Synthesis of propyl O-(α-L-rhamnopyranosyl)-(1→3)-[2,4-di-O-(2s-methylbutyryl)-α-L-rhamnopyranosyl]-(1→2)=(3-O-acetyl-β-D-glucopyranosyl)-(1→2)-βp-D-fucopyranoside,the tetrasaccharide moiety of Tricolorin A

Propyl O-(α-L-rhamnopyranosyl)-(1→3)-[2,4di-O-(2s-methylbutyryl)-α-L-rhamnopyranosyl]-(1→2)-(3-O-acetyl-β-glucopyranosyl)-(1→2)-β-D-fucopyranoside (1), the tetrasaccharide moiety of Ricolorin A, was synthesized in total 23 steps with a longest linear sequence of 10 steps, and overall yield of 3.7% from D-Glucose. The isomerization of the dioxolane-type benzylidene in the prance of NIS/AgOTf was observed. Tetrasaccharide 1 exhibited no activity against the cultured P388 cell as Tricolorin A did.     

Synthesis of end-functionalized (1 → 6)-2,5-anhydro-D-glucitols via anionic cyclopolymerization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol for preparing graft copolymers

End-functionalized (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitols ( 3a–c ) were synthesized by the anionic cyclopolymerization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol ( 1 ), followed by treatment with a terminating agent such as 4-vinylbenzyl ( 2a ), oxetanyl ( 2b ), and methacryloyl group ( 2c ). The end-functionalization proceeded in a high efficiency at 73–98%. The radical copolymerization of styrene with 3a yielded a polymer ( 5a ) whose GPC trace exhibited a unimodal peak. 5a was polystyrene with (1→6)-2,5-anhydro-3,4-di-O-methyl-D -glucitol as pendant groups whose structure was confirmed by the ¹H NMR spectrum.     

(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.     

双吲哚马来酰亚胺硫脲化合物的合成及抗肿瘤活性

基于双吲哚马来酰亚胺化合物和硫脲化合物的结构及多样的生物活性,通过1-氨基-3,4-二(吲哚-3-基)-3-吡咯啉-2,5-二酮与异硫氰酸酯反应,合成了17种新的3,4-二(吲哚-3-基)-2,5-二酮-1-吡咯亚胺硫脲类化合物,化合物的结构通过1H NMR、13C NMR、HRMS等进行了表征。该系列化合物的初步抗肿瘤活性测试表明,它们都对细胞周期分裂蛋白25B(CDC 25B)表现出良好的抑制活性(大部分化合物的抑制率在96%以上),具有潜在的抗肿瘤活性及应用价值。     

HIV-1 RT抑制剂研究I.1,3-二苄基-6-(3,4-环氧丁基)尿嘧啶的合成

报道了1,3-二苄基-6-(3,4-环氧丁基)尿嘧啶的合成新方法.以6-甲基尿嘧啶(1)为起始物,经1,3-二苄基-6-甲基尿嘧啶(2)及未见文献报道的1,3-二苄基-6-(3-丁烯基)尿嘧啶(3)和1,3-二苄基-6-(3-羟基-4-溴丁基)尿嘧啶(4),首次高收率合成了1,3-二苄基-6-(3,4-环氧丁基)尿嘧啶(5),并对其化学结构进行了表征.     

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     

3,4-二氢-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％．     

Synthesis of novel 3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones

An efficient method for the synthesis of novel 3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones from various 2-dimethylaminomethylidenecyclohexane-1,3-diones, (1,3-thiazol-2-yl)acetonitriles, and dimethylformamide dimethyl acetal was developed. These transformations proceeded through intermediate 2-[2-(4-aryl-1,3-thiazol-2-yl)-2-cyanoethenyl]-3-oxocyclohex-1-en-1-olates. They were isolated as piperidinium salts and used in further heterocyclization reactions with aromatic amines, giving novel 1-aryl-3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones. These compounds were also obtained by preparative three-step “one pot” synthesis under controlled microwave irradiation. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 412–417, February, 2008.     

