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Патент USA US3057870

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Unite States ‘atet
ice
E,?57,864
Patented Oct. 9, 1962
1
'
3,057,864
ALPHA AMINO SUBSTHTUTED METHYLENE
MALONONITRILES
Alexander T. Shulgin, Berkeley, Calif., assignor to The
Dow Chemical Company, Midland, Mich, a corpora
tion of Delaware
5
No Drawing. Filed Aug. 28, 1959, Ser. No. 836,581
4 Claims. (Cl. 260-247)
This invention concerns certain new substituted malo
10
nonitriles, and particularly certain monocyclic N-hetero
cyclic methylene malononitriles having a structure cor
responding to the formula
N ’-tert-butylpiperazinylmethylenernalononitrile
It will be apparent from the foregoing de?nition that
‘ON
when the heterocyclic group contains a second nitro
-CH=O/
gen atom, such second nitrogen atom is invariably a
ON
tertiary, that is to say, a fully substituted nitrogen atom
having a lower alkyl group as substituent thereupon.
wherein the free valence is occupied by a nitrogen atom,
When the only nitrogen atom in the heterocyclic group
the said occupying nitrogen being a member of a hetero
cyclic group having a total of not more than two ring 20 is the nitrogen atom which is attached to the methylene
nitrogen atoms, free of imino nitrogen atoms and hav
malonitrile group, such lower alkyl substituent, if pres
ing from three to six members in the ring and not more
than one ring substituent additional to the methylene
malononitrile group, each such additional substituent be
heterocyclic group.
ent, may be present in any available location upon the
These new compounds are crystalline solids somewhat
ing a lower alkyl group; each valence of said occupying 25 soluble in many common organic solvents and of very
low solubility in ethanol and in water. They are useful
nitrogen atom being attached to a separate carbon atom.
as parasiticides and are adapted to be employed for the
The term lower alkyl is used throughout the present
speci?cation and claims to designate an alkyl group con
taining from 1 to 5 carbon atoms, inclusive. In View
control of many household pests such as insects and
lowing:
heterocyclic secondary amine having a total of not more
than 2 ring nitrogen atoms one of which is an amino
agricultural parasites such as weeds and fungus diseases.
The new compounds may be prepared by causing a
of the present de?nition, it is apparent that compounds 30
lower alkoxymethylenemalononitrile to react With a
representative of the present invention include the fol
H20
ON
nitrogen atom, and having from 3 to 6 members in the
35 ring and not more than one ring substituent, each such
H20
0N
Ethyleniminomethylenemalononitrile
ON
40
substituent being a lower alkyl group; the imino nitro
gen being joined in the ring by the presence, upon each
ring valence bond thereof, of a separate carbon atom
which is also a member of the ring. Representative
heterocyclic secondary amines include ethylenimine, tri
methylenimine, pyrrolidine, piperidine, morpholine, thi
T1-imethyleniminomethylenemalononitrile
HzC—OH2
\
H
/
/N—G=O\
HQC~CH3
CN
Hg Hz
0-0
H2O
/CN
C-O
H2 H2
ON
Piperidinylmethylenemalononitrile
CHT‘CH;
ON
H
/
ylenemalononitrile. In the present speci?cation and
claims, the term lower alkoxy is used to designate an
alkoxy group containing from 1 to 5 carbon atoms, in
clusive.
‘
In carrying out the reaction, the lower alkoxy methyl
enemalononitrile is intimately contacted with a hetero
cyclic secondary amine of the sort hereinbefore de?ned.
Preferably, the contacting is carried out in an inert sol
55 vent which may conveniently be a lower \alkanol such as
methanol, or ethanol. The reaction is exothermic and
initiates readily atrtemperatures from 0° C. to 50° C.;
therefore, the contacting of the reactants is conveniently
carried out initially within such temperature range. Heat
evolved from the reaction raises the temperature of the
resulting reaction mixture, which may conveniently be
limited by the boiling temperature of the reaction solvent,
by regulating the rate of contacting of the reactants, by
external cooling, andrthe like. The desired products
ON
Thiamorpholinylmethylenemalononitrlle
/
clude ethoxymethylenemalononitrile, methoxymethylene
malononitrile, isopropoxymethylenemalononitrile, 3,3
dimethylpropoxymethylenemalononitrile, n-propoxymeth
CN .
