2-甲基-3-丁烯-2-醇合成3-甲基-2-丁烯-1-醇

[目的]2-甲基-3-丁烯-2-醇是异戊二烯间接皂化法生产3-甲基-2-丁烯-1-醇过程中产生的副产物,废物回收再利用是节能减排的有效措施.[方法]2-甲基-3-丁烯-2-醇经氯化、酯化和皂化得到3-甲基-2-丁烯-1-醇.[结果]结果表明:在优化条件下,氯化反应的产率可达87.25％,酯化和皂化反应的产率可达84.53％.[结论]该方法是2-甲基-3-丁烯-2-醇再利用的有效方法.     

2-氨基-4-氯-5-硝基苯酚的生产工艺

以2-氨基-4-氯苯酚为原料。经乙酰化、闭环、硝化、碱解和酸化合成2-氨基-4-氯-5-硝基苯酚,精制品总收率为64％。     

5-氯-2-甲基-4-异噻唑啉-3-酮的合成

以多硫化钠、丙烯酸甲酯、甲胺等为原料合成杀菌剂5-氯-2-甲基-4-异噻唑啉-3-酮,具有很好的杀灭细菌、霉菌的能力。     

3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸的合成研究

3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸是合成新型鱼尼丁受体杀虫剂氯虫酰胺(chlorantraniliprole)的关键中间体.以2,3-二氯吡啶为原料通过肼基取代、马来酸二乙酯环合、对甲基苯磺酰氯酯化、溴化氢溴化、浓硫酸氧化脱氢以及水解6步反应制得3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-...     

6-(4-羟基-3,5-二叔丁基苯氨基)-2,4-二氯-1,3,5-三嗪的合成

本文通过还原2,6-二叔丁基-4-亚硝基苯酚得到2,6-二叔丁基-4-胺基苯酚,再与三聚氰氯反应,生成6-(4-羟基-3,5-二叔丁基苯氨基)-2,4-二氯-1,3,5-三嗪。考察了溶剂用量、反应时间、反应温度和物料配比等对反应的影响,确定了最佳反应条件,产品收率稳定在89%。     

2-氨基-5-(2-苯基-1,3-硒唑-4-甲硫基)-1,3,4-噻二唑的合成

在氢氧化钾参与下,利用固-液相转移催化法合成了标题化合物,实验考察了不同催化剂、催化剂用量、反应物用量、反应温度对收率的影响,结果表明:以聚乙二醇-400为催化剂,且其物质的量为底物2-苯基-4-氯甲基硒唑的5%,2-苯基-4-硒唑基氯甲烷和2-氨基-5-巯基-1,3,4-噻二唑的物质的量比为1∶1.2,在丙酮中回流,为较佳反应条件,收率可达82.6%,目标物的结构经IR、1HNMR及ESI-MS等方法确证。     

5-卤代-2-(4-芳基-噻唑-2-基)-腙甲基-苯酚的合成

以5-卤代-水杨醛为原料,与氨基硫脲发生缩合反应,生成5-卤代-水杨醛缩氨基硫脲。然后分别与ω-溴代苯乙酮、对甲氧基-ω-溴代苯乙酮在甲醇或丙酮溶剂中回流反应10 min,得到6个5-卤代-2-(4-芳基-噻唑-2-基)-腙甲基-苯酚,最后通过红外、核磁、质谱对其进行了结构表征。     

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-硝基-4-二甲氨基甲基-5-羟基-1-甲基-2-苯硫甲基-1H-吲哚-3-羧酸乙酯的合成

以对苯醌和3-(甲基氨基)-2-丁烯酸乙酯为起始原料,经Nenitzescu反应、乙酰化、硝化、溴代、缩合、Mannich反应得到一个新化合物6-硝基-4-二甲氨基甲基-5-羟基-1-甲基-2-苯硫甲基-1H-吲哚-3-羧酸乙酯,总产率19.3％.反应中间产物和目标产物结构采用1 HNMR和质谱确认.     

