3-氧代-4-（2,4,5-三氟苯基）丁腈的合成

以2,4,5-三氟苯乙酸为起始原料,经氯化和酰化反应得2-氰基-3-羟基-4-（2,4,5-三氟苯基）丁-2-烯酸乙酯（2）; 2经水解脱羧合成了3-氧代-4-（2,4,5-三氟苯基）丁腈,总收率61.5%,纯度97.6%,其结构经¹H NMR和MS（ESI）确证。     

柱前衍生化法分离3-羟基丁酸乙酯光学异构体

采用三氟乙酸酐柱前衍生化在β-环糊精毛细管柱(CyclodexB)上分离3-羟基丁酸乙酯光学异构体.考察了衍生化反应条件对3-羟基丁酸乙酯衍生化反应的影响,柱温对3-羟基丁酸乙酯衍生物3-(2,2,2-三氟乙酰氧基)丁酸乙酯光学异构体分离的影响.通过光学异构体分离过程中的热力学参数的计算,探讨光学异构体分离过程的驱动力.实验结果表明,当三氟乙酸酐与3-羟基丁酸乙酯的摩尔比为5:1时,室温下反应5 min,3-羟基丁酸乙酯可定量转化成3-(2,2,2-三氟乙酰氧基)丁酸乙酯;在柱温为62℃时,3-(2,2,2-三氟乙酰氧基)丁酸乙酯光学异构体的分离因子(α)和分离度(R)分别为1.02和1.26.而且,3-(2,2,2-三氟乙酰氧基)丁酸乙酯光学异构体的拆分过程主要是一个焓驱动的过程,且β-环糊精表面与3-(2,2,2-三氟乙酰氧基)丁酸乙酯之间的相互作用在其分离过程中起了重要作用.     

铟参与的4-溴-1,1,1-三氟-2-丁烯与a-烷氧基醛亚胺的烯丙化反应:4,4,4-三氟-y-羟基缬氨酸的合成

铟参与的4-溴-1,1,1-三氟-2-丁烯与a-烷氧基醛亚胺的烯丙化反应以中等的产率和高非对映选择性生成了高烯丙基胺3.从甘油醛亚胺和4-溴-1,1,1-三氟-2-丁烯反应制备的高烯丙基胺3g出发,以7步反应24%的总产率合成了4,4,4-三氟-y-羟基缬氨酸11.     

铟参与的4-溴-1，1，1-三氟-2-丁烯与α-烷氧基醛亚胺的烯丙化反应：4，4，4-三氟-γ-羟基缬氨酸的合成

铟参与的4-溴-1,1,1-三氟-2-丁烯与α-烷氧基醛亚胺的烯丙化反应以中等的产率和高非对映选择性生成了高烯丙基胺3.从甘油醛亚胺和4-溴-1,1,1-三氟-2-丁烯反应制备的高烯丙基胺3g出发,以7步反应24%的总产率合成了4,4,4-三氟-γ-羟基缬氨酸11.     

对三氟甲硫基苯酚的合成研究

在偶极性质子溶剂N ,N 二甲基甲酰胺中 ,以对羟基苯硫酚为底物 ,硫代硫酸钠为自由基引发剂促进CF3 Br产生·CF3 ,·CF3 与底物反应生成对三氟甲硫基苯酚。实现了以CF3 Br为试剂进行三氟甲硫基化的合成路线。反应混合物经简单蒸馏后 ,得到的产物三氟甲硫基苯酚含量达 98% ,收率 81 .5 %。     

1-苯氧基(或对甲氧基苯氧基)-1-氟乙烯的合成

氟溴乙酸乙酯分别与苯酚或对甲氧基苯酚经取代反应得1-(苯氧基)-1-氟乙酸乙酯(3a)或1-(对甲氧基苯氧基)-1-氟乙酸乙酯(3b);3经Na2BH4还原后,将其羟基转化成溴原子,然后通过消除反应合成了两个新化合物——1-苯氧基-1-氟乙烯和对甲氧基苯氧基-1-氟乙烯,其结构经1H NMR和19F NMR表征。     

酵母静息细胞催化丙酮酸乙酯不对称还原制(S)-乳酸乙酯

从污水处理池及其附近土壤中分离到36株可将丙酮酸乙酯不对称还原成(S-乳酸乙酯的菌株,经多次复筛,最终得到一株具有较高催化活性的酵母菌BTY18-6.以BTY18-6的静息细胞为催化剂,在水相中进行丙酮酸乙酯不对称还原成(S)-乳酸乙酯的反应,并对反应条件进行了优化.结果表明,以2.5%葡萄糖为辅助底物,反应体系初始p...     

