Influence of electron-electron scattering on electron relaxation rates in three and four-level quantum cascade lasers in magnetic fields

The aim of this work is to calculate carrier relaxation rates from the upper laser level due to electron-electron interactions in three and four-level quantum cascade lasers (QCLs) in a strong magnetic field. The comparison between calculated results and previously obtained values for acoustical and optical-phonon scattering processes indicates that carrier-carrier scattering might have noticeable influence on laser output properties, depending on the structural design. Numerical results are presented for two λ ∼ 9 μm GaAs-based QCLs in magnetic fields between 20 T and 60 T and the band nonparabolicity is taken into account.     

Synthesis and mesomorphic properties of naphth-2-yl 2-pyridylmethyl ketones and their copper (II) complexes

The synthesis, characterization and mesomorphic properties of a homologous series of 6-alkoxy naphth-2-yl 2-pyridylmethyl ketones and their copper(II) complexes are reported. All the ligands and their copper complexes, with exception of the lowest homologues, exhibit enantiotropic mesophases. According to textural observations, the ligands display nematic and smectic transitions depending on the length of the alkoxy chain on the pyridine moiety, while the mesogenic complexes show exclusively smectic transitions. In comparison with the phenyl analogues, stabilization of the mesophase and a greater tendency to smectic ordering through incorporation of the naphthyl group into the molecules is confirmed.     

syn/anti Diastereoselectivity in the Aldol Reaction of Aldehydes with the C(3) Carbanion of 1,3‐Dihydro‐2H‐1,4‐benzodiazepin‐2‐one

The aldol reaction of the C(3) carbanion of 7‐chloro‐1,3‐dihydro‐1‐methyl‐5‐phenyl‐2H‐1,4‐benzodiazepin‐2‐one ( 2 ) with a series of aromatic and aliphatic aldehydes at −78° afforded threo/erythro diastereoisomers 3 – 16 of 7‐chloro‐1,3‐dihydro‐3‐(hydroxymethyl)‐1‐methyl‐5‐phenyl‐2H‐1,4‐benzodiazepinones, substituted at the C(3) side chain, in a ratio from 55 : 45 to 94 : 6 (Scheme 1). Lewis acids exhibited limited effect on the syn/anti diastereoselectivity of this reaction, and kinetic control of the reaction was confirmed. ¹H‐NMR Data suggested the assignment of the threo relative configuration to the first‐eluted diastereoisomers 3 , 5 , 7 , and 9 on reversed‐phase HPLC, and the erythro configuration to the second‐eluted counterparts 4 , 6 , 8 , and 10 , respectively. The structures and relative configurations threo and erythro of the diastereoisomers 5 and 6 , respectively, were established by single‐crystal X‐ray analysis, confirming the assignment based on the ¹H‐NMR data. A tentative mechanistic explanation of the diastereoselectivity invokes the enolate anion of 1,3‐dihydro‐2H‐1,4‐benzodiazepin‐2‐one as the reactive species (Scheme 2). Acid‐catalyzed hydrolytic ring opening of 3 afforded threo‐β‐hydroxy‐phenylalanine 17 , whereas from 4 , the N‐(benzyloxy)carbonyl derivative 18 of erythro‐β‐hydroxy‐phenylalanine was obtained (Scheme 3); in both cases, neither elimination of H₂O from the C(3)−CHOH moiety nor epimerization at C(3) were observed. This result opens a new pathway to various configurationally uniform α‐amino‐β‐hydroxy carboxylic acids and their congeners of biological importance.     

New synthesis of 7-bromo-1, 3-dihydro-3-hydroxy-5-(2′-pyridyl)-2H-1,4-benzodiazepin-2-one