Pyrrolidinyhnethylenemalononitrile
/
amorpholine, N-lower alkyl piperazine, and the like.
Representative lower alkoxymethylenemalononitriles in
65 prepared in the present method are stable under tem
ON
peratures at least somewhat greater than the melting tem
perature of the said product, at least to temperatures
such as ISO-175° C. The reaction by which the present
CN
products are obtained takes place between equimolecular
70 proportions of the heterocyclic secondary amine and the
HaC-N
lower alkoxymethylenemalononitrile reactant. However,
N’ -methylpiperazinylmethylenemalononitrile
the reactants may be employed in any proportions. If
3,057,864
3
4
Thiamorpholinylmethylenemalononitrile, from the re
employed proportions of reactants differ from equimo
action of thiamorpholine and ethoxymethylenemalono
lecular proportions, in general the reactant in excess
nitrile. Thiamorpholinylmethylenemalononitrile has a
thereof will appear as an impurity in, and may be removed
molecular weight of 179.2. The starting thiamorpholine
from, the resulting product.
Upon completion of the reaction, which is easily recog
reactant may be prepared in the manner set forth in the
Journal of the American Chemical Society, vol. 76 (June
1954), page 2902.
nized by the cessation of evolution of further heat of
reaction, the reaction mixture may be cooled to a tem
perature between room temperature and 0° C., where
N’-methylpiperazinyhnethylenemalononitrile, from the
reaction of N’-methylpiperazine and methoxymethylene
upon the desired product usually separates by crystallizing
from the reaction mixture. Alternatively, the reaction 10
malononitrile. N’-methylpiperazinylmethylenemalononi
mixture may be warmed under subatmospheric or atmos
trile has amolecular weight of 176.2.
pheric pressure to vaporize and remove reaction solvent
as well as lower alkanol by-product of reaction, to obtain
the reaction of N’-n-pentylpiperazine and n-propoxymeth
the desired product. When the desired product contains,
ylenemalononitrile.
puri?ed by conventional techniques such as by washing
with further portions of lower alkanol, and recrystalliza
enemalononitrile.
N’ - n - pentylpiperazinylmethylenemalononitrile, from
N’ - n - pentylpiperazinylmethylene
as impurity, unreacted starting material such material may 15 malononitrile has a molecular weight of 232.33.
N’ - tert - butylpiperazinylmethylenemalononitrile, from
be removed by washing with portions of a lower aikanol
the reaction of N’-tert-butylpiperazine and ethoxymethyl
such as ethanol. The resulting product may be further
N’ - tert - butylpiperazinylmethylene
malononitrile has a molecular weight of 218.3.
The N-loweralkylpiperazines to be employed as re
20
tion from various organic solvents.
actants according to the present invention may be pre
The following examples merely illustrate the present
pared in the general method set forth in the Journal of
invention but are not to be construed as limiting it.
the Pharmaceutical Society of Japan, vol. 74, pages1049
EXAMPLE 1
51 (1954).
Piperidinylmethylenemalononitrile
The new monocyclic N-heterocyclicmethylenemalono
nitriles of the present invention have been found to be
useful as parasiticides and are adapted to be employed
milliliters ethanol was added as a single portion to a
for the control of many pests. For such use, the products
solution of 4.1 grams (0.034 mole) of ethoxymethylene
may be dispersed on inert ?nely divided solids and em
malononitrile in 10 milliliters of ethanol warmed to
ployed as dusts. Also, such mixtures may be dispersed
approximately 40° C. A reaction resulted with the im 30 in water with the aid of a wetting agent and the resulting
mediate evolution of heat, as the resulting reaction mix
aqueous suspensions used as sprays. In other proce
ture became darker in color. The reaction mixture
dures, the products may be employed in oil, as oiI-in-water
achieved an upper limit temperature of somewhat less
emulsions, or water dispersions with or without the aid
than 80° C. The reaction mixture was then chilled over
of dispersing or emulsifying agents. In a representative
an ice bath for about 4 hours, during which time the
operation, the application as a thorough wetting spray to
desired product separated out of the reaction mixture as
young tomato plants of a composition containing piperi~
crystals, which were removed by ?ltration and recrystal
dinylmethylenemalononitrile at the rate of one half pound
25
A solution of 2.8 grams (0.033 mole) piperidine in 5
lized from further ethanol. As a result of these opera
tions there was obtained a piperidinylmethylenemalono
nitrile product as a tan, crystalline solid melting at 90°
92° C., and having a nitrogen content, by analysis, of
25 .54 weight percent as compared with a theoretical value
of 26.07 percent.
