N-乙基-3,6-二(3-苯基-1,3-丙二酮基)咔唑的合成

从咔唑的分子设计出发,合成了未见文献报道的双β-二酮——N-乙基-3,6-二(3-苯基-1,3-丙二酮基)咔唑(3),其结构经1H NMR,IR,MS和元素分析表征。研究了3的电子吸收光谱。     

1-(2-羟基苯基)-3-苯基-1,3-丙二酮及其铕(Ⅲ)配合物的合成和发光研究

以邻羟基苯乙酮和苯甲酰氯为原料, 经过酯化反应、 Fries重排合成了1-（2-羟基苯基）-3-苯基-1,3-丙二酮（HPPPD）及其与铕（Ⅲ）的配合物, 并通过IR, 热重-差热分析和^1H-NMR谱对其进行了表征. 研究了酚羟基的引入对稀土配合物发光性能的影响. 结果表明该配体与铕（Ⅲ）形成的配合物发出很强的铕（Ⅲ）的特征荧光, 并且以邻菲罗啉为第二配体的三元配合物的荧光强度明显高于二元配合物. 但是, 配体HPPPD与铽（Ⅲ）、钐（Ⅲ）和镝（Ⅲ）等形成的配合物, 无论是二元的, 还是三元的发光均很弱. 这是由于该配体的能级与不同稀土离子能级匹配程度的差别所致.     

2,2-二甲基-1-[5-二茂铁基-3-(三氟甲基)-1H-吡唑-1-基]丙-1-酮的合成及其电化学性质

以乙酰基二茂铁为原料,经3步反应合成了一个新型的二茂铁衍生物——2,2-二甲基-1-[5-二茂铁基-3-(三氟甲基)-1H-吡唑-1-基]丙-1-酮(4),其结构经1H NMR,ESI-MS,元素分析和X-射线单晶衍射表征。4属单斜晶系,P2(1)/c空间群,晶胞参数a=7.805 6(4),b=20.906 1(11),c=11.124 6(6),β=93.820(2)°,V=1 811.33(17)3,Z=4,Dc=1.482 g·cm-3,μ=0.872 mm-1,R1=0.034 8,wR2=0.089 2。采用循环伏安法研究了4的电化学性质。结果表明:4有一对可逆的氧化还原峰,Epa=0.640 V,Epc=0.482 V,ΔE=153 m V。     

天然产物1,3-二-(2-羟基-4-甲氧基苯基)丙烷和1,3-二-(2,4-二羟基苯基)丙烷的合成

1,3-二-(2-羟基-4-甲氧基苯基)丙烷(1)和1,3-二-(2,4-二羟基苯基)丙烷(2)是从菊叶薯蓣(Dioscorea composita Hemsl.)分离出来的天然产物, 以间苯二酚为起始原料, 分别经甲酰化和乙酰化得到2,4-二羟基苯甲醛和2,4-二羟基苯乙酮, 然后经选择性地甲基化、甲氧甲基化、羟醛缩合、还原、脱保护等步骤完成了上述两种天然产物的首次全合成. 产物通过¹H NMR, IR, MS进行了结构确证.     

二-(4-溴-2,5-二烷氧基苯基)甲烷及其类似物的合成

报道二-(4-溴-2,5-二烷氧基苯基)甲烷的一种简便合成方法.1,4-二乙氧基-2,5-二(烷氧基甲基)苯(1)在对甲苯磺酸催化下生成柱形杯[5]芳烃化合物2;2与N-溴代丁二酰亚胺(NBS)反应,生成二-(4-溴-2,5-二烷氧基苯基)甲烷(3).该方法反应条件温和、操作简单、选择性好、收率高.2与硝酸发生硝化反应,生成二-(4-硝基-2,5-二甲氧基苯基)甲烷(4).所合成的二-(4-溴-2,5-二烷氧基苯基)甲烷和二-(4-硝基-2,5-二甲氧基苯基)甲烷经过1H NMR,13C NMR和MS表征确认.     

1,5—双二茂铁基—4—己烯—1,3—二酮的合成

β-二酮是一类性能良好的螯合剂。化合物的一端引入二茂铁基,可使β-二酮与稀土离子的络合性能有所改变,但它对稀土金属的络合仍然没有选择性。为了寻找对稀土有不同络合能力的β-二酮,从而达到选择性地络合分离稀土的目的,我们首次合成了一种新的β-     

微波辐射下以1,3-二溴-5,5-二甲基乙内酰脲为溴代试剂合成3-溴黄酮

报道了在微波辐射下以1,3-二溴-5,5-二甲基乙内酰脲(DBDMH)为溴化试剂合成3-溴黄酮的新方法,系统考察了反应温度、时间及反应物配比对反应收率的影响.     

9-乙基-3,6-二(3-苯基-1,3-丙二酮基)咔唑的晶体结构及其光致发光性

用扩散法制备了一种双β-二酮化合物——9-乙基-3,6-二(3-苯基-1,3-丙二酮基)咔唑(1)的单晶。经X-射线单晶衍射仪测定1的晶体结构属于正交晶系,P2121空间群,非反演中心结构。晶胞参数为:a=29.58(4),b=7.708(10),c=12.151(6),α=β=γ=90°,V=2771(6)3,Z=4,R1=0.0802,Rw=0.1556。研究了1的光致发光性质。     

La(OTf)_3催化合成1,3-二噁烷-4,6-二酮化合物的研究

研究了在La(OTf)3的催化条件下,以丙二酸和酮为原料,缩合反应合成了3种1,3-二噁烷-4,6-二酮化合物.考察了酸酮物质的量之比、反应温度、反应时间、催化剂用量及催化剂的稳定性等因素对反应的影响.确定了其最佳反应条件为:取0.1mol丙二酸,n(丙二酸)∶n(酮)=1.0∶1.1,催化剂用量为0.3mol%,反应温度30℃,反应时间为3.0h,在上述反应条件下,产品收率可达62.3%～77.5%.     

