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Патент USA US2407161

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Patented Sept. 3, 1946
2,407,161
UNITED STATES PATENT OFFICE
2,407,161
ACYL DICYANDIAMIDES AND SALTS
THEREOFY'
Donaldv W. Kaiser'and Jack Thurston, River
s'ide, Conn, assignors to American Cyanannd
Company, New York, N. Y.', a corporation of
N6 mating. Application Ma; 30, 1942’,
serial No. 445,206
15‘Clainis. (Cicely-‘551)
I
2
This invention relates to new chemical com
pounds and their preparation, more particularly
eral acids such as I-ICl, HzSOt, H3PO4, HzSOs, etc.,
may be employed. Neutralization of the. alkaline
to acyl dicyandiamide and a method of preparing
reaction mixture with such acids will cause the
precipitation of the acyl dicyandiamide as such.
the same. .
Although dicyandiamide;
0
The crystalline product may then be recovered by
decantation or ?ltration and puri?ed by washing
and/or recrystallization as described in the spe
ci?c» examples.
is a compound having an almost completely neu
The reaction may be carried out with any Water
tral reaction in water, its dissociation constant 10 soluble alkali metal‘ or alkaline earth metal oxide
having been reported as (l.6><10—14 at 25° C., We
have found that it will react with acylating agents
in the presence of an alkali metal or alkaline
earth metal oxide or hydroxide and water to yield
acylated dicyandiamides.
‘
The reaction whereby our new acyl dicyandi
amides are prepared is brought about by simply
mixing dicyandiamide with a desiredacylating
agent of the type to be hereinafter described and
or hydroxide such‘ as those of sodium, potassium,
barium; strontium, lithium, etc. Since water is
present in’ the reaction mixture the addition of
an oxide is equivalent to the addition of a‘ corre
15 spending hydroxide, and hereinafter and in‘ the
claims, reference to the useof ,an alkali metal or
an‘ alkaline earth metal hydroxide contemplates
the use of the corresponding oxide. The amount
of alkali metal or alkaline earth metal hydroxide
a water-soluble alkali metal or alkaline‘ earth 2O employed should be su?icient‘ to give the reaction
metal oxide or hydroxide in the presence of water.
The amount of Water employed in the reaction
mixture should be comparatively small and in
mixture a strongly alkaline reaction and there
fore when employing acylat-ing agents having
neutralizable acid groups the amount of alkaline
some cases the water present in the reagents is
material should be su?icient’ to react with these
su?icient for the purpose... In order to conduct 25 groups and still provide an excess‘ alkali. It is
the reaction in a fluid medium the water may be
also pointed‘ out that. during the reaction an acid
supplemented with other solvents preferably‘ none
hydroxylated and also preferably miscible with
group is formed, vI-I'Cl when‘ using anacyl chlo
ride‘ and acarboxylio acid group when using an
acid anhydride as acylating agent, and there.
water. Non-hydroxylated' solvents are preferred
since hydroxylated solvents such as alcohol tend 30 fore su?icient alkali must be used to neutralize
to react with the acyl halides. \ Of these solvents,
these
groups.
I
_.
v
v
7
dioxane and acetone have been used with good
Although the mechanism of our reaction has
results. Ether and benzene may also be employed
not‘ been de?nitely established as‘ yet we believe
as solvents for the acylating agentbut since. they
that it involves the formation of, an alkali metal
are not miscible with water they are not usually 35 or alkaline earth metal salt of dicyand-iamide in
employed.
Ordinarily only enough solvent, in
clucling water, is employed to solubilize the re
actants.
,
Although the reaction is ordinarily carried, out
an. intermediate stage.
Accordingly an alkali
metaloran alkaline earthmetal salt of dicyandi
amide'.may'_be employedin the reaction mixture
and, the corresponding alkali’ eliminated. How
at about room temperatures it may in some cases 40 ever, the alkali metal or alkaline'earth metal of
be advantageous to cool the reaction mixture to
decrease the tendency of side reactions to occur.
