Hirotaka Shimanouchi

3-(9-Adenyl)propionyltryptamine Monohydrate

C18HlgNTO.H20, FW 367.41, triclinic, Pi, a = 9.289 (2), b = 20.013 (3), c = 5.018 (1) A, a = 96.81 (1), fl = 96.22 (2), ~,= 78.08 (2)°, Z = 2, Dx= 1.351, D m = 1.350 g cm -3, a(Mo K~0 = 1.01 cm -l. The structure was solved by the direct method using diffractometer data and was refined by a block- diagonal least-squares method. The final R value was 0.137 for 2493 reflexions. The molecule is fully extended. Two adenine bases, related by a centre of symmetry, are paired through two N(6)H--.N(1) hydrogen bonds. The adenine moiety links to the indole in a different molecule through an N(3)---HN(indole ) hydrogen bond. This mode of interaction is the same as that found in the 9-ethyl- adenine-indole complex, implying that a typical inter- action mode between adenine and tryptophane is present. squares method; the quantity minimized was E w(IFol - IFcl) 2, with w = 1/(a~ + qF2o), where op is due to counting statistics and q is 1-25 × 10 -5 (derived from the intensity variances of the monitored reflexions). In

Structural chemistry of the 8,8-dicyanoheptafulvene system. II. The crystal and molecular structure of 1,6-dimethyl-8,8-dicyanoheptafulvene

1,6-Dimethyl-8,8-dicyanoheptafulvene, CI2HloN2, crystallizes in yellow plates, space group P21/c, with a=8.787 (3), b= 13.274 (3), c=9.157 (3)/~, fl= 104.21 (3) ° and Z=4. The crystal structure was solved by the symbolic addition method and refined by the full-matrix least-squares method. The final R value was 0.086. The molecule has essentially m symmetry through the exocyclic double bond. The seven-membered ring takes a deep boat form and has a definite bond alternation. Some structuralchemical features of the 8,8-dicyanoheptafulvene system are discussed.

Photoinduced transformations. Part XXX. Photorearrangement of (22S,25S)-N-acetylveratra-5,8,13(17)-trienine-3β,11β,23β-triol 3,23-diacetate 11-nitrite, a fused cyclopentenyl nitrite, to two spiroisoxazolines

Irradiation of the title nitrite (3) in protic or aprotic solvents with Pyrex-filtered light induced an extensive rearrangement to afford two products with novel isoxazoline structures, designated photo-TVTTN and isophoto-TVTTN, in good yields. The structure and absolute configuration of photo-TVTTN (4) were determined by chemical and spectroscopic studies and by an X-ray crystallographic analysis of an iodine-containing derivative (14). The structure and absolute configuration of isophoto-TVTTN (5) were deduced by spectroscopic studies.A photoreaction carried out with monochromatic light (362 ± 4 nm) confirmed that light was only involved in homolysis of the O–NO bond, and that photo- and isophoto-TVTTN were formed via an unstable hydroxyimino-aldehyde (19), which was isolated. The hydroxyimino-aldehyde was transformed smoothly into photo- and isophoto-TVTTN on silica gel during t.l.c. Whereas the silica gel-induced transformation was non-stereoselective, leading to both photo-(4) and isophoto-TVTTN (5), the transformation of the hydroxyimino-aldehyde with acetic acid or [2H]acid was stereoselective, giving mainly isophoto-TVTTN (5) or [9β-2H]isophoto-TVTTN (21), respectively. Deuterium is incorporated into the TVTTNs in the course of intramolecular Michael reaction catalysed by acetic [2H]acid. This unusually ready intramolecular reaction seems to be the first reported example of a Michael addition of an oxime hydroxy-group to an αβ-unsaturated carbonyl system.

Crystal and molecular structure and absolute stereochemistry of cularine methiodide

The structure of cularine has been determined by three-dimensional X-ray diffraction analysis of its methiodide. Crystals are monoclinic, with Z= 4 in a unit cell of dimensions: a= 22·31(5), b= 8·43(12), c= 11·71(9)A, β= 90·9(1)°, space group P21. The structure was solved from photographic data by the heavy-atom method and refined by least-squares to R 0·100 for 1416 observed reflexions. The absolute configuration has been determined by the method of anomalous dispersion as L(S). On the basis of this work all cularine-type alkaloids also have the L(S)configuration.

Crystal structure of corynoline p-bromobenzoate

Crystals of the title compound (3) are monoclinic, space group P21/c with Z= 4 in a unit cell of dimensions: a= 12·598(88), b= 14·868(67), c= 13·592(79)A, β= 115·30(43)°. The structure was solved from diffractometer data by the heavy-atom method and refined by least-squares methods, to R 0·165 for 2008 observed reflexions. The B/C ring junction is cis-fused and rings B and C take the half-chair and the twist-half-boat conformations, respectively.