Dec. 28, 1937. H. B.

ALEXANDER 2,103,926
METHOD OF PRODUCING DIAZODINITROPHENOL AND PRODUCT THEREOF
Filled Aug. 8, 1936

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 Patented Dec. 28, 1937 2,103,926

2,103,926
METHOD OF PRODUCING DIAZODINITRo
r PHENOL AND PRODUCT THEREOF
Harvey B. ander, Kingston, N.Y., assignor
...Y

to Hercule
- -- --- - - - - - -- - - - - - - - - owder Company, Wilmington,

Del; a corporation of Delaware 2. S. ...

Application August 8, 193 , S al....No.ii..."95,014.
s

. .. .
4 Clai )
This invention relates to a method for the pro- duced in the shape shown in Figure 2 of the
duction of diazodinitrophenol, and more particu accompanying drawing. .. .
*I have found that addition to the reaction mix
larly to a method of producing diazodinitrophenol ture
directly in free-flowing form. . .'; comprising a salt of picramic acid, a soluble
5 Diazodinitrophenol has been known metal nitrite, and a strong acid, of pyrogallol, 5
hereto- -- - - - - - - - - -- -- - - - - - - - -- --
fore, and methods for its production: have been hydroquinone, phloroglucinol; catechol, resor. ...
cinol, p-methylaminophenol, 3,5-dinitrocatechol,
disclosed. For example, diazodinitrophenol and
a method for its production rare disclosed in p-aminophenol, isopicramic
cinol, o-aminophenol, acid, dinitroresor.
p-sulfanilic cid, 'o-ni
United States patents to Dehn, Nos. 1,404,687,
10 1,428,011, and 1,460,708. The compound is a tranilin; (3-naphthol, nitrosonaphtho
... very valuable composition for use-in blasting orange, hydroxylamine, 3,5,3',5'-tetranitri
caps. However, as generally produced, it is not 2-dihydroxyhydrazobenzene, -o- phenylenedi
sandy or free-flowing, and gives great difficulty amine, p-phenylenediamine, 2,4-diamino-6-initro
in loading blasting caps by mechanical means. nitrophenol, 2,4-dinitrophen w
phenol, 2,4,6-trinitrobenzoic' acid, 2-amino-4- '
l5. Attempts have been made to produce free-flow p-nitranilin,
ing diazo grains, e. g., as describeds in United sition formedorbyadecomposing
subst:
States Patent No. Re. 19,645 to Hancock and by alkali, or mother liquors fromdiazodinitrophenol
the manufacture
Pritchett,
tory.
but such has not been
.. . . . . . . . . . : ...
wholly
: . . .
satisfac
. ..... -- of sodium picramate, or substances present in the
20. In accordance with my invention a novel meth mother liquors from the manufacture of sodium 20
... od is provided for the production of diazodinitro picramate, or a mixture of any of the above, in
phenol: directly in free-flowing form, adapted to various amounts, depending upon the particular
mechanical loading into-blasting cap shells. compound employed, produces diazodinitrophenol
The method embodying this invention com in the shape of rounded, free-flowing crystals of
25 prises diazotization of a salt of picramic acid by the shape shown in Figure
ing drawing. .
2 of the accompany
. .. . . ."
25
a salt of nitrous acid and an acid, in the presence
I have been unable to determine any generic
of a substance adapted to promote the formationterm or group which comprises compounds having
of rounded grains of diazodinitrophenol. . . . . .
the property of producing diazodinitrophenol in
- Reference is made to the accompanying draw
30 free-flowing
ing, in which Figure 1 represents the needle-like form, under: the conditions of re- 30.
crystals of diazodinitrophenol produced by the action stated, particularly since I have found that
certain organic substances which, by analogy,
known processes from relatively pure ingredients,
and Figure2 represents the rounded, free-flowing should act, in the same: manner, do not-so: act.
forms of diazodinitrophenol-produced by: the Examples of the latter are methylene blue,
35 method in accordance with my invention. . . . . 3,5,3',5'-tetranitro-2; 2'-dihydroxyazobenzene, 35
It will be appreciated that the needle-like : 3,5,3,5-tetranitro-2,2'-dihydroxyazoxybenzene,
crystals shown in Figure 1 of the accompanying picric-acid; 3,5-dinitro-benzoic acid gum arabic,
drawing Willimat and pile like a mass of straw, phenol, anilin, and eosin. . . . . . . ; ; f.
As illustrative of the practical application of
without flowing through holes into a measuring
the method in accordance with my invention, 40
40 or loading plate, whereas crystals shown in Fig the
lure 2 of the accompanying drawing Will flow producefollowing examples are given, all of which
freely through such holes like sand or mercury diazodinitrophenol in free-flowing-form:
fulminate. Thus, crystals of the form shown Eacample I
in Figure 1 become impossible to load into blast About 21 parts by weight of recrystallized sodi- 4.5
45 ing caps by the usual procedure. um picramate and about 6.8 parts by Weight
With the use of a relatively pure salt of pic
ramic acid, e. g., sodium picramate, a relatively of relatively pure sodium nitrite were added to
pure sodium nitrite, and relatively pure Sul about 300 parts by weight of water in a vessel
phuric or hydrochloric acid, diazodinitrophenol having a cooling jacket, the slurry or suspension
50 is produced in the crystal form shown in Figure stirred and the temperature maintained at about 50
