大量制备4-苄氧基-2-羟基苯甲醛的新方法

以间苯二酚为原料,采用酚羟基的苄基保护、Vilsmeier反应及选择性去保护三步反应的新方法合成了4-苄氧基-2-羟基苯甲醛,总产率52%,其结构经1H NMR和13C NMR确认。     

四氢喹啉-4-醇类衍生物的合成

以1,2,3,4-四氢喹啉为初始原料,经N-酰基保护、氧化、脱保护、还原等反应合成了一系列1,2,3,4-四氢喹啉-4-醇类的衍生物,总产率17%~41%,其结构经1H NMR和13C NMR确证。     

新型多氧取代环己烯酮的合成

以莽草酸为起始原料,经酯化、丙酮叉保护顺式邻二羟基、叔丁基二甲硅烷保护羟基、还原、羟基酯化、脱保护基、保护反式邻二羟基、烯丙醇氧化,脱保护基共9步反应,合成了新型(5R,6S)-3-苯甲酰氧基亚甲基-5,6-二羟基-2-环己烯-1-酮,总产率19.3％,其结构经1H NMR,IR和HR-MS表征.     

(±)-2-甲基-5-羟基-2-(4'-甲基-3'-戊烯基)-二氢-1-苯并吡喃黄烷酮的全合成

以2,4,6-三羟基苯乙酮和柠檬醛为起始原料,经环化、保护酚羟基、羟醛缩合、脱保护、催化环化等反应以5.9%的总产率完成了天然产物(±)-2-甲基-5-羟基-2-(4'-甲基-3'-戊烯基)-二氢-1-苯并吡喃黄烷酮的全合成,其结构经1H NMR,13C NMR和HR-ESI-MS确证。     

合成2,3-氧-异亚丙基-5-氧-对甲苯磺酰基-D-核糖-1,4-内酯的新方法

以D-核糖为起始原料,经氧化、异亚丙基保护和酯化反应合成了2,3-氧-异亚丙基-5-氧-对甲苯磺酰基-D-核糖-1,4-内酯,总产率57.5%,其结构经1HNMR和IR表征。对合成工艺进行了优化。     

(+)-柳杉酚的简便合成

报道了两种(+)-柳杉酚(6)的简便合成路线。路线1:脱氢枞胺(1)经脱氨还原,12-位Friedele-Crafts乙酰化,Baeyer-Villiger氧化,7-位氧化和水解5步反应合成了6,总产率18.6%。路线2:1经脱氨还原和7-位氧化反应制得7-氧代脱氢松香烷(7);7与过氧化邻苯二甲酰反应,然后水解合成了6,总产率22.0%。6的结构经1H NMR,IR,TOF-MS和元素分析确证。     

二化螟性信息素组分(Z）-13-十八碳烯醛的合成

利用炔化物路线合成二化螟性信息素-（Z）-13-十八碳烯醛（1）。以1,12-十二烷二醇为原料,经单边溴化,羟基保护,偶联反应,选择性还原,去保护,氧化得到目标产物。反应共6步,总产率可达45%,各产物结构经¹H NMR确认。      

维生素D_2-A和CD片段醇的合成工艺改进

以维生素D_2(V-D_2)为原料,经高锰酸钾氧化、选择性切断和还原反应同时合成了维生素D_2-A(总产率30%)和CD片段醇(总产率45%),其结构经~1H NMR确证。     

25-羟基胆固醇的合成及路线优化

以猪去氧胆酸为起始原料,经酯化、上保护、还原、氧化、缩合、水解、酯化、环氧化、还原等九步反应,制备25-羟基胆固醇,总收率30%。目标产物结构经¹HNMR和¹³CNMR鉴定。     

欧洲葡萄花翅小卷蛾性信息素

欧洲葡萄花翅小卷蛾的性信息素主要成分为7E,9Z-十二碳二烯乙酸酯。从1,5-二溴戊烷出发,制成格氏试剂后与甲醛发生格氏加成反应得到1,7-庚二醇,单酯化得到7-羟基庚醇乙酸酯,氧化得到7-氧代庚醇乙酸酯,与(2,2-二甲氧基乙基)三苯基溴化膦进行Wittig反应并水解得到9-氧代-7E-壬烯乙酸酯,再与正丙基三苯基溴化膦进行Wittig反应合成了7E,9Z-十二碳二烯乙酸酯,总产率13%,其结构经¹H NMR和¹³C NMR确证。     

