5-溴-2,3-二氢苯并呋喃-7-磺酰氯的合成

以苯酚为原料,经取代、环合、溴代和氯磺化4步反应合成了含有二氢苯并呋喃骨架的杂环类磺酰氯衍生物5-溴-2,3-二氢苯并呋喃-7-磺酰氯。针对氯磺化步骤优化了工艺条件。优化条件为：n(5-溴-2,3-二氢苯并呋喃)∶n(氯磺酸)=1∶6、反应温度25℃、反应时间2.5 h。优化条件下目标产物收率达81%,其结构经¹H NMR、¹³C NMR、质谱和IR确证。     

苯并呋喃甲酰氯的气相色谱分析方法

2,7-二甲基-2,3-二氢-苯并呋喃-6-甲酰氯,(简称苯并呋喃甲酰氯)与无水甲醇反应,生成2,7-二甲基-2,3-二氢-苯并呋喃-6-甲酸甲酯(简称苯并呋喃甲酸甲酯)后,采用气相色谱法,选用5%OV-210/ChromosorbWAW-DMCS(80-100目),Φ3.2mm×1m柱,邻苯二甲酸二乙酯为内标物,分离测定呋喃虫酰肼的重要中间体苯并呋喃甲酰氯的含量。方法的平均标准偏差为0.18,平均变异系数0.22%,平均回收率99.99%。该方法快速、准确,可以实际应用于苯并呋喃甲酰氯的生产监测和质量控制。     

琥珀酸普芦卡必利有关物质的合成研究

以4-氨基-5-氯-2,3-二氢-7-苯并呋喃羧酸为起始原料,经缩合反应合成琥珀酸普芦卡必利的有关物质3-(4-(4-氨基-5-氯-2,3-二氢-7-苯并呋喃甲酰胺)哌啶-1-基)丙基-4-氨基-5-氯-2,3-二氢-7-苯并呋喃甲酰胺(简称琥珀酸普芦卡必利杂质A).以4-氨基-5-氯-7-苯并呋喃羧酸为起始原料,经缩...     

新除草剂RZH-01-004的合成及除草活性

通过7-氯-5-氟4异氰酸酯基-2,2-二甲基-2,3-二氢-1-苯并呋喃和2-羟基-甲基-3-丁烯酸乙酯发生加成环化反应制得除草剂3-（7-氯-5-氟-2,2-二甲基-2,3-二氢-1-苯并呋喃-4-基）-5-（1-甲基亚乙基）-1,3-噁唑烷．2,4-二酮,收率70％,含量97.8％。产品结构用CIMS,HNMR进行了确定。室内生测结果表明,RZH-01-004苗后茎叶处理对大多数阔叶杂草有较高的除草活性。     

2,3-二氢-2-苯基咪唑[2,1-b]苯并噻唑的合成研究

以2-氯苯并噻唑为原料,在N,N-二异丙基乙基胺存在下与D或L-苯甘氨醇反应后,不经分离直接与甲磺酰氯在N,N-二异丙基乙基胺作用下关环,一锅法合成了(R)或(S)-2,3-二氢-2-苯基咪唑[2,1-b]苯并噻唑,利用IR、~1HNMR、MS谱和旋光度对其结构进行了表征.通过优化研究2,3-二氢-2-苯基咪唑[2,1-b]苯并噻唑的合成工艺条件,可得到总收率为80%的(R)或(S)-2,3-二氢-2-苯基咪唑[2,1-b]苯并噻唑.     

