4-甲氧基环己酮的合成研究

以1,4-环己二酮-乙二醇缩酮为起始原料经两步法合成了4-甲氧基环己酮,通过对各步产物进行IR,1H NMR和13C NMR表征,确证所合成的产物为目标产物。并对由1,4-二氧螺环[4,5]癸烷-8-醇合成1,4-二氧螺环[4,5]癸烷-8-醇甲醚的合成条件进行了优化,得到最佳反应条件为:以THF为溶剂,氢氧化钠为催化剂,于反应温度为0℃,反应的收率可达85.9%。     

1,4-二氧杂螺[4.5]癸烷-8-酮的合成

以1,4,9,12-四氧杂二螺[4.2.4.2]十四烷为原料,采用酸性条件下水解缩酮选择性地脱除单侧羰基保护的方法合成了1,4-二氧杂螺[4.5]癸烷-8-酮.通过对盐酸、硫酸、甲酸、醋酸等催化性能的比较,对选择性的机理和影响因素进行了探讨,确定醋酸作为催化剂.优化了反应工艺条件,并对产品进行了IR、1HNMR的确认.结果表明,以冰醋酸作催化剂,反应溶剂V(冰醋酸):V(H2O)=5:1,反应浓度为0.05 g(mL(1,反应温度为65℃时,与原方法相比,反应时间由15 h缩短为约11 min, 产物的色谱收率由65%提高到80%.     

1，4-环己二酮单乙二醇缩酮的合成研究

对1,4-环已二酮的单保护反应进行了研究,在自制催化荆催化下,用n(乙二醇)∶n(1,4-环己二酮)=1∶1进行脱水缩合反应,在环己烷溶液中除去部分未保护的原料,在乙酸乙酯中用亚硫酸氢钠提取单保护产物,用10%的碳酸钠脱去亚硫酸氢钠,结晶精制而得产品1,4-环己二酮单乙二醇缩酮[1,4-二氧杂螺(4,5)癸烷-8-酮],收率为68.2%,气相色谱测定其纯度为99.8%.     

氧代螺环异吲哚啉衍生物的合成及表征

具有手性的氧代螺环异吲哚啉衍生物可作为天然药物的活性结构单元,这些化合物在医药和化工领域具有重要的研究价值。实验以1,4-二氧螺环[4.5]癸烷-8-酮和苯甲酸酐为原料,经过一系列反应制得2-(1-(4-氧代双环[4.1.0]庚基-1-)丙基-2-)异吲哚啉-1,3-二酮,并利用高效液相色谱(HPLC)、液质联用仪(LCMS)、核磁(NMR)对其结构进行表征。     

N-二氯乙酰基噁唑烷类衍生物的合成及生物活性

首先,选用硝基烷与醛反应,合成了4-硝基-3-己醇,3-硝基-4-庚醇及2-硝基-1-苯基丙醇,经铁粉还原得到4-氨基-3-己醇、3-氨基-4-庚醇及2-氨基-1-苯基丙醇。然后,以三乙胺为缚酸剂,以氨基醇、酮(或醛)和二氯乙酰氯为原料,合成了6个二氯乙酰基口恶唑烷类潜在的除草剂安全剂,分别为N-二氯乙酰基-2,2,4-三甲基-1,3-口恶唑烷、N-二氯乙酰基-4-甲基-2-丙基-1,3-口恶唑烷、N-二氯乙酰基-3-甲基-1-氧杂-4-氮杂螺[4.5]癸烷、N-二氯乙酰基-2,3-二乙基-1-氧杂-4-氮杂螺[4.5]癸烷、N-二氯乙酰基-3-乙基-2-丙基-1-氧杂-4-氮杂螺[4.5]癸烷及N-二氯乙酰基-3-甲基-2-苯基-1-氧杂-4-氮杂螺[4.5]癸烷,产率分别为54.58%、74.39%、53%、79%、88.52%及66.72%。产物结构进行了红外光谱、1HNMR、13CNMR及元素分析表征;并对Ⅲc物质进行了单晶结构解析。初步的生物测定实验表明,在每kg土含10 mg乙草胺的毒土中,化合物Ⅲc浸种浓度为50μmol/L时玉米株高恢复率达81.92%。     