合成1,2-环十二二酮的新方法

以十二烷二酸（１）为原料,与甲醇酯化生成十二烷二酸二甲酯（２）,收率为８６５％。化合物２经偶联 缩合得１,２ 二三甲基硅氧基环十二烯（３）,收率为６３１％。利用溴氧化化合物３得到１,２ 环十二二酮（４）淡黄色晶体,收率７９％,全过程收率达４３.１％,是合成１,２ 二酮的新方法。目标化合物结构经红外光谱、核磁共振氢谱和碳谱表征确认。     

Electrosynthesis of adipic acid by undivided cell electrolysis

A preparative method for synthesis of adipic acid in 47% yield was developed. The method is based on cyclohexanol oxidation in an undivided cell on the NiOOH electrode in aqueous alkali. A possibility of the step-by-step process was studied: oxidation of cyclohexanol to cyclohexanone (75% yield) and subsequent oxidation of cyclohexanone to adipic acid (52% yield). The electrosynthesis of adipic acid is accompanied by the formation of minor amounts (up to 10%) of glutaric and succinic acids.     

Synthesis of gallic acid: Cu(2+)-mediated oxidation of 3-dehydroshikimic acid

With the elaboration of high-yielding, high-titer syntheses of 3-dehydroshikimic acid from glucose using recombinant Escherichia coli, oxidation of this hydroaromatic becomes a potential route for synthesis of gallic acid. Conversion of 3-dehydroshikimic acid into gallic acid likely proceeds via initial enolization of an alpha-hydroxycarbonyl and oxidation of the resulting enediol. 3-Dehydroshikimate enolization in water was catalyzed by inorganic phosphate while Zn(2+) was used to catalyze enolization in acetic acid. Enediol oxidation employed Cu(2+) as either the stoichiometric oxidant or as a catalyst in the presence of a cooxidant. Gallic acid was produced in a yield of 36% when 3-dehydroshikimic acid in phosphate-buffered water reacted for 35 h with H2O2 and catalytic amounts of CuSO(4). 3-Dehydroshikimate-containing, phosphate-buffered culture supernatants reacted with stoichiometric amounts of CuCO(3)Cu(OH)(2) and Cu(x)(H(3-x)(PO4)(2) to give gallic acid in yields of 51% in 5 h and 43% in 12 h, respectively. Solutions of 3-dehydroshikimic acid in acetic acid reacted with stoichiometric amounts of Cu(OAc)(2) to afford a 74% yield of gallic acid in 36 h. Acetic acid solutions of 3-dehydroshikimic acid could also be oxidized by air using catalytic quantities of Cu(OAc)(2). ZnO accelerated these oxidations leading to a 67% yield of gallic acid in 4 h when an acetic acid solution of 3-dehydroshikimic acid was reacted with O(2) and a catalytic amount of Cu(OAc)(2).     

Nonanol-1 oxidation on nickel oxide electrode with the involvement of active oxygen forms

The process of nonanol-1 oxidation is studied on the nickel oxide electrode with the use of chemically bound active oxygen forms (AOF) electrochemically generated in situ from O₂, H₂O₂, and H₂O. The effect of electrolysis conditions (AOF generation schemes, current density, passed charge) on the yield of pelargonic acid is studied. The oxidation proceeds most efficiently at the current density of 5–10 mA cm^?2 as the theoretical charge is passed in the paired electrolysis mode. The current efficiency with respect to pelargonic acid is 83.7%; the substance yield is 83.8%. In addition to pelargonic acid, several oxidation side-products are found in the electrolyte. Their content increases with the increase in the charge passed as a result of further oxidation of pelargonic acid.     

Oxidation of substituted toluenes with molecular oxygen in the presence of N,N',N' '-trihydroxyisocyanuric acid as a key catalyst

N,N',N' '-Trihydroxyisocianuric acid (THICA) was found to be a very efficient catalyst for the oxidation of alkylbenzenes with dioxygen. Thus, a variety of meta- and para-substituted toluenes bearing an electron-withdrawing substituent such as cyanotoluene, chlorotoluene, and toluic acid under O(2) (1 atm) in the presence of THICA (5 mol %) and Co(OAc)(2) (0.5 mol %) at 100 degrees C were smoothly oxidized to the corresponding benzoic acids in almost quantitative yields. The aerobic oxidation of toluene by THICA was compared with that by N-hydroxyphthalimide. p-Xylene was efficiently oxidized by THICA to telephthalic acid in high yield (over 95%) under mild conditions.     

