is to prepare a solution of meta toluene
sulphonic acid, as probably obtained by Griffin, by the most promising
of the investigated methods and to find an acceptable one for isolating
the acid in the solid state. After a solution is obtained similar to
that found by Griffin, (loc. cit.), the intention is to remove as much
water as possible by distillation under diminished pressure and then
to precipitate the acid by the method of Kastle, (Amer. Chem. J., Vol.
44, page 483), namely saturate the remaining solution with gaseous
hydrochloric acid. It is hoped that in this way the solid acid may be
obtained which can then be studied.

As has been proved by previous experimenters and discussed above,
no direct method of sulphonating toluene will give any of the meta
sulphonic acid. Therefore to get a compound containing a methyl group
with a sulphonic acid group in the position meta to it some compound
with these already in that position and containing some other group
which can be replaced by hydrogen might be used, i.e. a disubstituted
toluene. The two groups which can be readily replaced by hydrogen are
the amino group and bromine, the former by the diazo reaction and
the latter by treatment with metallic sodium; the easier of the two
to prepare and replace is the amino group and this is the one made
use of in this synthesis. This replacement has been widely studied
(Amer. Chem. J., by Palmer 8, 243; Orndorff 9, 387; Graham 11, 319;
Dashiell 15, 124; Metcalf 15, 301; Parks 15, 320; Shober 15, 379;
Beeson 16, 244; and Dissertations by Weida, Cameron, and Chamberlain,
all 1894.), and the various conditions affecting it determined. The
foregoing investigators decomposed their diazo compounds with alcohols
sometimes using certain substances to cause the alkoxy or hydrogen
reactions to take place. Later investigators (Buchka, Berichte 23,
1628, St. Von Niemantowski, Ibid., 34, 3325 (1901), Ullman and Bieleck,
Ibid., 34, 2174, and Bigelow, J. Amer. Chem. Soc., Vol. 41, 1566), have
shown that this decomposition is greatly increased by the presence of
copper powder. As the first method has been more extensively studied it
was adopted in this case.

The action of methyl, ethyl, and n-propyl alcohols on diazo compounds
has been well studied by the above authors, and it has been shown that
the first two at ordinary pressures give the alkoxy reaction either
in whole or in part; n-propyl alcohol gives the hydrogen reaction
only. Also the first two give the hydrogen reaction in the presence
of zinc dust or sodium carbonate, but in these cases form salts of
the acid. On account of its rarity n-propyl alcohol was not used, but
n-butyl alcohol which is available in large quantities and in a pure
condition was employed. Recent advances in fermentation as applied
to organic chemistry have made this substance easily obtainable as
a byproduct in the production of acetone which was needed in large
amounts during the late war. Its use was found to be successful; it
boils at 117 and so can be easily distilled off after decomposition has
been effected without a great increase in temperature above the boiling
point of water, which increase Griffin (loc. cit.) showed to cause
carbonization. For this reason i-amyl alcohol although available was
not considered,--also higher alcohols because of this fact and because
of their rarity.

Of the four amino toluene sulphonic acids theoretically possible in
which the sulphonic acid group is in the meta position in reference to
the methyl group only two are commonly known, No. 1, and No. 2.


            CH_{3}          CH_{3}           CH_{3}            CH_{3}
            / \              / \              / \               / \
           /   \            /   \            /   \             /   \
          /     \NH_{2}    /     \          /     \NH_{2}     /     \
         |       |        |       |        |       |         |       |
         |       |        |       |        |       |         |       |
  HSO_{3} \     /          \     / HSO_{3}  \     /    NH_{2} \     / HSO_{3}
           \   /            \   /            \   /             \   /
            \ /              \ /              \ /               \ /
                            NH_{2}

Methods of preparing No. 1 and No. 2 were found but without details, so
a method had to be worked out to obtain them easily and in good yield.
After a little experimenting No. 1, or ortho toluidine sulphonic acid
was readily obtained in good yield and in a fairly pure condition. No.
2, or para toluidine meta sulphonic acid was obtained in only a ten per
cent yield and by means of a much more difficult method of procedure.
The preparation of this acid was undertaken first and consumed a long
time; Griffin did his work starting with this acid and I hoped to get
as far as he did earlier. It was then available in the market as was
the ortho toluidine sulphonic acid, but now neither are available.

