The microwave spectrum of urea

The microwave spectrum of urea has been recorded between 5 and 50 GHz. The rotational constants obtained from a least-squares fit of 47 b-type transitions are A = 11233.333, B = 10369.369, C = 5416.668 MHz. Centrifugal distortion constants were evaluated subject to the planarity constraints, giving satisfactory agreement up to at least J = 20. They are: τ_aaaa = ?0.04423, τ_bbbb = ?0.04075, τ_aabb = 0.02268, τ_abab = ?0.02806. The diagonal elements of the nuclear quadrupole coupling tensor are χ_aa = 2.16, χ_bb = 1.88, χ_cc = ?4.04. The dipole moment is μ = μ_b = 3.83 D (12.8 × 10^?30 Cm).     

Analysis of azanaphthalenes and their enzyme oxidation products by high-performance liquid chromatography, infrared spectroscopy and mass spectrometry

Adsorption and reversed-phase high-performance liquid chromatography (HPLC) have been successfully used to separate metabolites from the parent heterocycles (isoquinoline, 3-methylisoquinoline, phthalazine, quinazoline, quinoxaline and cinnoline). Retention data are reported. The metabolites, hydroxyazanaphthalenes, which arise as a result of aldehyde oxidase catalysed oxidation, could be extracted in microgram quantities from incubation mixtures by n-butanol. Complete identification of the oxidation products was achieved by collecting fractions corresponding to each compound from the HPLC eluate and subjecting these to infrared and mass-spectral analysis.     

The reactions of alkylamino substituted phosphines with I2 and (Ph2Se2I2)2: structural features of alkylamino phosphonium cations

The reactions of the tris-dialkylamino phosphines (Et2N)3P and (nPr2N)3P, and the pyrrolidinyl substituted phosphines (C4H8N)3P and tBuP(NC4H8)2, with I2 and (Ph2Se2I2)2, have been reported. The reactions with diiodine lead to the formation of [R3PI]I adducts, which are essentially ionic, but show a tendency to display long, soft-soft, II interactions in the solid state. The crystal structures of [(Et2N)3PI]I, (1), [(nPr2N)3PI]I, (2), and [(C4H8N)3PI]I, (3), have all been determined, and display II interactions varying between 3.5170(6) and 3.6389(14) A. The analogous reactions with (Ph2Se2I2)2 lead to the formation of phenylseleno-phosphonium salts, [R3PSePh]I. The structures of [(C4H8N)3PSePh]I, (6) and [(C4H8N)2tBuPSePh] I, (7), have been determined and do not display any soft-soft interactions between the selenium and iodine atoms. All of the phosphonium salts represent examples of structures containing tris-dialkylamino phosphine fragments which show no special nitrogen atom, i.e. all three nitrogen atoms are planar. This type of arrangement is usually observed when a C3 symmetric conformation is observed, (which is the case for 1 and 2), but not for the (C4H8N)3P adducts 3 and 6, where the conformation is closer to Cs, although the nitrogen atoms are still essentially planar. The P-N bonds in all the compounds reported herein are short, ranging between 1.599(12) A and 1.643(12) A, and are consistent with the previously reported short P-N bonds in phosphonium salts featuring tris-dialkylamino substituted phosphines.     

Properties of confined and sheared rhodamine B films studied by SFA-FECO spectroscopy

We have used a surface forces apparatus and multiple beam interferometry to measure the absorbance of thin films of rhodamine B in water/ethylene glycol solutions while applying and measuring normal and lateral (shear) forces. Both normal and shear forces induced changes in the absorption spectra indicating a change in molecular alignment, and rhodamine-rhodamine and rhodamine-surface interactions. We also measured differences in the absorbance spectra in different regions of the contact indicating, as expected, that the stresses are not uniform throughout the contact area. We also observed crystallization (solidification) parallel to the shearing direction.     

The total synthesis of d1-dihydrocallitrisin

Bromodiene $\text{2}$ is converted to $\text{dl}$-dihydrocallitrisin ($\text{1}$), a sesquiterpene lactone recently isolated from the heartwood of $\text{Callitris}$$\text{columellaris}$.     

The preparation of (-)-grandisine B from (+)-grandisine D; a biomimetic total synthesis or formation of an isolation artefact?

An efficient new alkyne-acetal cyclization procedure has been developed to prepare enantiopure indolizidine building blocks from l-proline and then applied to prepare the Elaeocarpus-derived alkaloids grandisine B and grandisine D in an efficient manner. However, evidence is presented which indicates that grandisine B does not occur naturally but is formed by reaction of grandisine D with ammonia during the extraction/purification process.     

Synthesis of indenoporphyrins, highly modified porphyrins with reduced diatropic characteristics

Indene-fused porphyrins have been synthesized starting from 2-indanone. Knorr-type reaction of oximes derived from benzyl or tert-butyl acetoacetate with 2-indanone and zinc dust in propionic acid gave good yields of indenopyrroles. Treatment with N-chlorosuccinimide then gave 8-chloro derivatives, and these reacted with 5-unsubstituted pyrroles to give dipyrroles incorporating the fused indene unit. Hydrogenolysis of the benzyl ester protective groups afforded the related dicarboxylic acids, but condensation with a dipyrrylmethane dialdehyde under MacDonald "2 + 2" reaction conditions gave poor yields of the targeted indenoporphyrins. However, when an indene-fused dipyrrole was converted into the corresponding dialdehyde with TFA-trimethyl orthoformate and then reacted with a dipyrrylmethane dicarboxylic acid, an indenoporphyrin was isolated in 26% yield. The porphyrin gave a highly modified UV-vis absorption spectrum with three strong bands showing up in the Soret region and a series of Q bands that extended beyond 700 nm. The proton NMR spectrum also showed a significantly reduced diamagnetic ring current where the meso-protons gave resonances near 9.3 ppm instead of typical porphyrin values of 10 ppm. Nickel(II), copper(II), and zinc complexes were also prepared, and these exhibited unusual UV-vis absorption spectra with bathochromically shifted Soret and Q absorptions. The diamagnetic nickel(II) and zinc complexes also showed reduced diatropic character compared to typical nickel(II) and zinc porphyrins.