新型希土4-羟基-7-三氟甲基-3-喹啉基甲酸乙酯配合物的光物理性质

首次合成了五种新型希土(Eu³⁺, Tb³⁺, Gd³⁺, Sm³⁺, Dy³⁺)配合物。配体为带有喹啉环的4-羟基-7-三氟甲基-3-喹啉基甲酸乙酯。并用元素分析、红外光谱和热分析方法确定了配合物的组成。通过测定钆配合物的低温磷光光谱表明4-羟基-7-三氟甲基-3-喹啉基甲酸乙酯的三重态能级为22000 cm^-1。配合物的光物理性质表明配体的三重态能级适于希土Eu³⁺, Sm³⁺, Dy³⁺和Tb³⁺，特别是Tb³⁺的发光。     

HPLC分离检测5-氟烟酸与5-氟烟酸乙酯

通过紫外光谱扫描获得两者混合溶液的最佳紫外吸收波长为271nm,以此为检测波长采用反相C18色谱柱,以甲醇+0.025mol.L-1磷酸二氢钾溶液(80+20)为流动相,分离检测了5-氟烟酸和5-氟烟酸乙酯。5-氟烟酸的相对标准偏差为1.9%,平均回收率为99.1%,线性范围为0.05~1.50g.L-1(r=0.9993),5-氟烟酸乙酯的相对标准偏差为1.7%,平均回收率为99.9%,线性范围为0.025~0.85g.L-1(r=0.9997)。     

微波辐射固相合成4-三氟甲基-7-羟基-6-氯香豆素

分别以无水氯化锌、对甲苯磺酸为催化剂,采用微波辐射法,在无溶剂条件下由4-氯间苯二酚与三氟乙酰乙酸乙酯缩合制备标题化合物;优化了反应条件.结果表明,在微波辐射下,无水氯化锌对该反应有较好的催化活性,相应的4-三氟甲基-7-羟基-6-氯香豆素的产率可达73.0%.优化的反应条件为:4-氯间苯二酚、三氟乙酰乙酸乙酯和无水ZnCl2的摩尔比为1∶1.1∶0.9,微波辐射功率800W,辐射时间20min,反应温度85℃.     

Methyltrifluoropyruvate imines possessing N-oxalyl and N-phosphonoformyl groups--precursors to a variety of alpha-CF3-alpha-amino acid derivatives

Convenient routes to methyl 2-oxalylimino- and 2-(phosphonoformimido)-3,3,3-trifluoropropanoates have been elaborated, based on the reaction of methyl trifluoropyruvate with ethyl oxamate or diethyl carbamoylphosphonate, respectively, followed by dehydration. The compounds obtained are useful synthetic intermediates toward a variety of novel 3,3,3-trifluoroalanine derivatives that are potential drug candidates.     

2-甲硫基-4-羟基-5-嘧啶甲酸乙酯的工艺优化

以S-甲基异硫脲半硫酸盐和乙氧基亚甲基丙二酸二乙酯为主要原料,乙醇为溶剂,合成出2-甲硫基-4-羟基-5-嘧啶甲酸乙酯,研究了2-甲硫基-4-羟基-5-嘧啶甲酸乙酯的工艺优化,考察了投料比、反应温度、反应时间等因素对产率的影响。 获得较好的反应条件:n(C₂H₆N₂S·1/2H₂SO₄):n(C₁₀H₁₆O₅):n(NaOH)=1.2:1:1.8,在室温下缓慢滴加NaOH溶液,搅拌反应6 h,酸化得白色固体产物,产率为81.1%。产物结构经熔点测定仪、¹H NMR、ESI-MS、FT-IR等技术手段得到验证。     

Asymmetric synthesis of the carbon-14-labeled selective glucocorticoid receptor modulator using cinchona alkaloid catalyzed addition of 6-bromoindole to ethyl trifluoropyruvate

We describe in this study the asymmetric synthesis of radioisotope (RI)-labeled selective glucocorticoid receptor modulator. This synthesis is based on optimization of the cinchona alkaloid catalyzed addition of 6-bromoindole to ethyl trifluoropyruvate and Negishi coupling of zinc cyanide to the 6-bromoindole moiety. [1?C] Labeled (-)-{4-[(1-{2-[6-cyano-1-(cyclohexylmethyl)-1H-indol-3-yl]-3,3,3-trifluoro-2-hydroxypropyl}piperidin-4-yl)oxy]-3-methoxyphenyl}acetic acid (-)-1 was synthesized successfully with high enantioselectivity (>99% ee) and sufficient radiochemical purity.     

3-Trifluoromethyl- and 3-difluoromethyl-thalidomides

Syntheses of racemic 3-trifluoromethyl- and 3-difluoromethyl-thalidomide starting from 2-(tert-butyloxycarbonylimino)-3,3,3-trifluoropropionate or -3,3-difluoropropionate as fluorine-containing building blocks are described.     

