4-Oxa(thia)-9-oxa-2-azabicyclo[4.2.1]nonane-3-on(thion) derivatives

The synthesis of 7,8-dihydroxy-2-(2-methoxycarbonylethyl)-4,9-dioxa-2-azabicyclo[4.2.1]nonane- 3-thione ( 16 ) and of its parents 9-oxa-4-thia-3-thione 17 , and 9-oxa-4-thia-3-one 18 is described. The conversion of 5′-deoxy-5′-iodo-2′,3′-O, O-isopropylidene-5,6-dihydrouridin ( 1 ) into the 2-O-methyl-5,6-dihydrouridine 5 , the 5′-O-acetyl-5,6-dihydrouridine 4 , and into the N-(5-O-acetyl-2,3-O, O-isopropylidene-β-D -ribofuranosyl)-N-(2-methoxycarbonyl thyl)-urea ( 6 ) invoked 2′,3′-O, O-isopropylidene-2,5′-anhydro-5,6-dihydrouridine ( 2 ) as the common intermediate.     

[4-(4-苯甲酰基苯氧基)苯]苯基碘鎓六氟磷酸盐的合成

紫外光固化反应分为自由基固化机理、阳离子固化机理,以及自由基-阳离子混杂固化机理。自由基-阳离子混杂固化是指在同一体系里同时发生自由基光聚合反应和阳离子光聚合反应[1],结合了前两类聚合反应的优点,表现出很好的协同效应[2]。[4-(4-苯甲酰基苯氧基)苯]苯基碘鎓六氟磷酸     

4-N-{2-[4-(2-巯基乙氧基)苯氧基]乙基}-1-N-对甲苯磺酰基哌嗪的合成

以对苄氧基苯酚为原料,经三步反应合成了2-[4-(2-溴乙氧基)苯氧基]乙醇(3); 3与1-对甲苯磺酰基哌嗪反应制得4-N-{2-[4-(2-羟乙氧基)苯氧基]乙基}-1-N-对甲苯磺酰基哌嗪(5);在5上引入乙酰巯基后再经碱性水解,合成了新化合物4-N-{2-[4-(2-巯基乙氧基)苯氧基]乙基}-1-N-对甲苯磺...     

新型2-[4-(3-吗啉基丙氧基)苯氧基]乙基异硫脲的合成

以对苄氧基苯酚为原料,经三步反应合成了2-[4-(3-氯丙氧基)苯氧基]乙醇(3);在3中引入吗啉基团制得2-[4-(3-吗啉丙氧基)苯氧基]乙醇(4);利用甲磺酰氯将4的羟基转化为离去基团,再引入硫脲基团成功地合成了新型含硫脲基的酚醚类衍生物——2-[4-(3-吗啉丙氧基)苯氧基]乙基异硫脲,其结构经1H NMR,13C NMR和MS表征。     

Ergebnisse der Verfahrensforschung,I. Synthese von o-{(+)-D-2-[4-(4-(Trifluormethyl)phenoxy)phenoxy]propionyl}-aceton-oxim

Results of process Research I. Synthesis of O-{(+)-D-2-[4-(4-(triluoromethyl)phenoxy)phenoxy]propionyl}-acetone oxime Efficient and simple procedures for the preparation of O-{L-[(sulfonyl)oxy]-propionyl}-oxime derivatives 7b-e have been developed. The alleviation of 4-[4-(trifluoromethyl)phenoxy]phenol ( 11 ) with 7d , the final step of a technical synthesis of 1 , has been studied in detail.     

