二乙胺基硫代甲酸钴(Ⅲ)的制备与结构

胺基硫代甲酸能与高氧化态的Ｃｏ(Ⅲ )、Ｎｉ(ＩＶ)、Ｆｅ(ＩＶ)和Ｍｎ(ＩＶ)等金属形成稳定的胺基硫代甲酸配合物。我们制备了单核钴配合物 [Ｃｏ(Ｓ2 ＣＮＲ2 ) 3],并经Ｘ 射线衍射方法确定了配合物的分子和晶体结构。1　实验部分1 1　仪器和试剂ＣａｒｌｏＥｖｂａ 1 1 0 6型元素分析仪 (意大利 ) ,ＪＡ96 975型电感耦合等离子直读光谱仪 ,Ｐｅｒｋｉｎ Ｅｌｍｅｒ783红外光谱仪。所用试剂均为分析纯。1 2　配合物的合成将乙酰丙酮钴 ( 1ｍｍｏｌ,0 .2 5 7ｇ)和二乙胺基硫代甲酸钠 ( 3ｍｍｏｌ,0 .5 1 3ｇ)的甲醇溶液 ( 4 0ｃｍ3)混合 …     

巯基乙酸锑配合物的合成与X射线粉末衍射数据指标化

一些锑和铋的配合物可以应用于医药研究[1,2 ] ,已合成了许多锑的有机配体配合物[3～ 7] ,但其中大多数没有生物活性。因此 ,研究锑或铋离子的配合物不仅对主族元素化学、生物无机化学而且对医药都有着非常重要的意义。我们用三氯化锑与巯基乙酸液相反应法合成的二巯基乙酸锑 (Ⅲ)配合物 ,其组成为ＨＳｂ(ＳＣＨ2 ＣＯＯ) 2 ,用Ｘ射线粉末多晶衍射数据指标化来研究配合物晶体结构[8] 。1　实验部分1 1　仪器与试剂ＥＡ - 1 1 0 6型元素分析仪 (意大利卡拉欧巴公司制造 ) ,Ｄ Ｍａｘ -ＹＢ型多晶Ｘ射线粉末衍射仪(日本理学 ,ＣｕＫα射线 ,…     

［M_x（FeCO_2）_yL_z］型配合物的合成、表征及CV性质研究（M＝Cu

［Ｍ＿ｘ（ＦｅＣＯ＿２）＿ｙＬ＿ｚ］型配合物可在ＴＨＦ中通Ｎ２条件下由ＦｅＣＯ＿２Ｈ和ＭＸ＿２·ｎＨ＿２Ｏ（Ｘ＝Ｃｌ￣－和Ａｃ￣－）经长时间反应制得．ＩＲ和１ＨＮＭＲ谱表明Ｃｕ（Ⅲ）、Ｃｏ（Ⅲ）属螯环配合物，Ｃｄ（Ⅱ）属四面体型配合物，Ｐｂ（Ⅱ）属线型化合物．Ｍ（Ⅱ）离子位于配合物中心．ＣＶ表明Ｍ（Ⅱ）呈多价态变化，受配体及敖合效应影响Ｆｅ（Ⅲ）Ｆｅ（Ⅱ）和Ｍ（Ⅱ）　Ｍ（０）Ｅｐ／２下降，Ｍ（Ⅱ）还原力上升．Ｍ（Ⅱ）　Ｍ（０）Ｅ＿ｐ／２随Ｍ（Ⅱ）＿（ａｑ）．性质呈现律性变化．     

