Nucleophilic Addition of Hydroxylamine, Methoxylamine, and Hydrazine to Malononitrileoxime

Article abstract of DOI:10.1021/jo991614t

The chemistry of malononitrileoxime, HONC(CN)₂, with respect to nucleophilic addition to ammonia, methylamine, hydroxylamine, methoxylamine, and hydrazine is reported. Whereas the poorly nucleophilic ammonia and methylamine do not react, hydrox

Full text of DOI:10.1021/jo991614t

J . Org. Chem. 2000, 65, 1139-1143
1139
Nu cleop h ilic Ad d ition of Hyd r oxyla m in e, Meth oxyla m in e, a n d
Hyd r a zin e to Ma lon on itr ileoxim e
Navamoney Arulsamy and D. Scott Bohle*
Department of Chemistry, University of Wyoming, Laramie, Wyoming 82071-3838
Received October 15, 1999
The chemistry of malononitrileoxime, HONC(CN)2, with respect to nucleophilic addition to ammonia,
methylamine, hydroxylamine, methoxylamine, and hydrazine is reported. Whereas the poorly
nucleophilic ammonia and methylamine do not react, hydroxylamine, methoxylamine, and hydrazine
add to the nitrile groups of the oxime, yielding the corresponding amidoximes and amidrazones.
Depending on the stoichiometry of the reactions, hydroxylamine and hydrazine add to one or both
of the nitrile groups; methoxylamine adds to only one of the nitrile groups. Three of the products,
namely, cyanoacetamidoxime (1), 3-amino-2,3-hydroxyiminopropionitrile monohydrate (2‚H2O), and
3,5-diaminopyrazolone-4-oxime monohydrochloride monohydrate (6‚HCl‚H2O), are characterized
by single-crystal X-ray diffraction data. All of the products exhibit exothermic decomposition
properties with heats of decomposition in the range of 500-1500 kJ mol-1
.
In tr od u ction
It is well-known that nitriles undergo addition reac-
tions with ammonia,14-17 hydroxylamine,15,16,18-22 and
hydrazine15,16,20,23-26 with the formation of amidines,
amidoximes, and amidrazones, respectively. Electron-
deficient nitriles also undergo hydration and base-
catalyzed alcohol addition reactions following a similar
nucleophilic addition mechanism.27 In general, electron-
deficient nitriles undergo addition reaction with a wide
variety of reagents including ammonia, whereas electron-
rich nitriles react only with the highly nucleophilic
hydroxylamine and hydrazine reagents. For example, the
barium salt of dicyanamide, Ba(N(CN)2)2, an electron-
rich nitrile, undergoes an ion exchange reaction with
ammonium sulfate in aqueous media to form the corre-
sponding ammonium salt, whereas its reaction with
hydrazinium sulfate yields two products, namely, the
corresponding hydrazinium salt at 20 °C and guanazole
at 50 °C.28
Salts of malononitrileoxime, M+[ONC(CN)2]-, where
M+ ) Ag+, Li+, Na+, K+, NH4+, and [C(NH2)3]+, exhibit
exothermic decomposition properties.1 Malononitrile-
oxime is obtained by the nitrosation of malononitrile with
nitrous acid in acetate buffer (pH 2.5-3). The anion of
malononitrileoxime is also known as nitrosodicyano-
methanide. Structural data available for the ammonium,1
barium,1 silver,2 and potassium3 salts reveal that the
anion has a significant resonance contribution for the
corresponding oximate, [OdN-C(CN)2]- T [O-Nd
C(CN)2]-. Electronic absorption spectra of the potassium
salt measured in aqueous media at acidic pH conditions
are consistent with the oximate structure.4 Although
structural features5-8 and coordination properties2,3,9-13
of [ONC(CN)2]- are well studied, the chemical reactivity
of the species has not been studied in detail. As part of
our efforts toward the synthesis of new propellants, we
were interested in the chemical reactivity of [ONC(CN)2]-
and its potential use as a precursor material in the
synthesis of new nitrogen-rich compounds.
