负载型蒙脱土催化芦竹碱的微波合成

以吲哚(1)、甲醛(2)和二甲胺(3)为原料,固载蒙脱土(MMT)/路易斯酸(L)为催化剂,通过微波辐射合成了芦竹碱(4),其结构经1H NMR确证。考察了MMT/L、反应温度、反应时间、溶剂和物料比r[n(1)∶n(2)∶n(3)]对4产率的影响。结果表明:在最优反应条件[甲醇为溶剂,MMT/Zn Cl2为催化剂,MMT/Zn Cl218 mg,1 1mmol,r=1.0∶1.3∶1.3,于50℃反应10 min]下合成4,产率93.8%。MMT/Zn Cl2循环使用3次,4产率60.0%     

开放骨架磷酸铝合成中F~-对有机胺结构导向效应的影响

研究了在开放骨架磷酸铝合成中氟离子对乙二胺(en)和二乙烯三胺(deta)的结构导向效应的影响.在水热条件下,以乙二胺为结构导向剂,分别从摩尔组成为n(Al2O3)∶n(P2O5)∶n(en)∶n(H2O)=1.0∶1.5∶18.0∶147和n(Al2O3)∶n(P2O5)∶n(en)∶n(HF)∶n(H2O)=1.0∶1.5∶18.0∶3.0∶147的初始混合物中晶化出二维层状磷酸铝Al2P2O9·NH3(CH2)2NH3(Ui O-13)和Al F(HPO4)·NH2(CH2)2NH2(1);以二乙烯三胺为结构导向剂,分别从摩尔组成为n(Al2O3)∶n(P2O5)∶n(deta)∶n(H2O)=1.0∶4.0∶3.0∶153和n(Al2O3)∶n(P2O5)∶n(deta)∶n(HF)∶n(H2O)=1.0∶4.0∶3.0∶3.0∶153的初始混合物中晶化出了三维开放骨架磷酸铝Al4P5O20(H2O)2·C4N3H16(Al PO-CJ31)和一维链状磷酸铝Al2P4O10(OH)3F·C4N3H15(2),表明凝胶中的F-显著改变了乙二胺和二乙烯三胺的结构导向效应.详细对比分析了Ui O-13和化合物1以及AlPO-CJ31和化合物2的结构,探讨了F-对乙二胺和二乙烯三胺的结构导向效应的影响及F-与有机胺的协同结构导向效应.     

结晶的稀土配合催化剂活性体

在3d族过渡金属配合催化剂结构的研究中,作为活性中心的模型,引人注意的是金属和铝摩尔比1∶1和1∶2的活性体,但其摩尔比2∶1的活性体尚未见报道. 在稀土配合催化剂本质的研究中,人们也一直把注意力集中于催化剂结构,但成功地合成或分离出结晶的活性体只有两种双金属配合物.Ballard等报道的Er(η-C_5H_4R)_2(CH_3)Al(CH_3)_2使乙烯聚合有活性,我们合成出的(CF_3CO_2)HLnCl(C_2H_5)Al(C_2H_5)_2使双烯烃聚合得到高顺式聚合物. 本文利用(i-C_3H_7O)_3Ln-Et_2AlCl-Et_3Al(三元体系)和(i-C_3H_7O)_2LnCl-Et_3Al(二元体系)的可溶性,合成了摩尔比为1∶2∶3=Al∶Ln∶Cl(Ln=Gd,Dy,Er,Tm.Lu-Al活性体中1∶1∶1=Al∶Ln∶Cl)的四种新的Ln-Al-Ln结晶活性体.     

对硝基邻苯二乙醚合成技术研究

以邻苯二酚与溴乙烷为原料、聚乙二醇为相转移催化剂合成邻苯二乙醚,再经过冰醋酸和硝酸硝化得到对硝基邻苯二乙醚。研究了反应温度、反应时间、原料摩尔比和催化剂用量等对反应收率的影响,获得了合成邻苯二乙醚的优化工艺条件:n(C6H4(OH)2)∶n(NaO H)∶n(C2H5Br)=1∶2.6∶2.4,反应温度80℃,反应时间4h,催化剂用量2g,该反应条件下邻苯二乙醚平均收率88%。混酸硝化条件下合成对硝基邻苯二乙醚的较佳工艺条件为n(C10H14O2)∶n(HNO3)=1∶1.2,乙酸25mL,反应时间30min,反应温度20℃,该反应条件下对硝基邻苯二乙醚平均收率为99%。     