新试剂3,5-二溴-4-氨基苯基荧光酮的合成及其应用研究

本文提供了新显色剂3,5-二溴-4-氨基苯基荧光酮的合成方法,较详细的研究了在表面活性剂增溶下,在盐酸介质中,试剂与锆(Ⅳ)的分光光度性质及反应条件,建立了分光光度法测定锆(Ⅳ)的高灵敏高选择性的新方法,并成功地用于铝锆合金中微量锆的测定。     

3-Ferrocenyl-3-(1-naphthyl)cyclopropene. Synthesis, structure, and chemical transformations

Crystalline 3-ferrocenyl-3-(1-naphthyl)cyclopropene was prepared by dehydrobromination ofZ- andE-2-bromo-1-ferrocenyl-1-(1-naphthyl)-cyclopropanes by Bu^tOK in DMSO. The resulting compound and the startingZ-monobromocyclopropane were characterized by X-ray diffraction analysis. The obtained cyclopropene reacts with 1,3-diphenylisobenzofuran to give a [4+2]-cycloadduct. The small ring opens upon treatment with HBF₄ etherate to afford isomericZ- andE-prop-1-enes and 1-ferrocenyl-3H-benzo[e]indene. Thermolysis of this cyclopropene results in the formation of 1-ferrocenyl-9bH-benzo[e]indene. In all cases, opening of the small ring is accompanied by exclusive alkylation of the naphthalene moiety. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 499–506, March, 1998.     

Synthesis of 4-alkoxy-4-methyl- and 4-alkoxy-4-fluoromethyl-1,3-benzoxazinones

Cyclization of 2-hydroxyacetophenone hydrazones with triphosgene resulted in the formation of 4-methylene-1,3-benzoxazinones. These compounds were converted to 4-alkoxy-4-methyl-1,3-benzoxazinones and 4-fluoromethyl-4-methoxy-1,3-benzoxazinones upon treatment with alcohols under refluxing conditions and F-TEDA-BF₄ in acetonitrile and methanol, respectively.     

The reaction of (N-isocyanimino)triphenylphosphorane with dialkyl acetylenedicarboxylates in the presence of 1,3-diphenyl-1,3-propanedione: a novel three-component reaction for the stereoselective synthesis of dialkyl (Z)-2-(5,7-diphenyl-1,3,4-oxadiazepin-2-yl)-2-butenedioates

Reactions of dialkyl acetylenedicarboxylates with (N-isocyanimino)triphenylphosphorane in the presence of 1,3-diphenyl-1,3-propanedione proceed smoothly at room temperature to afford dialkyl (Z)-2-(5,7-diphenyl-1,3,4-oxadiazepin-2-yl)-2-butenedioates in high yields. The stereochemistry of the final products were confirmed by single crystal X-ray structure determination. The reaction is completely stereoselective.     

K3PO4-promoted Cyclopropanation of Electron-deficient Alkenes with 2-Bromo-1,3-propanedione Compounds

An easy and efficient method for the synthesis of multisubstituted cyclopropane derivatives from electron-deficicent alkenes with 2-bromo-1,3-propanedione compounds was described. For this method, ethyl α-cyanocinnamate derivatives 1 and β,β-dicyanostyrene derivatives 4 can all smoothly react with 2-bromo-1,3-propanedione compounds 2 to afford the corresponding multisubstituted cyclopropane derivatives 3 and 5 in good to excellent yields(up to 100%) promoted by anhydrous K₃PO₄ in DMF at room temperature, respectively. A possible mechanism of this reaction was proposed. Structures of all the products were confirmed by ¹H NMR, ¹³C NMR and HRMS.     

Synthesis and molecular and crystal structure of 1-allyl-4-[2-cyano-2-(indan-1,3-dione-2-ylidene)ethylidene] -1, 4-dihydroquinoline

The reaction of 1-allyl-4-methylquinolinium bromide with 2-dicyanomethyleneindan-1,3-dione in the presence of a two-fold excess of triethylamine affords 1-allyl-4-[2-cyano-2-(indan-1,3-dione-2-ylidene) ethylidene]-1,4-dihydrogtiinoline, a representative of a new class of merocyanines. The structure of this compound has been established by X-ray structural analysis. A substantial intramolecular charge transfer and a hydrogen bond between the vinyl hydrogen atom and the indandione oxygen atom have been found.Dedeased in 1995Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 173–176, January, 1996.     

Synthesis of 3-(4-bromophenyl)-1-morpholino-2-phenylalkan-3-ol hydrochlorides

Reactions of 1-(4-bromophenyl)-3-morpholino-2-phenylpropan-1-one with various Grignard compounds in diethyl ether gave a broad series of tertiary amino alcohols, 3-(4-bromophenyl)-1-morpholino-2-phenylalkan-3-ol hydrochlorides, that can be regarded as Trihexyphenidyl analogs.     

Novel Synthesis of Isoquinoline Derivatives Derived from (Z)-4-(1,3-Diphenylpyrazol-4-yl)isochromene-1,3-dione

A series of isoquinoline derivatives were synthesized via the reaction of the (Z)-4-(1,3-diphenylpyrazol-4-yl)isochromene-1,3-dione with different hydrazides, primary amines, diamines, 2-aminothiophenol, 2-aminobenzoic acid, p-aminoacetophenone, and ethyl 2-amino-4,5,6,7-tetrahydrobenzo-[b]thiophene-3-carboxylate. All the synthesized compounds were characterized by infrared, ¹H NMR, and mass spectra besides the analytical data.