(14) Zilberman, E. N. Russ. Chem. Rev. 1962, 31, 615.
(15) Smith, P. A. S., Open Chain Nitrogen Compounds; Benjamin:
New York, 1965; Vol. 1, pp 137-231; 1966; Vol. 2, pp 29-63, 149-
171.
(16) Scha¨efer, F. C. In The Chemistry of the Cyano Group; Rap-
poport, Z., Ed.; Interscience: New York, 1970; pp 239-340.
(17) Gautier, J . A.; Miocque, M.; Farnoux, C. C. In The Chemistry
of Amidines and Imidates; Patai, S., Ed.; Interscience: New York, 1975;
pp 238-348.
(18) Eloy, F.; Lenaers, R. Chem. Rev. 1962, 62, 155.
(19) Metzger, H. In Methoden der Organischen Chemie (Houben-
Weyl); Muller, E., Ed.; Thieme Verlag: Stuttgart, 1968; Vol. 10, pp
209-213.
(20) Vaquero, J . J .; Fuentes, L.; DelCastillo, J . C.; Perez, M. I.;
Garcia, J . L.; Soto, J . L. Synthesis 1987, 33.
(21) Showell, G. A.; Gibbons, T. L.; Kneen, C. O.; MacLeod, A. M.;
Merchant, K.; Saunders: J .; Freedman, S. B.; Patel, S.; Baker, R. J .
Med. Chem. 1991, 34, 1086.
(22) Piskunova, I. P.; Eremeev, A. V.; Mishrev, A. F.; Vosekalna, I.
A. Tetrahedron 1993, 49, 4671.
(23) Neilson, D. G.; Roger, R.; Heatlie, J . M. W.; Newlands, L. R.
Chem. Rev. 1970, 70, 151.
(24) Watson, K. M.; Neilson, D. G. In The Chemistry of Amidines
and Imidates; Patai, S., Ed.; Interscience: New York, 1975; pp 491-
545.
(1) Arulsamy, N.; Bohle, D. S.; Doletski, B. G. Inorg. Chem. 1999,
38, 2709.
(2) Chow, Y. M.; Britton, D. Acta Crystallogr. 1974, B30, 1117.
(3) Skopenko, V. V.; Zub, Y. L.; Porai-Koshits, M. A.; Sadikov, G.
G. Ukr. Khim. Zh. (Russ. Ed.) 1979, 45, 811; Chem. Abstr. 1979, 91,
202606s.
(4) Iglesias, E.; Williams, D. L. H. J . Chem. Soc., Perkin Trans. 2
1989, 343.
(5) J ensen, H.; Klewe, B.; Tjelta, E. Acta Chem. Scand. 1970, 31A,
151.
(6) Scha¨dler, H.-D.; Ko¨hler, H. Z. Chem. 1990, 30, 67.
(7) J a¨ger, L.; Scha¨dler, H.-D.; Grobe, U.; Ko¨hler, H.; Nefedov, V. I.
Z. Anorg. Allg. Chem. 1992, 617, 123.
(8) Scha¨dler, H.-D.; J a¨ger, L.; Senf, I. Z. Anorg. Allg. Chem. 1993,
619, 1115.
(9) Bohle, D. S.; Conklin, B. J .; Hung, C.-H. Inorg. Chem. 1995, 34,
2569.
(10) J a¨ger, L.; Tretner, C.; Hartung, H.; Biedermann, M. Chem. Ber.
1997, 130, 1007.
(11) Hvastijova´, M.; Koz´ısˇek, J .; Kohout, J .; Mrozinski, J .; J a¨ger,
L.; Svobodo, I. Polyhederon 1997, 16, 580.
(12) Miklosˇ, D.; Potocnak, I.; Dunaj-J urco, M.; J a¨ger, L. Acta
Crystallogr. Sect. C (Cr. Str. Comm.) 1998, 54, 33.
(13) Dunaj-J urco, M.; Miklosˇ, D.; Potocnak, I.; J a¨ger, L. Acta
Crystallogr. Sect. C 1998, 54, 1763.
