The structure of the product of reaction between 3-methyl-1-phenyl-2-pyrazolin-5-one and tetracyanoethylene

The title reaction produces 6-amino-3,3’-dimethyl-5’-oxo-1,1’-diphenylspiro[pyrano[2,3c]pyrazole -4(1H),4’-[2]-pyrazoline]-5-carbonitrile 4, the structure of which has been determined by X-ray crystallography. It crystallizes in the orthorhombic space group Pna21, with two independent molecules in the asymmetric unit.


Introduction
Some years ago, Abdel Galil et al. 2 reported that tetracyanoethylene (TCNE) reacts with 3methyl-1-phenyl-2-pyrazolin-5-one 1 in ethanol to produce a product to which they assigned the dipyrazolylmethane structure 2 (Scheme 1).To explain the non-equivalence of the two pyrazole rings in the NMR spectra, they proposed that one ring exists as the OH tautomer and the other as the NH tautomer.We considered this to be extremely improbable, as structurally related compounds have been shown 3 to display equivalence of the pyrazole signals in their NMR spectra.Although pyrazolones are known to exhibit desmotropy, 4 it would be unprecedented for a pyrazolone ring to exist as different tautomers within the same molecule.Furthermore, the authors listed two nitrile signals in the 13 C NMR spectrum, a feature that is incompatible with structure 2. We now report the X-ray crystal structure of this compound.

Results and Discussion
Whilst Abdel Galil et al. 2 were unable to isolate the proposed dicyanomethylene intermediate 3, this compound can readily be prepared by reaction of 1 with TCNE in acetonitrile solution. 5We have found that reaction of 1 with either TCNE or 3, produces a product that on recrystallization from methanol affords needles suitable for X-ray crystal structure determination.This compound crystallizes in the orthorhombic space group Pna2 1 , with two independent molecules in the asymmetric unit, which are related by a non-crystallographic pseudo-center of inversion.
Figure 1 shows a perspective view of the structure which is a spiro[pyrano[2,3-c]pyrazole-4,4'-pyrazoline, a well-known heterocyclic ring system, 6 although this is the first report of an Xray crystal structure of such a compound.Structure 4 has independently been proposed by Metwally et al. 7 for the product of the reaction of 3 with 1, although curiously they report a different melting point.This compound clearly results from reaction of 1 with the C4 carbon of 3, rather than the exocyclic dicyanomethylene carbon that would lead to 2. Both these modes of reaction have been reported for 3 and structurally related compounds. 6,8,9he pyranopyrazole ring system is approximately planar, and orthogonal to the other pyrazoline ring (angle between meanplanes = 88.6(5) and 91.1(5)° for the two independent molecules).The N1 phenyl rings are inclined to the planes of the pyranopyrazoles at angles of 41.4(5) and 41.1(5) o , for the two independent molecules.The N1' phenyl rings are twisted by 29.5 (5) and 25.7(5)° from the planes of the attached pyrazoline rings.Intermolecular interactions are controlled by hydrogen bonds between symmetry related molecules.Specifically, each independent NH 2 hydrogen atom is hydrogen bonded to either N2 or O2 of an adjacent molecule, with distances ranging between 2.05 and 2.19 Å.
In conclusion, we have unambiguously identified the structure of the product of the title reaction as 6-amino-3,3'-dimethyl-

Experimental Section
Preparation of (4).Tetracyanoethylene (1.95 g, 0.0152 mol) and 3-methyl-1-phenylpyrazol-5one (5.3 g, 0.0304 mol) were refluxed in ethanol (75 mL) for two hours.The resulting solid was filtered off and recrystallized from methanol.Yield 2.8 g (45%), mp 192 °C, lit. 2 195 °C.X-Ray Crystallography.Intensity data were collected with a Nicolet P4s four-circle diffractometer using graphite-monochromatized Mo Kα radiation (λ 0.7107Å).Cell parameters were determined by least-squares refinement using the setting angles of 25 accurately centred reflections (2θ > 15°).Throughout data collection (ω scans) the intensities of three standard reflections were monitored and this showed no significant crystal decomposition.The intensities were corrected for Lorentz, polarisation and absorption effects.The structure was solved by direct methods using SHELXS 10 and refined on F 2 by full-matrix least squares procedures using SHELXL.

Figure 1 .Table 1 .
Figure 1.Perspective view of one of the two independent molecules of 4.