顺-8-三甲基锡烷基-6-辛烯醛分子内环化反应立体选择性的理论研究

用密度泛函方法在B3LYP/6-31G^*水平上研究了顺-8-三甲基锡烷基-6-辛烯醛分子内环化反应的机理,通过振动分析和内禀反应坐标对过渡态进行了确认,解析了三种反应途径.结果表明,反应具有很强的立体选择性,虽然-OSn(CH₃)₃和-C₂H₃基团均处于环的平伏位,是最稳定的产物构型,但是主要产物是经过活化能最低,且具有两个六元环椅式构象的过渡态形成的,主要产物中-OSn(CH₃)₃基团处于环的直立位.该结果与实验事实一致.     

Domino reactions between 6-ethyl-5,6-dihydro-4,5-dioxo-4H-pyrano[3,2-c]quinoline-3-carbonitrile and carbon nucleophilic reagents: Synthesis of novel heteroannulated pyridopyranoquinolines

A variety of novel heteroannulated pyrano[3,2-c]quinolines 2–12 was efficiently synthesized via a domino ‘Michael/retro-Michael/nitrile addition/heterocyclization’ reactions between 6-ethyl-5,6-dihydro-4,5-dioxo-4H-pyrano[3,2-c]quinoline-3-carbonitrile (1) and a diversity of carbon nucleophilic reagents. Pyrido[3′,2′:5,6]pyrano[3,2-c]quinolines 2–6 were synthesized from ring opening ring closure reactions of carbonitrile 1 with some methylene active nitrile namely malononitrile, cyanoacetamide, N-phenylcyanoacetamide, (phenylthio)acetonitrile and ethyl cyanoacetate, respectively. Reactions of carbonitrile 1 with dimer malononitrile and cyanoacetohydrazide showed different behavior producing the novel heteroannulated pyranoquinoline derivatives 7 and 8, respectively. Treatment of carbonitrile 1 with some methylene active ketones namely acetylacetone, acetoacetanilide, ethyl acetoacetate and ethyl benzoylacetate afforded pyrido[3′,2′:5,6]pyrano[3,2-c]quinolines 9–12, respectively. Structures of the synthesized products were deduced on the basis of their analytical and spectral data.     

Reactions of ethyl 3-(diethoxyphosphoryl)-3,3-difluoropyruvate with some nucleophilic reagents

Reactions of ethyl 3-(diethoxyphosphoryl)-3,3-difluoro-2-oxopropionate with a number of nucleophilic reagents were studied. New procedures were developed for the synthesis of difluoromethylphosphonate-substituted nitrogen heterocycles. The ketoester under study is much less reactive in C-hydroxyalkylation of aromatic amines than methyl 3,3,3-trifluoropyruvate. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1258–1260, July, 2000.     

3-取代苄氧基-6-取代氨基哒嗪衍生物的合成及其除草活性

通过3-取代苄氧基-6-氟哒嗪在75～80 ℃与二甲胺的绝对无水乙醇溶液封管反应, 或在回流条件下分别与吗啡啉或哌啶反应, 合成一系列新颖的3-取代苄氧基-6-取代氨基哒嗪类化合物, 它们的结构均经IR, ¹H NMR和元素分析确证. 初步的除草活性测定结果表明, 该类化合物具有一定的除草活性, 讨论了它们的结构与除草活性的关系.     

3-取代苯氧甲基-6-氯哒嗪的合成及其除草活性

通过3-氯-6-溴甲基哒嗪与各种取代的苯酚在K₂CO₃/DMF体系中反应, 合成了一系列3-取代苯氧甲基-6-氯哒嗪化合物. 它们的结构均经¹H NMR, IR和元素分析确证. 在浓度为100 μg•mL^－1时, 初步的生物活性测试结果表明, 所合成的化合物对油菜和稗草均有一定的抑制作用. 并讨论了其结构与除草活性的关系.     

The Colour Reaction of Mercury with 1-(6-Ethoxyl-2-benzothiazolyl)-3-(4-Nitrophenyl)-Triazene and its Application

Thetfiazenereagentswereusedforthedeterminationofcadmium,mercuryandzinc.Wehavesynthesizedthetriazenereagentscontainingheterocyclicring'-'.Recently,annewreagentEtOBTNPTwassynthesized.Becausethereagentcontainsanelectronpropellinggroup(-OCH,CH,)inoneendandanelectronwithdrawinggroup(-NO,)intheotherend,sotheconjugatesystemisenlargedinthemolecularstructure,thisresultinginadvantageofmigrationofelectroniccloud.ThesensitivityofthecolourreactionofEtOBTNPTwithmercuryissuperiortoothertfiazenereage…     

Effective Synthesis of Polysubstituted Pyrroles from (E)-Dimethyl 2-(Bromomethyl)-3-(diethoxyphosphoryl) Fumarate

Methyl 1-alkyl-4-(diethoxyphosphoryl)-5-oxo-2,5-dihydro-1H-pyrroles-3-carboxylate 4 was synthesized from the reaction of dimethyl 2-(bromomethyl)-3-(diethoxyphosphoryl) fumarate 3- E and primary amines in good yields.     