A new synthesis of 7-bromo-1,3-dihydro-3-hydroxy-5-(2′-pyridyl)-2H-1,4-benzodiazepin-2-one ( 5 ) is described. Starting from bromazepam ( 3 ), C(3) acylation with lead tetraacetate/potassium iodide in acetic acid affords 4 , while its mild hydrolysis according to our recently described method (5) gives 5 . Improved hexamine cyclization of 1 into 3 , via quaternary hexaminium salt 2 , is discussed, and identification of the intermediates 7 and 8 is performed. Compound 5 undergoes on melting, or on brief heating in glacial acetic acid, the thermal rearrangement into quinazolin-2-aldehyde ( 13 ), the structure of which is confirmed by oxidation into the ester 14 , which in turn was hydrolyzed to the acid 15 . The same compound ( 5 ) rearranges on heating with manganese(III) acetate in acetic acid into the 3-amino-2-quinolone derivative 6 . On heating in glacial acetic acid in the presence of lead tetraacetate/potassium iodide (or iodine), compound 4 , in addition to giving the aldehyde 13 , ester 14 and acid 15 rearrangement products, affords 1,2-dihydroquinazolin-2-carboxylic acid 16 .     

Absolute Conformation and Configuration of (2S, 3S)-3-Acetoxy-5-(dimethylaminoethyl)-2-(4-methoxyphenyl)-2,3-dihydro-1,5-benzothiazepin-4(5H)-one Chloride (Dilthiazem Hydrochloride)

Resolution of racemic cis-3-(2-aminophenylthio)-2-hydroxy-3-(4-methoxyphenyl) propionic acid ( 2 ) via the cinchonidine salt 3 , and brucine salt 4 , isolation of the calcium salts (+)- and (?)- 5 , as well as their cyclization to enantiomeric 1,5-benzothiazepines (+)- and (?)- 1 , are described. X-Ray single-crystal analysis reveals (2S, 3S) absolute configuration of (+)- 1 on the basis of tentative comparison of CD data with those for the 1,4-benzodiazepine derivative (+)- 8 of known absolute configuration.     

Two-step asymmetric synthesis of disubstituted N-tosyl aziridines having 98-100% ee: use of a phosphazene base

Unknown diaryl (1-3) and alkyl-phenyl (4, 5) N-tosyl aziridines have been successfully synthesized from pure (R,R,R,S(S))-(-)-sulfonium salt derived from Eliel's oxathiane, tosylimines 11a-f, and using a phosphazene base (EtP(2)) to generate the ylide. Both cis and trans aziridines have exceptionally high enantiomeric purities (98.7-99.9%). The (2R,3R)-configuration of trans-3 and the (2R,3S)-configuration of cis-4 have been determined by X-ray analysis using the Bijvoet method. The R-configuration found at C2 is consistent with the model and all previous results, therefore all trans-aziridines and cis-aziridines have been assigned the (2R,3R)- and the (2R,3S)-configurations, respectively. This two-step asymmetric synthesis can be easily used on gram quantities and involves no unstable/hazardous reagent. The chiral auxiliary is used in a stoichiometric amount but is recovered in high yield and reused.     

Chiral 1, 4-Benzodiazepin-2-one,template for enantioselective synthesis of α-amino acids and their α-deuterio congeners. Preliminary communication

Absolute conformation of 7-chloro-5-phenyl-1-[(S)-α-phenylethyl]-1, 3-dihydro-2H-1, 4-benzodiazepin-2-one ( 1c ) in crystal, and its inversion rate in solution were determined, enabling prognosis of direction of asymmetric induction during C(3)-alkylation.     

CD Spectroscopic Study of Absolute Conformation and Configuration of Some 4-Hydroxychromans

CD data of the optically active 4-hydroxy (1–5) and 4-acetoxy chromans (6–8) were analyzed by two different approaches. The Snatzke-Antus treatment of chiraly perturbed chromane chromophore revealed M absolute conformation and 4S absolute configuration of the alcohols, i.e. P absolute conformation and 4R absolute configuration of the acetates. The proposed absolute configuration of the optically active alcohols was confirmed for 1 and 2 by the chiral excitone coupling method applied on their benzoates 9 and 10.     

(−)-Isocamphoric Acid Building Block for Chiral Liquid Crystals

The synthesis and liquid-crystal properties of the novel chiral (−)-isocamphoric acid ester 8 are reported. Although the new material is not itself mesogenic, it induces chirality in the nematic and smectic-C phase of an achiral host. A proposed mechanism for the chiral induction according to the `intercalated chirality' model opens the possibility for fine-tuning the chiroptical properties of the induced chiral mesophases.