A Novel Synthesis of 3,4-Dihydro-(2H)-1,2,4-Benzothiadiaizine-1,1-Dioxides Promoted by Samarium Diiodide

Applicationsofsamariumdiiodideasamild,neutral,selectiveandversatilesingleelectrontransferreducingandcouplingreagentinorganicsynthesishavesignificantlygrowninthelastdecade'.PreviousworkonsomedeoxygenationandsomereductivecleavageofS-S,Se-Se,Te-TebondswithSml,wasreported'.ItiswellknownthatnitrocompoundscanbereducedeasilybySml2.However,theyarejustreducedtothecorrespondingammes',lit'tleattentionhasbeenconcernedontheintermediatederivedfromanitrogroupbySml,treatment,whichmaybeinducesomereactionsd…     

4-(3,4-二甲氧基苯基)-5-硝基哌啶-2-酮的合成

以3-(3,4-二甲氧基苯基)-4-硝基丁酸甲酯(4),氨水和甲醛为原料,异丙醇溶液为溶剂,经曼尼希-酯胺解偶联反应合成了新化合物4-(3,4-二甲氧基苯基)-5-硝基哌啶-2-酮,其结构经1H NMR,13C NMR和EI-MS表征。在最佳反应条件{4 1.0 mmol,n(4)∶n(27%氨水)∶n(37%甲醛)=1.00∶1.30∶1.05,异丙醇[V(异丙醇)∶V(水)=5∶1]7.5 m L,于100℃反应12 h}下,收率74.1%。     

3,4-二氢-1-(4-哌啶基)-2(1H)-喹啉酮的合成

以苄胺为原料,经6步反应得到新型抗高血压药OPC-21268的中间体3,4-二氢-1-(4-哌啶基)-2(1H)-喹啉酮,总收率13．9％．     

A Convenient Synthesis of 3-Aryl-2-Methyl-3,4-Dihydro-1(2H)-Isoquinolones and -1,2,3,4-Tetrahydroisoquinolines

A new methodology for the synthesis of 3-aryl-2-methyl-3,4-dihydro-2H-isoquinolin-l-ones and 3-aryl-2-methyl-1,2,3,4-tetrahydroisoquinolines is reported.     

5-羟基-3,4-二氢异喹啉-1-酮的合成

以异喹啉为起始原料,经成盐、磺化得异喹啉-5-磺酸(3),3与熔融的氢氧化钠和氢氧化钾反应得1,5-二羟基异喹啉(4),以5%Pd-C为催化剂还原4得5-羟基-3,4-二氢异喹啉-1-酮(1),总收率47.6%。1的结构经1H NMR和MS确证。     

(±)-6,7-丙酮缩二醇-3-酮-庚酸乙酯合成研究

用对甲苯磺酸-2,3-丙酮缩甘油酯(2)与乙酰乙酸乙酯盐、碳酸二乙酯反应, 制备β-酮酯类衍生物1. 以(±)-1,2-丙酮缩甘油为起始物, 经对甲苯磺酰化、亲核取代、脱羧等反应, 方便、高产率地合成了6,7-丙酮缩二醇-3-酮-庚酸乙酯(1). 试图通过对甲苯磺酸-2,3-丙酮缩甘油酯(2)和乙酰乙酸乙酯双阴离子反应制备6,7-丙酮缩二醇-3-酮-庚酸乙酯(1)未获成功. 所合成的化合物经元素分析, IR, ¹H NMR, ¹³C NMR和MS光谱表征.     

1-苯基-5-(3,4-二甲氧基苯基)-3-羟基吡唑的合成和晶体结构

标题化合物(I)是由 1-苯基-5-(3, 4-二甲氧基苯基)-3-吡唑烷酮在 FeCl3催化下被氧气氧化得到的。它的结构经过了元素分析、IR、1H NMR 的表征,用 X-射线衍射法测定了化合物的晶体结构。C17H16N2O3(I)的晶体学参数分别为:三斜晶系,P1空间群,a = 6.6600(13),b = 8.4200(17),c = 14.060(3) ?,α= 85.61(3), β= 76.89(3), γ= 81.18(3)?, Z = 2, Dc= 1.298g/cm3, V = 758.1(3) ?3, Mr = 296.32,μ= 0.090 mm–1, F(000) = 312, R = 0.048,wR = 0.1231。结构测定表明化合物的吡唑环存在着一个大的共轭体系,含有一个稳定的烯醇结构,分子通过分子间的氢键形成了网状的结构。     

An Efficient Synthesis of 3,4-Dihydro-4-Imino-2(1H)-Quinazolinones

A new one-pot convenient preparation of 3,4-dihydro-4-imino-2(1H)-quinazolinones (4) is described by the reaction of 2-aminobenzonitriles (1) with chlorosulfonyl isocyanate (2), while the reaction of 1 with chlorocarbonyl isocyanate (6) affords ureidobenzonitriles (7), which on thermal cyclization gives 4.     

Synthesis of (-) or (+) -threo-3-(3,4-dihydroxyphenyl) serine and (-) or (+) -erythro-3-(3,4-dihydroxyphenyl)-serine]

The known synthesis of DL -3-(3,4-dihydroxyphenyl)-serine (DOPS) has been modified so that the diastereomeric threo and erythro forms could be separated. These were resolved into their antipodes, whose chemical, physical, and spectrochemical properties are discussed.     