4-羟基-5-(4''''-氯苯基)双环[4,4,0]-1-氮杂癸烷的合成

以4′-氯哌醋甲酯为原料,研究了作为潜在的治疗可卡因滥用症的药物--4-羟基-5-(4′-氯苯基)双环[4,4,0]-1-氮杂癸烷的合成.4′-氯哌醋甲酯首先用乙酸酐在室温下进行乙酰基化,然后在-70 ℃下经二异丙基胺锂(LDA)作用关环得中间产物(±)-threo-2,4-二氧代-5-(4′-氯苯基)双环[4,4,0]-1-氮杂癸烷,产率60%.中间体先用硼氢化钠在甲醇中室温下选择性地将酮羰基还原,粗产物经V(石油醚)∶ V(乙酸乙酯)=1∶ 1重结晶后,在四氢呋喃中于回流温度下用乙硼烷-四氢呋喃络合物进一步还原酰胺基,得到(±)-threo-4α-羟基-5-(4′-氯苯基)双环[4,4,0]-1-氮杂癸烷,两步产率为67%.所得α位羟基产物经过Swern氧化,然后在四氢呋喃中在-78 ℃下用三(仲丁基)硼氢化钾选择性还原,立体专一性地得到(±)-threo-4β-羟基-5-(4′-氯苯基)双环[4,4,0]-1-氮杂癸烷,氧化-还原反应总产率为70%.     

4-羟基-5(4′-氯苯基)双环[4,4,0]-1-氮杂癸烷的合成

以 4′ 氯哌醋甲酯为原料,研究了作为潜在的治疗可卡因滥用症的药物———4 羟基- 5- (4′- 氯苯基 )双环 [4,4, 0]- 1 氮杂癸烷的合成。4′- 氯哌醋甲酯首先用乙酸酐在室温下进行乙酰基化,然后在 -70℃下经二异丙基胺锂(LDA)作用关环得中间产物(±)- threo -2, 4 -二氧代- 5- (4′- 氯苯基)双环[4, 4, 0] -1 氮杂癸烷,产率 60%。中间体先用硼氢化钠在甲醇中室温下选择性地将酮羰基还原,粗产物经V(石油醚)∶V(乙酸乙酯) =1∶1重结晶后,在四氢呋喃中于回流温度下用乙硼烷 四氢呋喃络合物进一步还原酰胺基,得到(±) threo 4α 羟基- 5 -(4′- 氯苯基 )双环[4, 4, 0]- 1 氮杂癸烷,两步产率为 67%。所得α位羟基产物经过Swern氧化,然后在四氢呋喃中在 -78℃下用三(仲丁基)硼氢化钾选择性还原,立体专一性地得到 (±) threo- 4β 羟基- 5 (4′- 氯苯基 )双环 [4, 4, 0]- 1 氮杂癸烷,氧化 还原反应总产率为 70%。     

N-乙酰基-1-氧杂-4-氮杂-螺[4,5]癸烷的合成与表征

用乙醇胺和环己酮为原料,脱水缩合得到1-氧杂-4-氮杂-螺[4,5]癸烷,再经过与乙酰氯的酰化反应制得标题化合物,产率分别为69.1%和63.5%.产物的结构经1HNMR、IR和元素分析表征.     

N-(3-异丙氧基-4-甲氧基苯基)-2-氧代环戊烷甲酰胺的合成

以3-异丙氧基-4-甲氧基苯胺(2)和1,4-二氧螺[4.4]壬烷-6-羧酸(3)为原料,经过缩合反应得到N-(3-异丙氧基-4-甲氧基苯基)-1,4-二氧螺[4.4]壬烷-6-甲酰胺(4),然后经过酸性条件下脱乙二醇保护得到N-(3-异丙氧基-4-甲氧基苯基)-2-氧代环戊烷甲酰胺(1),产物结构经~1H NMR、~(13)C NMR和ESI-MS确证。并确定脱乙二醇反应条件为:反应温度25℃,反应时间30min,在该条件下产物收率72.6%。     

螺虫乙酯的合成

cis-8-甲氧基-1,3-二氮杂螺[4.5]癸-2,4-二酮水解得到含有cis-4-甲氧基环己基-1-氨基甲酸的混合物,对该混合物进行纯化处理得到cis-4-甲氧基环己基-1-氨基甲酸.cis-4-甲氧基环己基-1-氨基甲酸在饱和氯化氢的甲醇溶液中酯化,接着酰化,环合,最后与氯甲酸乙酯发生取代反应,生成目标产物螺虫乙酯.反应总收率72%,含量97.5%(HPLC,面积归一法),产物经1H NMR、MS进行了表征.     

