乙酸酐、H2O2和1,5-二羟基萘酚一锅合成胡桃醌

由乙酸酐和H2O2在无硫酸存在下合成过氧乙酸,然后向其滴加1,5-二萘酚的甲醇溶液,在一锅内简便地合成了胡桃醌。产物用苯重结晶,其结构经HPLC、UV-Vis、FTIR、1H NMR和13C NMR测试技术进行了表征和证实。考察了原料摩尔比、反应温度和反应时间对产率的影响。最佳反应条件为:n(1,5-二萘酚)∶n(乙酸酐)∶n(H2O2)=1∶4∶8,反应温度为40~60℃,反应时间为5.5 h,产率68%。结果表明,一锅法合成不用硫酸,无需真空蒸馏纯化过氧乙酸,是合成胡桃醌的简便方法。     

"一锅法"合成5-氟-2-羟基-苯乙酮

对合成5-氟-2-羟基-苯乙酮的方法进行改进,将原来的两步反应合并为一步,去掉了中间产物酯的繁琐分离和纯化,大大缩短了反应时间,操作简便,收率88．9％,适用于工业化生产。     

铁卟啉催化氧化萘酚合成2-羟基-1,4-萘醌

羟基萘醌;铁卟啉催化氧化萘酚合成2-羟基-1;4-萘醌     

一锅法合成2-羟基-9-芴酮类化合物

芴酮骨架的构建对于相关天然产物合成、药物分子结构修饰以及光电材料开发等具有重要意义。以苯环作为桥连基团,将呋喃环及炔酮片段构建在同一个分子内,设计并合成了邻呋喃芳基炔酮底物(1a)。利用化合物1a分子内呋喃环与炔键的D-A反应,在酸性条件下环氧开环,进而芳构化,一锅法合成了2-羟基-9-芴酮衍生物2a～2e,收率89%～96%,其结构经¹H NMR,¹³C NMR和HR-MS(ESI)表征。其中,化合物2a结构由X-ray单晶衍射确定。2a(CCDC:2144829)属单斜晶系,空间群P2₁/c,晶胞参数a=3.9458(10)?,b=22.4460(7)?,c=14.7092(5)?,V=1294.1300(7)?³,Dc=1.3980 Mg/m³,Z=4,F(000)=568。     

一锅法合成2-硫脲嘧啶

采用一锅法合成了2-硫脲嘧啶,最佳反应条件为:硫脲33 mmol,n(乙酸乙酯)∶n(甲酸乙酯)∶n(甲醇钠)∶n(硫脲)=2.5∶2.0∶1.5∶1.0;乙酸乙酯与甲醇钠在甲苯(35 mL)中于80℃反应3 h;冷却后滴加甲酸乙酯,于25℃充分搅拌8 h后加入硫脲的乙醇(10 mL)溶液,回流反应3 h,收率54.7%。     

一锅法合成1,4-二叔丁氧羰基亚精胺

以丁二胺和丙烯腈为原料,采用一锅法制得N1,N4-二叔丁氧羰基-N4-(2-氰乙基)-1,4-丁二胺(3);以甲基叔丁基醚为溶剂,3经LiAlH4还原合成了1,4-二叔丁氧羰基亚精胺,其结构经1H NMR和MS确证。     

一锅法合成新型羟基环戊烯酮化合物

以二芳基乙酮（4a~4f）和取代丙酮（5a~5c）为原料,KHCO₃为碱,100 ℃空气条件下,在DMSO中经二芳基乙酮氧化、羟醛缩合一锅法合成了12个羟基环戊烯酮化合物（6a~6l）,其中6d, 6h和6i为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。     

一锅法合成间羟基苯甲醛工艺研究

以间硝基苯甲醛为原料,采用"一锅法"经氯化亚锡还原、重氮化、水解制得间羟基苯甲醛,研究了物料摩尔比、还原反应时间、还原反应温度、重氮化时间、亚硝酸钠用量等参数对产物收率的影响。结果表明,在优化工艺条件(间硝基苯甲醛与二水合氯化亚锡的摩尔比为1∶3、还原温度90℃、还原时间90min、重氮化时间75min、亚硝酸钠为1.4g)下,间羟基苯甲醛的收率达到76.5%。产物经红外光谱和核磁共振谱确认。该合成技术工艺过程简单,生产安全,环境友好,产品收率高,易于生产。     