Cyclocondensation of methyl 2-(5-methylisoxazol-3-yl)imino-3,3,3-trifluoropropionate with 1,3-binucleophiles

Cyclocondensation of methyl 2-(5-methylisoxazol-3-yl)imino-3,3,3-trifluoropropionate with 1,3-binucleophiles such as benzamidines, aminothiazoline, and 2-aminocrotonic acid nitrile results in trifluoromethyl-containing 3,5-dihydro-4-ones, 2,3-dihydro-6H-imidazo[2,1-b]thiazol-5-one, and 4,5-dihydro-1H-pyrrole-3-carbonitrile.     

Synthesis and Crystal Structure of 4-（4,6-Dimethoxylpyrimidin-2-yl）- 3-thiourea Carboxylic Acid Ethyl Ester

4-（4,6-Dimethoxyl-pyrimidin-2-yl）-3-thiourea carboxylic acid ethyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at room temperature. The crystal structure was determined by X-ray diffraction analysis. Crystallographic data： C10H14N4O4S, M, = 286.31, monoclinic, space group C2/c with a = 2.5309（3）, b = 0.67682（6）, c = 1.74237（19） nm, β = 114.744（3）°, V= 2.7106（5） nm3, Dc = 1.403 g/cm3, p = 0.225 mm-1, F（000） = 1200, Z= 8, R= 0.0514 and wR= 0.1529.     

Synthesis and Crystal Structure of 4-(4,6-Dimethoxylpyrimidin-2-yl)-3-thiourea Carboxylic Acid Ethyl Ester

4-(4,6-Dimethoxyl-pyrimidin-2-yl)-3-thiourea carboxylic acid ethyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine,potassium thiocyanate and methyl chloroformate in ethyl acetate.Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamidc at room temperature.The crystal structure was determined by X-ray diffraction analysis.Crystallographic data:C10H14N4O4S,Mr=286.31,monoclinic,space group C2/c with a=2.5309(3),b=0.67682(6),c=1.74237(19)nm,β=114.744(3)°,V=2.7106(5)nm3,Dc=1.403 g/cm3,μ=0.225mm-1,F(000)=1200,Z=8,R=0.0514 and wR=0.1529.     

Cyclocondensation of methyl 2-(1,3-benzothiazol-2-ylimino)-3,3,3-trifluoropropionate with C,N-binucleophiles

Reactions of methyl 2-(1,3-benzothiazol-2-ylimino)-3,3,3-trifluoropropionate with 1,3-C,N-binucleophiles, methyl 2-aminobut-2-enoate, 2-aminobut-2-enenitrile and N-substituted 6-aminouracils and 3-aminocyclohex-2-en-1-ones, led to the formation of trifluoromethyl-substituted heterocycles, dihydro-1H-pyrroles, hexahydro-1H-pyrrolo[2,3-d]pyrimidine-2,4,6-triones, and hexahydro-1H-indole-2,4-diones.     

PHOTOPHYSICS and PHOTOCHEMISTRY OF BIS-2-(9-ANTHRYL)ETHYL GLUTARATE

Abstract— The photochemistry and photophysics of bis-(2-(9-anthryl)ethyl glutarate 2 and 2-(9-anthryl) ethyl pivalate 3 have been examined as monomeric models for poly-2-(9-anthryl)ethyl methacrylate 1. The absorption and excitation spectra of 2 show no ground state interaction, but appreciable monomer (51%) and excimer (49%) emission. Delayed monomer and excimer fluorescence are also observed in fluid solution at room temperature. Photolysis of 2 at low temperature produces a photoproduct (44% yield) which is unstable at room temperature and presumably is the head-to-head (H-H) dimer. Steady state irradiation of 2 at room temperature (Λ 350 nm) cleanly produces a head-to-tail (H-T) dimer (6) derived from the singlet state and an additional unidentified adduct (7). The product distribution is concentration dependent, with 6 predominating at high concentrations (> 10⁻³ M ). The fluorescence spectra of the broken dimers derived from 6 and 7 indicate that substantial ir overlap exists in the transition state leading to each product.     

Six new 2-(2-phenylethyl)chromones from Agarwood

Six new chromones, 6-methoxy-2-[2-(3-methoxy-4-hydroxyphenyl)ethyllchromone (2), 6,8-dihydroxy-2-(2-phenylethyl)chromone (3), 6-hydroxy-2-[2-(4-hydroxyphenyl)ethyl]chromone (4), 6-hydroxy-2-[2-(2-hydroxyphenyl)ethyl]chromone (5), 7-hydroxy-2-(2-phenylethyl)chromone (6), and 6-hydroxy-7-methoxy-2-(2-phenylethyl)chromone (7) were isolated from the ether extract of agarwood in addition to a known compound, 2-(2-phenylethyl)chromone or flidersiachromone (1). Their structures were determined by spectroscopic methods including UV, IR, and NMR spectral data and comparisons with the calculated values using the hydroxyl and methoxyl substituent increments of the chromone ring.