EXAMPLE 2
l -Pyrr0lidinylmethylenemalononitrile
In procedures exactly like the foregoing except that the
employed heterocyclic reactant was pyrrolidine there was
prepared a l-pyrrolidinylmethylenemalononitrile product
as a light tan crystalline solid melting at 88-90” C.
EXAMPLE 3
Marpholinylmethylenemalononitrile
The present example was carried out in all respects in
the same manner as was Example 1 except that the em
per hundred gallons of ultimate composition afforded
40
commercially satisfactory protection against subsequent
innoculation with viable spores of the fungus Alternaria
solani whereas plants similarly innoculated with the
fungus but without protection from the present com~
pound were uniformly and heavily infested. Similar re
sults were obtained when employing, as sole toxicant, at
the same rate, the compound morpholinylmethylene
malononitrile.
Similarly, the compound pyrrolidinyl
methylenemalononitrile at the rate of one half pound
per hundred gallons afforded substantial protection against
subsequent innoculation with the spores of, on tomato
plants, Alternaria solani; and on young wheat plants,
Puccinia graminis tritici.
I claim:
1. A monocyclic N-heterocyclic methylenemalono
nitrile having a structure corresponding to the formula
ON
ployed heterocyclic reactant was morpholine. As a result
of these operations there was obtained a morpholinyl
methylenemalononitrile product as tan crystals melting
ON
60 wherein the free valence is occupied by a nitrogen atom,
at 148~150° C.
the said occupying nitrogen atom having each of its two
When the same preparation is carried out except that
other valences attached to a separate carbon atom and
there is employed isopropoxymethylenemalononitrile in
an amount equimolecular with the employed morpholine
there is obtained the same morpholinylmethylenemalono
nitrile product together with isopropanol of reaction.
In preparations similar to the foregoing the following
being therewith a component of ‘a saturated heterocycle
free from imino nitrogen and having a total of from 3 to
6, inclusive, ring atoms of which the said occupying
nitrogen is in the number 1 position; when the said hetero
cycle contains from 3 to 5, inclusive, ring atoms the ring
products are obtained:
comprises one trivalent nitrogen atom, all other ring
Ethyleniminomethylenemalononitrile, from the reac
atoms being carbon atoms; and when the said heterocycle
tion of ethylenimine (boiling at 56—57° C.) and ethoxy
methylenemalononitrile. Ethylenirninomethylenemalono 70 contains 6 ‘atoms, the atom in the number 4 position is
selected from carbon, trivalent nitrogen, oxygen, and
nitrile has a molecular weight of 119.13.
sulfur, all ring atoms other than those numbered 1 and
Trimethyleniminomethylenemalononitrile, from the re
4 being carbon atoms; said heterocycle having up to 1
action of azetidine (boiling at 66—69° C.) and 3,3-dimeth
lower alkyl substituent additional to the methylenemalono
ylpropoxymethylenemalononitrile. Trimethylenamino
methylenemalononitrile has a molecular weight of 133.2. 75 nitrile group.
3,057,864
5
6
'2. Pyrrolidinylmethylenemalononitri-le corresponding
4. Morpholinylmethylenemalononitrile corresponding
to the formula
to the formula
Hue-CH2
H2
GET-0H2
0N
\ H /
N~O=O\ 0N
-0§,
5
H Hz
E20
10
H
/CN
N——C=O
\C—-O/
H’ H’
ON
References Cited in the ?le of this patent
UNITED STATES PATENTS
3. Piperidinylmethylenemalononitrile corresponding to
the formula
/0-0\
H
0/
\N—-O=O/
\ OH‘F'C é’
\ ON
2,425,693
Cook et a1. __________ __ Aug. 12, 1947
2,883,368
Middleton ____________ __ Apr. 21, 1959
OTHER REFERENCES
\CN
Price et aL: Journal of the American Chemical Society,
15 vol. 68, page 1249 (1946).
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