一锅法合成3-腈基-4苯并吡喃酮类化合物

以各种取代的邻羟基苯乙酮为起始原料,经Vilsmeier试剂环合得中间体3-甲酰基色酮,不经分离纯化,直接与盐酸羟胺反应合成了一系列3-腈基-4苯并吡喃酮类化合物,总收率47%~74%,其结构经1HNMR,IR和MS确证。     

Synthesis and Transformations of 2-Hydroxy-3-arylazo-1,4-naphthoquinones

A series of 2-hydroxy-3-arylazo-1,4-naphthoquinones were prepared by coupling of 2-hydroxy-1,4-naphthoquinone with aryldiazonium chlorides. The reactivity of the products toward electrophilic and nucleophilic agents was studied. In reaction with o-phenylenediamine they give condensation products, the corresponding benzo[a]phenazines.     

One-pot Synthesis of 3-Aryl-1,5-bis（2-hydroxyaryl）pentane-1,5-diones

A simple method for the synthesis of 3-aryl-1,5-bis(2-hydroxyaryl)pentane-1,5-diones is developed by one-potreaction involving 2-hydroxyacetophenone and arylaldehyde in aqueous potassium hydroxide.     

Synthesis of Novel 1,4-Benzoxazine-2,3-Dicarboximides from Maleic Anhydride and Substituted Aromatic Amines

A series of novel 1,4-benzoxazine-2,3-dicarboximides starting from maleic anhydride and substituted aromatic amines were synthesized.     

Synthesis and efficiency of photolysis of methylated 2-dialkylamino- and 2-piperidino-1,4-naphthoquinones

2-Dialkylamino- and 2-piperidino-1,4-naphthoquinones with a methyl group in position 3 or 5(8) of the naphthoquinone were synthesized by reacting dimethyl- and diethylamines and piperidine with 2- and 5-methyl-1,4-naphthoquinones. The quantum yields of photoconversion of the synthesized compounds in benzene were determined. A 1.2- to 6.5-fold increase of the quantum yield over that of 2-dimethylamino-1,4-naphthoquinone was established. A comparison of the quantum yields with the calculated charges on the reaction centers in the excited (T ₁) state showed that there is not a linear relationship between them.Institute of Organic Chemistry, Russian Academy of Sciences, Siberian Branch, 630090 Novosibirsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 707–714, March, 1992.     

One-pot synthesis of benzo[f]indole-4,9-diones from 1,4-naphthoquinones and terminal acetylenes

In this paper, a concise one-pot method for the construction of benzo[f]indole-4,9-dione motifs is described. These transformations proceed via a sequential palladium- and copper-catalyzed coupling reaction of 1,4-naphthoquinones with terminal acetylenes, followed by a copper-catalyzed intramolecular cyclization reaction of the resulting coupling product.     

乙酸促进邻甲基苯磺酸铜选择性催化醛与乙酸酐合成偕二乙酸酯反应

在室温无溶剂条件下,考察了乙酸促进邻甲基苯磺酸铜催化一系列芳香醛或脂肪醛与乙酸酐生成相应的偕二乙酸酯反应.结果表明,在乙酸存在条件下,邻甲基苯磺酸铜用量仅需占醛的0.3%(摩尔比)就能使反应在较短时间内完成.反应结束后,邻甲基苯磺酸铜经简单相分离可多次重复使用,催化活性无明显下降.     

Synthesis of (+)-(3R,5R)-3-Hydroxy-5-decanolide and Massoialactone,and Formal Synthesis of Verbalactone

Total synthesis of (3R, 5R)-(+)-3-hydroxy-5-decanolide (1) and massoialactone (2), and formal synthesis of verbalactone (3), have been reported.