9-（n-氨基-4-氟甲基-3-吡咯）-2，6-二氯嘌呤的简便合成

反-羟基-d-脯氨酸;二氯嘌呤;含氟氮杂核苷;mitsunobu反应;二氟二甲基咪唑啉     

An Efficient One-Pot Synthesis of Hippuric Acid Ethyl Ester Derivatives

A rapid, one-pot procedure is described for the preparation of the ethyl esters of a number of ring-substituted N-benzoyl glycine (hippuric acid) derivatives from readily-available starting materials.     

Synthesis of 3(5)-(Nitroamino)-1,2,4-triazol-5(3)-carboxylic Acid and Its Ethyl Ester

Russian Journal of Organic Chemistry -     

Synthesis of Dehydroabietic Acid (2-Acryloyloxy) Ethyl Ester in Ionic Liquids

A simple ionic liquid methodology for the synthesis of a novel derivative of dehydroabietic acid is described. 1-Butyl-3-methylimidazolium tetrafluoroborate [bmim]BF₄, a typical ionic liquid, was used as an efficient and environmentally benign solvent in the synthesis of dehydroabietic acid (2-acryloloxy) ethyl ester by O-acylation reaction of dehydroabietic acid chloride with 2-hydroxyethyl acrylate. This new method showed the advantages of mild reaction conditions, short reaction times, good yields, and recyclable solvent.     

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。     

Simple Stereospecific Syntheses of (R)-2-Fluorohexanoic Acid Ethyl Ester

Simple stereospecific syntheses of 2-fluorohexanoic acid 5 were accomplished by conversion of optically pure L-(+)-norleucine to the optically pure hydroxy acid 3 via the classic diazotization reaction followed by substitution of the hydroxy functionality by the fluoro group. This was accomplished stereospecifically using DAST reagent or more practically by nucleophilic displacement of the corresponding mesyloxy group with fluoride ion.     

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.     

克唑替尼关键中间体(S)-1-(2,6-二氯-3-氟苯基)乙醇的不对称合成

(S)-1-(2,6-二氯-3-氟苯基)乙醇（2）是合成抗癌药物克唑替尼的关键手性前体。本文以1-(2,6-二氯-3-氟苯基)乙酮为起始原料,利用二异松莰基氯化硼［(-)-Ipc₂BCl］不对称还原制得光学纯的2;并将中间体2经Mitsunobu反应、还原、溴代、 Suzuki偶联及脱除Boc保护合成克唑替尼,其结构¹H NMR,¹³C NMR和HR-MS(ESI)确证。对关键中间体2的合成条件进行了优化,并其对反应机理进行了推测。     

除草剂中间体R-(+)-2-(4-羟基苯氧基)丙酸酯的不对称合成

报道了一种合成苯氧丙酸类除草剂重要中间体R－（＋）－2－（4－羟基苯氧基）丙酸乙酯（即R－（＋）－HPE）的方法，以L－乳酸为起始原料，先经酯化合成L－乳酸乙酯，再与对甲苯磺酰氯反应制备L－对甲苯磺酰乳酸乙酯，再与对苯二酚综合获得R－（＋）－2－HPE，产品的总收率为72.1%。通过元素分析和红外光谱测定，确定了所合成的R－（＋）－HPE的化学结构和纯度；由旋光度的测定，确定了所合成的R－（＋）－HPE的光学纯度为95.7%。     

An Alternative Synthesis and Crystal Structure Characterization of Nutrient Fortifier N-(1-(Phenylacetyl)-L-prolyl) Glycine Ethyl Ester

A nutritional fortifier N-(1-(phenylacetyl)-L-prolyl) glycine ethyl ester(4) was successfully synthesized through two synthetic schemes and characterized by IR, ~1H-NMR, ~(13)C-NMR, elemental analysis and X-ray single-crystal diffraction. The intermediate N-phenylacetyl-L-proline(2) was synthesized by the solid-liquid reaction of L-proline and phenylacetyl chloride directly. Compound 2(C13 H15 NO3, Mr = 233.26) belongs to the orthorhombic system, space group P212121 with a = 8.9468(3), b = 9.3190(3), c = 14.0453(4) ?, V = 1171.03(6) ?3, Z = 4, Dc = 1.323 g/cm3, μ = 0.773 mm-1, F(000) = 496.0, the final R = 0.0313 and wR = 0.0797 for all data. Compound 4(C17 H22 N2 O4, Mr = 318.36) is of orthorhombic system, space group P212121 with a = 6.5831(2), b = 8.5536(2), c = 28.9138(9) ?, V = 1628.11(8) ?3, Z = 4, Dc = 1.299 g/cm3, μ = 0.763 mm-1, F(000) = 680.0, the final R = 0.0353 and wR = 0.0816 for all data.     

3-(2-氧代环烷基)丙酸与(R)-2-硫代四氢噻唑-4-羧酸乙酯的反应

３－（２－氧代环烷基）丙酸与（Ｒ）－２－硫代四氢噻唑－４－羧酸乙酯的反应李叶芝,田颜清,黄化民（吉林大学化学,长春,１３００２３）关键词（Ｒ）－２－硫代四氢噻唑－４－羧酸乙酯,Ｎ－３－（２－氧代环烷基）丙酰－２－硫代四氢噻唑－４－羧酸乙酯,环合反应,...