Stereocontrolled synthesis of cis-dibenzoquinolizine chlorofumarates: curare-like agents of ultrashort duration

The quaternizations of dibenzoquinolizines 9 and 14 with 3-halo-1-propanols are highly cis-selective (94-100% cis), results consistent with the N-methylation of O-methylcapaurine (7b), but in contrast to the proposed trans-stereochemistry of dibenzo[a,h]quinolizine methiodide 10 and the analogous quaternizations of 1-benzyl- and 1-phenylisoquinoline congeners 5b and 5c. In this report, we describe stereoselective preparation of the unique cis-dibenzoquinolizinium propanols 15 and 16and their transformation into bis- and mixed-onium chlorofumarates 19, 20ab, and 26. Dibenzo[a,g]quinolizinium propanol 15 was prepared enantioselectively in three steps from dihydroisoquinoline 11. Asymmetric transfer hydrogenation of 11 in the presence of triethylamine/formic acid and Noyori's chiral ruthenium catalyst 12 produced R-(-)-5',8-dimethoxynorlaudanosine (13) in 98% yield and 87% ee. Pictet-Spengler cyclization of 13 in formalin/formic acid afforded the dibenzo[a,g]quinolizine 14 in 65% yield. Quaternization of 14 with 3-chloro-1-propanol under Finkelstein conditions generated cis-dibenzoquinolizinium propanol 15 in 85% yield with >94% cis-selectivity. The cis-dibenzo[a,h]quinolizinium propanol 16 was obtained as a single stereoisomer by reaction of the known tetramethoxyquinolizine 9 with neat 3-iodo-1-propanol. Bis-onium chlorofumarates 18 and 19 and the mixed-onium derivative 20ab were prepared by a pool synthesis procedure from (1R)-trans-6a, 16, and chlorofumaryl chloride (17). Mixed-onium alpha-chlorofumarate 26 was synthesized from (1S)-trans-6d, 15 and (+/-)-trans-2,3-dichlorosuccinic anhydride (22), employing a recently disclosed chlorofumarate mixed-diester synthesis. The title compounds (19, 20ab, and 26) displayed curare-like effects of ultrashort duration in rhesus monkeys.     

Using one- and two-dimensional NMR techniques to characterize reaction products bound to Chiron SynPhase crowns

Solid-phase MAS techniques have proved to be very useful in characterizing compounds bound to resin; however, little has been reported on using NMR to characterize compounds attached to Chiron SynPhase crowns. We have used proton, carbon, and COSY spectra obtained with a Varian Nano.nmr probe to characterize products from a published reaction sequence attached to MD (methacrylic acid/dimethylacrylamide copolymer) crowns. We have also performed solvent surveys to determine the best solvents for acquiring spectra of materials bound to both MD and PS (polystyrene) crowns.     

种植沙生植物--沙棘改善内蒙古地区生态环境

结合内蒙古地区现状，对沙棘的生物学和生态学特性、沙棘属植物化学成分和微量元素及种植沙生植物——沙棘的重要性和必要性进行了详细的研究和探讨。研究表明，沙棘属植物具有极强的生态适应性并富含多种营养成分和生物活性物质，并以耐干旱、耐瘠薄、萌蘖及固氮能力强等特点被称为治理非宜林地水土流失、改善生态环境的先锋树种。种植沙棘是治理内蒙古脆弱生态环境最经济、最有效的措施，是贫瘠的不毛之地发展经济、增加收入的经济树种。另外．种植沙棘的技术简便，容易掌握，投资少，见效快。     

Tandem Michael‐addition/cyclization synthesis and EGFR kinase inhibition activity of pyrido[2,3‐d]pyrimidin‐7(8H)‐ones

5‐Methoxy and 5‐anilinopyrido[2,3‐d]pyrimidin‐7(8H)‐ones 2a‐2f were obtained by a tandem Michael addition‐cyclization reaction of methanol and anilines with pyrimidinylpropynoate 5. Methoxy derivative 2a was obtained in 62% yield by treatment of 5 with methanol and potassium carbonate. Anilino derivatives 2b‐2f were prepared in 31–71% yields by reacting 5 with the corresponding anilines in refluxing methanol. This methodology accomplishes Michael‐addition and pyridopyrimidinone ring formation in one‐pot and affords the desired products in reasonable yield without chromatography. Propynoate 5 did not react with 4‐cyanoaniline under these conditions. Reaction of 5 with 2‐aminopyridine gave the unexpected arylpyrido[2,3‐d]pyrimidinone 8 in 58% yield and reaction of 5 with imidazole afforded Michael‐adduct 9 in 69% yield. Compounds 2a and 5 were submicromolar inhibitors of epidermal growth factor receptor (EGFR) tyrosine kinase.     

内蒙古地区天然植物沙棘果中黄色素的提取工艺及性质研究

以内蒙古地区沙棘果实为原料，研究了提取黄色素的工艺条件，同时对该色素的性质进行了初步探讨。结果表明，以95％的乙醇溶液作浸提剂，提取的黄色素浓度最高，工艺流程简单易行，且无毒，无污染。对提取的黄色素进行的性质试验表明，沙棘黄色素对光、热具有较好的稳定性，适用于酸性或弱碱性的食品中，葡萄糖、氧化剂(H2O2)、还原剂(Na2SO3)等食品添加剂均无明显影响以上结果为这种优良天然色素的开发与应用提供了参考。     

Solid-Phase Synthesis of a Monofunctional trans-a(2)Pt(II) Complex Tethered to a Single-Stranded Oligonucleotide

Cross-linking ability is possible with the oligonucleotide-tethered, monofunctional trans-Pt(II) complex shown. It was synthesized by a novel solid-phase approach comprising conjugation of immobilized tetrathymidylic acid with a trans-a(2)Pt(II) building unit, ammonolysis, and transformation of the resulting complex (R=1-N-cyclohexylmethylthyminate) into the chloro derivative (R=Cl). a=NH(2)CH(3), T=thymine.     

Stability of a microwave heated fluid Layer

When a time harmonic electromagnetic wave impinges on a slaba certain portion of the wave creates heat within the slab throughdipolar and ohmic heating. The electrical and thermal propertiesof the material dictate the dynamical nature of the heatingprocess, as well as the steady-state temperature profile. Thematerial considered here is a slab of fluid. We consider thecase where the fluid is bounded by thin rigid layers of transparentmaterial. The steady-state heating profile governs the typesof convective motions that can occur and also affects the stabilitycharacteristics of temperature, pressure and velocity perturbationsintroduced in the slab. The main objective here is to examinesuch stability characteristics, initially in the linear regime.Both rigid-rigid and rigid-free configurations are considered.