An efficient synthesis of the constrained peptidomimetic 2-oxo-3-(N-9-fluorenyloxycarbonylamino)-1-azabicyclo[4.3.0]nonane-9-carboxylic acid from pyroglutamic acid

[reaction: see text] Azabicyclo[X.Y.0]alkane amino acids are rigid dipeptide mimetics that are useful tools for structure-activity studies in peptide-based drug discovery. Herein, we report an efficient synthesis of three diastereomers of 9-tert-butoxycarbonyl-2-oxo-3-(N-tert-butoxycarbonylamino)-1-azabicyclo[4.3.0]nonane (3S,6S,9S, 3S,6R,9R, and 3S,6R,9S). Methyl N-Boc-pyroglutamate is cleaved with vinylmagnesium bromide to produce an acyclic gamma-vinyl ketone. Michael addition of N-diphenylmethyleneglycine tert-butyl ester produces the N-Boc-delta-oxo-alpha,omega-diaminoazelate intermediate, which, on hydrogenloysis, gives the fused ring system. Acidolytic deprotection followed by Fmoc-protection provided building blocks suitable for solid-phase synthesis.     

N-[4-氯-2-取代氨基甲酰基-6-甲基苯基]-1-芳基-5-氯-3-三氟甲基-1H-吡唑-4-甲酰胺的合成及生物活性

通过改变传统氯虫酰胺中吡唑环上氨基甲酰基与吡啶环之间的相对位置, 或以其它芳环取代原分子中的吡啶环, 设计合成了24个结构新颖的N-[4-氯-2-取代氨基甲酰基-6-甲基苯基]-1-芳基-5-氯-3-三氟甲基-1H-吡唑-4-甲酰胺类化合物. 所有目标化合物的结构均通过¹H NMR谱、 元素分析或高分辨质谱表征确定. 初步的生物活性测试结果表明, 部分化合物对东方粘虫具有较好的杀虫活性, 其中化合物6m在浓度为50 mg/L时具有80%的杀虫活性. 同时, 在浓度为50 mg/L时目标化合物对5种常见病菌具有明显的抑制作用, 其中化合物6n和6x对苹果轮纹菌的抑菌率达62.1%.     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

Synthesis of 9-(trifluoromethyl)pyrido[1′,2′:1,2]-imidazo[4,5-b]quinoxalines

9-(Trifluoromethyl)pyrido[1′,2′:1,2]imidazo[4,5-b]quinoxalines (9-CF₃-PIQs) were obtained from the cyclization of 2-amino-3-chloro-6-(trifluoromethyl)quinoxaline ( 1a ) with some substituted pyridines. 3-[2-(4-Pyridyl)ethenyl]-9-CF₃-PIQ, one of thus obtained 9-CF₃-PIQs, cyclized with another molecule of 1a to produce the dihydro bis-PIQ-ethene derivative.     

Facile syntheses of 4-(trifluoromethyl)-L-spinacine and 4-(trifluoromethyl)spinaceamine

Reaction of L-histidine with trifluoroacetaldehyde ethyl hemiacetal (TFAE) in boiling water provides 4-(trifluoromethyl)-L-spinacine, 4-(trifluoromethyl)-L-4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridine-6-carboxylic acid, in near quantitative yield. The product contains two diastereoisomers in the ratio 68 : 32. The isomers were separated (silica gel) as their protected derivatives, 5-N-(trifluoroacetyl)-4-(trifluoromethyl)-L-spinacine methyl esters, and were regenerated by acid hydrolysis. The analogous reaction with histamine provides 4-(trifluoromethyl)spinaceamine in 91% yield.     

Synthesis and characterization of 6-[4-(trans -4-pentylcyclohexyl)phenoxy]hexyl acrylate homopolymer and copolymers

The compound 6-[4-(trans -4-pentylcyclohexyl)phenoxy]hexyl acrylate (2) was prepared and homopolymerized. The block copolymer and copolymer of 2 with styrene were synthesized by photopolymerization and solution techniques, respectively. These polymers were characterized by IR and ¹H NMR spectra and size exclusion chromatography. Polarizing optical microscopy (POM) and X-ray diffraction (XRD) studies revealed that these polymers exhibited smectic A (SmA) phases. POM showed that the homopolymer showed a higher order SmA phase than did the block copolymer and copolymer. After magnetically forced alignment the samples exhibited similar optical texture but the domain size of the liquid crystalline phase increased. Differential scanning calorimetry, POM and XRD data suggest that the SmA domain size decreased in the order hompolymer > block copolymer > copolymer.