According to the above results the "alkene-created part" of the pyrrolidines obtained by [1,3]-anionic cycloaddi-tionr2] always has the configuration of the alkene used in the reaction, thus indicating stereospecific cis-addition of the alkenes (no alternative in the case of acenaphthylene). In the "azaallyl-created part" the phenyl residues of the pyrrolidines always have cis-configuration, thus proving that the stereospecific addition always involves the same 1,3-diphenyl-2-azaallyl anionr5'. The findings are best interpreted in terms of a symmetry allowed one-step [n41 + n2,]-cycloaddition of 1,3-(trans,trans)-( I ) or 1,3-(cis,cis)-diphenyl-2-azaallyl anion ( 5 ) according to the principle of conservation of orbital symmetry [']. The trans,trans configuration of the anion undergoing addition is thus much more probable since the anion of the comparable 1,3-diphenyl-allyllithium in THF at 0°C is always present in this configurationr5. 61. The transpans configuration of the 1,3-diphenyl-2-azaallyl anion at 0°C can also be deduced from the irreversible, and obviously quantitative configurational rearrangement of 1,3-(cis,trans) -diphenyl-2-azaallyl anion (6) on warming from -60°C to O°C[81, since the thermodynamic stability should increase along the series cis& < cis,trans < trans,trans (completely coplanar, strain-free conformation is possible only in the case of transpans). However, confirmation of the trans,trans conformation by direct NMR investigation has not, as yet, been reported.

with a coupling constant of 16 Hz. The signal of the phenyl protons ortho to the imino nitrogen atom is a multiplet centered at 7 = 2.4 (relative intensity 2); and that of the remaining aromatic protons is a multiplet centered at T ~ 2.8 (relative intensity 8). Analogous substances provide an indication of the shift of signals of the CH2 protons on the four-membered ring to lower field owing to the neighboring nitrogen atom. Further, we also derive structure ( I ) from the mass spectrum, specifically from the appearance of the ion M-42 and of a fragment at m ' e 42 (H~C-N-CHZ). The compound is found to have molecular weight 234. The UV spectrum (in alcohol) includes a n absorption band at 244 nm (E = 12200). In the I R spectrum (KBr) the C = N absorption is at 6.2 pm and, remarkably, three absorption bands occur between 9.98 p n and 10.16 pm. It is tempting t o ascribe the formation of ( I ) to addition of ketene phenyl imine t o phenylazirine. According t o Smolinsk y 111, phenylazirine and ketene phenylimine coexist after pyrolysis of c/.-azidostyrene. The characteristic ketene imine absorption[ll at 5 pm in the IR spectrum of our reaction mixture after photolysis can be explained by presence of a small amount of ketene phenyl imine. However, no trace of ( I ) is t o be found in the gas chromatogram after pyrolysis of a-azidostyrene at 350 "C. Nor is any trace of ( I ) t o be found in the mixture obtained o n addition of azidostyrene t o boiling phenylazirine (ca. 180 "C). From our results, together with the observation that ( I ) is also formed on photolysis of phenylazirine, we conclude that it is formed by photochemical and not by thermal activation. This is thus the first case of intermolecular photocycloaddition t o a carbonnitrogen double bond. [3] Mercury high-pressure lamp: Philips HPK 125 W. 141 The NMR spectra were measured with a Varian A-60 apparatus for CC14 solutions with tetramethylsilane as internal standard. The synthesis of Ru~C15[P(n-C4H9)3]4 has been described recently and the results of chemical investigations suggest 111 the structure ( I ) . The complex has a magnetic moment of 0.75 B.M. per ruthenium atornI21 corresponding to one unpaired electron in the molecule. The dark red crystals are monoclinic, space group P21,'c with a = 13.866, b = 16.003, c = 30.545 A, p = 110.0". There are four molecules in the unit cell and the observed density gives a molecular weight of 1170.7 (theoretical 1188.8). The intensities were measured on a linear diffractometer [31 and the structure was determined by Patterson and Fourier methods.A least squares refinement of 3776 planes gives a current R-factor of 0.083. The standard deviations of the Ru-CI and Ru-P bond lengths are 0.0052 and 0.0054 8, respectively.+ 2 333 1 2 3 2 6The X-ray analysis confirms the structure ( I ) and the Ru-CI and Ru-P distances are shown in the figure. The coordination round the ruthenium atoms is approximately octahedral (the largest angular distortion is 12.4 ") and the environments of these atoms are very similar. The Ru....R...

munication on a total synthesis16] we now publish our results on a biogenetically oriented indole-camptothecin rearrangement.Using the easily accessible indolic compound (3)"l as starting material, the indole-quinoline conversion could be carried out in two simple steps.

7 6 5 4 3 2 1 (3) ( 3 ) ( 4 ) ( 4 ) 14) Figure. ' H -N M R spectrum of bis(dipivaloylmethyl)rnercury(rI) ( 4 ) in CDCI, at -40°C. a: HC (ketone); b: HC (enol); c: (H,C),C (ketone); d: (H,C),C (enol). Styrene 20 [b] 2,2,3-Triphen-85 86-87 ylpyrrolidine Tolan 20 [bl 2,2,3,4-Tetra-43 138-139 phenylpyrroline ylpyrrolidine Styrene 0 2,3,5-Triphen-75 68 frans-0 2,3,4,5-Tetra-39 110-1 1 1 Stilbene phenylpyrrolidine Tolan 40 [cl 2,3,4,5-Tetra-73 215-2171dl phenylpyrrole reaction of the $-diketones (7) and (8) with bis(hexamethy1-disi1ylamido)mercury ( 9 ) 18991 in dry ether. In this manner it was possible t o prepare for the first time the sparingly soluble compound (5) in analytically pure form. The methods given in the literature[los '11 always lead t o products which contain OH, acetate, or C1 as ligands, and which are ca. 3 % deficient in carbon, and exhibit several intense bands in the C=O region of the IR spectrum[121. Since pure (S), like ( 4 ) (in KBr), shows only one sharp C=O band at 1678 cm-1, the metal in mercury(rr) acetylacetonate (5) must also be bonded t o the central C atom. Bis(diucefylmethyl)inercury(rlJ (5)A solution of acetylacetone (8) (12.02 g) in ether (SO ml) is added with stirring t o a solution of ( 9 ) (3.24 g) in absolute ether (30 ml). A finely crystalline, colorless precipitate is formed immediately, yield 2.51 g (100 %). After recrystallization from acetylacetone, compound (5) decomposes at temperatures above 254 "C. The compound is very sparingly soluble in all common solvents. Bis(dipivaloylmethyl)mercury(~~) (4) has been prepared inthe same way; yield 91 %, m.p. 1 9 S 1 9 7 ' C (dec.). Its IR spectrum can be superimposed o n that of the compound prepared from (7) and mercury(rr) acetate according t o the method given in ref. 161,

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