Synthesis of 4-hetaryl-5,6-(2,5-dimethyl-3-thienyl)-2-phenyl-4h-thiazines and investigation of their photochromism

The polar [4+2] cycloaddition reaction of 1,2-bis(2,5-dimethyl-3-thienyl)acetylene with thiobenzamide and certain aldehydes of the thiophene and furan series catalyzed by boron trifluoride etherate gives the corresponding 4-hetaryl-5,6-di(2,5-dimethyl-3-thienyl)-2-phenyl-4H-1,3-thiazines. The photochromic properties of the products have been studied.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 100–106, January, 2005.     

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…     

Prebiotic Potential of Oligosaccharides Obtained by Acid Hydrolysis of α-(1→3)-Glucan from Laetiporus sulphureus: A Pilot Study

Increasing knowledge of the role of the intestinal microbiome in human health and well-being has resulted in increased interest in prebiotics, mainly oligosaccharides of various origins. To date, there are no reports in the literature on the prebiotic properties of oligosaccharides produced by the hydrolysis of pure fungal α-(1→3)-glucan. The aim of this study was to prepare α-(1→3)-glucooligosaccharides (α-(1→3)-GOS) and to perform initial evaluation of their prebiotic potential. The oligosaccharides were obtained by acid hydrolysis of α-(1→3)-glucan isolated from the fruiting bodies of Laetiporus sulphureus and then, characterized by HPLC. Fermentation of α-(1→3)-GOS and reference prebiotics was compared in in vitro pure cultures of Lactobacillus, Bifidobacterium, and enteric bacterial strains. A mixture of α-(1→3)-GOS, notably with a degree of polymerization of 2 to 9, was obtained. The hydrolysate was utilized for growth by most of the Lactobacillus strains tested and showed a strong bifidogenic effect, but did not promote the growth of Escherichia coli and Enterococcus faecalis. α-(1→3)-GOS proved to be effective in the selective stimulation of beneficial bacteria and can be further tested to determine their prebiotic functionality.     

Preparation of 3-(3′-,4′-Hydroxyphenyl)sydnones

3-(3′-,4′-Hydroxyphenyl)sydnones were prepared by dealkylation of 3-(3′-,4′-alkoxyphenyl)sydnones with concentrated sulfuric acid at room temperature in a range of 59 to 86% yield.     

Synthesis of 1-(alkylamino)- and 1-(dialkylamino)benzimidazoline-2-thiones

Unlike 1-aminobenzimidazoles, 1-alkylaminobenzimidazoles are thiolated on fusing with sulfur without elimination of theN-amino group, yielding the previously unknown 1-(alkylamino)benzimidazoline-2-thiones. These compounds can be more conveniently obtained on a preparative scale by thiolation of 1-alkylacetamidobenzimidazoles with subsequent hydrolytic elimination of the acetyl group. When 1-(dialkylamino)benzimidazoles are fused with sulfur, they are converted into 1-(dialkylamino)benzimidazoline-2-thiones. By alkylation of 1-(methylamino)- and 1-(diethylamino)benzimidazoline-2-thiones with methyl iodide in alkaline media the corresponding 2-(methylthio)benzimidazoles were prepared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2231–2235, November, 1995.The authors are grateful to the Contest Center of Basic Natural Science at St. Petersburg University for financial support of this study.     

Synthesis, Characterization, Spectroscopic Properties of 2-（4-Dimethylaminophenyl）-5-fluoro-6-（morpholin-4-yl）-1H-benzimidazole and its Interaction with Calf Thymus DNA

Benzimidazole compounds have attracted a renewed interest recently owing to theirpotential applications in high-performance composite materials, electronic chemicals,photosensitive materials, and their special potentials in biological and/or medicinalapplication1,2. Typically, aromatic compounds with near planar structures and contain-ing hydrogen-donor groups or groups, which are capable of being protonated, havespecial interactions with DNA via intercalation, hydrogen-bonding, and so on3.Me…     

Iron(III) complexes bearing 2-(benzimidazole)-6-(1-aryliminoethyl)pyridines: Synthesis, characterization and their catalytic behaviors towards ethylene oligomerization and polymerization

A series of iron(III) complexes ligated by 2-(benzimidazole)-6-(1-aryliminoethyl)pyridines was synthesized and examined by ¹H NMR, ESI-MS, IR spectroscopic, elemental analysis and X-ray photoelectron spectroscopy (XPS). Activated with methylaluminoxane (MAO), all ferric complexes exhibited good activities (up to 5.38 × 10⁶ g mol⁻¹(Fe) h⁻¹) of ethylene oligomerization and polymerization, and resultant oligomers and polyethylene waxes showed high α-olefin feature, meanwhile the distribution of oligomers mostly resembled Schulz-Flory rules. The various reaction parameters were investigated in detail, and the less bulky and electron-withdrawing substituents of ligands could enhance the catalytic activities of their ferric complexes. The observations explain the cause for unstable activities performed by stored iron(II) complexes.     