二氢呋喃和二氢吡喃2-位醚化的合成方法研究

以对甲苯磺酸吡啶盐作催化剂,2,3-二氢呋喃和2,3-二氢吡喃为起始原料,与醇通过加成反应制备得到2-甲氧基四氢呋喃和2-(2-溴代)乙氧基四氢吡喃,并通过Gabriel伯胺合成法得到O-(四氢-2H-吡喃-基)羟胺。对甲苯磺酸吡啶盐催化的收率均在85%以上,其结构经1H NMR和MS确证。此法广泛应用于羟基和氨基的保护,具有操作简便、条件温和、原料成本低等优点。     

琥珀酸普芦卡必利的合成

以4-(乙酰基氨基)-2,3-二氢苯并呋喃-7-羧酸甲酯和1-(3-甲氧基丙基)-4-哌啶胺为起始原料,经水解、酰胺化、氯取代及成盐等一系列反应合成了标题化合物,收率67.6%,产物的结构经IR、1HNMR、13CNMR、MS和元素分析得到确证。     

3,4-二氢-2(1H)喹啉酮衍生物的合成研究

对3,4-二氢-2(1H)喹啉酮衍生物1,2,3(R= NO2,NH2,OH;R= H,NO2,NH2)的合成进行了研究。以苯胺和3-氯丙酰氯为原料,制得N-苯基-3-氯丙酰胺,然后经环合得到3,4-二氢-2(1H)喹啉酮,再经由硝化、还原、重氮化水解合成了一系列3,4-二氢-2(1H)喹啉酮衍生物:6-硝基-3,4-二氢-2(1H)喹啉酮(1a),6,8-二硝基-3,4-二氢-2(1H)喹啉酮(1b),6-氨基-3,4-二氢-2(1H)喹啉酮(2a),6,8-二氨基-3,4-二氢-2(1H)喹啉酮(2b),6-氨基-8-硝基-3,4-二氢-2(1H)喹啉酮(2c),6-羟基-3,4-二氢-2(1H)喹啉酮(3a)和6-羟基-8-硝基-3,4-二氢-2(1H)喹啉酮(3b),其中化合物(2c)及(3b)为新化合物。单步产率均在86%以上,路线简单,操作简便,反应条件温和。采用MS,1HNMR对产品进行了定性及结构表征。     

奈必洛尔的合成方法研究进展

叙述了目前已公开报道的5条合成奈必洛尔的路线.叙述了以对氟苯酚、消旋6-氟-3,4-二氢-2H-1-苯并呋喃-2-甲酸和消旋6-氟-3,4-二氢-2H-1-苯并呋喃-2-甲醛为原料的合成方法,其中消旋6-氟-3,4-二氢-2H-1-苯并呋喃-2-甲酸和消旋6-氟-3,4-二氢-2H-1-苯并呋喃-2-甲醛又可以以对氟苯...     

2,3-二甲氧基-5-甲基-6-(3-甲基-2-烯-1-丁基)-1,4-苯酚的合成及其副产物的研究

2,3-二甲氧基-5-甲基-1,4-苯酚与2-甲基丁烯醇在BF3OEt2的催化下进行傅-克烷基化反应合成2,3-二甲氧基-5-甲基-6-(3-甲基-2-烯-1-丁基)-1,4-苯酚。对鲜见文献报道的副产物2,2,5-三甲基-3-氢-6-羟基-7,8-二甲氧基-苯并吡喃进行了结构鉴定并推测了其形成机理,在原料辅酶Q0、甲基丁烯醇和BR的配比为1：1.5：0.19(摩尔比),反应温度45℃,滴加时间30min,反应时间2h的条件下收率达90.24％。     

6-2-氨丙基-2,3-二氢苯并呋喃的合成

以3-甲氧基苯甲醛为原料,经亨利反应、还原硝基和双键、氨基保护、傅-克酰基化、脱甲基、环合、羰基还原等反应,合成目的产物6-2-氨丙基-2,3-二氢苯并呋喃。并对硝基和双键的还原反应、傅-克酰基化和脱甲基反应的工艺条件进行了优化,得出较佳工艺条件:(1)化合物Ⅱ的还原反应:反应温度40℃,氢气压力4.0 MPa,Raney-Ni用量为化合物Ⅱ质量的8%,产物收率为78.6%;(2)合成化合物Ⅵ的反应:反应温度45℃,n(氯乙酰氯)/n(化合物Ⅳ)=1.4,反应时间6 h,产物收率为68.8%。     

