2-羟基-4-(3-甲基-2-丁烯基)氧苯乙酮的合成研究

以2,4-二羟基苯乙酮和异戊烯基溴为原料,合成了药物中间体2-羟基-4-(3-甲基-2-丁烯基)氧苯乙酮。通过TLC得到优化反应条件如下:以丙酮为溶剂、反应温度为65℃、n(2,4-二羟基苯乙酮)∶n(K2CO3)=1∶1.8、n(2,4-二羟基苯乙酮)∶n(异戊烯基溴)=1∶1.8,此时反应时间最短,目标产物收率达73%。     

中间体2,4-二羟基苯乙酮合成工艺研究

介绍了合成2,4-二羟基苯乙酮的工艺路线：在催化剂的作用下,由原料间苯二酚和冰醋酸经付-克反应合成2,4-二羟基苯乙酮。最佳反应条件为：冰醋酸用量12 g、催化剂用量16 g、反应时间1.5 h、反应温度135℃。产品经紫外、红外、熔点和Rf值鉴定为2,4-二羟基苯乙酮。     

天然产物Rubraflavone A的三甲氧基化合物的合成

以2,4-二羟基苯乙酮和2,4-二甲氧基苯甲酸为起始原料依次经过成酯、Claisen重排、香叶基取代、酸性条件下关环4步反应,以13.5%的总收率合成了天然产物Rubraflavone A的三甲氧基化合物.其关键步骤包括香叶基的引入和引入后的关环反应.     

Willgerodt-Kindler法合成系列芳基乙酸化合物

以各种芳基乙酮为原料,通过Willgerodt-Kindler重排反应、水解反应合成了8个相应的芳基乙酸类化合物。通过2,4-二羟基苯乙酸的合成考察了反应时间、物料配比和水解过程对反应的影响。结果表明,重排反应最佳条件为:反应时间8 h,2,4-二羟基苯乙酮∶吗啉的物质的量比为1∶3.75。在此条件下,收率75%。     

4-羟基-3-甲氧基苯乙酮肟环钯配合物催化Suzuki偶联反应的研究

以4-羟基-3甲氧基苯乙酮为原料,通过肟化反应合成了4-羟基-3甲氧基苯乙酮肟,并以氯钯酸锂为钯源,合成了4-羟基-3-甲氧基苯乙酮肟环钯配合物。通过傅立叶红外(FT-IR)和紫外-可见漫反射光谱(UV-vis-DRS)对合成的配合物进行了表征。考察了溶剂与溶剂含水量、碱、催化剂用量等反应条件对4-羟基-3甲氧基苯乙酮肟环钯配合物催化Suzuki偶联反应的影响。当以碳酸钾为碱,乙醇水溶液(50vol%)为溶剂,催化剂量为0.01%(1×10-4mmol),60℃下催化对溴苯乙酮与苯硼酸Suzuki偶联反应,反应15min时,产品收率可达98.76%,表明4-羟基-3-甲氧基苯乙酮肟环钯配合物催化剂具有很高的催化效率。     

5-二乙氨甲基-6-甲基-2,4-二羟基嘧啶的合成及抗炎活性

6-甲基-2,4-二羟基嘧啶(6-MU)在无水乙醇中与甲醛和二乙胺反应,生成5-二乙氨甲基-6-甲基-2,4-二羟基嘧啶。实验研究了影响反应收率的各种因素,确定了优化的反应条件:6-MU∶二乙胺∶甲醛(摩尔比)=1∶2∶2,反应溶剂无水乙醇,溶剂量60 mL,反应时间3 h,产物收率34.9%。LS-MS和1H NMR对产品进行了结构鉴定,确定产品为5-二乙氨甲基-6-甲基-2,4-二羟基嘧啶。通过小鼠耳肿胀实验对该化合物进行抗炎活性的初步研究,结果表明低中高剂量组的5-二乙氨甲基-6-甲基-2,4-二羟基嘧啶与空白对照组比较均有显著差异,具有显著的抗炎作用。     