(25) Rusanov, A. L. Russ. Chem. Rev. 1974, 43, 795.
(26) Smith, R. F.; Kinder, L. L.; Walker, D. G.; Buckley, L. A.;
Hammond, J . M. J . Org. Chem. 1977, 42, 1862.
(27) Scha¨efer, F. C.; Peters, G. A. J . Org. Chem. 1961, 26, 412.
(28) Frankel, M. B.; Burns, E. A.; Butler, J . C.; Wilson, E. R. J . Org.
Chem. 1963, 28, 2428.
10.1021/jo991614t CCC: $19.00 © 2000 American Chemical Society
Published on Web 01/28/2000

1140 J . Org. Chem., Vol. 65, No. 4, 2000
Arulsamy and Bohle
Sch em e 1
F igu r e 1. Views of the two cyanoacetamidoxime molecules
in the crystallographic asymmetric unit. In this and the
following structures, 50% thermal ellipsoids of the atoms are
shown.
ing on the stoichiometry, either one or both of the nitrile
groups undergo addition reaction with hydroxylamine
and hydrazine. The reaction with O-methylhydroxyl-
amine did not proceed beyond the addition of 1 equiv of
the reagent despite prolonged reflux of the reaction
mixture containing 1 equiv of KONC(CN)2 and 2 equiv
of O-methylhydroxylamine in ethyl alcohol. The observa-
tion reveals that the nitrile group of the 1 + 1 addition
product, namely, 3-amino-2-hydroxyimino-3-methoxy-
iminopropionitrile (4), is significantly deactivated in
comparison to the nitrile groups of malononitrileoxime.
The reaction of KONC(CN)2 with 0.5 equiv of N2H4‚
2HCl in aqueous medium yields N,N′-di-3,3′-(3-amino-
2-hydroxyiminopropionitrilo)hydrazone (5) as follows.
The reaction mixture is light yellow colored immediately
after the mixing of the reactants. However, the color
turns slowly to deep red on standing the solution for ca.
12 h, and reddish brown crystals of the hydrazone 5 begin
to separate from the solution. The reaction reaches near
completion in 3 d, with the crystallization of the product
in 86% yield. The presence of a strong absorption band
at 2238 cm-1 in the IR spectrum together with the
analytical data obtained for the product unambiguously
demonstrate the assigned structure 5. The product is
soluble in dimethyl sulfoxide, slightly soluble in water,
and insoluble in solvents such as acetone, methanol,
THF, and acetonitrile. In dimethyl sulfoxide solution, the
hydrazone undergoes rapid reorganization, forming pro-
tonated pyrazoloneoxime and malononitrileoximate an-
ion. The 13C NMR spectrum measured in DMSO-d6,
exhibits two sets of peaks, as described in the Experi-
mental Section, corresponding to the two species in
solution.
Str u ctu r a l Da ta . Compounds 1, 2‚H2O, and the new
heterocyclic compound, 6‚HCl‚H2O, have also been char-
acterized by single-crystal X-ray crystallography. Views
of the structures are given in Figures 1-3. Selected bond
distances and angles are listed in Table 1.
1. Crystals of the compound contain two structurally
similar HONC(CN)(CONH2) molecules in the crystal-
lographic asymmetric unit. The molecules are planar,
consistent with the presence of sp2 and sp hybridized
carbon atoms and delocalization of π bonds in the
structure. The dihedral angle between the planes passing
through the two molecules is 54°. The oxime hydrogen
atoms of the two molecule are intermolecularly hydrogen
bonded to the amide oxygen atom of the neighboring
molecule with corresponding O‚‚‚O distances of 2.580(3)
Although the acid-catalyzed hydration reaction of
[ONC(CN)2]- is known,29 similar reactions with ammonia,
hydroxylamine, and hydrazine still remain unknown.
