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Organic Syntheses

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[1] Jahresb. 1863, 415; Ber. 10, 1934, 2005 (1877); 16, 687
(1883); 19, 1468 (1886); 20, 2283 (1887); 31, 1524 (1898); Ann.
200, 240 (1880); 215, 127 (1882).

[2] Ann. 27, 268 (1838).

[3] Ann. 51, 152 (1844) j Am. Chem. J. 14, 555 (1892).

[4] Jahresb. 1863, 415.

5 Jahresb. 1863, 422.

6 Ann. 159, 7 (1871); Ber. 8, 760 (1875).

[7] Ber. 8, 760 (1875).

[8] Ann. 107, 233 (1858).

[9] Ber. 10, 1934 (1877); 34, 1285 (1901).

[10] Ann. 89, 247 (1854); Ber. 34, 1162 (1901).

[11] Ber. 30, 1870 (1897).

[1b] Ber. 31, 1458 (1898); Am. Chem. J. 26, 20 (1901).

[2b] Ann. chim. phys. (5) 22, 270 (1881).

[3b] Ber. 18, 2915 (1885); 21, 889 (1888).

[4b] D. R. P. 109,012; Frdl. 5, 664 (1900); D. R. P. 117,129; Frdl.
6, 112 (1901); J. Soc. Dyers and Colourists, 36, 138 (1920).

[5b] D. R P. 117,129; Frdl. 6, 112 (1901).

[6b] D. R. P. 117,251; Frdl. 6, 109 (1901); U. S. Pat.
1,322,580 (1919); C. A. 14, 287 (1920); Rev. produits chim.
21, 219 (1918); 21, 288 (1918).

[7b] U. S. Pat. 1,318,631 (1919); C. A. 14, 70 (1920).



XXIII

SODIUM _p_-TOLUENESULFINATE

2CH3C6H4SO2Cl + 3Zn--> (CH3C6H4SO2)2Zn + ZnCl2 (CH3C6H4SO2)2Zn +
Na2CO3--> 2CH3C6H4SO2Na + ZnCO3

Prepared by FRANK C. WHITMORE and FRANCIS H. HAMILTON Checked
by J. B. CONANT and PAUL ALLEN, JR.


1. Procedure

FIVE HUNDRED grams of technical _p_-toluenesulfonyl chloride are ground
in a mortar to break up all lumps. Three liters of water are placed
in a 12-l. crock provided with a large brass stirrer and a tube
for passing steam directly into the liquid. Dry steam is passed
into the water until the temperature reaches 70'0. The steam is then
shut off and 400 g. of zinc dust (90 to 100 per cent pure) is added.
The sulfonyl chloride is then added in small portions by means
of a porcelain spoon. The addition takes about ten minutes.
The temperature rises to about 80'0. Stirring is continued
for ten minutes after the last of the chloride has been added.
Steam is then passed into the mixture until the temperature
reaches 90'0. If it is heated any hotter, bumping takes place.
The steam is shut off, and 250 cc. of 12 _N_. sodium hydroxide
solution is added. Finely powdered sodium carbonate is then
added in 50-g. portions until the mixture is strongly alkaline.
The mixture froths considerably, but this causes no trouble unless
too small a crock is used. The stirrer is loosened and the crock
is removed. The mixture is filtered by suction in a large funnel.
The filtrate has a volume of about 4.5 l. The cake of unchanged
zinc dust and zinc compounds is transferred to a 3-l. battery jar
and placed under the stirrer, and the latter is clamped in place.
Water (750 cc.) is added, the stirrer is started, and steam
is passed in until the mixture starts to froth too violently.
The steam is then shut off, but the stirring is continued
for ten minutes. The mixture is filtered and the filtrate
is added to the main solution in a large evaporating dish.
The liquid is evaporated over a large burner to a volume of about
1 l., or until a considerable crust forms around the edges.
The mixture is then cooled. Large, flat, transparent crystals separate.
The thoroughly cooled mixture is filtered by suction,
and the crystals are air-dried until efflorescence just starts.
They are then bottled. The product is CH3C6H4SO2Na<.>2H2O. Yield 360 g.
(64 per cent of the theoretical amount). Careful acidification
of the mother liquor with dilute hydrochloric acid yields 15 g.
of the free sulfinic acid.