离子液体Et3_NHCl-xAlCl_3催化合成2,4-二羟基苯乙酮

以Et3NHCl-xAlCl3离子液体为催化剂,间苯二酚与冰醋酸发生付-克酰基化反应合成2,4-二羟基苯乙酮。讨论了离子液体x值、反应物与离子液体物质的量之比与反应时间等因素对间二苯酚酰基化合成2,4-羟基苯乙酮的影响,在最佳条件下产率达到了65.2%。     

固体酸催化合成3,5-二乙酰氧基苯乙烯

以3,5二-羟基苯乙酮(4)为原料,经三步反应制得3,5二-乙酰氧基苯乙烯(1)。在硫酸催化下化合物(4)与乙酸酐反应,得到3,5二-乙酰氧基苯乙酮(3),收率92%,对于化合物(3)进行了1H NMR表征;化合物(3)经催化加氢,得到1-(1羟-基乙基)-3,5二-乙酰氧基苯(2),收率98%,对于化合物(2)进行了1H NMR表征;化合物(2)在固体酸催化下反应得到3,5二-乙酰氧基苯乙烯(1),制备化合物(1)的反应条件为:m[化合物(2)]∶m(固体酸)=5∶1,110℃回流5 h,收率95%,纯度98%,对化合物(1)进行了IR,1H NMR,MS表征,并对化合物(1)的1HNMR,MS表征结果进行了进一步分析。     

2-羟基-4-苄氧基二苯甲酮的合成

以间苯二酚、三氯甲苯和苄基氯为原料,通过两步反应合成2-羟基-4-苄氧基二苯甲酮。第一步采用以间苯二酚和三氯甲苯为原料,在十六烷基三甲基溴化铵作为相转移剂时,合成了中间体2,4-二羟基二苯甲酮,其反应的适宜条件为:反应原料n(三氯甲苯)/n(间苯二酚)比为1.4、滴加温度为60℃、反应温度为70℃、反应时间为0.5 h和催化剂用量为3.0 g/mol(以间苯二酚计),产品收率在95%以上。第二步采用以中间体2,4-二羟基二苯甲酮和苄基氯为原料,合成最终产物2-羟基-4-苄氧基二苯甲酮,结果表明,反应原料n(苄基氯)/n(2,4-二羟基二苯甲酮)比为1.0、Na2CO3为106.0 g/mol(以2,4-二羟基二苯甲酮计)、环已酮为40 mL和反应时间为6 h,产率在77%以上。得到的中间体和产物通过红外光谱、元素分析和1H-NMR进行表征。     

光稳定剂2-羟基-4-丙烯酰氧乙氧基二苯甲酮合成研究

在相转移催化剂存在下,以2,4-二羟基二苯甲酮、丙烯酸(2′-氯乙基)酯为原料合成2-羟基-4-丙烯酰氧乙氧基二苯甲酮,分别研究了反应温度、反应时间、原料配比、催化剂用量、阻聚剂用量等条件对合成反应的影响,确定了最佳工艺条件是:反应温度110℃;反应时间6h;n(2,4-二羟基二苯甲酮)∶n(丙烯酸(2′-氯乙基)酯)∶n(氢氧化钠)=1∶1.15∶1.2;溶剂用量为40mL,催化剂用量为0.8g、阻聚剂用量0.6g(相对于0.1 mol 2,4-二羟基二苯甲酮),产品收率可达到85.71%。     

O-甲基异脲硫酸盐的合成新工艺研究

以尿素和硫酸二甲酯为原料二步反应合成O-甲基异脲硫酸盐。(1)尿素和硫酸二甲酯经缩合(甲基化反应)、酸解、水解反应得O-甲基异脲硫酸氢盐,收率43％;(2)O-甲基异脲硫酸氢盐和氢氧化钠在甲醇溶液中反应制得游离O-甲基异脲,游离O-甲基异脲和氢盐中和制得O-甲基异脲硫酸盐,收率78％。     

Experimental and Computational Studies on the Thermal Degradation of Nitroazidobenzenes

