3′,4′,5′-三氟-2-氨基联苯的合成研究

3′,4′,5′-三氟-2-氨基联苯是合成新型杀菌剂氟唑菌酰胺的重要中间体,目前合成3′,4′,5′-三氟-2-氨基联苯的路线较多,但收率均不高。为了提高收率,降低成本,本文以1,2,3-三氯苯为起始原料,经氟化、溴化、格氏、偶联、加氢还原等5步反应合成了3′,4′,5′-三氟-2-氨基联苯,总收率55%以上,含量99%以上。该路线原料易得,操作方便,具有工业化前景。     

Cobaltacarboranes [closo-(9-R2N-1,7,9-C3B8H10)-commo-2,(3′)-Co-(1′,2′-C2B9H11)] (where R=H and Me) — crossover complexes between metallatricarbollides and metalladicarbollides

Reactions between 7-L-nido-7,8,9-C₃B₈H₁₀ compounds (where L=Bu^tNH₂ and Me₂NH) and [NMe₃H]⁺[7,8-C₂B₉H₁₂]⁻ in the presence of NaH, followed by the addition of anhydrous CoCl₂ and prolonged heating in diglyme at reflux, resulted in the isolation of mixed-ligand 12-vertex cobaltacarboranes [closo-(9-R₂N-1,7,9-C₃B₈H₁₀)-commo-2,(3′)-Co-(1′,2′-C₂B₉H₁₁)] (where R=H or Me). These represent neutral, crossover complexes between metallatricarbollides and metalladicarbollides and contain amino groups attached to p-positions with respect to the metal centre.     

2-(3′,4′-二氯苯氧基)乙基二乙胺的合成方法

研究了以 3,4-二氯苯胺为原料合成植物生长调节剂 2 - ( 3′,4′-二氯苯氧基 )乙基二乙胺的合成新方法 ,3,4-二氯苯酚的产率 81 .6% ,1 -氯 - 2 - ( 3′,4′-二氯苯氧基 )乙烷的产率 94% ,2 - ( 3′,4′-二氯苯氧基 )乙基二乙胺的产率 84%     

2′,4′-二氟-4-羟基-(1,1′-联苯)-3-羧酸的制备

以2，4－二氟苯胺为起始原料，经联苯化作用，Friedel-Crafts酰化反应、Baeyer-Villiger重排、水解和羧基化作用5步反应制得2′，4′－二氟－4－羟基－（1，1′－联苯）－3－羧酸，总收率可达38．4％。     

3′,4′,5′-三氟联苯-4-硼酸的合成及表征

使用工业上易得的原料通过3步反应合成标题化合物.苯硼酸与3,4,5-三氟溴苯作为起始原料,在K2CO3水溶液和甲苯体系中,Pd/C催化反应生成3,4,5-三氟联苯,产率80%.接着3,4,5-三氟联苯在CCl4中经过Fe+I2催化溴化得到4′-溴-3,4,5-三氟联苯,产率75%.4′-溴-3,4,5-三氟联苯与n-BuLi在-78 ℃下反应生成3′,4′,5′-三氟联苯-4-锂,然后与硼酸三正丁酯-78 ℃反应,最后在室温下酸性条件下水解生成目标产物,产率86%.合成路线的总收率达到51.6%.合成的化合物用元素分析、FT-IR、1HNMR和13CNMR等手段进行了表征.     

Synthesis of cis- and trans-[M(CN)2(1-CH3-C6H10-NC)4] (M = Fe,Ru) and crystal structure of trans-[Ru(CN)2(1′-CH3-C6H10-NC)4]

The reaction of the metal carbonyls Fe₂(CO)₉ or Ru₃(CO)₁₂ with 1-isocyano-1-methyl-cyclohexane produces the octahedral metal(II) cyano complexes [M(CN)₂(1-CH₃-C₆H₁₀-NC)₄] in good yields. The cis-isomer is not isolated as a pure compound due to rearrangement processes that yield the sterically less crowded trans-isomer. The molecular structure of the trans-isomer of the ruthenium complex shows the expected almost ideal octahedral coordination of the central ruthenium ion with two cyanide and four isocyanide ligands. This reaction again indicates that isocyanides exhibiting quarternary carbon atoms in α-position with respect to the isocyano substituent in general react with di- or trinuclear metal carbonyls to yield cyano complexes with oxidized metal centres and concomitant reductive cleavage of the respective isocyanide.     