2. Notes

The free sulfinic acid may be prepared by dissolving the sodium salt in
cold water and carefully acidifying the solution with hydrochloric acid.
An excess of the latter must be avoided, as it dissolves the acid
to a certain extent. The sulfinic acid is difficult to dry without
partial conversion into the sulfonic acid.


3. Other Methods of Preparation

Toluenesulfinic acid and its salts have been prepared by three
general methods: (1) The reduction of the sulfonyl chloride.
The reagents which have been used for this are sodium amalgam,[1] zinc
dust in alcohol or water,[2] sodium sulfite,[3] sodium sulfide,[4]
potassium hydrosulfide[5] (the thio acid being first formed)
and sodium arsenite.[6] (2) From toluene by the Friedel and
Crafts reaction, using either sulfur dioxide and hydrogen chloride[7]
or sulfuryl chloride.[8] (3) From _p_-toluidine by diazotization
and subsequent treatment with sulfur dioxide and finely divided
copper.[1b] The compound has also been obtained in certain
reactions which, however, would not be suitable for preparative work;
thus it is formed by hydrolysis and reduction of certain thio
derivatives[2b] prepared from the acid itself and also by the
decomposition of ditolylsulfonmethylamine.[3b]


[1] Ann. 142, 93 (1867).

[2] Ber. 9, 1586 (1876).

[3] Ber. 3, 965 (1870).

[4] D. R. P. 224,019; Chem. Zentr. 1910, (II), 513.

[5] Ber. 42, 3821 (1909).

[6] Ber. 41, 3351 (1908); Ber. 42, 480 (1909).

[7] Ber. 41, 3318 (1908); J. Chem. Soc. 93, 754 (1908).

[8] Rec. trav. chim. (2) 30, 381 (1911).

[1b] Ber. 32, 1141 (1899); J. Chem. Soc. 95, 344 (1909).

[2b] Ber. 15, 130 (1882); 20, 2088 (1887); 41, 3351 (1908).

[3b] J. prakt. Chem. (2) 63, 170 (1901).



XXIV

1,3,5-TRINITROBENZENE

C6H2(NO2)3CO2H--> C6H3(NO2)3 + CO2

Prepared by H. T. CLARKE and W. W. HARTMAN. Checked by J. B. CONANT
and J. J. TOOHY.

1. Procedure

THE crude trinitrobenzoic acid obtained by oxidation of 360 g.
of trinitrotoluene (prep. XXV, p. 95) is mixed with 2 l.
of water at 35'0 in a 5-l. flask provided with a stirrer.
Fifteen per cent sodium hydroxide solution is added,
with continuous stirring, until a FAINT red color is just produced.
(See Notes.) The color is then immediately discharged by means
of one or two drops of acetic acid, and the liquid is filtered
from unchanged trinibrotoluene. The filtrate is transferred
to a 5-l. flask, and 70 cc. of glacial acetic acid are added.
The mixture is then gently heated, with continuous stirring,
when trinitrobenzene separates in crystalline condition,
and floats on the surface of the liquid as a frothy layer.
After about one and a half hours the evolution of gas ceases;
at this point the crystals begin to stir into the solution.
The heating and stirring is continued for three-quarters of an hour,
when the mixture is allowed to cool, and the crystals filtered off.
A sample of the filtrate should be tested for undecomposed
trinitrobenzoic acid: if a precipitate is produced by
the addition of sulfuric acid the process must be continued.
After recrystallization from glacial acetic acid, the product
melts at 121-122'0. The yield is 145-155 g. (43 to 46 per cent
of the theoretical amount calculated from the trinitrotoluene). 2.
Notes

During the solution of the trinitrobenzoic acid, the temperature should
not be below 35'0, owing to the slight solubility of trinitrobenzoic
acid in cold water. The heat of neutralization raises the temperature
to 45-55'0, but the latter temperature should not be exceeded,
since any trinitrobenzene formed at this point would later be removed
with the unreacted trinitrotoluene.

