2-氨基-4-甲氧基氯代苯甲酸的合成研究

以2-氨基-4-甲氧基苯甲酸甲酯为原料,通过氯代反应,再分别通过酯水解反应得到化合物2-氨基-5-氯-4-甲氧基苯甲酸和2-氨基-3-氯-4-甲氧基苯甲酸。其中间体及产物结构经~1H NMR、~(13)C NMR和ESI-MS确证,并考察了最佳氯代反应条件。结果表明:物料配比为n(2-氨基-4-甲氧基苯甲酸甲酯)∶n(NCS)=1∶1. 2,反应溶剂为N,N-二甲基甲酰胺,反应时间为16 h,两种氯代产物2-氨基-5-氯-4-甲氧基苯甲酸甲酯和2-氨基-3-氯-4-甲氧基苯甲酸甲酯收率分别为47%和39%。     

2-甲基-4-甲氧基苯基苯胺的合成

邻硝基甲苯在甲醇、乙酸和硫酸混合溶液中, 在Pt/C的催化下发生氢化和Bamberger重排生成2-甲基-4-甲氧基苯胺. 后者在Pd/C的存在下以苯酚为反应介质与环已酮缩合生成2-甲基-4-甲氧基苯基苯胺, 反应总产率63.0%. 文中给出了产物与中间产物的核磁共振氢谱和质谱, 同时讨论了影响反应的因素.     

天然产物5,7-二甲氧基-4′-羟基异黄酮的合成

以4-羟基苯乙酸和3,5-二甲氧基苯酚为原料,通过一条包括苄基化、酰氯化、酯化、氢化、Fries重排、以及Vilsmeier-Haack反应等6步反应的路线合成了天然产物5,7-二甲氧基-4′-羟基异黄酮,目标产物的总收率为33%.利用1HNMR、13C NMR及元素分析确证了化合物的结构.     

2-甲氧基-3-氟-4-碘吡啶的合成

2-甲氧基-3-氟-4-碘吡啶是一个重要的医药化工中间体,其合成路线未见文献报道。以2-甲氧基-3-氟-5-氯吡啶为起始原料,经氢解和碘代两步反应合成标题化合物,总收率62.8%,其结构经¹H NMR, ¹³C NMR和MS确证。     

合成4-叔丁基-4′-甲氧基二苯甲酰甲烷的新方法

对叔丁基苯甲醛与对甲氧基苯乙酮在甲醇钠作用下缩合生成1-(4-甲氧基苯基)-3-(4-叔丁基苯基)-2-丙烯-1-酮(1,收率91%);1经溴加成,甲醇钠脱溴合成4-叔丁基4′-甲氧基二苯甲酰甲烷(收率89%),总收率81%,其结构经UV-Vis和1H NMR表征.     

4-氯-6-甲氧基-7-(N-甲基-4-哌啶甲氧基)喹唑啉的合成

凡德他尼(vandetanib)是由阿斯利康公司研发的口服小分子多靶点酪酸激酶抑制剂,可同时作用于肿瘤细胞EGFR、VEGFR和RET酪氨酸激酶[1,2],2006年1月获欧洲罕见病药品委员会(COMP)批准推荐,用于治疗髓甲状腺癌、乳腺癌、骨髓瘤等[3].     

2-氯-4-苯基喹唑啉的合成

以邻苯甲酰苯甲酸为原料,依次经氯代、酰胺化、Hofmann重排、成环及氯化共5步反应合成了2-氯-4-苯基喹唑啉,总收率20.8%,其结构经¹H NMR和¹³C NMR确证。     

新方法合成4-氰基-1-茚酮

以邻氰基氯苄和丙二酸二乙酯为原料,经缩合、碱水解、脱羧和Friedel-Crafts酰化反应合成了4-氰基-1-茚酮,总收率32.1%,其结构经1H NMR和13C NMR确证。     

羧甲基壳聚糖-g-(2-氯乙酰氧基-4-甲氧基-二苯甲酮)的合成及其紫外吸收性能

2-羟基-4-甲氧基二苯甲酮(紫外线吸收剂)与一氯乙酰氯反应制得功能中间体2-氯乙酰氧基-4-甲氧基-二苯甲酮(1);在碱性条件下1与羧甲基壳聚糖(CMC)在异丙醇中通过N-烷基化反应实现1在CMC上的接枝,合成了一系列新型CMC接枝物——CMC-g-1n(2-G,G=接枝率),其结构经UV,IR和XRD表征.并测试了2-G的吸湿性、保湿性以及溶解性.结果表明,2-G在311 nm处有最大紫外吸收;吸湿性随G的增大减小;保湿性随G的增大提高;2-G有较好的水溶性.     