Although elevated temperatures may be em
ployed temperatures in excess of about 60° C.
should not be maintained for any appreciable
time because of the tendency of dicyandiamide
and the reaction product itself to decompose at
dicyandiamide hydrolyzes sov easily’ in the pres
ence of water that ineiie'ct the reaction mixture
comprises ‘an acyl'atin'g aglenty dic'yandiamide and
an alkalinietal iorpalkaline earth metai hydroxide.
45, ‘11,11 thereaction mixture we may use acylating
agents‘ such as the acyl halides and acid‘ anh'yg
drides. Of the acyl‘halideswe prefer the acyl
high temperatures. ,
1
chlorides because of their greater availability and
v The product formed in the alkaline ‘reaction
cheapness but‘we may use the acyl. bromides and
mixture is the corresponding", alkali metal.‘ or 50 in some cases the acyl iodides to good advantage.
alkaline earth metal" salt of an acyl dicyandi
Th'e's‘e aeylating agents may be aliphatic, alicyclic
amide; The a‘cylated dicyand'iamide' itself vmay
or aromatic in character and the alkyl, cycloalkyl
be recovered as such from magnetron of its salt
by ‘neutralization with an acid pre'ferably‘a weak
acid such as acetic or propionic, although min
or- aryl radical
be substituted with a wide
variety of substituents; ,Repr'esentative of the
‘aliyl‘e‘i‘firig agénts‘uiatmay be employed amine
time
.
3
,
4,
,
ing solid product was ?ltered, dissolved in water
and acidi?ed with acetic acid. ,The crystalline
precipitate, benzoyl dicyandiamide, was recovered
by filtration with a yield of 40%.‘
acid halides or anhydrides of straight and
branched chain, saturated and unsaturated, pri
mary, secondary and tertiary aliphatic carboxylic
acids such as acetic, propionic, caproic, caprylic,
lauric, oleic, palmitic, stearic, etc.; ‘substituted
CI
"
aliphatic carboxylic acids such as on brom caproic,
'
‘EXAMPLE 3
' Acetyl dicycmdiamide
9,11rdi-Ch101‘O-S'D92J‘1C, v-nitrovaleric, c-N-acrstylf
butylaminopropionic, w-hydroxydecanoic, w-car
, To a. solution (r422 g. of 95% sodium hydrox
ide in ‘100 cc. of water was added 50.4 g. of di
Other acylating agents which may be employed
cyandiamide and 250 cc. of acetone. The mix
by us in our process include the acid halides or
ture was stirred and 51 g. of acetic anhydride-was
‘anhydrides of aliphatic and aromatic polycar- ,
added atysuch a rate that the temperaturewas ”
' .boxylic acids such as sebacic. acid, adipic acid; ' ‘maintained at 35V-i&0°.C. After addition of the
boxyvaleric, etc.
‘
I
Y
Z
succinic acid, 'y-methylitaco-nic acid, citric acid,'
acetic anhydride, water was added and the clear
phthalic acid, hexahydrophthalic acid and others. ~ , solution acidi?ed with acetic acid whereupon col.
We may also employ the acid halides or anhyg
drides of acids such as benzoic acid, p-amino;v
benzoic acid, p-acetylaminobenzoic acid, p-nitro~
benzoic acid, p-hydrcxybenzoic acid, p-acetoxy—
benzoic acid, a-naphthoic acid, ,c-5-su1fonaph
thoic acid, cyclohexylacetic acid, hexahydro~
vbenzoic acid, cyclopentylacetie acid and others, of
related character.
,
'
" orless crystals of acetyl dicyandiamide were,v ob
tained. The product was washed well with water
and allowed to dry.
