糖基异硫氰酸酯的合成及其应用

作为一类重要的有机合成中间体,糖基异硫氰酸酯广泛地应用于具有生理活性化合物的制备。本文对糖基异硫氰酸酯的结构、制备方法,以及作为中间体在糖基硫脲、糖基杂环、胍基糖苷、糖基缀合物等重要化合物的合成中的应用作了较详尽阐述。在对这些研究现状进行分析的基础上,对该研究领域下一步的发展方向提出了我们的观点。     

2,2,6,6-四甲基哌啶氧自由基氧化糖类物质伯羟基研究进展

2,2,6,6-四甲基哌啶氧自由基(TEMPO)属于亚硝酰自由基类,能选择性氧化糖类物质的伯羟基,氧化产物的应用非常广泛。本文对TEMPO氧化糖类物质伯羟基的研究进展作一综述。     

甘草次酸衍生物的合成及其抗癌活性

设计合成了6种甘草次酸衍生物,用元素分析、波谱分析鉴定了它们的结构,并比较了它们的体内、体外抗癌活性,均表现出较好的活性,尤其是化合物Ⅰa,Ⅰb口服效果比盐酸氮芥还好,表现出甘草次酸对氮芥有明显的增效应用。     

新型4-羟基香豆素烯醚衍生物的合成

氮气保护下,以4-羟基香豆素类化合物和2-丁炔酸酯类化合物为原料,1,8-二氮杂二环十一碳-7-烯(DBU)为催化剂,乙腈为溶剂,经Michael加成反应合成了11个新型4-羟基香豆素烯醚衍生物（3a~3k）,其结构经¹H NMR, ¹³C NMR, IR和HR-MS（ESI）表征,其构型经H-H NOESY谱确定为Z构型。考察了投料比r[n(2-丁炔酸乙酯,2a) : n(4-羟基香豆素,1a)］、溶剂、催化剂、反应温度和反应时间对3a收率的影响。结果表明：在最优条件［r=1.2,乙腈为溶剂,DBU作催化剂,于80 ℃回流反应18 h］下,3a收率最高（70%）。     

环丙烷衍生物的简便合成

报道了4-甲氧基．2-溴代丁烯内酯(4)与几种醇通过串联的双。Michael加成及分子内的亲核取代反应，简便地得到了环丙烷类化合物8。经元素分析、IR、^1HNMR、^13CNMR和MS对目标产物进行了结构表征，其中8a通过单晶培养和x射线晶体测定，确定了它的立体结构。     

诺卜醇衍生物的合成及其13C化学位移分析

诺卜基醚;诺卜基酯;诺卜醇衍生物的合成及其13C化学位移分析     

邻羟基α-叠氮苯乙酮衍生物的合成

以邻羟基苯乙酮衍生物为原料,经溴化反应和叠氮化反应合成了一系列邻羟基α-叠氮苯乙酮衍生物,其结构经1H NMR,13C NMR,IR及HR-MS表征.     

8-羟基喹啉及其衍生物的锌配合物合成研究进展

简述了有机发光材料8-羟基喹啉金属螯合物的发展,综述了固相法和液相法合成8-羟基喹啉锌,例举了在喹啉环上的2、5和7号位引入供电子基团或大共轭基团的8-羟基喹啉衍生物的锌配合物性质,介绍了通过改变聚合度制备8-羟基喹啉衍生物的锌配合物方法,杂环和8-羟基喹啉共同做锌的配体合成新的发光材料的方法;最后对8-羟基喹啉和8-羟基喹啉衍生物的锌配合物的合成进行总结和展望。     

苯并异喹啉酮衍生物的合成及其荧光性质

苯并异喹啉酮衍生物的合成及其荧光性质;苯并咪唑苯并异喹啉酮;萘酰亚胺;荧光量子产率;亲核取代反应;合成     

新型三噻吩衍生物的合成及其液晶性能

近晶A相;新型三噻吩衍生物的合成及其液晶性能     

Solvent Free One-Pot Synthesis of 2-thioxo-1,3-thiazinane-4-one Derivatives

Abstract

An efficient one-pot synthesis of 2-thioxo-1,3-thiazinane-4-one derivatives through the reaction of primary amines and carbon disulfide in the presence of acryloyl chloride is described. This reaction is carried out under solvent-free condition and without any catalyst at room temperature within 15 min. The structures of products were deduced from their elemental analysis and IR, ¹H NMR, and ¹³C NMR spectroscopy, and mass spectrometric data.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures.]     

N-糖基-N'-(6-取代色酮-3-基-亚甲氨基)硫脲类化合物的合成

糖基异硫氰酸酯(1a～1c)与无水肼反应, 生成糖基氨基硫脲2a～2c, 再与6-取代-3-甲酰基色酮3a～3d反应, 得到一系列新的N-糖基-N-(6-取代色酮-3-基-亚甲氨基)硫脲类化合物4a～4d, 5a～5d, 6a～6d. 所有新化合物的结构均经IR, ¹H NMR, MS谱和元素分析证实. 所得糖的衍生物构型保持不变, 均为β-型.     