氢溴酸达非那新的合成研究

以(S)-(-)-3-羟基吡咯烷盐酸盐为原料,经氨基和羟基同时保护、取代、脱N-保护基、氰基水解,与L-(+)-酒石酸成盐等4步反应,制得3-(S)-(-)-(1-氨甲酰基-1,1-二苯基甲基)四氢吡咯酒石酸盐,经皂化后与5-(2-溴乙基)-2,3-二氢苯并呋喃缩合、成盐制得氢溴酸达非那新,总收率为23.4%。产物经1H NMR和质谱进行了确认。对文献工艺条件进行了优化,适合于工业化生产,同时对文献报道目标化合物的旋光度数据进行了修正。     

Amino-thieno[2,3–c]pyrazole und Amino-thieno[2,3–b]pyrrole

Amino-thieno[2,3–c]pyrazoles and Amino-thieno[2,3–b]pyrroles The synthesis of thieno[2,3–c]pyrazoles and thieno[2,3–b]pyrroles is described. From the dithioliumsalt ( 1 ) and potassium hydroxide the potassium-(2,2-dicyan-1-methylthio-ethen-1-yl)-thiolate ( 2 ) is formed. This reacts with hydrazine hydrate to form the 3-amino-5-thioxo-pyrazol-4-carbonitrile ( 3 ) S-Alkylation with α-chlorocarbonyl compounds yielding ( 6a–c ) leads via Thorpe-Ziegler-cyclization to 3,4-diamino-thieno[2,3–c]pyrazoles ( 9 ) if the position 1 is alkylated ( 8 ). Acetyl acetone yields 2-mercapto-pyrazolo[1,5–a]pyrimidine ( 5 ). After S-alkylation ( 10a–d ) are immediately cyclized to thieno [2′,3′:3,4]pyrazolo[1,5-a]pyrimidine ( 11a–d ). The ketone ( 6a ) can be cyclized to the pyrazolo [5,1–b]thiazole ( 12 ). 3 reacts with oxalyl chloride to form the 2,3-dioxo-6-thioxo-imidazo[1,2-b]pyrazole ( 13 ) of which S-phenacyl derivative ( 14 ) because the NH-proton cannot be cyclized. The 5-amino-3,4-dicyano-pyrrol-2-thiolate ( 16 ) shows the analogous behaviour. The S-alkylation is followed by cyclization, and 3,5-diamino-thieno[2,3–b]pyrroles ( 18a–b ) arise. Reaction of 5-amino-2-alkylthio-pyrrol-3,5-dicarbonitrile ( 17 ) with acetyl acetone provides pyrrolo[1,2-a]pyrimidine ( 20a–c ) which can be cyclized to form thieno[3′,2′:4,6]pyrimidines ( 21a–c ) very easily.     

3-Alkylated (R)-2,3-Dihydroxyalkyl p-Toluenesulfonates – homochiral building blocks for modified steroid side chains

Oxidative cleavage of 1,2:5,6-di-0-cyclohexylidene-D-mannitol ( 2 ) with lead (IV) acetate yields (R)-2,3-0-cyclohexylideneglyceraldehyde, which was transformed by oxidation and esterification into methyl 2,3-0-cyclohexylideneglycerate. Grignard reaction with various alkylmagnesium halides followed by acid-catalyzed removal of the acetal group and reaction with p-toluenesulfonyl chloride in pyridine furnished the title compounds ( 8a – d ) in good chemical overall yield and high enantiomeric purity. The compounds were prepared as intermediates for the synthesis of a series of steroids with a modified side chain.     

Cathodic reduction of benzil in acetone and in dichloromethane

The cathodic reduction of benzil has been carried out at a controlled potential on a mercury cathode in two different SSE (solvent-supporting-electrolyte) conditions: (a) acetone/lithium perchlorate in absence of electrophile where 2,3-diphenyl-5-methyl-furan and 1,2-diphenyl-2-hydroxy-1,4-pentanedione were obtained as main products and (b) dichloromethane/tetrabuthylammonium chloride with the addition of oxalyl chloride as electrophile, where a fast electron transfer took place.     