Die Nitril-Carboxamid-Umlagerung

The Nitrile Carboxamide Rearrangement By reaction of cyclohexanone-2-carboxamide ( 4 ) with cyan amide 1-cyano-cyclohex-1-en-2-yl-urea ( 6 ) is formed via nitrile carboxamide rearrangement. Whilst compound 6 with 1,2-diaminobenzene hydrochloride forms 11-amino-1 H-2,3,4,5-tetrahydrodibenzo[b,e][1,4]diazepin hydrochloride ( 8 and 8a ), compound 6 and 1,2-diaminobenzene form hexahydro-benzimidazo[1,2-c]-quinazolin-6-one ( 12 ). Compound 8 with sodium hydroxide yields 11-amino-1 H-2,3,4,11a-tetrahydrodibenzo[b,e]-[1,4]diazepin ( 9 ). Compound 6 reacts with cyclohexylamine to form N-(1-cyanocyclohex-1-en-2-yl)-N′-cyclohexyl urea ( 10 ). Compound 10 with 1,4- or 1,2-diaminobenzene hydrochloride yields compound 7 and 8 . In alkaline solution 10 cyclises to 4-amino-3-cyclohexyl-2,3,5,6,7,8-hexahydroquinazolin-2-one ( 11 ). Compound 4 and malonitrile form either 3-amino-4-cyano-1,2,5,6,7,8-hexahydro-isoquinol-1-one ( 13 ) or 1-amino-4-cyano-2,3,5,6,7,8-hexahydro-isoquinol-3-one ( 14 ). Compound 13 and alkaline formaldehyde react to cyanooctahydroisoquinoline-[2,3-c] [1,3,5]oxdiazin-6-one ( 17 ). 2-Cyanoethyl-cyclohexan-one-2-carboxamide ( 22 ), prepared by Michael-reaction from 4 and acrylonitrile, forms via nitrile carboxamide rearrangement 10-cyano-1,2,3,4,5,6,7,10-octahydroquinolin-2-one ( 24 ) and 2-(1′-cyano-cyclohexyl-2′-one)-propionic acid ( 25 ). Nucleophilic attack of the NH₂-group at the cyanogroup of compound 22 forms 5-(spirocyclohexan-2′-one)-hexahydropyridin-2,6-dione ( 27 ).     

高速逆流色谱法分离纯化散斑竹根兰中的抗癌活性成分

采用高速逆流色谱法（HSCCC）,以正己烷-乙酸乙酯-乙醇-水组成二相系统作为固定相与流动相,对散斑竹根兰的抗癌活性部位进行了分离纯化。结果发现：以正己烷-乙酸乙酯-乙醇-水（体积比为1∶1∶1.1∶0.9）组成的系统可以从散斑竹根兰的抗癌活性部位中分离出其中的抗癌活性成分之一3-（4′-hydroxy-benzyl）-5,7-dihydroxy-6-methyl-8-methoxyl-chroman-4-one,纯度可达95%以上。     

Mechanism and kinetics of the free radical ring-opening polymerization of cyclic allylic sulfide lactones

The polymerization of 7-, 8- and 11-membered lactones, 6-methylene-1,4-oxathiepan-7-one, 3-methylene-1,5-oxathiocan-2-one and 3-methylene-1-oxa-5-thiacycloundecan-2-one in benzene at 70, 40–70 and 40–65 °C, respectively, is presented. All polymerizations proceeded with complete ring-opening up to approximately 25% conversion, where insoluble polymer was formed. Evidence is given attributing polymer double bond loss to crosslinking, although redistribution of the molecular weights via addition to polymer double bonds followed by β-fragmentation also appears to occur for polymerizations of the 8- and 11-membered lactones. Michael adducts of lactones with 2-methyl-2-propanethiol were prepared as models for chain-transfer products of hydrogen abstraction by carbon-centred radicals. Polymerization rates were found to increase marginally with ring size. Arrhenius parameters obtained for the polymerizations of the 8- and 11-membered lactones indicated that the addition step was more important than fragmentation in determining the rate of propagation.     

Produktzusammensetzung der Kohlenwasserstoffgemische nach der BIRCH-Reduktion substituierter Benzene und säurekatalysierte Addition von Alkoholen an alkylsubstituierte Cyclohexene und Cyclohexa-1,4-diene

Composition of Mixtures of Hydrocarbons after BIRCH -Reduction of Substituted Benzenes and Acid Catalyzed Addition of Alcohols to Alkylsubstituted Cyclohexenes and Cyclohexa-1,4-dienes . 10 different benzene hydrocarbons 1 , indane, tetraline, anisol and phenol are reduced by sodium in liquid ammonia in the presence of methanol to the BIRCH products 2 . The product mixture compositions are determined through capillary GLC. On storage at + 6°C some rearomatization of the 1,4-cyclohexadienes 2 occurs. Data of the ¹H- and ¹³C-n.m.r. spectra and also mass spectra of the BIRCH 1,4-dienes 2 are given. For comparison 4-alkoxycyclohexenes 4 and 1-alkoxy-1-methylcyclohexanes 8 are prepared and spectroscopically characterized. Acid-catalyzed addition of alcohols to the 1,4-cyclohexadiene systems is a slow process and gives the 4-alkoxy-4-alkylcyclohex-1-enes ( 4 ) only in moderate yields up to 30 %. Most of the products are dimers 5 and also oligomers 6 of the parent hydrocarbons 2 .     