of the accompanying drawing. 14.5° C. to about 15.5° C., then about 0.4 part
I have found, however, that when certain sub to about 0.04 part by weight of pyrogallol in 10
stances are added to the reaction mixture which parts by weight of water and one drop of an
produces diazodinitrophenol, rounded, sandy, aqueous 20% caustic soda solution added, then
5s free-flowing grains of diazodinitrophenol are pro about 50 parts by weight of 20% sulfuric acid 55
 2 2,108,926,
added at the rate of about 20 drops per minute. added to the slurry before starting the addition
After all the sulfuric acid is added, the diaZO of the hydrochloric acid.
dinitrophenol is isolated in a free-flowing form The procedures given in the above illustrations
by filtration, and purified by Washing with Cold
by Way of example, may be varied widely with
Water. Out departing from this invention. Likewise,
Eacd.imple II Various picramates, nitrites, and acids may be
The same method is used as in Example I, but used in varying proportions, and conditions of di
the pyrogallol is replaced by hydroquinone, aZotization, e. g., temperature, concentrations,
phloroglucinol, Catechol, or resorcinol. etc., may be varied widely within operative
0 limits. 10
Eacan.ple III The method in accordance with this invention
The same method is used as in Example I, ex is not dependent upon the use of any particular
cept that the sodium hydroxide is omitted. form of apparatus, means for cooling, stirring,
Eacample IV
or the like.
15 What I claim and desire to protect by Letters 15;
Patent is:
The same method is used as in Example I, ex 1. Method of producing free-flowing diazodi
cept that 0.4 part by weight of dinitroresorcinol nitrophenol which includes reacting a salt of
is used in place of the pyrogallol.
Eacample V
picramic acid, a soluble nitrite, and a strong acid;
20 in the presence of mother liquor derived from 20:
About 4.2 kg. of pure, dry sodium picramate the2. manufactue of picramic acid.
Method of producing free-flowing diazodi
hydrate was placed in a glass-lined tank, fitted
with an agitator, and about 40 liters of water nitrophenol Which includes reacting a salt of
picramic acid, a Soluble nitrite, and a strong acid,
25 added. Then about 1.4 kg. of pure sodium ni in the presence of a substance produced by de 25,
trite dissolved in 5 liters of Water was run into
the tank. To this Slurry in the tank was then Composition of diaZOdinitrophenol by an alkali.
3. Method of producing free-flowing diazodi
added 1.5 liters of a solution of decomposed di nitrophenol
aZOdinitrophenol prepared by adding gradually Which includes reacting a salt of
30 OVer a period of 3 hours about 160 cc. of 10% picramic acid, a soluble nitrite, and a strong acid
Sodium hydroxide to 42 g. of pure diazodinitro in the presence of mother liquor obtained from 30,
phenol. The slurry Was then diluted with water the manufacture of sodium picramate. .
to about 52.7 liters, and agitation started. The 4. The method of producing free-flowing di
temperature was adjusted to about 14° C. and aZodinitrophenol which includes reacting a salt
there maintained during the reaction. About acid of picramic acid, a soluble nitrite, and a strong
35 6.7 kg. of approximately 6 N hydrochloric acid in the presence of an added. Stubstance ca- :
Was added at the constant rate of about 23.4 cc. pable, under the conditions of diazotization, of
per minute, so that diazotization, as shown by Controlling the Crystallization of the diazodini
trophenol formed so as to produce rounded, free
the Starch iodide test for nitrous acid, was con flowing particles, of diazodinitrophenol; said
plete in about 275 minutes. Agitation was then
40 added substance being Selected from the group 40
stopped and the charge in the tank transferred consisting of pyrogallol, hydroquinone, phloro
to a Suction filter, the mother liquor drawn off, glucinol, catechol, resorcinol,
and the granular diaZOdinitrophenol produced p-methylamino
Was Washed. With cold Water to free it from im phenol, 3,5-dinitrocatechol, p-aminophenol, iso
purities. picramic acid, dinitroresorcinol, o-aminophenol,
45 Eacample VI p-Sulfanilic acid, o-nitranilin, B-naphthol, nitro
Sonaphthol, methyl orange, hydroxylamine,
The same method is used as in Example V, 3,5,3',5'-tetranitro - 2,2' - dihydroxyhydrazoben
except that, instead of adding the decomposed Zene, o-phenylenediamine, p-phenylenediamine,
diaZOdinitrophenol solution, 6.7 kg. of mother 2,4-diamino-6-nitrophenol, 2,4,6-trinitrobenzoic
50 liquor from the manufacture of SOdium picramate acid, 2-amino-4-nitrophenol, 2,4-dinitrophenol,
(by reduction of sodium picrate by sodium sul trinitro-m-cresol, p-nitranilin, a substance of un
fide) was added before starting the diazotization. known composition formed by decomposing di
Eacample VII a2Odinitrophenol by alkali, and a substance of
unknown composition present in the mother
55 The same method is used as in Example W, ex liquors from the manufacture of sodium pic
cept that, instead of the decomposed diazodini ramate.
trophenol, about 4.2 g. of hydroquinone was HARVEY B. ALEXANDER.