水相法合成二氯二甲茂钛与水杨酸类配合物

Ｃｐ2 ＴｉＣｌ2 具有很好的抗癌活性 ,已成为第三代抗癌药物[1 - 3] 。为了寻求活性更高的抗癌药物 ,探索抗癌机理 ,我们用 (ＭｅＣｐ) 2 ＴｉＣｌ2 、水杨酸或其衍生物 ,按水相法合成了甲茂钛的水杨酸类配合物。合成路线如下图所示 :其中 :Ⅰ为ｐＨ <4 ,Ｘ =Ｈ ,Ｙ =Ｈ的产物 ;Ⅱ为ｐＨ <4 ,Ｘ =Ｈ ,Ｙ =ＮＯ2 的产物 ;Ⅲ为ｐＨ >6 ,Ｘ =ＮＯ2 ,Ｙ =ＮＯ2 ,Ｚ =Ｏ的产物 ;Ⅳ为ｐＨ >6 ,Ｘ =Ｈ ,Ｙ =Ｈ ,Ｚ =Ｓ的产物。 (Ⅰ～Ⅳ为新化合物 )1　实验部分1 .1　仪器与试剂水杨酸、ＴｉＣｌ4,ＡＲ ;5 -硝基水杨酸、3,5 -二硝基水杨酸、5 -磺基…     

自制简易气体量管系列在中学科学素质教育中的应用(三)——Al-Mg合金的测定

3　Ａｌ-Ｍｇ合金的测定3.1　简易气体量管的制作 (第 9期原图 1所示 )3.2　测定原理 (第 9期原图 2 - 3所示 )设 :(Ｚ1,Ｚ2 分别为Ｍｅ1Ｍｅ2 价态 ,物质的量之比为Ｘ∶Ｙ)由反应 (Ｍｅ1Ｍｅ2 ) +ｍＨＣｌ→Ｍｅ1ＣｌＺ1·Ｍｅ1ＣｌＺ2 +(Ｚ1Ｘ +Ｚ2 Ｙ) 1 2Ｈ2 ↑(ａ)反应前 :Ｐ空 Ｖ0 =ｎ0 ＲＴ0 (克氏方程 )　Ｐ水 =Ｈ ＬＰ空 +Ｐ水 =1ｎ0 ＲＴ0 =(1-Ｈ Ｌ)Ｖ0 (1)(ｂ)反应终了 :Ｗｉ(ｇ)合金与过量 5ｍｏｌ Ｌ的ＨＣｌ反应 ,生成Ｈ2的物质的量为ｎｉ 水位下降了Ｙｉ ｃｍ可有 (2 )成立 :　　Ｐ混(Ｖ0 +ＳＹｉ) =(ｎ0 +ｎｉ)ＲＴ0Ｐ’水…     

Zn(Ⅱ)与氯苯基苯并咪唑配合物的合成、表征和晶体结构

带咪唑、苯并咪唑等配位基团的过渡金属配合物是一类很重要的物质[1～ 9] 。本文探讨它与Ｚｎ(Ⅱ )的配位性质及配合物的晶体结构。1　实验部分1 .1　标题配合物的合成及表征将 92ｍｇ 2 (0 氯苯基 )苯并咪唑和 40ｍｇＺｎＣｌ2(ＡＲ)分别溶于无水乙醇(ＡＲ)后混合均匀 ,于室温下静置 3 0天 ,析出长方体形无色晶状物 ,产率为 47%。采用Ｐｅｒｋｉｎ Ｅｌｍｅｒ 2 4 0Ｃ元素分析仪测定配合物中Ｃ、Ｈ、Ｎ含量。用ＤＤＳ 1 1Ｃ数显电导率仪 ,以ＤＭＦ为溶剂测定配合物的摩尔电导。采用Ｎｉｃｏｌｅｔ5ＤＸ Ｂ傅立叶变换红外光谱仪 ,ＫＢｒ压…     