7
, ,
20 g. of acetyl dicyandiamide were crystallized
from hot water containing about 10% of Cello
solve. After ?ltering and drying an amorphous
appearing solid was obtained which decomposed
at 240° C. when immersed in a hot oil bath at this
,
When employing as acylating agents the hal
temperature. Chemical analysis of the purified
ides of polycarboxylic acids such as sebacyl chlo
sample gave the following results: ‘
ride, adipyl chloride, hexahydrophthalyl chloride,
phthalyl chloride,‘etc., products are obtained hav
ing two .dicyandiamide radicals such'as sebacyl
bis-dicyandiamide and adipyl"bis-dicyandiam-ide.
These compounds are also acylated dicyandi
Per cent
-
Oalculatedfor ciao-N40 ________
Found ____________________________ __
amides and fall within the scope of our invention.
Per cent
Per cent
c
'
N
38.08
4.76
44.44
38._19
4.98
44.18
Our invention ‘will now be illustrated by means 7
of the following speci?c examples which are
given, however, by way of illustration only, and
,4
are not to be construed as limiting our invention
thereto; since obviously other acylating agents ‘
'.
163.5 g. of 95% sodium hydroxide dissolved in
?ask provided with a ‘stirrer, dropping funnel,
of capro-yl'chloride. After the addition was ‘com
63 g. of pulverized dicyandi
pleted the reactionmixture was diluted with wa~
.ter and acidi?ed with acetic acid'whereby'a col~
'orless solid'was precipitated. The material was
amide was added to the/sodium hydroxide solu
150 cc. of ace-r
tone Was then added. The resulting double layer
was agitated thoroughly and the temperature
kept between 20—25° C. while ‘70.25 g. of benzoyl
tion with stirring until dissolved. 7
clear, very light yellow solution.
Acidi?cation of ‘
filtered. and washed well with water. When dry
the crystals melted at 171-173" C. Crystalliza
tion of 103 g. of the product, caproyl .dicyandi
amide, from 95% ethyl alcohol gave 76g. of beau
tiful, large plate-like crystals which melted at
, 179-180" c.
alysis of the puri?ed product gave the following
water and allowed to air dry. The product, ben
results:
zoyl dicyandiamide, was recovered with a yield
‘
'
'
.
.
Dilution of the ?ltrate gave an ad
ditional crop of crystals/weighing 18 g. when
dried and melting at 179—l80° C. Chemical an
the solution with acetic acid precipitated a color
less solid which was ?ltered, washed well with
of 71.5%.
‘
60
Per cent
A sample of the above product was puri?ed by
rapid crystallization from butanol to yield beau
tiful plate-like crystals decomposing at 190-191°
C. when heated. Chemical analysis of the prod~ £65
uct checked closely with the calculated values for
cgnsmo.
1
Y
mometer and two dropping funnels. 126 g. of di
cyandiam'ide and 300 cc. of acetone were added
to the caustic soda solution in the flask. The
‘mixture in the ?ask was stirred and maintained
. at 20° C. while the second portion of the alkali
solution was added simultaneously with 134.5 g.
‘
chloride was added in the course of 1/2 hour.
During this time a solid separated but addition
of water. after the reaction was complete gave a
'
three-necked ?ask equipped with a stirrer, ther
125 cc. of water were placedin a three-necked
and thermometer.
4
in 300 cc. ofiwater was prepared and divided into
two equal portions. One part
placed in a
set forth in the appended claims. .
Benzoyl dicyancliamide
" EXAMPLE
i ‘A solution of 84.4 g. of 95% sodium hydroxide
and reaction conditions may be employed with
out departing from the scope of the invention as
EXAMPLE 1
~
Cdproyl dicyandiamide
"
Per cent
o
‘Calculated for oanlmlo, ________ _.
52. 74 i
Found ___________________________ _ .
52. 95
H
.
Per cent
.
-
1
7; 69
30.76
7. 77
so. 45
EXAMPLE 5
EXAMPLE 2
Bcnzoyl dicyandiamide
To 16.8 grams of ?nely pulverized dicyandi
amide and 13 g; of 95% sodium hydroxide sus
pended in 250 cc. of dioxane, 28.1 g. of benzoyl
chloride was added gradually with stirring. The
temperature of the reaction mixture was kept be
low 40° 0. throughout the reaction. The result.