Dunaj-J urco et al. have observed addition of methanol
to one of the two nitrile groups of malononitrileoxime
during their attempted synthesis of copper(II) malono-
nitrileoxime complexes.13,30 We undertook a comprehen-
sive study of the reactions of malononitrileoxime with
ammonia, methylamine, hydroxylamine, O-methylhy-
droxylamine, and hydrazine. In this paper, we wish to
report the details of the reactions and the characteriza-
tion and thermal decomposition properties of the prod-
ucts.
Resu lts a n d Discu ssion
The ion metathesis reaction of AgONC(CN)2 with NH4-
Cl in aqueous media at room temperature yields the
corresponding ammonium salt as reported previously.1
To examine if ammonia addition can be achieved at
higher temperatures, the filtrate from the metathesis
reaction of AgONC(CN)2 with NH4Cl was allowed to
reflux overnight. The reaction did not yield the expected
amidine; instead the hydrolysis product, HONdC(CN)-
(CONH2) (1) is isolated in 65% yield. Similarly, a reaction
between equimolar amounts of KONC(CN)2 and methyl-
amine hydrochloride in ethanol was carried out by
refluxing the mixture overnight, and the reaction also
yielded the hydrolysis product and not the expected
N-methylamidine. The formation of 1 in these reactions
indicates poor nucleophilicity of ammonia and methyl-
amine under these experimental conditions and is also
consistent with the known acid-catalyzed hydration of
malononitrileoxime.29
The reactions of KONC(CN)2 with hydroxylamine,
O-methylhydroxylamine, and hydrazine yield nucleo-
philic addition products as shown in Scheme 1. Depend-
(29) Ko¨hler, H.; Seifert, B. Z. Anorg. Chem. 1970, 379, 1.
(30) Dunaj-J urco, M.; Miklosˇ, D.; Potocna´k, I.; J a¨ger, L. Acta
Crystallogr., Sect. C. 1996, C52, 2409.

Nucleophilic Additions of Malononitrileoxime
J . Org. Chem., Vol. 65, No. 4, 2000 1141
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles (d eg)
for 1, 2‚H2O, a n d 6‚HCl‚H2O
1
O(1)-N(1)
1.359(3)
1.223(4)
113.5(2)
N(1)-C(1)
1.283(3)
1.329(4)
123.4(3)
C(3)-O(2)
C(3)-N(3)
O(1)-N(1)-C(1)
O(2)-C(3)-N(3)
2‚H2O
O(1)-N(1)
1.367(3)
1.289(3)
111.7(2)
C(1)-N(1)
1.284(3)
1.416(2)
127.2(2)
C(3)-N(4)
N(4)-O(2)
N(4)-C(3)-N(3)
O(1)-N(1)-C(1)
6‚HCl‚H2O
N(1)-N(2)
1.415(4)
1.298(4)
1.491(5)
1.471(5)
1.353(4)
127.7(3)
106.1(3)
N(1)-C(3)
C(1)-N(3)
C(2)-N(4)
C(3)-N(5)
1.310(5)
1.322(5)
1.280(5)
1.311(5)
N(2)-C(1)
C(1)-C(2)
C(2)-C(3)
N(4)-O(1)
N(5)-C(3)-N(1)
N(1)-C(3)-C(2)
N(5)-C(3)-C(2)
C(2)-N(4)-O(1)
126.1(3)
113.2(3)
Ta ble 2. Differ en tia l Sca n n in g Ca lor im etr y Da ta for th e
Com p ou n d s
compound
Tonset, °C
Tmax, °C
∆H, kJ mol-1
1
188 ( 2
115 ( 2
131 ( 1
175 ( 2
180 ( 1
204 ( 1
265 ( 1
224 ( 2
270 ( 1
194 ( 2
124 ( 2
150 ( 5
215 ( 5
185 ( 1
212 ( 1
307 ( 1
242 ( 2
284 ( 1
1110 ( 20
1500 ( 20
1320 ( 240a
730 ( 20
2‚H2O
3
4
5
1430 ( 40
F igu r e 2. Views of the two pairs of 3-amino-2,3-di(hydroxy-
imino)propionitrile and solvated water molecules in the crys-
tallographic asymmetric unit.