In this combined experimental and theoretical study the thermal degradation of 2‐nitroazidobenzene ( I ), 2,4‐dinitroazidobenzene ( II ) and 2,4,6‐trinitroazidobenzene ( III ) to yield benzofuroxan ( IV ), 4‐nitrobenzofuroxan ( V ), and 4,6‐dinitrobenzofuroxan ( VI ) were investigated by thermoanalytical (TG, DSC) and computational methods. In contrast, furoxan formation was not observed for 4‐nitroazidobenzene ( VII ) under heating due to the para position of the nitro group in the benzene ring. All compounds were characterized by elemental analysis, vibrational (IR) spectroscopy and mass spectrometry. The crystal structure of compound III was determined by single‐crystal X‐ray diffraction. DFT‐based structure optimizations and frequency analyses were performed at the B3LYP/cc‐pVDZ level of theory. The structural parameters of the fully optimized compound III showed very good agreement with the single‐crystal X‐ray data. The enthalpies of formation for compounds I , II , III , IV , V , and VI were calculated using the complete basis set (CBS‐4M) method of Petersson and co‐workers in order to obtain accurate energies. The enthalpies of degradation for compounds I , II , and III were obtained from calculated enthalpies of formation according to the Hess Law and were compared with the experimental values, which were available from DSC analysis and were found to be in very good agreement.     

手性烯唑醇为活性组分的杀菌聚合物的合成

以杀菌剂烯唑醇（Ⅰ）为底物，（-）-孟氧基乙酸为拆分试剂进行手性拆分，得到具有高杀菌活性的（R）-（E）-1-（2，4-二氯苯基）-2-（1，2，4-三唑-1-基）-4，4-二甲基-1-戊烯-3-醇（Ⅱ）。Ⅱ与丙烯酰氯反应生成了具有生物活性的可聚合单体（R）-（E）-1-（2，4-二氯苯基）-2-（1，2，4-三唑-1-基）-4，4-二甲基-1-戊烯-3-醇丙烯酸酯（Ⅲ），Ⅲ经自聚或与丙烯酸或甲基丙烯酸甲酯共聚制得了杀菌聚合物（Ⅳ，Ⅴ，Ⅵ），并进行聚合物活性组分的水解释放实验。总体上，在碱性介质中聚合物的活性组分水解释放速率大于在中性或弱酸性介质中的。Ⅳ和Ⅵ活性组分水解释放速率很低，而聚合物Ⅴ，随时间的延长，有大量的活性组分释出，初始释出质量浓度也较高，符合农用杀菌剂的速效性和持效性的要求，有实用意义。     

青霉烷酸二苯甲酯亚砜的合成方法探索

由6-APA合成了他唑巴坦的重要中间体--青霉烷酸二苯甲酯亚砜.在氧化反应中,使用双氧水作氧化剂,在消去溴的反应中,使用铝粉代替锌粉,合成了目标化合物,三步总收率为60.7%,为该化合物的合成提供了新的路线.     

Hydrothermal catalytic conversion of biomass for lactic acid production

The production of lactic acid has increased owing to growing polymer markets, increased demand in the chemical sector and many applications in the food industry. Biomass hydrothermal decomposition is potentially a method for lactic acid production. To obtain a higher yield of lactic acid, the influence of metal ions (Zn(II), Ni(II),Co(II) and Cr(III)) on biomass decomposition in sub‐critical water (T = 300 °C) was investigated and the catalyst function in the complex reaction network of biomass degradation was discussed. In comparison with a non‐catalytic process, the addition of 400 ppm Ni(II) catalyst increased the yield of lactic acid from 3.25% to 6.62% at 300 °C and 120 s for microcrystalline cellulose. The lactic acid yield for glucose was 9.51% for 400 ppm Co(II) catalyst at 300 °C and 120 s. In the case of Cr(III) and Ni(II), the conversion of maize straw, sawdust and rice husk first increased, and then decreased from 0 to 800 ppm. For catalyst Cr(III), Zn(II) and Ni(II), the conversion of wheat bran indicated a decreasing trend. Transition metal ions have a great influence on raw materials conversion to lactic acid. In the conversion of pyruvaldehyde to lactic acid, the ionic catalyzed Cannizzaro‐type reaction would take place. Copyright © 2007 Society of Chemical Industry     