5,6-二甲基-2-氧代-1,2-二氢吡啶-3-甲酸的合成研究

以2-丁酮为起始原料,依次与甲酸乙酯反应得到2-甲基-3-氧代-丁醛2(酮酯缩合)、与氰基乙酰胺缩合成5,6-二甲基-3-氰基-2-羟基吡啶3、氰基水解得到5,6-二甲基-2-氧代-1,2-二氢吡啶-3-甲酸1,总收率为30.1%。     

2-氯-5-甲基吡啶的合成方法

介绍了2-氯-5-甲基吡啶的四种类型的合成方法,包括以3-甲基吡啶-N-氧化物为原料的氯化法、2-氨基-5-甲基吡啶氯化法、环合氯化法、3-甲基吡啶直接氯化法等     

Ring opening metathesis polymerization of dicyclopentadiene catalyzed by titanium tetrachloride adduct complexes with nitrogen‐containing ligands

Ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) catalyzed by titanium tetrachloride adduct complexes such as TiCl₄ · 2L [L = pyridine (1), 2‐methylpyridine (2), 2,4,6‐trimethylpyridine (3), 3‐aminopyridine (4), 2‐hyroxypyridine (5)] and CH₃Li as cocatalyst was reported. The polymer was characterized by IR and ¹H‐NMR methods. Five influencing factors were also discussed. The catalyst systems TiCl₄ · 2L/CH₃Li (L = 2‐methylpyridine, 2,4,6‐trimethylpyridine) appeared to be very active for the ROMP of DCPD. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3247–3251, 2000     

紫外线吸收剂UV-326的合成

4-氯 - 2 -硝基苯胺 ( 1 )用亚硝酸钠 ( 2 )和硫酸重氮化后与 2 -特丁基 - 4-甲基苯酚 ( 3)反应制成 2 -硝基 - 4-氯 - 2′-羟基 - 3′-特丁基 - 5′-甲基偶氮苯 ( 4 )。其摩尔比为 ( 1 )∶ ( 2 )∶ ( 3) =1∶ 1 .0 5∶ 1 .1 0 ,( 4 )用硫化钠还原制成 2 - ( 2′-羟基 - 3′-特丁基 - 5′-甲基苯基 - ) - 5-氯苯并三唑 N-氧化物 ( 5) ,( 5)用锌粉还原制成最终产品 2 - ( 2′-羟基 - 3′-特丁基 - 5′-甲基苯基 ) - 5-氯苯并三唑 ( 6) ,亦即 UV- 32 6。光老化试验表明它是聚烯烃、ABS、聚酯和其他树脂的优良的光稳定剂。已建成 2 0 0 t/a工业装置并投入生产。     

3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑的合成

3 (4 氯 2 氟 5 甲氧基苯基 ) 1 甲基 5 三氟甲基 1H 吡唑是合成除草剂的中间体。它通过以下途径制得 :邻氯对氟苯甲醚在冰水浴下与甲基二氯甲基醚和四氯化钛反应得 4 氯 2 氟 5 甲氧基苯甲醛 ;后者经甲基格氏试剂作用 ,然后在酸性条件下用三氧化铬氧化 ,转变为 4 氯 2 氟 5 甲氧基苯乙酮 ;4 氯 2 氟 5 甲氧基苯乙酮在甲醇钠 /甲醇体系中 ,与三氟乙酸乙酯反应得相应的 β 二酮 ;然后用水合肼闭环 ,再用硫酸二甲酯甲基化即得产品。总收率 6 3 5 %。最后一步用硫酸二甲酯甲基化时 ,反应在酸性条件下进行可减少副产品的生成。产品结构经质谱、核磁共振氢谱、碳谱确认     

当今热点农药的含氟中间体开发

叙述近年来国内外发展的新农药如氟虫腈、溴虫腈、七氟菊酯、四氟苯菊酯、氯氟吡氧乙酸、吡氟禾草灵等相关的含氟中间体的开发,包括对-三氟甲基苯胺、2,6-二氯-4-三氟甲基苯胺、2,6-二氯-4-三氟甲基苯肼、3,5-二氯-4-氨基-6-氟吡啶酚、2,3,5,6-四氟苄醇、2,3,5,6-四氟-4-甲基苄醇、2-氯-5-三氟甲基吡啶、2.3-二氯-5-三氟甲基吡啶和2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈等     