多变参数间歇精馏提纯四甲基哌啶酮

采用多变参数间歇精馏技术对四甲基哌啶酮粗品进行了提纯实验研究。色谱分析证明,得到的哌啶酮产品质量分数达98.6%以上,一次收率超过64%;复蒸2#馏出物后得到的塔顶产品经过色质联用分析后确定为4-甲基-3-戊烯-2-酮及同分异构体4-甲基-4-戊烯-2-酮的混合物,其中4-甲基-3-戊烯-2-酮质量分数达88%以上。     

Preparation of novel 2-(2-oxo-2H-chromen-4-yl)-3- arylthiazolidin-4-one derivatives using an efficient ionic liquid catalyst

An eco-friendly procedure for synthesis of 2-(2-oxo-2H-chromen-4-yl)-3-arylthiazolidin-4-one derivatives by three-component reaction of 2-oxo-2H-chromene-4-carbaldehydes, aromatic amines and thioglycolic acid, with tetramethylbutane-1,4-diammonium acetate as a low-cost ionic liquid catalyst under reflux condition is described. The use of an ionic liquid as a catalyst has the advantages of high yields, short reaction time and environmentally friendly reaction media.     

Oxidative Kupplung CH-acider Verbindungen mit p-Phenylendiaminen. III [1]. Reaktivität 4-substituierter 3-Methyl-1-phenyl-pyrazolin-5-one gegenüber N,N-Diethylchinondiimin

Oxidative Coupling of CH-acid Compounds with p-Phenylene Diamines. III. Reactivity of 4-Substituted 3-Methyl-1-phenyl-pyrazolin-5-ones with N,N-Diethyl-quinone-(1,4)-diimine Substitution products 2–28 of 3-methyl-1-phenyl-pyrazolin-5-one 1 , with a wide variety of substituents in the 4-position, were synthesized. Most of these compounds react with N,N-diethyl-quinone-(1,4)-diimine by elimination of the substituent giving the same azomethine dye as that formed by oxidative coupling of the 4-unsubstituted compound. A study of the influence of side reactions by measurement of dye yields has been undertaken.     

催化加氢合成6-氨基-7-氟-2H-1,4-苯并口恶嗪-3(4H)-酮

6-氨基-7-氟-2H-1,4-苯并口恶嗪-3(4H)-酮(Ⅱ)是合成除草剂丙炔氟草胺的关键中间体,该文采用雷尼镍催化加氢还原7-氟-6-硝基-2H-1,4-苯并口恶嗪-3(4H)-酮(Ⅰ)高收率的制得了目标化合物Ⅱ,确定了最佳合成工艺条件:反应温度80℃,反应时间5 h,催化剂用量为原料质量的5%,氢气压力6 MPa,产品的收率95.2%,质量分数98.5%,溶剂和催化剂循环使用5次,对收率和产品质量分数无影响。产品结构经元素分析、红外光谱、核磁共振确证。     

退役锂电池放电废水特征有机污染物解析

为研究退役锂电池盐水溶液放电产生的放电废水有机物的种类与来源,首先采用单因素优化方法对萃取剂类型、pH、萃取次数3个因素进行液-液萃取前处理优化实验,获得最佳萃取预处理条件。接着采用气相色谱与质谱联用(GC-MS)程序中分流比和升温模式对比实验,建立了放电废水有机成分定性分析方法,并对检出的有机污染物进行分类与来源判断。研究结果表明,选取乙酸乙酯为萃取剂,调节放电废水pH至9.38,以8000r/min离心5min (4℃),且采用间歇三次萃取时分离效果最优。对放电废水SIM定性扫描检测出10类有机污染物,其中酸酯类、酰胺类、烷烃类物质较多,且来源于反应衍生物与电解液添加剂的占比较大,分别为33.3%与20%,包括电解质增塑剂间苯二甲酸二(2-乙基己基)酯,电解液溶剂效应产物1,4-环己烷二羧酸二甲酯、磷酸三(2-氯乙基)酯,电解液添加剂硬脂酰胺、十六碳酰胺、十四酰胺、1,4-环己烷二甲醇二乙烯醚,退役锂电池塑料外壳中抗氧剂原料3,5-二叔丁基苯酚等。这些物质对水环境均具有不同程度的毒性危害,需进一步检测各有机物浓度并揭示其迁移转化规律,建立退役锂电池放电废水重点关注有机污染物清单。