Care must be taken that no more alkali is added than is just sufficient
to produce the faint red color. If an excess of alkali is added it
produces a permanent color, which is not removed by acid and colors
the final product.

When once the evolution of carbon dioxide sets in, the flame must
be cut down so as to avoid the formation of a thick layer of froth
which might foam over.


3. Other Methods of Preparation

1,3,5-Trinitrobenzene can be prepared by heating _m_-dinitrobenzene
with nitric acid and sulfuric acid to 120'0;[1] by heating
2,4,6-trinitrotoluene with fuming nitric acid in a sealed tube
at 180'0 for three hours;[2] by heating 2,4,6-trinitrobenzoic acid
or its sodium salt with water, alcohol, dilute sodium carbonate
or other suitable solvent.[3]


[1] Ber. 9, 402 (1876); Ann. 215, 344 (1882).

[2] Ber. 16, 1596 (1883).

[3] D. R. P. 77,353; Frdl. 4, 34 (1894).



XXV

2, 4, 6-TRINITROBENZOIC ACID

C6H2(NO2)3CH3 + 3O(Na2Cr2O7 + H2SO4)--> C6H2(NO2)3CO2H + H2O

Prepared by H. T. CLARKE and W. W. HARTMAN. Checked by J. B. CONANT
and J. J. TOOHY.

1. Procedure

To 3600 g. of concentrated sulfuric acid, in a 5-l. flask placed
in an empty water bath, are added 360 g. of technical trinitrotoluene,
while the mixture is stirred mechanically. Sodium dichromate
(Na2Cr2O7 2H2O) is now added in small quantities (PRECAUTION: see Notes),
with constant stirring, until the temperature of the mixture reaches 40'0;
the empty water bath is now filled with cold water and the addition
of sodium dichromate continued at such a rate that the temperature
remains at 45-55'0. In all 540 g. of sodium dichromate are added,
the addition taking one to two hours. When all has been added,
the mixture, which has now become very thick, is stirred for two
hours at 45-55'0, and poured into a crock containing 4 kg.
of crushed ice. The insoluble trinitrobenzoic acid is filtered off,
and carefully washed with cold water until free from chromium salts.
On drying it weighs 320-340 g.

The product is now mixed with 2 l. of distilled water at 35'0
in a 5-l. flask provided with a stirrer, and 15 per cent sodium
hydroxide solution is dropped in with continuous stirring until
a FAINT red color is just produced. Should this disappear,
it is restored by the addition of a few drops more. When it has
persisted for five minutes, the color is discharged by the addition
of a few drops of acetic acid, and the insoluble unattacked
trinitrotoluene filtered off and washed with a little water.
The trinitrobenzoic acid is precipitated from the filtrate
by the addition of a slight excess of 50 per cent sulfuric acid.
The solution is chilled, and the acid filtered and washed free
from salts with ice water. When dried in air it weighs 230-280 g.
(57 to 69 per cent of the theoretical amount).

2. Notes

The mother liquors and washings lose carbon dioxide on boiling,
and the insoluble trinitrobenzene separates see preparation XXIV);
after filtering, washing, and drying, it weighs 15-20 g.
(4 to 6 per cent of the theoretical amount).

It is essential that the stirring should be most efficient,
so that when the mixture becomes thick the dichromate will be evenly
distributed throughout the liquid, as rapidly as it is added.
If the stirring is not efficient, local reactions of extreme violence
(in certain cases leading to conflagration) will occur.
An iron stirrer may be employed in the oxidation reaction,
but not in the purification.

Technical sodium dichromate generally contains a certain amount
of chlorides, and the chlorine liberated from these tends
to cause a troublesome foam towards the end, of the reaction.
Only a very efficient stirrer, which draws down the surface of the liquid,
is able to combat this difficulty. The amount of solid sodium
dichromate given is for the dry crystalline compound containing
two molecules of water of crystallization.

Great care should be taken in dissolving the crude acid in the alkali.
If an excess of alkali persists for any length of time, a permanent
color is produced which will discolor the final product.
The acid is fairly soluble in cold water and should be washed with care.