6‚HCl‚H2O
6
500 ( 40
830 ( 10
a
Sample cup shattered due to explosion during the experiment.
with each of the two 2-hydroxyimino oxygen atoms as
reflected in the O(1W)‚‚‚O(2W), O(1W)‚‚‚O(3), and O(2W)‚‚‚
O(1) interatomic distances of 2.748(3), 2.671(3), and
2.632(3) Å, respectively. In both molecules the amine
nitrogen atoms are involved in intramolecular hydrogen
bonding interaction with the amidoxime oxygen atoms,
with the corresponding interatomic distances O(2)‚‚‚N(3)
and O(4)‚‚‚N(7) being 2.604(3) and 2.614(3) Å, and the
with the two 2-hydroxyimino nitrogen atoms, with the
associated N(1)‚‚‚N(3) and N(5)‚‚‚N(7) interatomic dis-
tances being 2.753(3) and 2.745(3) Å, respectively.
6‚HCl‚H2O. The structure consists of well-separated
protonated 3,5-diaminopyrazolone-4-oxime species, chlo-
ride anions, and solvated water molecules. All non-
hydrogen atoms of the pyrazoloneoxime are nearly pla-
nar, with the maximum deviation being that of the oxime
nitrogen atom at 0.0153 Å. The two double bonds of the
two nitrogen atoms in the five-membered ring are
significantly longer while the rest of the three bonds are
shorter than typical C-N double bonds and C-C and
N-N single bonds, respectively. The C-N and N-O bond
distances involving the oxime group also exhibit a similar
trend (Table 1), indicating the presence of π-bond delo-
calization over the protonated species.
Th er m a l P r op er ties. Differential scanning calorim-
etry data obtained for the products reveal exothermic
decomposition behavior (Table 2). None of these com-
pounds exhibited sensitivity toward shock or static
electricity during the studies. Compounds 4 and 6‚HCl‚
H2O exhibit a sharp endotherm corresponding to the
melting of the solids, together with exothermic peaks at
158 and 136 °C, respectively. Whereas the DSC plots of
the remainder of the compounds contain single exother-
mic peaks, the plot of 5 exhibits three closely spaced
exothermic peaks, indicating that the compound under-
goes stepwise decomposition. It was also observed that
F igu r e 3. View of protonated 3,5-diaminopyrazolone-4-oxime
and solvated water molecule in the crystals of 6‚HCl‚H2O.
and 2.684(3) Å, leading to a layer-like arrangement of
the molecules.
2‚H2O. In this crystal also the crystallographic asym-
metric unit contains two structurally similar molecules
of 3-amino-2,3-di(hydroxyimino)propionitrile molecules,
together with two water molecules. In each of the
propionitrile molecules, the oxime groups are disposed
in trans geometry with respect to the dioxime C-C bond.
All atoms of each of the molecules with the exception of
the hydrogen atoms are nearly plana,r with the maxi-
mum deviations from their least-squares planes being
0.0427 Å (Oamidoxime) and 0.0577 Å (Namidoxime), respectively.
The observed relatively shorter C-Namine and longer
C-Noxime bond distances together with the remaining
C-Noxime and N-O distances are indicative of extended
delocalization of π bonds in the structure. Specifically,
the C-Namine bond exhibits significant π character. The
two water molecules in the structure are involved in
intermolecular hydrogen bonding with one another and

1142 J . Org. Chem., Vol. 65, No. 4, 2000
Arulsamy and Bohle
3-Am in o-2,3-d i(h yd r oxyim in o)p r op ion itr ile Mon oh y-
d r a te (2‚H2O). To a solution of NH2OH‚HCl (0.695 g, 10
mmol) in absolute ethanol (100 mL) was added KONC(CN)2
(1.33 g, 10 mmol). The suspension was heated to reflux for 6
h. Colorless crystals of KCl formed on cooling to room tem-
perature were filtered off. The solvent from the colorless
filtrate was stripped off under reduced pressure, and the white
solid formed was recrystallized from hot water as colorless
crystals. Yield: 1.25 g (86%). IR (KBr, cm-1): ν(CN) 2246. UV-
vis (water) λmax, nm (ꢀ, M-1cm-1): 298 (6160). 1H NMR (400
MHz, DMSO-d6): 3.52 (b, 2H), 5.78 (s, 2H), 10.72 (s, 1H), δ
13.77 (b, 1H). 13C NMR (400 MHz, DMSO-d6): δ 108.7, 126.7,
146.4. Anal. Calcd for C3H6N4O3: C, 24.66; H, 4.14; N, 38.35.
Found: C, 24.86; H, 4.10; N, 38.41.