紫外线吸收剂2,4-二(3′,5′-二甲苯基)-6-(2′-羟基-4′-辛氧基)苯基-1,3,5三嗪的合成

采用三聚氯氰与间二甲苯在三氯化铝存在下于50℃反应36h合成中间体Ⅰ,将其与间苯二酚于110℃反应4h,合成了中间体Ⅱ。将中间体Ⅱ与NaOH及溴辛烷在DMF中于70℃反应1h,经冷却、抽滤,用二氯甲烷重结晶,得到淡黄色的紫外线吸收剂2,4-二(3′,5′-二甲苯基)-6-(2′-羟基-4′-辛氧基)苯基-1,3,5三嗪各步骤的收率依次为93%,94%,88%。讨论了反应温度、时间及反应物配比对各步反应的影响。与苯并三唑类紫外线吸收剂Tinuvin326的应用对比结果表明,三嗪类紫外线吸收剂Cyasorb UV-1164具有较好的抗老化能力。     

N,N′-双[3-(3′,5′-二叔丁基-4′-羟基苯基)丙酰]己二胺的合成新工艺

以 3- (3′,5′-二叔丁基 - 4′ -羟基苯基 )丙酸甲酯 (简称 3,5 -甲酯 )与己二胺为原料 ,有机锡为催化剂 ,二甲苯为溶剂合成了N ,N′ -双 [3- (3′,5′ -二叔丁基 - 4′ -羟基苯基 )丙酰 ]己二胺。通过实验考察了反应温度、催化剂及催化剂用量、反应时间及物料配比等因素对反应的影响。结果表明 ,最佳的反应条件是 :反应温度为 135～ 14 5℃ ,催化剂为有机锡 ,用量为 3,5 -甲酯的 2 % ,反应时间为 3.5h ,3,5 -甲酯与己二胺物质的量比为 2 .10 ∶1。在此条件下 ,收率在 97%以上 ,放大到 10 0 0mL ,收率在 99%以上 ,产品熔点为 16 1～ 16 2℃ ,产品纯度较高 ,通过元素分析、红外光谱分析、核磁氢谱对产品进行了结构表征     

Hydrothermal synthesis,crystal structure and physical properties of {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} · 2H2O · 2Cl

A bimetallic 4f–3d tetranuclear complex {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} · 2H₂O · 2Cl (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characterized by a tetranuclear Gd₂Zn₂ structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. The tetranuclear species of {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} link to isolated chlorine ions and water molecules via π?π interactions and hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title complex displays an emission in ultraviolet region. The solid-state diffuse reflectance spectra of 1 reveal the presence of a sharp optical gap of 3.66 eV.     

1,4-二(2′-芳基-1′,3′,4′-二唑基)-1,3-丁二烯的合成与性质

以自制的N,N-二酰基肼在SOCl_2作用下脱水环化.合成了6个1,4-二(2′-芳基-1′,3′,4′-二唑基)-1,3-丁二烯类化合物,通过 ~1HNMR、FT-IR和MS对其结构进行表征.研究了它们的紫外-可见吸收光谱和荧光光谱.结果表明:在 336～350 nm出现最大吸收,发射强的蓝色荧光,最大发射峰出现在390～477 nm,是一类稳定的蓝光发光材料.     

2′,3′,5′-三乙酰肌苷的电位滴定

通过对精密度、准确度、线性、相关杂质对测定结果干扰等的确定,建它了以电位滴定法定量测定三乙酰肌苷的方法.结果表明,此法定量测定三乙酰肌苷简单易行,可作为三乙酰肌苷分析测定的常规手段.     

Semi-rigid N-para-ferrocenyl(benzoyl)amino-acid esters for biomaterials: synthesis and characterization of Fc-C6H4CONHCH(R)CO2Me where Fc = (η5-C5H5)Fe(η5-C5H4) and R=H,CH3,CH2CH(CH3)2,CH2C6H5 and the X-ray crystal structures of Fc-C6H4CO2Me and the l-alanine derivative Fc-C6H4CONHCH(CH3)CO2Me

A series of N-para-(ferrocenyl)benzoyl amino-acid esters, para-Fc(C₆H₄)CONHCH(R)CO₂CH₃ {Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄); R = H, CH₃, CH₂CH(CH₃)₂, CH₂C₆H₅}, 3–6 have been prepared by coupling para-(ferrocenyl)benzoic acid to the amino-acid esters (gly, l-Ala, l-Leu, l-Phe) using the standard 1,3-dicyclohexylcarbodiimide (DCC), 1-hydroxybenzotriazole (HOBt) protocol. The compounds were fully characterized by a range of spectroscopic techniques including FAB-MS. The X-ray crystal structures of the parent para-(ferrocenyl)benzoyl methyl ester, Fc-C₆H₄CO₂Me, 1 and a chiral derivative N-{para-(ferrocenyl)benzoyl}-l-alanine methyl ester, Fc-C₆H₄CONHCH(CH₃)CO₂Me, 4 have been determined.     