3. Other Methods of Preparation

2,4,6-Trinitrobenzoic acid has been prepared by heating trinitrotoluene
with fuming acid in a sealed tube to 100'0, for two weeks,[1a]
the oxidation being only partial. It can also be prepared by heating
trinitrotoluene under a reflux condenser, with a mixture of 5 parts
of concentrated nitric acid and 10 parts of concentrated sulfuric
acid;[1] this method is, however, unsuitable in the laboratory
owing to the difficulty of devising suitable apparatus.
Another method is to dissolve trinitrotoluene in nitric acid and,
to this solution (at 95'0), to add potassium chlorate at such a rate
that the temperature does not fall;[2] this method has been found
to be difficult to control on a laboratory scale.


[1a] Ber. 3, 223 (1870)

[1] D. R. P. 77,559; Frdl. 4, 34 (1894)

[2] D. R. P. 226,225; Frdl. 10, 167 (1910).


The method described above is a modification of a patented process,[3]
in which trinitrotoluene suspended in sulfuric acid is treated
with chromic anhydride.

[3] D. R. P. 127,325; Frdl. 6, 148 (1901).



INDEX

A

Acetic acid, 18, 33, 64 Acetone, 41 Acetophenone, 1 Ammonium carbonate,
75 Ammonium hydroxide, 37, 75 Aniline, 71, 79 Anthranilic acid, 47

B

Benzalacetophenone, 1 Benzaldehyde, 1, 5 Benzoic acid, 5 Benzyl alcohol,
5 Benzyl benzoate, 6 Benzyl chloride 9 Benzyl cyanide, 9-11, 27,
57, 63 Bromostyrene, 67

C

Carbon tetrachloride, 23 Chlorine, 37 Copper sulfate, 38

D

Dibenzyl ether, 6 a, g-Dichloroacetone, 13-15 Dimethylaminobenzaldehyde,
17-21 Dimethylaniline, 17, 47

E

Ethyl alcohol, 23, 27 Ethyl oxalate, 23-26 Ethyl phenylacetate, 27-28

F

Ferrous sulfate, 79 Formaldehyde, 17

G

Gelatine solution, 37 Glycerol, 29, 33, 79 Glycerol a,
g-dichlorohydrin, 29-31 Glycerol a-monochlorohydrin, 33-35

H

Hydrazine sulfate, 37 40 Hydrochloric acid, 17, 30, 34, 47,
71 Hydroquinone, 85

M

Mesitylene, 41-45 Methyl red, 47-61

N

Naphthol, 61 Nitric acid, 57 Nitrobenzene, 79 _p_-Nitrobenzoic acid,
63-66 _p_-Nitrobenzyl cyanide, 67-58, 59 _p_-Nitrophenylacetic acid,
6940 Nitrosodimethylaniline hydrochloride, 17 Nitroso-,3-naphthol,
61-62 Nitrotoluene, 53

O

Oxalic acid, 23

P

Phenylacetic acid, 10, 63-65 Phenylacetylene, 67-69 Phenylhydrazine,
71-74 Phthalic anhydride, 75 Phthalimide, 7~78 Potassium hydroxide, 67

Q Quinoline, 79 83 Quinone, 86 88 S

Sodium acetate, 48 Sodium benzylate, 6 Sodium cyanide, 9 Sodium dichromate,
13, 53, 85, 95 Sodium hydroxide, 1, 37, 61, 93 Sodium hypochlorite,
37 Sodium, metallic, 5, 42

Sodium nitrite, 17, 47, 61, 71, 80 Sodium sulfite, 71 Sodium
_p_-toluene sulfinate,--91 Sulfur dioxide, 71 Sulfuric acid,
13, 27, 30. 34, 37, 41, 43, 53, 57, 59, 63, 79, 85, 95

T Toluene, 48 Toluenesulfonyl chloride, 89 I, 3, s-Trinitrobenzene, 93--
94, 96 2, 4, 6-Trinitrobenzoic acid, 93, 96 97 2, 4, 6-Trinitrotoluene, 93,
95 Zinc dust, 89

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