3 explodes at ca. 130 °C during the DSC experiments,
shattering the sample cup.
The exothermic decomposition pattern observed for the
compounds is consistent with the general behavior of
nitroxy groups (such as nitro, nitroso, or oximino) sub-
stituted organic compounds.31 The relatively lower heat
of decomposition (∆H) observed for 4 and 6‚HCl‚H2O and
6 could be attributed to the presence of the electron-
donating methoxy or amino groups in the structures.
Con clu sion s
The reactivity of malononitrileoxime toward a number
of nucleophilic reagents has been studied. The observed
moderate reactivity of the nitrile groups of malononitrile-
oxime results from the electron-withdrawing property of
the oxime substituent. A series of nitrogen-rich molecules
with exothermic decomposition properties analogous to
the parent species and oximes are synthesized. The
reaction between equimolar amounts of KONC(CN)2 and
N2H4‚2HCl yields a new heterocyclic compound, namely,
3,5-diaminopyrazolone-4-oxime as its monohydrochloride
monohydrate. It may be possible to further modify some
of the products described in this paper. For example,
under suitable experimental conditions, it may be pos-
sible to effect ring closure in the explosive propionitrile-
dioxime 3, leading to the formation of 4-nitroso-3,5-
diaminoisoxazole-2-oxime, and it may also be possible to
oxidize the nonexplosive pyrazoloneoxime 6 to 3,5-dini-
tropyrazolone-4-oxime or 2,3,4-trinitropyrazole.
1,3-Dia m in o-1,2,3-tr i(h yd r oxyim in o)p r op a n e (3). To a
solution of NH2OH‚HCl (1.39 g, 20 mmol) in absolute ethanol
(100 mL) were added KONC(CN)2 (1.33 g, 10 mmol) and
NaOMe (0.54 g, 10 mmol). The suspension was stirred at room
temperature for 2 h and then heated to reflux for 6 h. Colorless
crystals of KCl and NaCl formed on cooling to room temper-
ature were filtered off. The solvent from the colorless filtrate
was stripped off under reduced pressure, and the white solid
formed was recrystallized from hot water as colorless fibrous
crystals. Yield: 1.45 g (90%). UV-vis (water) λmax, nm (ꢀ, M-1
-
1
cm-1): 264 (4850). H NMR (400 MHz, DMSO-d6): δ 5.49 (s,
2H), 6.17 (s, 2H), 9.33 (b, 1H), 10.12 (s, 1H), 11.98 (b, 1H). 13
C
NMR (400 MHz, DMSO-d6): δ 143.8, 145.3, 148.2. Anal. Calcd
for C3H7N4O3: C, 22.36; H, 4.38; N, 43.47. Found: C, 22.17;
H, 4.33; N, 42.95.
3-Am in o-2-h yd r oxyim in o-3-m et h oxyim in op r op ion i-
tr ile (4). To a solution of NH2OMe‚HCl (0.835 g, 10 mmol) in
absolute ethanol (25 mL) was added KONC(CN)2 (1.33 g, 10
mmol). The suspension was heated to reflux for 6 h. The
precipitated KCl on cooling to room temperature was filtered
off. The solvent from the colorless filtrate was removed by
rotary evaporation, and the yellow solid formed was recrystal-
lized from hot water as fine needles. Yield: 1.21 g (85%). IR
Exp er im en ta l Section
(KBr, cm-1): ν(CN) 2244. UV-vis (water) λmax, nm (ꢀ, M-1
-
Ma ter ia ls a n d Meth od s. All chemicals were obtained
commercially and used without further purification. Infrared
spectra were obtained as KBr disks with an FTIR Spectro-
photometer. UV-vis spectra were measured in water solvent.