2,3,6,7,10,11-六甲氧基苯并菲的合成工艺改进

以1,2-二甲氧基苯(1)为原料,二氯乙烷为溶剂,氯化铁为催化剂,合成了2,3,6,7,10,11-六甲氧基苯(2)。在142 mmol,n(FeC l3)∶n(1)=4∶1,50℃反应2 h的最佳反应条件下,2的收率达81.48%。     

新型含双长链和苄基的有机硅季铵盐的合成

以双十二胺(1)为原料,与氯化苄经取代反应制得中间体苄基双十二胺(2);2与γ-氯丙基三甲氧基硅烷(3)经季铵化反应合成了一种新型的含双长链和苄基的有机硅季铵盐(4),其结构经UV-Vis和FT-IR表征。通过正交实验L9(34)优化了2和4的反应条件。合成2的最佳工艺条件为:以乙腈为溶剂,1 5 mmol,n(1)∶n(Bn Cl)=1.0∶1.2,回流反应20 h,收率80.4%。合成4的最佳工艺条件为:以乙二醇为溶剂,2 5mmol,n(2)∶n(3)=1.0∶1.6,于110℃密闭反应80 h,收率57.8%。     

敞开体系制备含铝中孔分子筛

在敞开体系中 ,以工业用水玻璃为硅源 ,以Al2 (SO4) 3 为铝源 ,以三甲基十六烷基溴化铵 (CTMAB)为模板剂 ,用H2 SO4调节浆料的pH值 ,在浆料混合物摩尔比组成为n(SiO2 )∶n(Na2 O)∶n(CTMAB)∶n(Al2 (SO4) 3 )∶n(H2 O) =7∶2 .0 8∶1.4∶(0 .0 875～ 0 .7)∶5 30的范围内 ,10 0℃搅拌晶化 2 4h ,合成出了含铝中孔分子筛 .利用XRD ,IR和化学分析对产物晶体的长程有序性和骨架铝进行了表征 ,讨论了n(Si) /n(Al)的摩尔比值和浆料pH值对分子筛晶化的影响 .     

新型环磷腈类化合物的合成

六氯环三磷腈(1)分别与间苯二胺(2)和二苯氨基脲(3)经亲核取代反应合成了两个新型的环磷腈类化合物——六间苯二胺环三磷腈(4)和六二苯氨基脲环三磷腈(5),其结构经1H NMR,31P NMR和IR表征。合成4的最佳反应条件为:1 7.2 mmol,n(2)∶n(1)=6.17,于70℃反应12 h,产率72.68%。合成5的最佳反应条件为:1 2.8 mmol,n(3)∶n(1)=6.10,于70℃反应12 h,产率46.57%。     

1,3,5-三甲氧基苯的绿色合成工艺

以间苯三酚(PG)为原料,碳酸二甲酯(DMC)为甲基化试剂,在K2CO3/(Bu)4NBr催化下合成了1,3,5-三甲氧基苯,其结构经1H NMR,13C NMR和HR-ESI-MS确证。最佳工艺条件为:PG 10 mmol,n(DMC)∶n[(Bu)4NBr]∶n(K2CO3)∶n(PG)=12∶0.15∶1.5∶1,于160℃反应24 h,收率76.0%。     

离子液体介入的均苯三甲酸氧钒催化氧化异丁香酚制香草醛

合成了系列均苯三甲酸氧钒配合物催化剂,并进行了FT-IR、紫外-可见漫反射光谱(DR UV-Vis)及TG表征。 系统考察了催化剂、不同种类的离子液体助剂、离子液体用量和反应时间等因素对异丁香酚氧化制备香草醛的影响。 结果表明,n(VO2+)∶n(BTC(均苯三甲酸根))=1∶1时制备的催化剂VO(BTC)-1性能较佳。 以VO(BTC)-1为催化剂、氯化1-十二烷基-3-甲基咪唑([C12mim]Cl)为助剂、丙酮为介质,当n(异丁香酚)∶n(H2O2)∶n([C12mim]Cl)=1∶2∶0.01时20 ℃反应24 h,异丁香酚可转化完全,香草醛收率达到87.2%。 基于离子液体介入的催化剂光谱特征及反应结果,推测[C12mim]Cl/VO(BTC)-1与H2O2形成了高效的氧化反应体系从而有利于异丁香酚的温和转化。     

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.