2,3-二氯-5,6-二氰基苯醌在有机反应中的应用进展

2,3-二氯-5,6-二氰基苯醌(DDQ)是有机反应常用的氧化试剂,近几年在多种有机反应中的应用方面有了新的进展.本文综述了其作为氧化脱氢、苄基位和烯丙位氧化、氧化偶联环合及保护和脱保护等方面的研究成果.     

Regiospecific oxidation of an alkyl group of aromatic amine to carbonyl group by DDQ in aq.medium

The regiospecific oxidation of alkyl group of both sterically hindered and unhindered aromatic amine to corresponding carbonyl compound was done in aq. medium by using DDQ. The optimized reaction protocol was found to be most simple, high yielding and novel method for oxidation of alkyl group of aromatic amine in to its carbonyl compound.     

The Synthesis of Podophyllotoxin Derivatives with Macrocyclic Dilactone

Podophyllotoxin1andmanyofitsderivatives,includingC-2epimer,picropodophyllin2.areantimitoticagents'.Thesemi'syntheticderivativesofIetoposide(VP-16-213)andteniposide(VM-26)areinclinicaluseasanti-canceragents'.SomeanaloguesofIwithamodifiedlactoneringhavebeensynthesizedandfoundtobestillantimitotic'.therebyindicatingthatthelactoneringisnotrequiredforantimitoticactivityin1.Anjanamurthyetap.ha.esynthesizedaderivativebyenlargingthefive-memberedlactoneringinItoasix-memberedone.Sincethen.however.nos…     

Synthesis of 4-Alkenylated Pyrazolinones by 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-Mediated Oxidative Coupling Reaction

1,3-Diarylpropenes firstly serve as efficient alkenylated reagents for the functionalization of pyrazolinones. In the presence of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), it undergoes oxidative coupling and final dehydrogenation to give the highly substituted E,E-α,β,γ,δ-dienpyrazolinones in moderate to excellent yields.     

Benzylic modifications of meso-alkyl-substituted porphyrins via oxidation with DDQ

The reactions at the benzylic positions of meso-alkyl-substituted porphyrins have been achieved via the reaction with DDQ in the presence of alcohol or water for the first time, and ethenyl porphyrins from methoxylated porphyrins and an acetoxy porphyrin from the hydroxyl porphyrin were prepared.     

Chemoselective deprotection of N-allylic amines using DDQ

A highly chemoselective and simple method for the deprotection of N-allylic amines using DDQ has been developed. The use of DDQ in dichloromethane–water provides a mild and efficient one-step deallylation of a wide variety of orthogonally protected tertiary amine derivatives.     

Synthesis of New Fluorinated Podophyllotoxin Derivatives

Five fluorinated podophyUotoxin derivatives were synthesized using dimethylamino-sulfurtrifluoride (DAST).     

N-取代吩噻嗪和DDQ的电荷转移络合作用

具有盼嘤酸化学结构的化合物有广泛的用途I‘－＼其中吩嘤埃衍生物在医学上用作抗精神病药物特别受到药理学家们的注意，发现其药理作用与其分子提供电子的能力有关卜‘」但是我们应该注意到，作为抗精神病药物的吩嚷嚷衍生物，其吩座爆分子的氮原子都连有一个叔胺基链问，例如氯丙障（I）和奋乃静（11）．而我们知道，胺类特别是叔胺类有强的提供电子的能力＊；在上述的药物分子中是主要的提供电子因素，因此以这类化合物作为给体研究其供电子能力，是不能实际反映吩嘤嗓分子本身的给电子能力的．吩嘤噪类属于二苯并杂环化合物，分子中既…     

DDQ induced oxidative cyclisations of 1,2-dihydronaptho[2,1-b]furans

The DDQ mediated oxidative cyclisation reactions of a series of dihydronaptho[2,1-b]furans were examined. In the presence of an acid catalyst, the reaction yielded polycyclic ethers and lactones in good to excellent yields.     

抗癌活性鬼臼毒素衍生物的合成与构效关系研究

合成了１３个新的鬼臼毒素衍生物５－１７，经元素分析ＩＲ，ＭＳ，ＥＳＲ和＾１ＨＮＭＲ分析确证了其组成和结构，并对它们进行了抑制小鼠淋巴白血病Ｐ３８８和人胃腺癌ＳＧＣ－７９０１细胞体外筛选，发现新化合物５，７－１０对两种瘤株均有显著抑制活性，４′－Ｏ－去甲基鬼臼毒素５，１０－１３的抗癌活性大于相应的４′－甲氧基类似物６，１４－１７，用“－Ｏ－”桥取代Ｃ－４位的“－ＮＨ－”桥可导致抗癌活性降低。     

Copper-and Silver-Mediated Cyanation of Aryl Iodides Using DDQ as Cyanide Source

A new copper and silver‐mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, providing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles.     