To a solution containing 66g. of 85% potas-v
sium hydroxide in 200 cc. of water was added 126
g. of dicyandiamide and 300 cc. of acetone. The
' mixture was cooled to 20° C. and stirred while
219 g. of lauroylchloride was slowly added simul
taneously with another solution of 766 g. of potas
sium hydroxide in 100 cc. of water.
The mix
2,407,161
5
6
‘ture was then acidi?ed with acetic acid diluted
with water and the precipitated product ?ltered
as dry as possible. The damp solid was dissolved
.in hot acetone and a little Cellosolve, decolorizing
was then diluted with water, neutralized, and ?l
tered. The material Was then puri?ed by dis
solving in an excess of potassium hydroxide solu
tion and cooling, whereupon the potassium salt
of p-nitrobenzoyl dicyandiamide was precipitated.
The acyl dicyandiamide was recovered from its
salt by dissolving in water and neutralizing with
hydrochloric acid. On analysis the product com
pared with the theoretical analysis of p-nitro
benzoyl dicyandiamide as follows:
carbon was added and the material ?ltered.
On
cooling, glistening, colorless plates separated. A
portion of these crystals were dissolved in methyl
ethyl ketone and recrystallized to give beautiful
plates which melted at l66—l67° C.
On chemical
analysis the carbon, hydrogen and nitrogen val
ues gave close agreement with the theoretical
values for the lauroyl dicyandiamide, C14H26N40.
Per cent
Per cent
0
H
Per cent
_
N
EXAMPLE 6
(A) Scbacyl bis-dicyandiamide
(B) w-c'arborypelargonyl dicyandiamide
p-Nitrobenzoyl dicyandiamide. __ __
46. 35
3. 0
30. 04
Found ____________________________ _ _
46. 62
3. 41
30. 49
EXAMPLE 9
168 g. of dicyandiamide was suspended in a
mixture of 100 cc. of water and 200 cc. of acetone
and 320 cc. of 50% aqueous solution of sodium 20
hydroxide was added to the cold suspension. 179
g. (.75 mole) of crude sebacyl chloride, prepared
by treating sebacic acid with a slight excess of
thionyl chloride and heating until no more HCl
was evolved, was added slowly over a period of
1.5 hours, during which time the solution was
vigorously stirred and cooled to 5-l0° C. Stirring
was continued for 1/2 hour more and the reaction
mixture made neutral with hydrochloric acid.
A gray white precipitate of sebacyl bis-dicyandi
amide was obtained. The product was puri?ed
by dissolving it in 2 liters of water containing
100 cc. of 50% sodium hydroxide. The solution
was then ?ltered and the product precipitated by
w-Carboxypmpionyl dicyandiamide
29.2 g. of succinic anhydride was dissolved in
100 cc. of acetone and added to a cooled mixture
of 33.6 g. of dicyandiamide, 72 cc. of a 50% aque
ous solution'of sodium hydroxide, 25 cc. of water
and 50 cc. of acetone with stirring over a period
of 1%. hour while maintaining the temperature of
the reaction mixture between 5-8° C. At the end
of this time 50 cc. of water were added and the
mixture stirred continuously for 1/2 hour vat 0~5° C.
The mixture was then diluted with water, neu
" tralized carefully with concentrated HCland the
bulk of the acetone removed. The product, or
carboxy-propionyl dicyandiamide, was recovered
by adjusting the resulting solution to a pH of
making the solution neutral with hydrochloric
7 about 3 and cooling. It was further puri?ed by
acid. After washing with water the product was
" redissolving in an alkaline solution and reprecipi
vacuum dried.
The ?ltrate obtained from the recovery of the
crude sebacyl bis-dicyandiamide was further
acidi?ed to a pH of about 3.0 and 37.8 g. of im
pure w-carboxypelargonyl dicyandiamide was ob
tained as a gelatinous material.