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins were prepared by reaction of substituted salicylaldehydes and hetarylacetonitriles. Alkylation and acylation of 3-hetaryl-7-hydroxycoumarins were studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 432–434, September–October, 2005.     

BTAB与铁形成的配合物组成的研究

研究了3 -(6-溴苯并噻唑-2-偶氮)- 2,6-二羟基苯甲酸(简称BTAB)与铁的配合反应.用摩尔比法、等摩尔连续变化法、平衡移动法和双峰双波长法四种方法详细研究并测定了3 -(6-溴苯并噻唑 -2-偶氮)- 2,6-二羟基苯甲酸与铁显色形成配合物的配合比和稳定常数,建立了光度法测定铁的新方法.结果表明,在溴代十六...     

1-(6-硝基-2-苯并噻唑)-3-(5-溴-8-喹啉)-三氮烯与Co(Ⅱ)的高灵敏显色反应及其应用

报道了在CPB 存在下,新试剂1-(6-硝基-2-苯并噻唑)-3-(5-溴-8-喹啉)-三氮烯(NBTBQT)与钴的显色反应.在pH 9.5的硼砂-NaOH缓冲介质中,试剂与钴形成2:1 深蓝色络合物,其最大吸收波长位于655 nm处,表观摩尔吸光系数为1.94×105 L·mol-1·cm-1,钴的质量浓度在0～0.24 mg/L 的范围内符合比尔定律.方法应用于维生素B12注射液和水系沉积物的测定.     

Reduction of 3-(2-hydroxyethyl)-1,5-dinitro-3-azabicyclo[3.3.1]non-6-ene

Reduction of the nitro groups in 3-(2-hydroxyethyl)-1,5-dinitro-3-azabicyclo[3.3.1]non-6-ene was studied. The structures of the reaction products were confirmed using ¹H and ¹³C NMR spectroscopy.     

Novel Stereoselective Synthesis and Molecular and Crystalline Structure of 3-Allyl-4-(4-bromophenyl)-3-cyano-6-oxopiperidine-2-thione

The stereoselective synthesis of 3-allyl-4-(4-bromophenyl)-3-cyano-6-oxopiperidine-2-thione has been carried out by refluxing N-methylmorpholinium 5-[1-(4-bromophenyl)-2-cyano-2-thiocarbamoylethyl]-2,2-dimethyl-1,3-dioxa-6-oxo-4-cyclohexen-4-olate with allyl bromide in ethanol. The structure of the product was confirmed by X-ray investigation.     

Cytoprotective Activity of Newly Synthesized 3-(Arylmethylamino)-6-Methyl-4-Phenylpyridin-2(1H)-Ones Derivatives

Currently, studies are being conducted on the possible role of the cytoprotective effect of biologically active substances in conditions of cerebral hypoxia or cardiomyopathies. At the same time, oxidative stress is considered one of the important mechanisms of cellular cytotoxicity and a target for the action of cytoprotectors. The aim of this study is to search for derivatives of 3-(arylmethylamino)-6-methyl-4-phenylpyridin-2(1H)-ones. The probability of cytoprotective action was assessed by measuring cell viability using two tests (with neutral red dye and MTT test). It was found that some derivatives of 3-(arylmethylamino)-6-methyl-4-phenylpyridin-2(1H)-ones under the conditions of our experiment had a pronounced cytoprotective activity, providing better cell survival in vitro, including the MTT test and conditions of blood hyperviscosity. To correlate the obtained results in vitro, molecular docking of the synthesized derivatives was also carried out. The standard drug omeprazole (co-crystallized with the enzyme) was used as a standard. It was shown that all synthesized derivatives of 3-(arylmethylamino)-6-methyl-4-phenylpyridin-2(1H)-ones had higher affinity for the selected protein than the standard gastro-cytoprotector omeprazole. The studied derivatives of 3-(arylmethylamino)-6-methyl-4-phenylpyridin-2(1H)-ones also fully satisfy Lipinski’s rule of five (RO5), which increases their chances for possible use as orally active drugs with good absorption ability and moderate lipophilicity. Thus, the results obtained make it possible to evaluate derivatives of 3-(arylmethylamino)-6-methyl-4-phenylpyridin-2(1H)-ones as having a relatively high cytoprotective potential.     