The methods employed by earlier investigators when they wished to
isolate their diazo compounds was to suspend the substance to be
diazotized in alcohol, and then pass in nitrous fumes generated by
dropping concentrated nitric acid onto arsenious oxide. The diazo
compound from ortho toluidine sulphonic acid is so nearly insoluble in
water that it was found possible to diazotize it in water suspension,
and generate the nitrous fumes in the solution itself by adding
a solution of sodium nitrite to the water suspension containing
hydrochloric acid. After a short time the diazo compound separates
out and can be filtered off, washed and dried. It is a very stable
substance as compared with other diazo compounds. This method was
worked out, there being no mention of it in the literature.



SULPHONATION OF ORTHO TOLUIDINE


Of the possible sulphonic acids of ortho toluidine the commercial
product of former days was the one in which the sulphonic acid group
was in the para position to the amino group, and meta to the methyl
group; thus this acid could find use in preparing the toluene meta
sulphonic acid if a method of replacing the amino group by hydrogen
could be found. This acid is not now on the market in America because
of its limited use in dyestuffs. It is mentioned in Schultz and Julius,
(“Farbestoff Tabellen”, 1894 Edition, Trans. by F. C. Green), Cain,
(“The Manufacture of Intermediate Products for Dyes”) and Nevile and
Winther, (Ber. d. chem. Ges. 13, 1940.), which latter give a method of
preparation which was used industrially,--the baking of ortho toluidine
sulphate. Their description is rather indefinite but after a few
preliminary trials a suitable method was found. I will describe all the
experiments attempted, and include the one finally adopted. The ortho
toluidine used was (“Practical.”) obtained from Eastman Kodak Co.


Experiment 1.

Ortho toluidine was suspended in water and conc. sulphuric acid added
with vigorous stirring until all the amine had dissolved. The solution
was heated to boiling until the sulphate had dissolved, and then cooled
and the crystals thus obtained filtered off and dried. This was then
powdered and ground with some powdered oxalic acid. These mixtures with
and without oxalic acid were then baked until a sample was completely
soluble in sodium hydroxide. The mass had become a deep grayish
purple. It dissolved in water to give a deep red solution. Nothing
satisfactory was obtained from any of these bakes, the formation of a
red dyestuff as mentioned by Nevile and Winther seeming to be formed in
a great quantity and very easily. Hence this method was discarded.


Experiment 2.

In this case an excess of sulphuric acid was used. After the oxalic
acid had all been decomposed or driven off the mass turned black and
became very pitchy. Nothing could be done with it so it was thrown away.


Experiment 3.

In this case an excess of ortho toluidine was used. The red dyestuff
was formed in great amount and very easily. The temperature was kept
below 195 to lose none of the toluidine which boiled at 199.


Experiment 4.

This method gave the best results and is the one employed in the
preparation of all the material used in the thesis. Equal weights of
ortho toluidine and sulphuric acid (100gms. of each were used; 100gms.
of ortho toluidine is 108cc., and 100gms. of sulphuric acid (s. g.
1.84) are 56cc.), were mixed and baked at 190-195 until a sample would
dissolve in ten per cent sodium hydroxide solution to give a clear
solution; this took one and a half hours. The mixture at first melts
in the solution of the sulphate and sulphuric acid formed by the heat
of combination; as heating is continued it gradually becomes solid and
finally very hard; it has become gray in color. When it is perfectly
dry a test is made to see if it dissolves in sodium hydroxide giving a
clear solution. If so, sulphonation is complete. By using an oven with
a glass door the reaction mixture can be watched and the completion of
the baking observed. However the test for complete solubility should
always be made. The addition of powdered oxalic acid to the reaction
mixture did not seem to be of advantage, because no visible reaction
commenced until this had been driven off or decomposed. It is usually
added in producing sulphonic acids by baking the sulphates of the
amines to increase the porosity of the mass and thus facilitate removal
of the product. However here the only effect seemed to be to retard
the reaction, as the product was the sane hard grayish mass as without
the acid, and it was just as difficult to dig it out. It took an hour
longer to complete the reaction with the addition of the oxalic acid.

The best results were obtained when the temperature of the oven was
kept at 193, although five degrees variation did not appreciably affect
the product. A lower temperature gives little or no action, while a
higher one drives off the ortho toluidine and also seems to favor the
formation of the red dyestuff.