3-硝基-2-氨基苯甲酸的合成

以邻苯二甲酸酐为起始原料,经硝化、脱水、酰胺化、霍夫曼重排4步反应合成了3-硝基-2-氨基苯甲酸,总收率19%,其结构经1H NMR, IR和元素分析表征.探讨了酰胺化和霍夫曼重排反应条件对产率的影响.结果表明, n(脲素) ∶ n(3-硝基邻苯二甲酸酐)=2.0 ∶ 1.0,于50 ℃～60 ℃反应5 h～6 h,酰胺化反应收率85%～91%.n(NaClO) ∶ n(3-硝基-2-甲酰胺基苯甲酸)=1.2 ∶ 1.0,于60 ℃反应3 h,重排反应收率94%.     

合成5－氯2－氨基苯膦酸的新方法

报道了以２．５－二氯苯胺为原料合成５－氯－２氨基苯膦酸的新方法，总产率达４１％，是文献报道的以间氯苯胺为原料的合成方法的总产率的近３倍。     

5-氯-2-甲氧基苯甲酸与1,10-邻菲啰啉稀土配合物的合成、表征及热分解机理

合成了三种稀土配合物[Ln(5-Cl-2-MOBA)3phen]2(Ln=Nd(1),Eu(2),Ho(3);5-Cl-2-MOBA:5-氯-2-甲氧基苯甲酸根;phen:1,10-邻菲啰啉),通过元素分析、热重-微分热重-差示扫描量热(TG-DTG-DSC)、红外光谱(IR)、紫外光谱(UV)及摩尔电导等技术对标题配合物进行了表征.荧光光谱表明配合物(2)发出铕离子的特征荧光.用热分析/傅里叶变换红外(TG-DSC/FTIR)联用技术,阐明标题配合物的热分解反应机理,并分析了逸出气体的三维(3D)红外光谱.     

A Validated HPLC Method for Simultaneous Determination of 2-Hydroxy-4-methoxybenzaldehyde and 2-Hydroxy-4-methoxybenzoic Acid in Root Organs of Hemidesmus indicus

A reverse phase HPLC method was developed and validated for the simultaneous determination of 2-hydroxy-4-methoxybenzaldehyde and 2-hydroxy-4-methoxybenzoic acid in the root extracts of Hemidesmus indicus. A comprehensive validation of the method including sensitivity, linearity, reproducibility, accuracy, limit of detection (LOD) and limit of quantification (LOQ) was conducted using the optimized chromatographic conditions. The method was found to be linear (r > 0.998) in the range of 5–350 μg mL⁻¹ for 2-hydroxy-4-methoxybenzaldehyde and for 2-hydroxy-4-methoxybenzoic acid (r > 0.999) in the range 10–300 μg mL⁻¹. The method was found to be precise with inter-day precision values (% RSD) in the ranges of 0.61–1.76% for 2-hydroxy-4-methoxybenzaldehyde and 1.3–2.8% for 2-hydroxy-4-ethoxybenzoic acid while intra-day precisions (% RSD) of two analytes were in the range of 0.41–1.07 and 0.95–2.5%. The limits of detection (LODs) for 2-hydroxy-4-methoxybenzaldehyde and 2-hydroxy-4-methoxybenzoic acid were 0.84 and 2.34 μg mL⁻¹. The described method was fast, sensitive and reproducible, and thus well suited for routine analysis of these two compounds from root extracts of H. indicus and other plants.     

A Novel Method for the Synthesis of 4-Nitro-Dibenzo-14-Crown-4

The mixed solvent effect of dioxane-HMPA on the synthesis of 4-nitro-dibenzo-14-crown-4 markedly increased the yield by 19 times greater than that in n-butanol alone, and effected easier separation of the final compound.     

4-Chloro-2,6-Pyridinedicarboxylic Acid Functionalized Mesoporous Silica Nanocomposites for the Synthesis of Sinapaldehyde

Kinetics and Catalysis - 4-Chloro-2,6-pyridinedicarboxylic acid (CPDA) functionalized mesoporous silica SBA-15 nanocomposites (SBA/5CPDA) were synthesized and characterized for the Knoevenagel...     

4-Hydroxyquinol-2-ones. 85. Synthesis of 2-Chloro-4-hydroxyquinoline-3-carboxylic Acid Ethyl Ester

The behavior of 2-chloro-4-hydroxy- and 4-chloro-2-oxoquinoline-3-carboxylic acids under acid catalyzed esterification conditions with methanol has been studied. A method is proposed for obtaining 2-chloro-4-hydroxyquinoline-3-carboxylic acid ethyl ester. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1195–1197, August, 2005.     

A Novel Method for Synthesis of 2, 3, 4-Trisubstituted Furans

Intermolecular addition-cyclization of 1, 3-dicarbonyl compounds with arylbromoallenes in K2CO3 mediated condition afforded 2, 3, 4-trisubstituted furans in good yield.     

A Novel Asymmetric Synthesis of S-(+)-2-Amino-4-Phosphonobutanoic Acid

A novel asymmetric synthetic route to S(+)-2-amino -4-pbosphonobutanoic acid through the cyclic condensation of ethyl-4-diethoxyphosphonyl-2-oxo-butanoate with L-erythro-(+)-1, 2-diphenyl-2-hydrozyethylamine, followed by reduction and hydrolysis is described.