5-(2’-羧乙基)-6-烷基-3,4-二氢吡喃酮的合成

吡喃酮是许多天然产物的结构单元,我们曾由4-异丁酰基庚二酸在过量醋酸酐及乙酰氯存在下回流得到7-氧代-8,8-二甲基-△~9-六氢香豆素.本文由二氰乙基-β-二酮进行酮解水解反应得到4-酰基庚二酸1_(a-c)。 在过量醋酸酐、乙酰氯存在下由1_a、1_c为底物进行反应没有得到双环的香豆素衍生物.其产物和单纯以乙酐为缩合剂时的产物2_a、2_c相同,产率分别为68％、63％。2_c可在硫酸铁催化     

3-(未)取代苄氧基-6-氟哒嗪的合成及其除草活性

通过3,6-二氟哒嗪与(未)取代苄醇在NaOH/CH₃CN体系反应, 合成了一系列未见报道的3-(未)取代苄氧基-6-氟哒嗪, 其结构均经¹H NMR, IR和元素分析确证. 初步的生物活性测试结果表明, 所合成的化合物对油菜和稗草均有一定的抑制作用, 讨论了其结构与除草活性的关系.     

3-O-(β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪的合成与表征

利用6-(4-卤代苯基)-3(2H)-哒嗪酮的银盐(2)与2,3,4,6-四-O-乙酰基-1-溴-1-脱氧-α-D-吡喃葡萄糖(3)发生Koenigs-knorr反应, 合成了3-O-(2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪(4),4用干燥的氨气在0℃～-5℃下处理脱乙酰基保护基得相应的3-O-(β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪(5).其结构经元素分析,IR及1H NMR证实.     

(3S,6S)-及(3S,6R)-3-苄氧甲基-6-甲基-吗啉-2,5-二酮的 制备及其晶体结构

以2-溴丙酸和N-叔丁氧羰基-O-苄基-L-丝氨酸为起始试剂首先制得N-(2-溴丙基)-O-苄基-L-丝氨酸(BPBS), 在N,N-二甲基甲酰胺(DMF)/三乙胺(Et3N)溶剂中80 ℃经9 h后BPBS发生分子内环化反应生成(3S,6S)-3-苄氧甲基-6-甲 基-吗啉-2,5-二酮[(3S,6S)-BMMD]及(3S,6R)-BMMD共存体, 产率70%. 将所制得的共存体以乙酸乙酯为重结晶溶剂, 采用微分重结晶法, 经4次“溶解-部分重结晶”操作循环制得两种纯光学构型的(3S,6S)-BMMD和(3S,6R)-BMMD. 将两种光学纯双手性中心的BMMD分别溶于乙酸乙酯, 室温下培养得(3S,6S)-BMMD和(3S,6R)-BMMD的单晶体, 以X射线衍射法测定上述两种BMMD的分子结构.     

Pd-catalyzed synthesis of 3-(diarylmethylene)-2-oxindoles and 3-(arylmethylene)-2-oxindoles

An efficient method for the stereoselective synthesis of 3-(diarylmethylene)-2-oxindoles and 3-(arylmethylene)-2-oxindoles via carbopalladation is described. In this approach, an Ugi-4-component reaction (4-CR) adduct was used as the starting material. A one-pot sequence involving intermolecular carbopalladation C-H activation/C-C bond formation efficiently afforded the oxindole derivatives.     

Synthesis of 4-Hydroxy- and 4-Amino-2-Methyl-3-(2-Methylindol-3-Yl)methylquinolines and Their 6- and 8-Substituted Derivatives

A method has been developed for the synthesis of substituted 4-hydroxy- and 4-amino-2-methyl-3-(2-methylindol-3-yl)methylquinolines by treating the corresponding 4-hydroxy(chloro)-2-methyl-3-(3-oxobutyl)quinolines with phenylhydrazine hydrochloride. It was found that nucleophilic substitution occurred in the case of the 4-chloroquinolines together with subsequent rearrangement to give the 4-amino derivatives. The thiosemicarbazones of the corresponding 4-hydroxy-2-methyl-3-(3-oxobutyl)quinolines were also obtained.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 554–557, April, 2005.     

用异丙肾上腺素检定[Fe(CN)6]3-

将医用药物异丙肾上腺素引入分析化学作新显色剂,报道了异丙肾上腺素与[Fe(CN)6]3-进行显色反应的最佳条件、灵敏度、选择性和允许共存比.建立了微量的[Fe(CN)6]3-简便检定新方法,检出限为0.055μg,稀释限为14.5×106.