ChemInform Abstract: NEUE DARST. DER PHOSPHOLE, EXPERIMENTELLE ERGAENZUNGEN, SPEKTRALE ANGABEN

Abstract

Die Phosphine (I) reagieren mit den Dienen (II) zu Additionsverbindungen, aus denen unter Einwirkung der Bicycloverbindung (III) die Phosphole (IV) entstehen.

Phosphaferrocene

“…The endodisulfide unit in 6 could be prepared under carefully chosen conditions which precluded further oxidation and other side reactions. 5 Specifically, upon treatment of 5 with 1.5 equiv of active manganese dioxide in degassed toluene at -20 °C for 40 min under argon,6 6 was formed along with minimal side products, and could be isolated in 86% yield after column chromatography on silica gel using cyclohexane-ethyl acetate (4:1) as eluent. Removal of the tetrahydropyranyl ether from disulfide 6 (acetic acid-water-tetrahydrofuran, 12:3:2) at 40 °C for 1 h afforded the disulfide analogue of PGH2 (1) in 49% isolated yield; [a] lsD +3.6°( c 0.6, chloroform).7 The structural assignment follows from (a) the mass spectrum (molecular ion at m/e 398.1959, caled 398.1949); (b) the IR spectrum; and (c) a negative Ellman test8 on TLC assay.9…”

“…Structure of the phosphaferrocene 5 showing the 50% probability ellipsoids. Selected bond distances (in Á) are: C(l)-C(2),1.408 (7); C(2)-C(3), 1.414(6);C(3)-C(4), 1.403(7); P-C(l),1.758 (5); P-C(4),1.768 (5);C(2)-C(5),1.503 (8); C(3)-C(6),1.516 (8); C(7)-C(8),1.378 (12); C(8)-C(9),1.411 (9);C(9)-C(10),1.412 (10); C(10)-C(l 1),1.393…”

Rhodium(I) and (III) Complexes of Some Phospholes and Their Behavior as Homogeneous Hydrogenation Catalysts

“…I-Phenylphosphole (14), the other phosphole ligands (1 ), hydridocarbonyltris(triphenylphosphine)rhodium(l) (15), chlorobis(carbonyl)rhodium(l) (16), and chlorobis(ethylene)rhodium(I) (17) were prepared as described in the literature. Rhodium trichloride hydrate was obtained from Engelhard Industries.…”

Polycyclic carbon-phosphorus heterocycles

“…Thermal cycllzation of arenephosphonic acids in vacuo at elevated temperatures (350-370 °C) has afforded, in limited cases, polycyclic C-P compounds in low yields (20- dibenzo [ c,e] phosphepin (261) as the major product (30%) resulting from a rather unusual cyclodephosphonation process.296…”

“…Freshly prepared PPA has also been employed to effect cyclization of the acid 282a to the oxide 283a (50 % ).311 Phosphine 282 283 (50%) a, R = Ph; b, R = OH; c, R = OMe oxide 283a (mp 222-223 °C) showed absorptions in the UV spectrum (ethanol) at 240 (shoulder, log c 5.26), 261 (4.93), and 284 (4.96) nm and a parent peak at m/e 304 in the mass spectrum. 311 The mass spectrum of the related systems 283b and 283c have also been studied in some detail.132 A notable feature in the mass spectrum of 283b was the loss of P02H and C=0 from the molecular ion (m/e 244) to give intense ions at m/e 180 (100%) and m/e 216 (64%).…”