Synthese von Hetaryl‐pyridiniumsalzen und kondensierten 3‐Amino‐pyrid‐2‐onen

1‐(3‐Coumaryl)‐pyridinium salts 3 and 1‐(3‐coumaryl)‐tetrahydrothiophenium salts 5 were synthesized from 2‐acylphenyl chloro‐ or bromoacetates 2 . 2‐Chloro‐N¹‐(3,4‐dimethoxyphenyl)‐acetamide and substituted 2‐chloro‐N¹‐(2‐thienyl)‐acetamides 8 react with acetyl chloride and pyridine to yield the quinolinyl‐ and (thieno[2,3‐b]pyridin‐5‐yl)‐pyridinium salts 10 . Fused thieno[2,3‐b]pyridin‐ones 19 were formed from N‐chloroacetyl‐2‐aminothiophen‐3‐carbonitriles 16 with pyridine via Thorpe‐Ziegler cyclization and followed by cyclodehydrogenation. In presence of pyridine alkyl 2‐chloro‐acetylaminobenzoates 21 yield 3‐(1‐pyridinio)‐quinoline‐4‐olates 23 . Zincke‐cleavage of 10 and 23 with hydrazinium hydroxide leads to fused 3‐amino‐pyridine‐2‐ones 11 and 3‐amino‐4‐hydroxy‐quinoline‐2‐ones 24 , respectively. Oxazoloquinolines 25 were synthesized from 24 with acetic anhydride.     

Palladium‐Catalysed Regioselective Sequential C‐5 and C‐2 Direct Arylations of 3‐Acetylpyrroles with Aryl Bromides

The PdCl(C₃H₅)(dppb)/KOAc system was found to be effective for the direct regioselective C‐5 arylation of 3‐acetylpyrroles with ortho‐substituted aryl bromides. This procedure has been found to be tolerant to a variety of functional groups at C‐2 of the aryl bromide such as methyl, formyl, nitrile, nitro, hydroxymethyl, chloro, fluoro or trifluoromethyl. The sequential direct C‐5 arylation followed by C‐2 arylation of such 3‐substituted pyrroles allows the synthesis of 2,5‐diaryl‐3‐acetylpyrroles in high yields.     

Enantioselective Synthesis of 4‐(Dimethylamino)pyridines through a Chemical Oxidation‐Enzymatic Reduction Sequence. Application in Asymmetric Catalysis

Enantiomerically pure 4‐(dimethylamino)‐3‐(1‐hydroxyalkyl)pyridines and 4‐(dimethylamino)‐3‐[hydroxy(phenyl)methyl]pyridine have been prepared through efficient chemoenzymatic routes. For this purpose different lipases and oxidoreductases have been tested in the preparation of optically active 4‐chloro derivatives and baker’s yeast was found to be an excellent catalyst for the bioreductions of the corresponding ketones. Their applications as enantioselective nucleophilic catalysts have been studied, important catalytic properties were observed in the stereoselective construction of quaternary centers.     

Synthesis and characterization of the new pyridine‐containing poly(azomethine‐urethane)s: The effect of methyl substituent as electron‐donating group on some physical properties

In this study, a series of pyridine‐ring based poly(azomethine‐urethane)s were synthesized to investigate the effect of electron‐donating group on some physical properties such as thermal stability, optical, and electrochemical properties. For this reason, firstly the Schiff bases were synthesized using amino‐methyl pyridines (2‐amino‐3‐methyl pyridine, 2‐amino‐4‐methyl pyridine, and 2‐amino‐6‐methyl pyridine) with 2,4‐dihydroxy benzaldehyde by the condensation reaction. Then, these Schiff bases were converted to poly(azomethine‐urethane) derivatives via step‐polymerization reaction. Secondly, structural characterizations were carried out by FTIR, NMR, and UV–Vis. Cyclic voltammetry was used to determine the electrochemical oxidation‐reduction characteristics. Optical properties were investigated by UV–vis and fluorescence analyses. Thermal properties were clarified by TG‐DTA and DSC techniques. The molecular weight distributions of polymer were determined by size exclusion chromatography. POLYM. ENG. SCI., 54:1664–1674, 2014. © 2013 Society of Plastics Engineers     

2,4—二氯甲苯的合成

以３－氯对甲苯胺为原料,先制成盐酸盐,再用亚硝酸钠反应,得到２－氯－４－重氮基甲基的盐,用氯化亚铜将重氮基转化为氯,并经分离提纯,得到２,４－二氯甲苯。对反应条件的控制进行了讨论。该法后处理工艺简单,收率较高。