As stated above, complete sulphonation is shown by the solubility of
the acid in ten per cent sodium hydroxide solution. If any unchanged
amine is present as sulphate the solution will become milky due to
liberation of the insoluble amine. On boiling a solution of the acid a
slight hydrolysis takes place so that the smell of ortho toluidine is
present, yet the solution is always perfectly clear.

The product or “bake” appears as a hard grayish mass, slightly porous.
It is dug out, pulverized, boiled up in a large evaporating dish,
containing water and a little (10cc.) hydrochloric acid, with animal
charcoal and filtered. The solution should be almost colorless. The
effect of the slight amount of hydrochloric acid was accidental; the
first solutions were always a deep red color due to some of the red
dyestuff seeming to be present, and the longer the solution was boiled
the redder it got. A little acid seems to prevent this entirely. The
solution is evaporated on a water bath until a scum has formed on the
surface when it is allowed to cool and crystallize. It crystallizes in
small almost white needles, which appear to fill the entire liquid;
this is deceptive as on filtering the bulk is considerably reduced.
They fall to a powder when they are dry. If they are colored red or
pink they are washed while still on the filter with water; alcohol does
not remove this color.

The acid as formed has no melting point, but chars and decomposes on
heating. A sample was tested for nitrogen and sulphur with very good
positive results. On fusion with caustic soda and acidification of the
product a positive reaction was obtained on the addition of bromine
water as is customary with phenols.

It was identified as identical with the acid of Nevile and Winther
(loc. cit.) by conversion thru the diazo compound into dinitro ortho
cresol, melting at 85.8 as described under the description of the diazo
compound.



SULPHONATION OF PARA TOLUIDINE


Metcalf, (loc. cit.), gives a method for the preparation of the
sulphonic acids of para toluidine, and states that both the possible
acids are formed, with the meta position (referred to the methyl
group) in good yield. Schultz and Julius, (“Farbestoff Tabellen”,
1894 Edition, Trans, by F. C. Green), and Nevile and Winther, (loc.
cit.), say that the sulphonation of para toluidine gives a mixture of
the sulphonic acids, with the ortho (referred to the methyl group)
sulphonic acid in a much greater yield. As the sulphonation of para
nitro toluene gives (Dissertation, R. S. Norris, BPL. 5976.109) a
ninety-five per cent yield of the ortho sulphonic acid, it would seem
as though the amino compound should give a large yield of the acid
(sulphonic acid group ortho to the methyl group,) and such was found to
be the case.

I followed Metcalf’s directions as follows: in an apparatus fitted with
an automatic stirrer and a thermometer I placed 200 grams (110cc.) of
twenty per cent fuming sulphuric acid. I then slowly added with rapid
stirring 100grams of powdered para toluidine which was obtained from
the Newport Chemical Works. The addition took thirteen minutes. The
initial temperature of the solution was 18°C. The maximum was obtained
when about half the toluidine had been added and was 148°C. The final
temperature was 130°C. After addition was complete I stirred for five
minutes, and then slowly heated the mixture to 180°C. and kept it
there for an hour. Sulphonation was then complete. I then poured it
into an equal volume of cold water (220cc.) in an evaporating dish and
allowed it to stand over night. The next day the dish seemed filled
with grayish crystals; these were filtered off. The solution was
allowed to stand for four weeks with no results. (Metcalf says that the
disulphonic acid separated in three weeks from his solution.)

I dissolved the crude acid obtained as above in ten liters of water
(Metcalf’s directions) and precipitated the excess of sulphuric acid
with barium hydroxide, and then filtered the solution. It was a clear
brownish color. I then evaporated to 100cc. A smell of para toluidine
was always present in the vapor indicating a probable hydrolysis of the
acid. (Nevile and Winther (loc. cit.) say that this sulphonic acid can
be hydrolyzed by heating with water), A test after sulphonation and
before evaporation showed a sample to be completely soluble in water,
and no cloudiness was produced when a sample was dissolved in sodium
hydroxide, as is the case if a solution of para toluidine sulphate is
dissolved in the same reagent. When the volume had reached 100cc. a
light brown crust had formed on top of the liquid and on cooling and
filtering two products were obtained; a light brown powdery substance
in larger amount (47.5 grams.), and a small amount of hard square brown
crystals. On evaporating the filtrate nearly to dryness more material
separated which did not look like either of the above substances; it
weighed twenty grams. This has not been investigated as yet.