1,3-取代吲哚-2-酮衍生物的合成与肿瘤细胞毒活性研究

以苯胺为原料,通过肟化、环合生成二氢吲哚-2,3-二酮,再对其进行N-烷基化、亲核加成和磺酰化反应得到目标化合物5a～5g和7a～7e。通过¹H NMR、¹³C NMR确认其结构。采用噻唑蓝（MTT）法测试了目标化合物对乳腺癌细胞MDA-MB-231、鼠黑色素瘤细胞B16、鼠结肠癌细胞CT26三种肿瘤细胞的体外抑制活性。结果表明,化合物7d、7e具有明显的肿瘤细胞毒活性,其中化合物7d对MDA-MB-231的细胞毒活性比阳性药五氟尿嘧啶更强,IC₅₀为4.63±0.14μmol/L。本文结果可为进一步研究具有肿瘤细胞毒活性的吲哚酮类衍生物提供参考。     

Addition of Sulfinic Acids to Methacrylic Derivatives

Abstract

The kinetics of the addition of arenesulfinic acids to methacrylic derivatives were studied. The reactions were found to be second order over a range of concentrations from 0.01 to 0.10 M. For pH values ranging from 4 to 8, the following rate constants were obtained pH the methylacrylate, chloromethylacrylate, and bromomethylacrylate with benzenesulfinic acids (278 K) were investigated: 2.37 (± 0.2).10^?4 M^?1s^?1, 2.60 (± 0.1).10^?4 M^?1s^?1, 3.15 (± 0.3).10^?4 M^?1s^?1.

GRAPHICAL ABSTRACT     

Switching the Photochromic Activity of Acenaphthylene Derivatives through a Tandem Nucleophile‐Promoted Addition Reaction

New acenaphthylene‐based dithienylethenes have been prepared. Surprisingly they did not show photochromism. However, they readily underwent a tandem addition of a nucleophile and an electrophile, leading to a small library of dearomatized colourless analogues, which, on the contrary, were endowed with photochromic activity. In the absence of the electrophile, the intermediate obtained by C‐attack readily aromatizes to give, surprisingly, a final product of direct aromatic nucleophilic substitution, which was not photochromically active.     

N-糖基硫代亚脲基—(硫代)磷酰胺二芳基和二烷基酯的合成

二芳氧基磷酰肼(2a，2b)或二乙氧基硫代磷酰肼(4)与糖基异硫氰酸酯(5a-5b) 反应，生成相应的N-糖基硫代亚脲基—磷酰胺二芳基酯(6a-6d,7a-7d)和N-糖基硫 代亚脲基—硫代磷酰胺二乙基酯(8a-8d)．     

Stereoselective Synthesis of 4,5-Dihydroisoxazole Derivatives from 1,1-Dicyanocyclopropanes and Hydroxylamine Hydrochloride

An efficient approach was developed for the synthesis of 4,5-dihydroisoxazole derivatives from substituted 1,1-dicyano-cyclopropanes and hydroxylamine hydrochloride in ethanol through FeCl₃-catalyzed cascade addition reactions. This procedure gives a useful method to afford stereoselectively poly-substituted 4,5-dihydroisoxazoles in good yields.     

N-(糖基硫代亚脲基)-芳基硫代磷酰胺芳基酯的合成

The Reaction of arylatrloxythiophosphoric hydrazide 2a ～ 2d with glycosyl isothioeyanates 3a ～ 3d gave the corresponding aryl N-( glyeosylthioureylene)-arylthiophosphoramidates 4a ～ 4d, 5a ～ 5d, 6a ～ 6d, 7a ～ 7d. The resulted compounds contained glyeosyhhioureylene and thiophosphorie amide fragments. The glycosyl isothioeyanates 3a～ 3d were prepared by the reaction of α-D-glyeosyl bromides with Pb(SCN)2. The biologic activities of the representative compounds were studied.     

Synthesis and Studies of Some Ketosulfones,Part I

New ketosulfones have been prepared. Their chemical composition and structure were proved by analytical and spectral methods. The kinetics of 1,4-addition of arenesulfinic acids to 1,3-diphenyl-2-nitropropenone and 3-nitro-4-phenyl-3-butene-2-on were studied by LC. The overall reaction is second order, while it is first order regarding each reagent and substrate. On the basis of the experimental results for the dependence of rate constants on the temperature and the influence of the substituents on the rate, a probable mechanism of the nucleophilic addition was suggested.     

Investigation of the Protection of the C4 Hydroxyl Group in Macrobicyclic Kdo Donors

Chemical synthesis of 3-deoxy-d-manno-2-octulosonic acid (Kdo)-containing glycans, such as bacterial lipopolysaccharides (LPSs) and capsular polysaccharides (CPSs), is in high demand for the development of vaccines against pathogenic bacteria. We have recently achieved the complete α-stereoselective glycosidation of Kdo using a macrobicyclic donor tethered at the C1 and C5 positions. In this study, to expand the scope of Kdo glycosidation, we sought to protect the 4-OH group, thereby shortening the reaction time and ensuring the conversion of the glycosyl acceptor via its selective removal. The protection of the 4-OH group influenced the reactivity of the Kdo donor, and the triisopropylsilyl (TIPS) group acted as a selectively removable booster. The 4-O-TIPS donor allowed the synthesis of the α(2,4)-linked dimeric Kdo sequence, which is widely found in bacterial LPSs.