苯甲酰脲类杀虫剂伏虫隆合成新工艺

以2,4-二氟硝基苯和2,6-二氯苯腈为起始原料,经过6步反应合成伏虫隆,总收率为75.3%。以2,4-二氟硝基苯为原料,经过氯化、还原反应合成3,5-二氯-2,4-二氟苯胺(I),产率为84.5%;以2,6-二氯苯腈为原料,经过氟化和水解,制得2,6-二氟苯甲酰胺(Ⅱ),产率为87.7%;将Ⅱ与二(三氯甲基)碳酸酯(BTC)酰化,合成2,6-二氟苯甲酰异氰酸酯(Ⅲ),产率为91.3%;Ⅲ与Ⅰ加成,得到杀虫剂伏虫隆,产率为95%。产物结构经元素分析、IR和1H NMR表征。该工艺具有原料易得、收率高、质量好、对环境污染小等特点。     

Synthesis and Catalytic Activities of Silica-Supported Multifunctional Azo-Containing Schiff Base Complexes with Cu(II), Co(II), Ni(II) and Mn(II)

A novel 4-((5-formyl-2,4-dihydroxyphenyl)diazenyl)benzylphosphonic acid (FPABP) ligand was synthesized and bound to silica-gel which was activated with 3-aminopropyltriethoxysilane (APTES). Cu(II), Co(II), Ni(II) and Mn(II) complexes of silica-supported ligand (FDPDABP) were synthesized. The ligand and its complexes were characterized by using NMR, FT-IR, elemental analysis, ICP-OES and scanning electron Microscope (SEM). Catalytic properties of the complexes were investigated for the selective oxidation of cyclohexane under microwave power. SiO₂-FDPDABP-Cu(II) complex showed good catalytic activitiy for the selective oxidation of cyclohexane to cyclohexanol with 35.61% yield and cyclohexanone with 7.74% yield.     

A convenient preparative method for carboxylic acids containing the dichlorocyclopropane ring system

Various carboxylic acids containing the dichlorocyclopropane ring system were prepared from the direct reaction of unsaturated carboxylic acids with dichlorocarbene. For example, 2-(2,2.dichloro-1-methylcyclopropyl)-ethanoic acid ( II ) was prepared from 3-methyl-3-butenoic acid ( I ), 50% aqueous sodium hydroxide solution and benzyltriethylammonium chloride (BTEAC) in 80% yield. Similarly, 3-(2,2-dichloro-3,3-dimethyIcyclopropyl)-2,2-diethyl propanoic acid ( IV ) was obtained in 80% yield from 2,2-diethyl-5-methyl-4-hexenoic acid ( III ). The dichlorocyclopropane compounds, ( II ) and ( IV ), are potent insecticides against houseflies (Takatsuki strain in Japan).     

Distribution Studies of Actinides Using a Tetradentate Extractant, 4,4′-Nonanedioyl-Bis(2,4-Dihydro-5-Methyl-2-Phenyl-3H-Pyrazol-3-One)

Abstract

The extraction of Th(IV), UO₂(II), Am(III), and Eu(III) from aqueous acid by a tetradentate extractant, 4,4′-nonanedioyl-bis(2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one), H₂NDBP, has been studied and compared with two bidentate model compounds, 4-hexanoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one, HHMPP, and 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one, HBMPP. The distribution coefficients of UO₂(II), Am(III), and Eu(III) were somewhat larger using H₂NDBP relative to the model compounds under the conditions studied. However, the Th(IV) extraction using H₂NDBP was greatly enhanced when compared to HBMPP or HHMPP. The distribution coefficient for Th(IV) from 0.5 M HNO₃ was 11.6 using 3.0 × 10^?3 M H₂NDBP compared with values of D < 0.01 using 3.0 × 10^?3 M HBMPP or HHMPP.     

磺化硅胶催化合成2,4-滴丁酯

以2,4-二氯苯氧乙酸和正丁醇为原料,磺化硅胶为催化剂,催化合成除草剂2,4-二氯苯氧乙酸正丁酯(2,4-滴丁酯)。考察催化剂用量、原料配比及回流时间对反应的影响。结果表明,最佳反应条件为:催化剂用量为2,4-二氯苯氧乙酸质量的1.4%,n(正丁醇):n(2,4-二氯苯氧乙酸)=10:1,回流时间为1.0 h,2,4-二氯苯氧乙酸正丁酯的收率为98.7%。