As the brownish powdery substance was mixed with the flat crystals
produced above, a method had to be found to separate them and purify
each. I screened them as much as possible with good results. I
removed the last of the fine powder by dissolving it off with hot
water. Metcalf said that they could be separated by their difference
in specific gravity in fifty per cent alcohol but this method was
unsuccessful. I boiled up the aqueous solution of the powdery substance
with animal charcoal, filtered and evaporated to crystallization.
Square, flat, white crystals were obtained identical in all but color
with those mentioned above. They are soluble with difficulty in cold
water, readily in hot, and insoluble in alcohol. In these properties
and in appearance they compare to the ortho sulphonic acid of para
toluidine as made and described by Parks, (Dissertation, 1892).
Metcalf and Nevile and Winther say that the meta sulphonic acid of
para toluidine forms needles, but I obtained nothing that could in any
way be called needles. This sulphonic acid had no melting point, but
charred and decomposed. A test for elements showed nitrogen and sulphur
to be present. The aqueous solution had a strong acid reaction to
litmus.

In order to see if this might be the desired acid I tried to prepare
an acid chloride with phosphorus pentachloride in the usual way, and
then intended to convert it into the amide and get a melting point
for identification. I used equal weights of the acid and phosphorus
pentachloride. I ground them together at ordinary temperature in
a mortar: no result. I heated it on a water bath: no result. I
heated it on a gauze over a flame: no result except decomposition and
carbonization. However I poured water into the mixture and decomposed
the excess of phosphorus pentachloride, and filtered. A gummy brownish
mass remained which was insoluble in all reagents tried, (methyl
and ethyl alcohol, benzine, petroleum ether, (40-60), water, carbon
tetrachloride, dilute hydrochloric acid, acetone, and acetic acid.)
Ethyl ether extracted a very small amount, just enough to color it
yellow, and leave a yellow color on porcelain on evaporation, but
not enough to make a study of the properties. On shaking up with
concentrated ammonia the mass became very finely divided, but no
solution appeared to take place; on filtering and evaporating to
dryness there was no residue.

The material mentioned above as being the final product from the
sulphonation of para toluidine, obtained in a yield of twenty grams or
ten per cent yield and then uninvestigated, has since been identified
as the acid I was looking for, or para toluidine meta sulphonic acid. A
small amount was cooled and diazotized in the usual manner; the diazo
compound seemed to be insoluble in the amount of water used, for a
white crystalline needle-like precipitate appeared. This was decomposed
by boiling with dilute nitric acid (Nevile and Winther, loc. cit.),
and on cooling small tufts of yellow needles separated. These were
filtered off and dried, then recrystallized from alcohol. The best
portions of these were then recrystallized from ether and the melting
point determined. They melted at 79.5-79.8 (uncorr.). Nevile and
Winther gave 79-80, showing that they did not purify their compound.
The product is dinitro para cresol, or 3-nitro, 4-hydroxy, 5-nitro
toluene.



DIAZOTIZATION OF ORTHO TOLUIDINE SULPHONIC ACID.


Nevile and Winther (loc. cit.), stated that they obtained a diazo
compound from their ortho toluidine sulphonic acid and described a few
properties, but gave no details of manipulation, so I made several
trials to determine the best acceptable method.


Experiment 1.

I suspended some ortho toluidine sulphonic acid in denatured alcohol,
and passed in a rapid current of nitrous fumes, generated by dropping
concentrated nitric acid into a saturated solution of sodium nitrite,
for fifteen minutes. The suspension became slightly warm, and rather
pasty at the end. I allowed it to stand a half hour, and at the end of
that time it had become very thick and pasty. I then filtered it off by
suction, washed with ether, and dried.


Experiment 2.

The procedure used was the same as above using ethyl alcohol in place
of denatured alcohol, but for some reason no diazotization appeared to
take place. The acid was filtered off and used again.


Experiment 3.

A saturated water solution of the acid was made by boiling some of
it up with water, cooling and filtering. No precipitate appeared on
passing in nitrous fumes.


Experiment 4.