A Tail Does Not Always Make a Difference: Assembly of cds Nets from Co(NCS)2 and 1,4-bis(n-Alkyloxy)-2,5-bis(3,2′:6′,3″-terpyridin-4′-yl)benzene Ligands

The consistent assembly of a (6⁵.8) cds net is observed in reactions of cobalt(II) thiocyanate with 1,4-bis(n-alkyloxy)-2,5-bis(3,2′:6′,3″-terpyridin-4′-yl)benzene ligands in which the n-alkyloxy substituents are n-propyl (ligand 3), n-butyl (4), n-pentyl (5), n-hexyl (6), n-heptyl (7), and n-octyl (8). Crystals were grown by layering a methanol solution of Co(NCS)₂ over a 1,2-dichlorobenzene solution of each ligand. The choice of crystallization solvents is critical in directing the assembly of the cds net. Single-crystal structures of [Co(NCS)₂(3)]_n^.3.5nC₆H₄Cl₂, [Co(NCS)₂(4)]_n^.5.5nC₆H₄Cl₂, [Co(NCS)₂(5)]_n^.4nC₆H₄Cl₂, [Co(NCS)₂(6)]_n^.3.8nC₆H₄Cl₂, [Co(NCS)₂(7)]_n^.3.1nC₆H₄Cl₂, and [Co(NCS)₂(8)]_n^.1.6nC₆H₄Cl₂^.2nMeOH (C₆H₄Cl₂ = 1,2-dichlorobenzene) are presented and compared. The n-alkyloxy chains exhibit close to extended conformations and are accommodated in cavities in the lattice without perturbation of the coordination framework.     

Synthesis of 3,3-Dialkyl-1-(3-coumarinyl)-3,4-dihydroisoquinolines

The reaction of dialkylbenzylcarbinols with 3-cyanocoumarin in the presence of sulfuric acid gave 3,3-dialkyl-1-(3-coumarinyl)-3,4-dihydroisoquinoline.     

<Emphasis Type="Italic">sym</Emphasis>-triazines. 8. Synthesis and some reactions of 4,6-disubstituted 2-(1H-pyrrolyl)-1,3,5-triazines

We have studied the reaction of 2,5-dimethoxytetrahydrofuran with 4,6-disubstituted 2-amino-1,3,5-triazines with the aim of obtaining novel coupled polyheterocyclic systems with potential bioactivity. Reaction conditions were optimized. A series of novel 4,6-disubstituted 2-(1H-1-pyrrolyl)-sym-triazines was obtained. It was found that the product yields depended on the nature of the substituent in the 4 and 6 positions of the triazine ring and on the reaction conditions. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 440–451, March, 2008.     

Reaktionen des 1,1′, 3,3′-Tetrakis(dimethylamino)-1λ5, 3λ5-diphosphets mit S?H-aciden Verbindungen

Reaction of 1,′, 3,3′-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete with S? H Acidic Compounds. Reaction of 1,′,3,3′-tetrakis(dimethyl-amino)-1λ⁵,3λ⁵-diphosphete ( 1 ) with hydrogen sulfide yields bis(dimethylamino)thiophosphonylmethylidene-methyl-bis(dimethylamino)phosphorane ( 5 ).Water eliminates dimethylamine from 5 and forms bis(dimethyl-amino)thiophosphonyl-methyl(dimethylamino)phosphonylmethylene 6 . The reaction of 1 with ethylmercaptane yields the 2,4-bis(ethylthio)-derivative of 1 , i.e. compound 8 and bis(dimethylamino)phosphanylmethylidene-methyl-bis(dimethylamino)phosphorane ( 9 ), which is also formed from 1 and 2,4,6-trimethylphenylphosphane. Thiophenol protonates 1 to give the corresponding cation which is isolated as its thiophenolate, 10 . Properties, nmr and mass spectra of 5, 6 and 8 – 10 are described and discussed.