Proton and 13C NMR spectra were recorded in dimethyl
sulfoxide-d6 on a 400 MHz NMR Instrument. Thermograms
were obtained using a Differential Scanning Calorimeter
equipped with a cooling can for cooling measurements. Ap-
proximately 2 mg of the sample was placed in aluminum
sample cups and crimped with a cover. The DSC runs were
performed under a steady flow of argon gas and at the heating
rate of 10 °C per min in the temperature range 25-500 °C.
Rea ction s of Ma lon on itr ileoxim e. A number of new
products were synthesized from the reactions of the silver or
potassium salts of malononitrileoxime with ammonium chlo-
ride, methylamine hydrochloride, hydroxylamine hydrochlo-
ride, methoxylamine hydrochloride, and hydrazine dihydro-
chloride as described below.
cm-1): 234 (4310), 296 (6805). 1H NMR (400 MHz, DMSO-
d6): δ 2.81 (s, 3H), 6.10 (b, 2H), 13.97 (s, 1H). 13C NMR (400
MHz, DMSO-d6): δ 61.6 (q, J ) 143.3 Hz), 108.4, 125.8, 146.0.
Anal. Calcd for C4H6N4O2: C, 33.81; H, 4.25; N, 39.42. Found:
C, 33.88; H, 4.27; N, 39.51.
A similar reaction of KONC(CN)2 with 2 equiv of NH2OMe‚
HCl also yielded 4 and did not yield the expected 1 + 2 addition
product.
N,N′-Di-3,3′-(3-a m in o-2-h yd r oxyim in op r op ion it r ilo)-
h yd r a zon e (5). To an aqueous solution (50 mL) of N2H4‚2HCl
(0.525 g, 5 mmol) was added KONC(CN)2 (1.330 g, 10 mmol)
at room temperature with stirring. The light yellow solution
was allowed to stand at room temperature for 3 d. Large
reddish brown crystals formed were filtered and dried in vacuo
overnight at room temperature. Yield: 0.950 g (86%). IR (KBr,
cm-1): ν(CN) 2238. UV-vis (water) λmax, nm (ꢀ, M-1cm-1): 310
(24166), 396 (2558). Anal. Calcd for C6H6N8O2: C, 32.44; H,
2.72; N, 50.44. Found: C, 32.44; H, 2.80; N, 50.28. The product
underwent structural reorganization in dimethyl sulfoxide
solution as evident from its 13C NMR spectrum (in DMSO-d6)
forming protonated 3,5-diaminopyrazolone-4-oxime and mal-
ononitrileoximate anion. 1H NMR (400 MHz, DMSO-d6): δ
9.8-6.8 (b). 13C NMR (400 MHz, DMSO-d6): 142.4, 143.3,
152.2 and 107.6, 111.0, 116.3. The first set of peaks corre-
sponds to the protonated 3,5-diaminopyrazolone-4-oxime, and
the second set corresponds to [ONC(CN)2]-. The small dis-
crepancy between the first set of peaks to those of 6‚HCl‚H2O
in the 1H and 13C NMR spectra is attributable to the possibility
of deutrium exchange during structural reorganization of 5,
difference in the associated anions, and absence of solvated
water molecule in 5.
Cya n oa ceta m id eoxim e (1). To a suspension of AgONC-
(CN)2 (1.04 g, 5 mmol) in water (10 mL) was added a solution
of NH4Cl (0.272 g, 5 mmol) in water (10 mL) with stirring.
