Tetrakis(1‐naphthylamino)silane and its tetrahydrofuran trisolvate

In both title structures, C₄₀H₃₂N₄Si and C₄₀H₃₂N₄Si·3C₄H₈O, the angles around the Si atom deviate significantly from the tetrahedral value [104.34 (7)–116.63 (7)° in the nonsolvate and 99.91 (15)–116.85 (15)° in the solvate]. The amino H atoms in the solvated structure are involved in hydrogen bonding with two of the tetrahydrofuran solvent molecules.     

Group theory for tetraammineplatinum(II) withC 2v andC 4v point group in the non-rigid system

The non-rigid molecule group theory (NRG) in which the dynamical symmetry operations are defined as physical operations is a new field of chemistry. Smeyers in a series of papers applied this notion to determine the character table of restricted NRG of some molecules. In this work, a simple method is described, by means of which it is possible to calculate character tables for the symmetry group of molecules consisting of a number of NH3 groups attached to a rigid framework. We study the full non-rigid group (f-NRG) of tetraammineplatinum (II) with two separate symmetry groups C2v and C4v. We prove that they are groups of order 216 and 5184 with 27 and 45 conjugacy classes, respectively. Also, we will compute the character tables of these groups.     

Stereospecific rearrangements during the synthesis of pyrrolidines and related heterocycles from cyclizations of amino alcohols with vinyl Sulfones

Conjugate additions of amino alcohols derived from alpha-amino acids to vinyl sulfones, followed by N-benzylation, chlorination, and intramolecular alkylation, provide a convenient route to substituted pyrrolidines. The process is accompanied by the stereospecific rearrangement of substituents from the alpha-position of the amine to the beta-position of the product and takes place via the corresponding aziridinium ion intermediates. Another type of rearrangement was observed during the reaction of (2-piperidine)methanol or 2-(2-piperidine)ethanol with phenyl trans-1-propenyl sulfone, in which the methyl group appears to migrate from the beta- to the alpha-position of the sulfone moiety. This process involves the isomerization of phenyl trans-1-propenyl sulfone to phenyl 2-propenyl sulfone by the addition-elimination of catalytic benzenesulfinate anion to the former vinyl sulfone, followed by conjugate addition of the amino group to the latter sulfone. Chlorination and intramolecular alkylation then afford the corresponding rearranged indolizidine and quinolizidine derivatives, respectively.     

Highly diastereoselective synthesis of new, carbostyril-based type of conformationally-constrained β-phenylserines

We have demonstrated that the readily available amido-keto compounds 5, with prearranged carbonyl and glycine moieties, under strongly basic conditions easily undergo complete and highly diastereoselective cyclization, affording a generalized and practical access to the conformationally constrained phenylserine derivatives 4. High chemical yields, virtually complete diastereoselectivity combined with the operational convenience of the experimental procedures render this method useful for preparation of these diastereomerically pure derivatives.     

Experimental study of effect of void volume fraction on neutron diffusion parameters in water

The dependence of the diffusion parameters including slowing down area, neutron diffusion length and migration length on the voided volume fraction in water has been studied experimentally. For this purpose, the PIEAS Neutron Transport Facility (PNTF) comprised of a 10 Ci Am–Be neutron source and a water filled aluminum tank with Perspex voided tubes has been designed and fabricated. A BF₃ detector was used for the neutron counting. The slowing down area was determined at the cadmium cutoff level. The diffusion parameters were determined first in the absence of voids. The experimentally measured values of the slowing down area, the diffusion length and the migration length have been found in good agreement with the corresponding values determined by other workers. By varying void volume fraction from 0% to 7.5%, the experimental measurements show a monotonic increase in the slowing down area from 58.71±2.6 to 71.28±3.2 cm², in the diffusion length from 2.95±0.13 to 3.11±0.13 cm and in the migration length from 8.21±0.165 to 8.99±0.169 cm. Our measurements show that the diffusion parameters exhibit a quadratic dependence on the void volume fraction.     

Three tetrahydroisoquinolinedione derivatives

N‐(2‐Chloro­benzyl)‐1,2,3,4‐tetra­hydro­iso­quinoline‐1,3‐dione, C₁₆H₁₂ClNO₂, crystallizes in P2₁/n with three crystallographically independent mol­ecules in the asymmetric unit, which differ slightly in conformation, N‐(2‐bromo‐4‐methyl­phenyl)‐1,2,3,4‐tetra­hydro­iso­quinoline‐1,3‐dione, C₁₆H₁₂BrNO₂, crystallizes in P2₁/n with one mol­ecule in the asymmetric unit andN‐(2,3‐di­chloro­phenyl)‐1,2,3,4‐tetra­hydro­iso­quinoline‐1,3‐dione, C₁₅H₉Cl₂NO₂, crystallizes in P2₁/c with one mol­ecule in the asymmetric unit. In all three structures, the heterocyclic rings adopt approximately planar conformations. The pyridine rings are orthogonal to the substituted phenyl rings. In all three structures, the crystal packing is stabilized by intermolecular C—H?O hydrogen bonds.     

The α‐ and β‐epoxides of 3β‐acet­oxy‐5α‐lanost‐9(11)‐en‐7‐one

The structures of 3β‐acet­oxy‐9α,11α‐ep­oxy‐5α‐lanost‐9(11)‐en‐7‐one and 3β‐acet­oxy‐9β,11β‐ep­oxy‐5α‐lanost‐9(11)‐en‐7‐one, C₃₂H₅₂O₄, differ in their respective substituted cyclo­hexa­none rings but adopt similar conformations in the other three rings. In both of the crystal structures, weak inter­molecular C—H⋯O inter­actions are present.     

Studies of the formation of all-carbon quaternary centres, en route to lyngbyatoxin A. A comparison of phenyl and 7-substituted indole systems

Copper mediated allylic substitutions and conjugate additions to geranyl, cinnamyl and allylic indole compounds have been investigated with the aim of finding a method for the creation of the all-carbon quaternary centre present in the natural product lyngbyatoxin A. Reaction conditions have been found giving a 68% SN2' selectivity in the copper mediated addition of PhMgBr to geranyl chloride, as well as 99% and 95% SN2' selectivity in the copper catalysed addition of EtMgBr to cinnamyl chloride and acetate, respectively. When the optimised reaction conditions were applied to the corresponding allylic compounds containing a 7-substituted indole moiety, the regioselectivity was reversed giving only the SN2 product. The allylic indole-containing substrates were also found to be unproductive in Pd- or Mo-catalysed SN2'-type substitution reactions. In related studies, copper catalysed conjugate addition of EtMgBr to the tricyclic lactam 6-methyl-pyrrolo[3,2,1-ij]quinolin-4-one gave a maximum of 20% of the 1,4-addition product.