5750
J . Org. Chem. 1990,55, 5750-5756
1.36 cm-'; F(000) = 512, T = 295 K. (Na2S04). Evaporation of the solvent left a pale yellow residue (110 mg). This was chromatographed on silica gel with etherA clear colorless 0.10 X 0.20 X 0.45 mm crystal, shaped like pentane (l:l), giving first the cubane 6 (37 mg, 39%) and then a rectangular prism, was used for data collection on an automated the cuneane 7 (32 mg, 34%). 6: mp 112-113 "C; IR (KBr) v 2991, Nicolet R3m/V diffractometer with incident beam monochro2982,2938,1695,1415,1383,1093,1041,750,569cm-'; 'H NMR mator. Lattice parameters were determined from 30 centered 6 4.34 (m, 4 H), 3.88 (m, 2 H), 2.79 ppm (s, 6 H);13CNMR 6 162.5, reflections within 20 5 20 5 30'. The data collection range of 67.8,54.8,42.6, 27.5 ppm; m/e 188 (P+,80), 162 (100). Anal. Calcd hkl was: 0 I h I 10, -6 S k S 0, -17 SI S 17, (sin(0)/A),, = for CllH12NzO:C, 70.19; H, 6.42; N, 14.88. Found: C, 70.11; H, 0.5384 Three standards were monitored every 60 reflections 6.47; N, 14.72. 7: mp 78-79 "C; IR (KBr) u 3043,3011,2923,1699, and exhibited a maximum random variation of 2.0% during data 1684, 1427, 1377, 1087,923,809,750,574,467 cm-'; 'H NMR 6 collection. A total of 1562 reflections were measured in the 8/28 mode with a variable 20 scan rate, ranging from 10.0 to 31.2 3.07 (m, 2 H), 2.77 (s, 6 H), 2.63 ppm (m, 4 H); 13cNMR 6 161.5 deg/min. There were 1262 unique reflections, and 1121 were (s), 67.8 (s), 46.2 (d, J = 154 Hz), 3.16 (d, J = 180 Hz), 28.1 (4) observed with F, > 3a(F,). The structure was solved by direct ppm; m/e 188 (P+,lo), 162 (100). Anal. Calcd for CIlH12N20: C, 70.19; H, 6.42; N, 14.88. Found: C, 70.08; H, 6.31; N, 14.75. methods with the aid of program SHELXTL.17 The full-matrix least-squares refinement varied 188parameters: atom coordinates, 3,5-Dinitro-3,5-diazahexacyclo[5.4.0.02~6.Oz~1o.O6~s.Oe~11]undeanisotropic thermal parameters for all non-H atoms, and isotropic can-4-one (8). 100% Nitric acid (315 mg, 5.00 mmol)I4 was thermal parameters for the hydrogens. Final residuals were R injected dropwise into a stirred solution of dry CHzC12(3 mL) = 0.034 and R, = 0.041 with final difference Fourier excursions and acetic anhydride (510 mg, 5.00 mmol) at 0 "C under argon. of 0.17 and -0.23 e A-3. After 30 min at 0 "C, the reaction mixture was allowed to warm to room temperature and then recooled to 0 "C. Powdered cuAcknowledgment. This work was supported by the banourea 2 (65 mg, 0.41 mmol) solid was added all at once; stirring Office of the Naval Research arid the U.S. Army Research, was continued at 0 "C for 2 h. Crushed ice was then added, and Development and Engineering Center (via Geo-Centers, the mixture was extracted with CH2C1, (3 X 10 mL). The extract was washed with water, dried (NaZSO4),and evaporated under Inc.). reduced pressure to give fine crystalline needles of 8 (83 mg, 82%): Registry No. 1, 129103-49-7;2, 129103-50-0;5, 129103-52-2; mp 210 "C dec, IR (KBr) u 1802, 1573, 1310, 1160, 1140, 1015, 6, 129103-53-3; 7, 129103-54-4; 8, 129103-55-5; cubane-1,2-di279 nm (e 5500); 'H NMR 883,729,699 cm-'; UV (CH3CN) A,, carboxylic acid, 129103-51-1. 