The precipitated AgCl was removed by filtration, and the
filtrate was allowed to reflux overnight. The solution was
filtered, rotary evaporated to a small volume (5 mL), and
allowed to stand at room temperature. The crystalline product
formed was characterized as 1. Yield: 0.370 g (65%). IR (KBr,
cm-1): ν(CΝ) 2239. UV-vis (water) λmax, nm (ꢀ, M-1cm-1): 228
1
(5482), 286 (5396). H NMR (400 MHz, DMSO-d6): δ 7.85 (d,
J ) 41.5 Hz). 13C NMR (400 MHz, DMSO-d6): δ 109.3, 128.1,
160.2. Anal. Calcd for C3H3N3O2: C, 31.87; H, 2.67; N, 37.16.
Found: C, 31.92; H, 2.67; N, 37.05.
Another reaction with equimolar amounts of KONC(CN)2
and MeNH2‚HCl in absolute ethanol solvent after overnight
reflux also yielded 1.
3,5-Dia m in op yr a zolon e-4-oxim e Mon oh yd r och lor id e
Mon oh yd r a te (6‚HCl‚H2O). In this synthesis equimolar
amounts of KONC(CN)2 and N2H4‚2HCl (1.050 g, 10 mmol)
were used. The reddish brown crystals formed over a period
of 3 days were filtered and dried in vacuo overnight at room
temperature. Yield: 1.65 g (91%). UV-vis (water) λmax, nm (ꢀ,
(31) Chemistry of Energetic Materials; Olah, G. A.; Squire, D. R.,
Eds.; Academic Press: San Diego, 1991.

Nucleophilic Additions of Malononitrileoxime
J . Org. Chem., Vol. 65, No. 4, 2000 1143
M-1cm-1): 310 (12355), 386 (1376). 1H NMR (400 MHz, DMSO-
d6): δ 7.41 (t, J ) 50.7, 1H), 8.4-7.8 (b, 4H), 14.59 (b, 1H).
13C NMR (400 MHz, DMSO-d6): δ 143.5, 144.3, 151.4. Anal.
Calcd for C3H8N5O2Cl: C, 19.84; H, 4.44; N, 38.57; Cl, 19.52.
Found: C, 20.05; H, 4.43; N, 38.34; Cl, 19.35. A similar reaction
using N2H4‚H2O instead of N2H4‚2HCl yielded the free pyra-
zoloneoxime (6) as orange-red crystals. Yield: 1.10 g (87%).
UV-vis (in water) λmax, nm (ꢀ, M-1cm-1): 310 (14010), 394
(1722). 1H NMR (400 MHz, DMSO-d6): δ 7.5-5.9 (b, 4H), 11.02
(s, 1H). 13C NMR: δ 141.8 (b), 143.9, 153.5. Anal. Calcd for
C3H5N5O: C, 28.35; H, 3.96; N, 55.10. Found: C, 28.50; H,
3.90; N, 54.95.
Cr ysta llogr a p h ic Da ta . X-ray diffraction data were col-
lected for 1, 2‚H2O, and 6‚HCl‚H2O on a P4 diffractometer.
Single crystals of the compounds were mounted on a glass fiber
using epoxy resin. Three standard reflections measured after
every 97 reflections exhibited no significant loss of intensity
for any of the crystals. The data for 6‚HCl‚H2O were corrected
for Lorentz-polarization effects and absorption, whereas those
of 1 and 2‚H2O were not corrected for absorption. The
structures were solved by direct methods and refined by least-
squares techniques on F2 using SHELXTL program.32 In the
three structural refinements, all atoms were located in the
difference maps during successive cycles of least-squares. The
positions of the non-hydrogen atoms were refined anisotropi-
cally, whereas those of the hydrogen atoms were refined
isotropically.
Ack n ow led gm en t. We gratefully acknowledge fi-
nancial support from the Air Force Office of Scientific
Research, Grants F49620-96-1-0417 and 98-1-0461.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal-
lographic data and positional parameters, bond distances and
angles, anisotropic displacement parameters, and hydrogen
atom coordinates for 1, 2‚H2O, and 6‚HCl‚H2O. This material
is available free of charge via the Internet at http://pubs.acs.org.
J O991614T
(32) Sheldrick, G. M., SHELXTL Version 5.04; Siemens Analytical
X-ray Instruments, Inc.: Madison, WI, 1996.