含氨茂铁异核金属配合物合成和性质研究

Ｐｄ（Ⅱ）、Ｐｔ（Ⅱ）ＤＭＡＦ配合物已合成，并已定结构。本文采用ＭＸ２（Ｍ－Ｎｉ（Ⅱ），Ｃｏ（Ⅱ），Ｚｎ（Ⅱ）、Ｃｕ（Ⅱ）；Ｘ＝Ｃｌ，Ｂｒ，Ｉ）在ＣＨ２Ｃｌ２中和ＤＭＡＦ作用合成［ＭＸ２．２ＤＭＡＦ］型配合物。由ＮｉＣｌ２．２ＤＭＡＦ．Ｃ７Ｈ８晶胞参数推知属于对称链状四配位结构。ＩＲ谱表明，该化合物化学式为ＭＸ２．２ＤＭＡＦ。ＣＶ表明配合物中Ｍ（Ⅱ）和Ｆｅ（Ⅱ）存在。由于金属离子互相影响。Ｅｐ／２     

2001年全国高中学生化学竞赛（决赛）理论试题答案

第 1题1- 1　Ａ :ＮＨ4 ＨＣＯ3[或 (ＮＨ4 ) 2 ＣＯ3]　Ｂ :ＫＣｌ　Ｃ :Ｋ2 ＳＯ4 　Ｄ :ＮＨ4 Ｃｌ　Ｅ :Ｆｅ2 Ｏ3　Ｆ :ＣＯ21- 2　反应 (1) :(ｍ +ｎ)ＦｅＳＯ4 + 2 (ｍ +ｎ)ＮＨ4 ＨＣＯ3=Ｆｅｍ +ｎ(ＯＨ) 2ｎ(ＣＯ3) ｍ↓ + (ｎ +ｍ) (ＮＨ4 ) 2 ＳＯ4 + (2ｎ +ｍ)ＣＯ2 ↑ +ｍＨ2 ＯＮＨ4 ＨＣＯ3 写成 (ＮＨ4 ) 2 ＣＯ3,Ｆｅｍ +ｎ(ＯＨ) 2ｎ(ＣＯ3) ｍ 写成 (1)Ｆｅ2 (ＯＨ) 4-2ｍ(ＣＯ3) ｍ,(2 )Ｆｅ2 (ＯＨ) 2 ＣＯ3,(3)Ｆｅ(ＯＨ) 2 和ＦｅＣＯ3 且配平的 ,也给分。反应 (2 ) :2Ｆｅｍ +ｎ(ＯＨ) 2ｎ(ＣＯ3) ｍ+ ｍ +ｎ2 Ｏ2…     

Na3Fe(C2O4)3·5H2O的热解过程和FAB-MS断裂规律

以红外光谱法为主要手段，原位“跟踪”测定铁（Ⅲ）与乙二酸形成的配合物Ｎａ３Ｆｅ（Ｃ２Ｏ４）３．５Ｈ２Ｏ的热解过程，分析了气、固相热解产物。并以色谱分析、差热－热重分析和Ｘ－射线粉末衍射法定性、定量地验证其结果。测定了该配合物快原子轰击质谱，提出了断裂规律。铁的二元羧酸配合物的质谱尚属首见。     

微波法固相合成二茂铁基α、β-不饱和酮

由于二茂铁具有芳香性,氧化还原可逆性,稳定性高,亲电性,毒性低等特点,其衍生物在材料学、电化学、生物学、医学等方面有广泛的应用[1,2]。本文报道以负载于氧化铝上的氟化钾为固体碱催化剂,使用微波法合成了一系列二茂铁基α、β 不饱和酮,并研究了芳香醛上取代基对反应的影响。Ａｒ:ａ,Ｃ6Ｈ5 ;ｂ,4 ＭｅＯＣ6Ｈ4;ｃ,2 Ｆｕｒｙｌｄ,4 Ｍｅ2ＮＣ6Ｈ4;ｅ,Ｆｅｒｒｏｃｅｎｙｌ;ｆ4 ＮＯ2 Ｃ6Ｈ4.1　实验部分1 1　试剂和仪器所用药品均为国产ＡＲ或ＣＰ级试剂。ＸＰＣ 1显微熔点测定仪(温度计未校正)(四川大学科仪厂);Ｃａｒｌｏ Ｅｒｂ…     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.