Some of the acid was dissolved in sodium carbonate solution, sodium
nitrite solution added, and after cooling, concentrated hydrochloric
acid added drop by drop. Nitrous fumes were given off, but no
precipitate appeared.


Experiment 5.

This seems to be the best method and the one employed hereafter in the
preparation of all the material subsequently used. The solid ortho
toluidine sulphonic acid is suspended in concentrated hydrochloric
acid and vigorously stirred. The solution becomes warm and the
crystals change in appearance, probably due to the formation of the
hydrochloride. The mass is then cooled to 5°, and sodium nitrite
solution added slowly with stirring. Immediate reaction takes place,
and the mass becomes very pasty as in the first experiment. After
obtaining a reaction with starch iodide paper the mixture was allowed
to stand a half hour, then filtered by suction, washed with ether and
dried. In appearance it was identical with the diazo compound obtained
in experiment 1, and can be kept in the same way.

That it was a diazo compound was shown as follows: It was spotted on
a piece of filter paper with an alkaline solution of H acid--a red
coloration indicates the formation of a red azo dyestuff.

Some of the diazo compound was boiled with dilute nitric acid as
described by Nevile and Winther, and a yellowish precipitate of needles
obtained, which on recrystallization from denatured alcohol gave
light yellow needles of dinitro ortho cresol, (3-hydroxy 3,5-dinitro
toluene), melting at 83.5-84° uncorr. (Nevile and Winther gave 85°
for the pure substance.) This dinitro compound was obtained in nearly
quantitative yield indicating that the diazo compound was presumably
pure.



PHYSICAL PROPERTIES OF THE DIAZO COMPOUND


It is almost insoluble in water, and is insoluble in denatured alcohol
and ether.

It is a white solid which can be dried and kept without apparent
decomposition; it gradually turns pink when exposed to the light
for several days, so is kept in a brown bottle if not required for
immediate use. It does not explode when struck with a hammer, but
deflagrates violently if a flame is brought near or if heated on
porcelain.



DECOMPOSITION OF THE DIAZO COMPOUND


(1) With n-Butyl alcohol in the presence of sodium carbonate.

A portion of the dry diazo compound was placed in a flask connected
with a reflux condenser, and solid sodium carbonate and n-butyl
alcohol added. No reaction took place at ordinary temperature so heat
was applied. Decomposition started at 65° and evolution of hydrogen
proceeded evenly and smoothly until all the diazo compound had
disappeared. The alcohol, at first colorless, became an orange and
finally a brown color. The solution was then refluxed an hour to ensure
complete decomposition of the diazo compound. The smell of an aldehyde
was evident indicating that the hydrogen reaction was taking place; the
solution was tested with Schiff’s reagent and with ammoniacal silver
nitrate with distinct positive results in both cases, showing aldehyde
was present. The alcoholic solution was filtered from the sodium
carbonate remaining, and the alcohol distilled off on an oil bath. A
yellowish-orange porous solid was left in such a small amount that
no derivatives could be made and studied. It was free from the diazo
compound, shown by its giving no color with an alkaline solution of H
acid.


(2) With n-Butyl Alcohol alone.

The previous experiment showed that n-butyl alcohol would decompose
the diazo compound in the presence of sodium carbonate and replace
the amino group by hydrogen, so this time a decomposition with the
alcohol alone was tried. Decomposition took place evenly and smoothly
as before at the same temperature, and the solution became a clear
brownish-orange. Aldehyde was given off and tested for as before with
positive results. The alcohol was removed by distillation and a thick
brownish syrupy liquid was left. This was easily soluble in water,
so was dissolved, filtered, and the solution used in the following
experiments. At this point it is similar in every way to the solution
obtained by Griffin (loc. cit.) from the diazo compound of para
toluidine meta sulphonic acid.

Subsequent preparations of this syrup were made in the above way with
similar results in every case. The only precaution to be observed is
that no part of the flask containing the reaction mixture be allowed
to become too hot as the diazo compound is then decomposed violently
leaving a grayish ash.



A STUDY OF THE SOLUTION OBTAINED BY THE DECOMPOSITION OF THE DIAZO
COMPOUND


The syrup which remained after distilling off the n-butyl alcohol was
a thick brown viscous fluid in all cases. It has an acid reaction and
is completely soluble in water. On testing it showed the presence of
sulphur in quantity and the absence of nitrogen. Some was dissolved in
water, filtered, and evaporated on the water bath. After its volume had
been considerably reduced it turned a very dark brown, then blackish,
and smelled very tarry. It did not crystallize at all, finally becoming
very black. To a drop on a watch glass, a drop and then an excess of
concentrated hydrochloric acid was added but with no apparent result.