固相法合成1-二茂铁基-3-(3′,4′,5′-三甲氧基苯基)-2-丙烯-1-酮

以没食子酸为原料合成3,4,5-三甲氧基苯甲醛(TMB),利用活性基团拼接原理,将TMB和乙酰基二茂铁通过固相缩合,制得1-二茂铁基-3-(3',4',5'-三甲氧基苯基)-2-丙烯-1-酮。目标化合物结构经元素分析、IR、1H NMR、13C NMR确认。     

2,6-二(2′,4′,6′-三硝基-3′-氨基苯胺基)-3,5-二硝基吡啶的合成

由间硝基苯胺硝化制得2,3,4,6四硝基苯胺(1),由化合物1用盐酸氯化制得2,4,6三硝基3氨基氯苯(2),由化合物2与2,6,二氨基吡啶缩合制得2,6二(2,4,6三硝基3氨基苯胺基)吡啶(3),最后由化合物3硝化制得标题化合物4     

Synthesis,structure and properties of a new copper (II) complex, [Cu2(4,4′-bpy)5(H2O)4](ClO4)4(4,4′-bpy)(DMF)2(H2O)2

A new copper (II) complex with formula [Cu₂(4,4′-bpy)₅(H₂O)₄](ClO₄)₄(4,4′-bpy)(DMF)₂(H₂O)₂ has been synthesized by reaction of 4,4′-bpyridine (4,4′-bpy) with Cu(ClO₄)₂. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H?O bonds, anion?π and C–H?π interactions are also evident in the structure. The preliminary investigation on the thermal property of the complex is presented.     

Two novel cadmium(II) coordination polymers based on bis-functionalized ligand 4′-(4-carboxyphenyl)-2, 2′:6′, 2″-terpyridine

Two novel cadmium(II) coordination polymers [Cd(cptpy)₂]_n·nH₂O (1) with a 1D double chain structure and [Cd₂(cptpy)₂(ox)]_n·2.5nH₂O (2) with an interesting 3-connected uninodal six-fold interpenetrating ths network (Hcptpy = 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine, H₂ox = oxalic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, single crystal X-ray diffraction and fluorescence spectra.     

3,6-二氯-2′,4′,5′,7′-四溴荧光素光度法测银的研究

本文研究了银(Ⅰ)在1,10-菲啰啉(phen)存在下与3,6-二氯-2′,4′,5,7′-四溴荧光紊(DCTBF)形成三元络合物的条件和组成。络合物的组成为:Ag:phen:DCTBF=1:2:1。其最大吸收波长为590毫微米。摩尔吸光系数ε_(590)=7.6×10~4。用EDTA和柠檬酸铵掩蔽干扰离子以增强选择性。本法可用于金属、污水等试样中微量银的测定。方法简便、快速、重现性较好。     

Synthesis of ferroelectric liquid crystalline polysiloxanes containing (S)-2-methylbutyl 4-alkyloxybiphenyl-4′-carboxylate and (2S, 3S)-2-chloro-3-methylpentyl 4-alkyloxybiphenyl-4′-carboxylate

The synthesis of side-chain liquid crystalline polysiloxanes containing (S)-2-methylbutyl-4-alkyloxybiphenyl and (2S, 3S)-2-chloro-3-methylpentyl 4-alkyloxybiphenyl-4-carboxylate moieties as mesogenic units and aliphatic spacers containing respectively three to eleven methylene units is presented. Differential scanning calorimetry, optical polarizing microscopy and X-ray diffraction measurements reveal chiral smectic mesomorphism for most of the obtained polymers. Two polysiloxanes that contain respectively three methylene units in their spacers exhibit an enantiotropic smectic A phase or no mesophase. Four polysiloxanes that contain respectively five, six and eleven methylene units in their spacers exhibit enantiotropic smectic A and chiral smectic C phases. The results seem to demonstrate that the tendency toward chiral smectic C mesomorphism increases with increasing spacer length. Incorporation of a chloro-containing chiral end group into the mesogenic core of a polymer will decrease the thermal stability of the mesophase formed.