6 4.69 (m, 4 H), 4.19 ppm (m, 2 H); I3C NMR 6 141.2, 63.1, 54.9, Supplementary Material Available: 13C NMR spectra of 43.6 ppm. Anal. Calcd for CSH6N4o5:C, 43.21; H, 2.41; N, 22.39. compounds 1 and 5; numbered ORTEP drawings of compounds 2 Found: C, 43.,07; H, 2.27; N, 22.13. and 8; tables of atomic position parameters, Cartesian coordinates, Single-crystal X-ray diffraction analysis of 3,5-dinitrobond distances, bond angles, torsion angles, and anisotropic 3,5-diazahexacyclo[ 5.4.0.02~6.02J0.06~s.0e~11]undecan-4-one: thermal parameters for both X-ray structures (11 pages); tables CSH6N4o5,FW = 250.2; monoclinic space group P2,/c; a = 9.669 of observed and calculated structure factors (12 pages). Ordering (3), b = 5.972 ( l ) ,c = 16.584 (6) A; /3 = 91.12 (3)"; vol. = 957.3 information is given on any current masthead page. (5) A3; 2 = 4; pcslc = 1.736 g/cm3; X(Mo Ka) = 0.71073 A; p =
Photochemistry of Functionalized Diphosphiranes Maryse Gouygou, Christine Tachon, and Max Koenig* URA 454, Uniuersit6 Paul Sabatier, 31062 Toulouse Cedex, France
Antoine Dubourg Facult6 de Pharmacie, Avenue Charles Flahaut, 34060 Montpellier, France
Jean-Paul Declercq Universite Catholique de Louuain, I , Place L. Pasteur, B-2348 Louuain-La-Neuue, Belgium Joel Jaud and Guita Etemad-Moghadam Laboratoire de Chimie de Coordination du CNRS, 205, Route de Narbonne, 31077 Toulouse Cedex, France Received February 21, I990 The structure of the functionalized trans-diphosphiranes la-e, obtained by reaction of halogenocarbenes with the trans-diphosphene is confirmed by X-ray diffraction. The photolysis of la-e lead to the functionalized cisand trans-1,3-diphosphapropenes2a-e as major products, via the diphosphiranyl7 and the diphosphapropenyl 8 radical intermediates. The latter are characterized by ESR spectroscopy using the spin-trap method. The trans configuration of 2a is also confirmed by X-ray diffraction. The mechanism of the ringopening, involving P-P bond rupture, is discussed.
Whereas gem-dihalocyclopropanes are known to undergo thermally promoted skeletal rearrangements t o 1,Z-dihaloprop-2-ene derivatives' (Figure 1, reaction A), their (1) (a) Duffey, D. C.; Minyard, J. P.; Rane, R. H. J . Org. Chem. 1966, 31, 3865-38. (b) Baird, M. S.; Lindsay, D. C.; Reese, C. B. J . Chem. SOC. C 1969. 1173-1178.
0022-3263/90/1955-5750$02.50/0
photochemistry is different. For example, the irradiation of gem-dichloroarylcyclopropaneswith UV light produces a dichlorocarbene (Figure 1, reaction B),2characteristic of reactions analogous to the photochemical fragmentation (2) Jones, M., Jr.; Sachs, W. H.; Kulczycki, A,, Jr.; Waller, F. J. J . Am. Chem. SOC.1966, 88, 3167-3168.
0 1990 American Chemical Society
Photochemistry of Functionalized Diphosphiranes
J . Org. Chem., Vol. 55, No. 22, 1990 5751
Figure I . IAJThermal ring opening uigrm-dihal~.vclopri~p~es tX = CI. Br). (R) Photochemical fraRmenration uf grm-dirhlorocycluprupanes. ((:) Photochemical ring opening and photoreduction of gem-dibromocyclopropanes. CIS Ar\ @ ffP-P\ar
*r=
* :c