[2＋2] Photocycloaddition of [60] Fullerene with Podophyllotoxin Derivative Containing Cyclohexadienone Group

Photochemical [2 2] cycloaddition of C60 with podophyllotoxin derivative containing a cyclohexadienone group in o-dichlorobenzene afforded an isomeric mixture of adducts and a pure adduct of C60-fused podophyllotoxin derivatives. The structures of the products were characterized by MS, NMR and IR spectra.     

Synthesis and Characterization of a Novel Podophyllotoxin Derivative Containing a Cyclohexadienone Group

4β-Azido-4-demethyl-4'-O-demethyl-epipodophyllotoxin reacted with phenyliodonium diacetate in MeOH at room temperature to synthesize a novel podophyllotoxin derivative containing a cyclohexadienone group with the original configurations of C2 and C4,which are required for the antitumor activities.The component and structure of the pro-duct were confirmed using elemental analysis,high-resolution mass spectrum,1H and 13C NMR spectra,and infrared spectrum.Furthermore,the fragmentation routes of the product were fully assigned with electron-impact time-of-flight mass spectrometry(EI-TOF MS),which can also be used for the structural elucidation based on the molecular ion at m/z 455(16%)and three novel characteristic fragment ions at m/z 183(37%),425(7%),and 199(5%).The cyclohexadienone product is sensitive to acidic media.When it is treated with a trace of acid,another novel derivative containing an orthoquinone moiety is formed,which links with the metabolism of the cancer inhibitors.     

Reactions of vinylidenecyclopropanes with xanthydrol and xanthene

Vinylidenecyclopropanes undergo ring-opening reactions with xanthydrol in the presence of BF₃·OEt₂ or with xanthene in the presence of DDQ at 0 °C in 1,2-dichloroethane to give the corresponding conjugate triene derivatives in moderate to good yields. Plausible reaction mechanisms have been discussed on the basis of previous literature and the control experiments. The further transformation of these trienes has been disclosed in DCE in the presence of BF₃·OEt₂ along with a plausible reaction mechanism.     

鬼臼毒素及其衍生物的瞬态粒子分析

分析了鬼臼毒素及其衍生物与还原性自由基(氢自由基、水合电子)作用、氧化性自由基羟基自由基和激光等作用后产生的各种瞬态粒子，对各粒子的生成和衰减过程进行跟踪，获得了各瞬态粒子的生成和衰减速率常数，进一步探讨了鬼臼毒素治疗肿瘤的构效关系。     

A facile synthesis of 2-oxazolines using a PPh3–DDQ system

A facile and efficient synthesis of 2-oxazolines from N-(2-hydroxyethyl)amides using a triphenylphosphine–2,3-dichloro-5,6-dicyanobenzoquinone (PPh₃–DQQ) system is described. The reaction proceeds under neutral and mild conditions, and excellent yields are obtained.     

自旋标记鬼桕类化合物圆二色谱的研究

给已知抗癌药物分子中引入稳定氮氧自由基,合成较母体药物高效低毒的抗癌药物已引起国内外学者的重视.我们在具有抗癌活性的鬼桕毒分子中引入稳定氮氧自由基,药理试验表明其活性保持或增加,而毒性却显著地降低.     

Synthesis of 2H-pyrroles by treatment of pyrrolidines with DDQ

A mild and efficient synthesis of 2,2-dialkyl-3,5-diaryl-2H-pyrroles is described. Treatment of 2,2-dialkyl-3,5-diarylpyrrolidines with DDQ in dioxane for 12-24 h at rt afforded the corresponding 2H-pyrroles in 55-81% overall yields.     

Synthesis of New Conjugates of Modified Podophyllotoxin and Stavudine

To find podophyllotoxin compounds with superior bioactivitiy and less toxicity, a series of novel conjugates of ring‐A‐modified 4‐epipodophyllotoxin and stavudine with amino acids as spacers were synthesized, i.e., the N‐[(2′,3′‐didehydro‐3′‐deoxythymidin‐5′‐O‐yl)carbonyl]‐substituted L ‐amino acid rel‐(3aR,4S,9R,9aR)‐1,3,3a,4,9,9a‐hexahydro‐6,7‐dimethoxy‐1‐oxo‐9‐(3,4,5‐trimethoxyphenyl)naphtho[2,3‐c]furan‐4‐yl esters 8a – 8f .     

Spectroscopic Study of the Complexation of DDQ with 1,10-Diaza-18-crown-6 in Chloroform Solution

The formation of charge transfer complexes with 1:1 and 2:1 stoichiometries (acceptor-to-donor) between DDQ and 1,10-diaza-18-crown-6 in chloroform solution was investigated spectrophotometrically. The stepwise formation constants of the resulting complexes were evaluated from the non-linear least-squaresfitting of the absorbance-mole ratio data. The enthalpies and entropiesof the complexation reactions were determined from the temperature dependence of the stepwise formation constants. The resulting 1:1 and 2:1 complexes were isolated in crystalline form and characterized. The results are consistent with the ionic structure of the resulting charge transfer complexes.