2,3-二氟-4-羟基苯硼酸的合成

本文以邻二氟苯为原料,利用其定位效应,通过与丁基锂、硼酸三甲酯直接作用得到2,3-二氟苯硼酸,再通过与H2O2反应得到2,3-二氟苯酚。以所合成的2,3-二氟苯酚为原料,通过叔丁基二甲基氯硅烷保护酚羟基,再在低温下与丁基锂、硼酸三甲酯等作用得到2,3-二氟-4-羟基苯硼酸,5步反应总产率为83%。     

Silica-Supported Ionic Liquids Prompted One-Pot Four-Component Synthesis of Pyrazolopyranopyrimidines, 3-methyl-4-aryl-4,5-dihydro-1H-pyrano[2,3-c]pyrazol-6-ones,and 1,6-diamino-2-oxo-1,2,3,4-tetrahydropyridine-3,5-dicarbonitriles

Three methods have been used for synthesis of pyrazolopyranopyrimidines, 3-methyl-4-aryl-4,5-dihydro-1H-pyrano[2,3-c]pyrazol-6-ones, and 1,6-diamino-2-oxo-1,2,3,4-tetrahydropyridine-3,5-dicarbonitrile derivatives via four-component reactions under solvent-free conditions. Silica-bonded 5-n-propyl-octahydro-pyrimido[1,2-a]azepiniumchloride (SB-DBU⁺Cl^?), silica-bonded n-propyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride (SB-DABCO⁺Cl^?), and nano silica-bonded 5-n-propyl-octahydro-pyrimido[1,2-a]azepinium chloride (NSB-DBU⁺Cl^?) as silica-supported ionic liquids catalyzed these reactions. These green, heterogeneous catalysts are separated from the reactions by simple filtration. The catalysts were recovered for at least four times without significant loss of their catalytic activities.     

Synthesis of polymers with benzo-13-crown-4 and benzo-9-crown-3 units via cyclopolymerization

Summary Polymers containing crown ether units were synthesized by cyclopolymerization of divinyl and diepoxide monomers. These are 1,2-bis-(2-ethenyloxyethoxy)-benzene (1) and 1,2-bis-(2,3-epoxypropyl)-benzene (3) producing polymers with 13 and 9-membered rings 4 and 5, respectively. Both the monomers and polymers were characterized by IR, ¹H NMR and ¹³C NMR spectroscopy. Finally, the polymers were contacted with an aqueous solution of lithium chloride.     

Catalytic decomposition of 2,3-dihydrobenzofuran to monomeric cyclic compounds over Pd/XCs2.5H0.5PW12O40/OMC (ordered mesoporous carbon) (X = 10–30 wt.%) catalysts

A series of Pd/XCs_2.5H_0.5PW₁₂O₄₀/OMC (ordered mesoporous carbon) (X = 10, 15, 20, 25, and 30 wt.%) catalysts with different Cs_2.5H_0.5PW₁₂O₄₀ contents (X, wt%) were prepared by a sequential incipient wetness impregnation method for use in the catalytic decomposition of 2,3-dihydrobenzofuran to monomeric cyclic compounds. 2,3-Dihydrobenzofuran was used as a lignin model compound for representing β-5 linkage of lignin. Acidity of Pd/XCs_2.5H_0.5PW₁₂O₄₀/OMC catalysts served as an important factor determining the catalytic performance in the reaction. Conversion of 2,3-dihydrobenzofuran and total yield for main products (2-ethylphenol and ethylcyclohexane) increased with increasing acidity of Pd/XCs_2.5H_0.5PW₁₂O₄₀/OMC catalysts.     

由α-异佛尔酮催化合成3,5,5-三甲基-1,2-环己二酮的研究

以α-异佛尔酮为原料,经过碱性条件下过氧化氢环氧化和固体酸催化重排合成3,5,5-三甲基-1,2-环己二酮。考察了反应温度、反应时间、反应溶剂对重排反应的影响。优化条件为:以无水氯化锌作催化剂,二氯甲烷作溶剂,回流反应30min,2,3-环氧异佛尔酮于回流温度下可完全转化,产物的选择性达87.4%。