8414
J. Am. Chem. SOC. 1992, 114, 8414-8416
A New Three-Dimensional Cycloaddition Compound and Its Inclusion Complexes Formed by 1,3-Dipolar Cycloaddition Reaction of p-Phenylenebis( 3-sydnone) and N-Phen ylmaleimide Kiyoshi Taka@,* Motoo Shire,+ Sadamu Takeda,' and Nobuo Nakamuraf Contribution from the Department of General Education, Kochi National College of Technology, Monobe. Nangoku-shi, Kochi 783, Japan, Shionogi Research Laboratories, Shionogi & Co. Lid., Fukushima, Osaka 553, Japan, and Department of Chemistry, Faculty of Science, Osaka University, Toyonaka, Osaka 560, Japan. Received March 13, 1992
Abstract: A new three-dimensional heterocyclic compound was synthesized from p-phenylenebis( 3-sydnone) and N -
phenylmaleimide. This compound incorporates solvent molecules into the crystal lattice to form new inclusion complexes. The structure and the desolvation process were examined by the use of X-ray diffraction, thermogravimetry, differential thermal analysis, FT-IR spectra, 'HNMR spectra, and solid-state high-resolution I3C NMR spectra. The host compound may possibly be one of the precursory materials of novel ladder polymers.
Sydnones are very reactive agents and have been widely used for the syntheses of a number of cycloaddition compounds.'-7 We found previously that 3-phenylsydnone reacts with N-phenylmaleimide to produce a diimide derivative of tetracarboxylic acid, 3,5,9,1l-tetraoxo-4,10,13-triphenyl1,4,10,13-tetrazatetracyclo[5.5.1 .0.2~608~lz]tridecane.8~9 We now apply this method of synthesis to a more complex 1:4 cycloaddition reaction between pphenylenebis( 3-sydnone) and N-phenylmaleimide (Scheme I). A mixture of pphenylenebis(3-~ydnone), which was synthesized from p-phenylenediamine by a standard methodlo and Nphenylmaleimide" with a molar ratio of 1:4, was dissolved in MqSO, DMA, or DMFI2 and stirred for 60 min at 130 OC; white polycrystalline crystals deposited were filtered and recrystallized from the appropriate solvent. The product was a new compound, 3,5,9,11-tetraoxo-4,1O-diphenyl-( 1,4-bis( 1,4,10,13-tetrazatetracyclo[5.5.1.0.2*608312]-1 3tridecy1)benzene) (I). However, chemical analysis,13 thermogravimetry (TG), and differential thermal analysis (DTA) of the neat crystalline product indicated that it is a new type of inclusion complex between the host compound I and each solvent with the composition of 1:2. The TG and DTA experiments were carried out using Seiko Model SSC-560H thermal analyses instruments under a nitrogen atmosphere from room temperature to about 350 OC. Table I records the results of DTA and TG of three complexes. In each complex, the weight of the specimen began to decrease at about 180 OC, and a remarkable endothermic peak was detected at the temperature cited in Table I. The overall weight loss at this stage corresponds to complete desolvation. The remaining host compound I is a pale yellow powder and stable up to 324 OC, at which temperature it decomposes with emission of an appreciable amount of heat. Pure I can also be obtained on heating at 200 OC under reduced pressure for 2 h. The inclusion complex can be reproduced by dissolving I in the appropriate solvent. The crystal structures of the I-DMA and I-DMF complexes were determined by a single-crystal X-ray diffraction method. Crystal data. I-DMA: C48H34N808*2C4H9N0, mol wt = 1025.09, monoclinic, P21/c, a = 13.720 (5) A, b = 12.347 (5) A, c = 17.257 (9) A, B = 118.74 (4)O, V = 2563 (2) A3,Z = 2, d(ca1cd) = 1.328 g cm-', R = 0.070 for 1867 reflections. I-DMF C48H34N808.2C3H,N0.'/2(H20), mol wt = 1006.05, monoclinic, P2,/c, a = 13.692 (5) A, b = 12.231 (7) A, c = 17.140 (2) A, fl = 118.82 (2)O, V = 2515 (2) A3,Z = 2, d(calcd) = 1.328 g *Address correspondence to this author at Kochi National College of Technology. Shionogi Research Laboratories. 'Osaka University.