Another portion of the syrup was dissolved in water, boiled with
purified animal charcoal, and filtered. The filtrate was colorless.
It was then evaporated on the water bath and solidified completely.
Some of this solid was ignited and a white ash was left; had it been a
sulphonic acid there would have been no residue. A qualitative analysis
of the ash was made and much phosphate and calcium found present;
therefore this solid was presumed to be a mixture of calcium phosphate
from the animal charcoal and perhaps the calcium salt of the sulphonic
acid. This showed that animal charcoal could not be used for purposes
of purification.

“Activated charcoal” has been advocated for decolorizing solutions as
well as for absorbing toxic gases; the author had become acquainted
with this material while in the Chemical Warfare Service, and had
obtained small samples of “Dorsite” and “Carbonite”. Some of this was
powdered and the brown solution boiled with it until most of the color
was removed. The solution was then filtered and evaporated on the
water bath; a white crystalline solid was again left. Investigation of
the activated charcoal showed that concentrated acids extracted some
substance which was thrown down in a flocculent white precipitate on
making alkaline with ammonia. Therefore another sample of the activated
charcoal was boiled with concentrated nitric acid, filtered, and the
charcoal washed free from acid; this sample did not decolorize well.

A sample of a specially prepared charcoal for decolorizing purposes
manufactured by the Barneby-Cheney Co. was obtained and tried, but was
unsuccessful; the color was not removed.

Infusorial earth, kiesel guhr, and “Sil-o-cel” were also tried
unsuccessfully; Fullers Earth made a very clear solution but no color
was removed.

Some of the brown viscous solution was dissolved in water, the solution
filtered and evaporated to a constant volume (estimated when no more
vapor could be seen to condense) under diminished pressure (water
pump) until it became more brown. It was then allowed to cool, and
dry hydrochloric acid gas passed in, first to expel all air or other
vapor present, and then under pressure. The solution became slightly
warm. A few fine crystals formed on the interior surface of the flask
where some of the solution had spattered during distillation, which
however were quite indistinct and seemed to be in the center of a drop
of water or solution. On allowing the flask to stand over night the
whole of the solution seemed to be filled with crystals. They were too
indistinct to enable their crystalline form to be determined so an
attempt was made to remove some for examination. As soon as they came
into contact with the air they disappeared and left a very viscous
solution, indicating that they are very hygroscopic. A small amount was
removed and placed in a dish in a vacuum desiccator which was evacuated
and left for a month, with periodical examinations. No solid appeared
at any time.

This is as far as the investigation has been carried at the present
time, April twenty-fifth, but its study is being continued.



CONCLUSION


The results of this investigation may be briefly summarized as follows:

    (1) Ortho toluidine may be easily converted into its sulphonic acid
    in which the sulphonic acid group is in the position meta to the
    methyl group.

    (2) Para toluidine is converted into a mixture of two isomeric
    sulphonic acids of which the one with the sulphonic acid group in
    the position meta to the methyl group is obtained in a ten per cent
    yield.

    (3) Ortho toluidine sulphonic acid may be easily diazotized using
    sodium nitrite and concentrated hydrochloric acid.

    (4) The diazo compound is very stable.

    (5) The diazo compound is easily decomposed with n-butyl alcohol,
    the hydrogen reaction taking place.



BIBLIOGRAPHY


In addition to the references made in the thesis itself the following
authorities have been consulted for the theoretical discussion:

Beilstein, F. C., “Handbuch der organischen Chemie” 1886-1890. Voss,
Hamburg.

Victor von Richter, “Organic Chemistry” Trans. 1899-1900. P.
Blakiston’s, Philadelphia, Pa. B.P.L. 3974.160

Meyer and Jacobson, “Lehrbuch der organischen Chemie” 1893. Veit & Co.,
Leipzig. B.P.L. 3973.143


[Transcriber’s Note:

Table of contents added by transcriber.

Obvious printer errors corrected silently.

Inconsistent spelling and hyphenation are as in the original.]





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