A Convenient Synthesis of N-Substituted 1,6-Dihydro-3(2H)-Pyridinones

N-Substituted 1,6-dihydro-3(2H)-pyridinones have been synthesised from N-substituted piperidine-3,5-diones via the methyl enol ethers. Reduction of the latter with sodium borohydride (NaBH₄) is described.     

Synthesis of 3-(L-Threo-Glycerol-l-YL)-6,7-Dimethyl-Pyrazolo[3,4-b]Quinoxalines

Abstract

Reaction of dehydro-L-ascorbic acid with 1,2-diamino-4,5-dimethylbenzene and arylhydrazines afforded 3-[l-(aryl)hydrazono-L-threo-2,3,4-trihydroxybutyl]-6,7-dimethyl-lH-quinoxalin-2-ones. Their dehydrative cyclization gave 1-aryl-3-(L-threo-glycerol-1-yl)-6,7-dimethylpyrazolo[3,4-b] quinoxalines, whose acetylation and periodate oxidation were studied.     

1,4-二氢-2,6-二甲基-4-(3-硝基苯基)-3,5-吡啶二羧酸二(2-甲氧基乙基)酯的合成

对1，4－二氢吡啶类钙拮抗剂西尼地平进行了结构修饰。以双乙烯酮和乙二醇单甲醚为原料，经酯化、缩合、氨化和Hantzsch环化等反应合成了1，4－二氢－2，6二甲基－4－（3－硝基苯基）－3，5－吡啶二羟酸二（2－甲氧基乙基）酯，总收率71％。目标产物结构经^1H NMR和MS确证。     

Synthesis of Novel New 2-(2-(4-((3,4-Dihydro-4-oxo-3-aryl quinazolin-2-yl)methyl)piperazin-1-yl)acetoyloxy)-2-phenyl Acetic Acid Esters

Stereoselective diazotization of (S)-2-amino-2-phenyl acetic acid (L-phenyl glycine) (4) with NaNO₂ in 6% H₂SO₄ in a mixture of acetone and water gave optically pure (S)-2-hydroxy-2-phenyl acetic acid (L-mandelic acid) (5). Esterification, gave (S)-2-hydroxy-2-phenyl acetic acid esters (6). The latter was treated with chloroacetyl chloride in the presence of triethylamine (TEA) in dichloromethane (DCM) to yield (S)-2-chloroacetyloxy phenyl acetic acid ester (2). In another sequence, the reaction of 2-(chloromethyl)-3-arylquinazolin-4(3H)-one (9) treated with N-Boc piperazine, followed by deprotection of the Boc group, to obtain 3-aryl-2-((piperazin-1-yl)methyl) quinazolin-4(3H)-one (3). Reaction of 2 with 3 in the presence of K₂CO₃ and KI gave the title compound, 2-(2-(4-((3,4-dihydro-4-oxo-3-arylquinazolin-2-yl)methyl)piperazin-1-yl) acetoyloxy)-2-phenyl acetic acid esters (1). The structures of all the new compounds obtained in the present work are supported by spectral and analytical data.     

2,6-二甲氧基-3-烷基-1,4-苯醌的合成

取代的1,4-苯醌类化合物广泛存在于自然界的植物和动物体内。其中有一部分已证明具有明显生理活性。最重要的取代1,4苯-醌类化合物是泛醌(ubiquinone)和质体醌(plastoquinone)。它们是动物线粒体呼吸链和植物光合作用链中重要的非蛋白电子载体。2,6-二甲氧基-1,4-苯醌(4)存在于许多植物的树皮和木心中。它的生理作用目前还知道得     

Synthesis,Structure and Cytotoxicity Testing of Novel 7-(4,5-Dihydro-1H-imidazol-2-yl)-2-aryl-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-Imine Derivatives

The appropriate 1-arylhydrazinecarbonitriles 1a–c are subjected to the reaction with 2-chloro-4,5-dihydro-1H-imidazole (2), yielding 7-(4,5-dihydro-1H-imidazol-2-yl)-2-aryl-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-imines 3a–c, which are subsequently converted into the corresponding amides 4a–e, 8a–c, sulfonamides 5a–n, 9, ureas 6a–I, and thioureas 7a–d. The structures of the newly prepared derivatives 3a–c, 4a–e, 5a–n, 6a–i, 7a–d, 8a–c, and 9 are confirmed by IR, NMR spectroscopic data, as well as single-crystal X-ray analyses of 5e and 8c. The in vitro cytotoxic potency of these compounds is determined on a panel of human cancer cell lines, and the relationships between structure and antitumor activity are discussed. The most active 4-chloro-N-(2-(4-chlorophenyl)-7-(4,5-dihydro-1H-imidazol-2-yl)-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-ylidene)benzamide (4e) and N-(7-(4,5-dihydro-1H-imidazol-2-yl)-2-(p-tolyl)-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-ylidene)-[1,1′-biphenyl]-4-sulfonamide (5l) inhibits the growth of the cervical cancer SISO and bladder cancer RT-112 cell lines with IC₅₀ values in the range of 2.38–3.77 μM. Moreover, N-(7-(4,5-dihydro-1H-imidazol-2-yl)-2-phenyl-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-ylidene)-4-phenoxybenzenesulfonamide (5m) has the best selectivity towards the SISO cell line and induces apoptosis in this cell line.