Scheme I OC-CH
0- N
CH
N-0
'@
/
'co
DMSO DMAc DMF
I
A G=GUEST a
: Me150
:;:>
H
S=O b : DMA
CHI CHI,
N-
1
-CHI
c
: DMF
CHl/N-;---H
0
0
Table I. Desolvation Temperatures and Weight Losses of Three Inclusion Complexes Measured by the DTA-TG Method guest temp/' C wt loss/%"
Me,SO 243 DMA 193 DMF 189 "Calculated weight loss in the release stage of
16 (15.5) 16 (17.0) 13 (14.6)
two guest molecules.
R = 0.061 for 2363 reflections. Intensity data were collected on a Rigaku AFC-5R diffractometer using graphite-mono( 1 ) Earl, J. C.; Mackney, A. W. J. Chem. SOC.1935,899. (2) Eade, R. A.; Earl, J. C. J. Chem. SOC.1946,591. (3) Backer, W.; Ollis, W. D.; Poole, V. D. J . Chem. SOC.1950, 1542. (4) Backer, W.; Ollis, W. D. Q. Rev., Chem. SOC.(London) 1957,II,15.
(5) Huisgen, R.; Grashey, R.; Gotthardt, H.; Schmidt, R. Angew. Chem. 1962,74. 29. (6) Huisgen, R.; Gotthardt, H.; Grashey, R. Angew. Chem. 1962,74, 30. (7) Weintraub, P. M. J . Chem. Soc., Chem. Commun. 1970,760. (8) Oda, R.; Takagi, K.; Shono, T. J. Polym. Sci. 1969,8 7 , 11. (9) Takagi, K. Bull. Kochi Tech. Coll. 1969,4, 45. (10) Yashumskii, V. G.; Kholodov, L. E . Zh. Obshch. Khim. 1%2,32,366; Chem. Abstr. 1963,58, 13939. ( 1 1 ) Cava, M. P.; Deana, A. A.; Muth, K.; Mitchell, M. J. Org. Synrh. 1973,V , 944. (12) Me,SO: dimethylsulfoxide; DMA: N,N-dimethylacetamide; DMF: N,N-dimethylformamide.
0002-7863/92/1514-8414$03.00/00 1992 American Chemical Society
Cycloaddition of 3-Sydnone and N - Phenylmaleimide
J . Am. Chem. SOC.,Vol. 114, No. 22, 1992 8415 Table 11. Selected Bond Distances (A) and Bond Angles (deg) in I-DMA and I-DMF I-DMA Bond Lengths 1.202 (8) 1.215 (8) 1.482 (8) 1.469 (8) 1.422 (8) 1.537 (8) 1.401 (8) 1.370 (8) 1.441 (9) 1.501 (8) 1.514 (8) 1.542 (8) 1.507 (8) 1.412 (17) 1.150 (19) 1.578 (19) 1.546 (16) 1.495 (19)
22
Figure 1. ORTEP plot of I-DMA with the atom numbering system. Ellipsoids are scaled to enclose 30% of the electronic density.
chromatized Cu Kcr radiation (A = 1.541 78 A). The structures were solved by the use of the program MULTAN-84.14 The guest molecule was assumed to be disordered because the different sites of the disordered molecules were not located in a difference Fourier map. The structure was refined by the blockdiagonal least-squares method using the positional and anisotropic thermal parameters for the non-H atoms. Hydrogen atoms, excluding those of the guest molecule, were refined with the fixed temperature factors set equal to B 's of the bonded atoms. Absorption corrections were applied &er isotropic least-squares refinement by an empirical method based on the differences between the observed and calculated structure factors.I4 Atomic scattering factors were evaluated by f = Z[ai exp(-biA-2 sin%)] + c ( i = 1, ... 4).15 Weights were taken as w = [a2(F,) 0.00421Fo12]- 1 for the reflections with W I / ~ (< M4,~and w = 0 otherwise. No peaks larger than 0.2 e were found in the last difference electron density map. The comparatively large R values may be due to the poor quality of intensity data measured by using very small and inferior crystals and to the disordered structure of the guest molecules. Computations using the programs PLUT0I6 and KPACK86 SHIONOGI" were performed on a FACOM X-730 computer a t Shionogi Research Laboratories. A perspective view of the host and the guest molecules in I-DMA (with a different numbering system from that of Scheme I) is shown in Figure 1, and some of the bond distances and bond angles are listed in Table 11. The host molecule occupies a centrosymmetric site with mostly normal bond lengths and angles. The two phenyl rings, C(13)