EXAMPLE 7
(A) Adz'pyl bis-dicyandiamide
(B) w-c’arboacy-n-valeryl dicyandiamide
To 109 g. of dicyandiamide suspended in a‘ mix
ture of 150 cc. of water and 400 cc. of acetone was
added 240 cc. of aqueous 50% sodium hydroxide.
92 g. (0.5 mole) of crude adipyl chloride pre
pared by treating adipic acid with a slight excess
of thionyl chloride was added slowly over a period
of about one hour during which time the tem
perature was maintained at about 5° C. and the
reaction mixture was well stirred. The clear solu
tion was then made neutral with hydrochloric
acid and adipyl bis-dicyandiamide was precipi
tated as a ?nely divided solid. The product was
?ltered, washed and dried in a desiccator.
The ?ltrate from the above precipitation was
acidi?ed to a pH of about 3 whereupon w-carboxy
n-valeryl dicyandiamide was precipitated. The
product was ?ltered, recrystallized from meth
anol, recovered and dried. On heating a sample
of the product was found to decompose at about
170° C.
EXAMPLE 8
p-Nitrobenzoyl dicyandiamide
18.5 g. of p-nitrobenzoyl chloride was dissolved
in 50 cc. of acetone and added to a cold mixture
tating at a pH of about 3.
EXAMPLE 1O
o-Carboarybenzoyl "dicyandiamide
126 g. of dicyandiamide was added to a mixture
of 100 cc. of water and 300 cc. of acetone. 280 cc.
of a 50% aqueous solution of sodium hydroxide
was then added at 5—8° C. 180 g. of powdered
phthalic anhydride was added to the reaction
mixture in the course of 1e to 1% hours at 5-8° C.
and the mixture stirred at this temperature for
1/2 hour more. 500 cc. of water was then added
and then sufficient concentrated HCl to make the
Most of the acetone was then
removed under vacuum. The product, o-carboxy
benzoyl dicyandiamide was recovered by acidi
fying the resulting solution to a pH of about 3.
. solution neutral.
.Upon‘?ltering, washing with water and drying,
the product was obtained with a 74% yield.
A
sample, puri?ed by twice dissolving in alkali and
precipitating it at a pH of 3, was found to'de
compose on heating to a temperature of 136-133"
C., and analyzed 24.63% nitrogen which compared
well with the calculated values of 24.13% nitro
gen for o-carboxylbenzoyl dicyandiamide.
EXAMPLE 11
p-Hyd’rorylbeneoyl dicyandiamide
79 g. of dicyandiamide suspended in 70 cc. of
water was cooled to 10° C. and 360 cc. of an aque
ous solution of 50% sodium hydroxide addedwith
stirring.
259 cc. of acetone was then added and
was followed by the addition of 100 g. (0.5 mole)
of crude p-acetoxybenzoyl chloride,
of 20 cc. of 50% sodium hydroxide, 10 g. of di
onto 0 o-Qo o 01
cyandiamide, 50 cc. of acetone and 20 cc. of water.
The temperature was kept at 5-10° C. and the
with stirring over a period of about 1 hour while
addition was complete in 1/2 hour. The mixture 75 maintaining the temperature of the reaction mix
2,407,161
10
amount of water being not substantially in excess
of that required to dissolve the reactants.
13. The new compounds formed by neutraliza
tion of the reaction product obtained upon mix
ing together and reacting at temperatures not in
14. Cationic salts of the new compounds of
claim 11.
15. The new compound formed by mixing to
gether and reacting at a temperature not in ex
cess of about 60° C. benzoyl chloride, dicyandi
excess of about 60° C. a carboxylic acid chloride,
amide, an alkali-metal hydroxide, and a small
amount of water.
DONALD W. KAISER.
dicyandiamide, sodium hydroxide and water, the
amount of water being not substantially in excess
of that required to dissolve the reactants.
JACK T. THURSTON.
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