钨酸催化氧化环己烯合成己二酸

以钨酸/有机酸性添加剂为催化体系, 在无有机溶剂、相转移剂的情况下, 催化30%过氧化氢氧化环己烯合成己二酸. 当钨酸∶有机酸性添加剂∶环己烯∶过氧化氢＝1∶1∶40∶176(摩尔比, 钨酸用量为2.5 mmol)时, 使用有机酸性添加剂考察钨酸的催化性能, 结果表明以钨酸/间苯二酚催化氧化环己烯的催化效果最优, 反应8 h时己二酸分离产率达90.9%、纯度为～100%; 而不使用有机酸性添加剂时, 己二酸分离产率只有72.1%, 产品纯度为96.2%. 当使用磺酸水杨酸、草酸、水杨酸为有机酸性添加剂时, 随反应时间的增加, 己二酸分离产率均升高, 但反应6 h以后, 己二酸分离产率随时间的变化不明显. 当磺酸水杨酸用量为2.5 mmol时, 己二酸分离产率和纯度均较高. 钨酸-磺酸水杨酸催化体系重复使用五次后, 己二酸分离产率仍可达到80.5%.     

2,2,6,6-四甲基哌啶氧自由基/Ca(ClO)2催化氧化甲基葡糖苷制备葡醛酸

采用2,2,6,6-四甲基哌啶氧自由基/Ca(ClO)2体系选择氧化甲基葡萄糖苷(简称甲苷)合成了葡萄糖甲苷酸盐,再用硫酸酸解葡萄糖甲苷酸盐,得到葡萄糖醛酸和副产物硫酸钙。考察了氧化工艺条件对葡萄糖醛酸收率的影响;用pH计监控反应过程,反应中间体和终产物用UV和HPLC检测。结果表明,该体系对甲苷伯羟基的氧化具有较好的催化活性和反应选择性,葡萄糖醛酸收率达到92%,且金属离子易于去除。和传统的淀粉HNO3氧化法工艺相比,该方法具有资源节约、环境友好的特点。     

Studies on pyrazines. 9 . The facile synthesis of pyrazine 1-oxides substituted at C-2 with cyano,methoxycarbonyl and carboxy groups

The peroxysulfuric acid oxidation of 2-cyanopyrazine ( 1 ) gave its 1-oxide 3 (18% yield) and pyrazinecarb-oxamide (8% yield), while that of methyl pyrazinecarboxylate ( 2 ) provided the 1- and 4-oxides in 15 and 7% yields, respectively. On the other hand, pyrazinecarboxylic acid 1-oxide ( 7 ) was prepared by condensation of 2-methylpyrazine 1-oxide ( 8 ) with benzaldehyde followed by oxidative cleavage (47% overall yield).     

Oxidation of alcohols with hydrogen peroxide catalyzed by soluble iron and osmium derivatives

Summary Osmium chloride OsCl₃ efficiently catalyzes (yields of products up to 90%, turnover numbers (TON) up to 1500) the oxidation of 2-cyanoethanol with hydrogen peroxide to produce the corresponding aldehyde and acid. Oxidation of isopropanol over OsCl₃ gave acetone in 58% yield. The reactions were carried out either in acetonitrile or without any solvent. The analogous iron compound FeCl₃ was found to be less efficient in the oxidation of 2-cyanoethanol (yields of products up to 67%, TON up to 135). Oxidation of isopropanol in this case gave acetone (yield 53%) and acetic acid (yield 11%). Some other soluble derivatives of iron or osmium exhibited noticeably lower catalytic activity in the alcohol oxidation with H₂O₂.     

2,3-二甲基-4-氯吡啶-N-氧化物的合成工艺改进

对2,3-二甲基-4-氯吡啶-N-氧化物(4)的合成工艺进行了改进。以2,3-二甲基吡啶为原料,经氧化(钨酸钠为催化剂,双氧水为氧化剂,收率96.5%),硝化(65%的浓硝酸为硝化剂,收率86.3%,纯度99.0%)及氯化(乙酰氯为氯化剂,收率86.8%,纯度98.6%)合成了4,总收率72.2%,4的结构经1H NMR表征。