Untersuchungen zur Chemie von 3-Chlormethyl-3-methyl-2,3-dihydro-1,4-benzoxathiinen

Investigations on the Chemistry of 3-Chloromethyl-3-methyl-2,3-dihydro-1,4-benzoxathiines A series of 3-chloromethyl-2,3-dihydro-1,4-benzoxathiines 3 were prepared by the reaction of several β-methallylphenylethers 1 with sulfur dichloride. In some cases intermediate sulfenyl chlorides 2 were isolated and characterized as substituted thiazolidin-2-ones. The thermal regioisomerization of selected sulfenyl chlorides and one of the thiazolidinone products was achieved. Starting from 3-chloromethyl-2,3-dihydro-1,4-benzoxathiine 3o several derivatives were obtained by nucleophilic displacement at the 3-chloromethyl position, activated by S-3-neighboring group partizipation. The structure of the 3-acetoxymethyl derivative was determined by x-ray crystal structure analysis. Further special derivation with selected chiral reagents led to diastereomeric compounds. The separation of the diastereomers by crystallization and chromatography was attempted. HPLC-separation was achieved in one case.     

Derivate des 2-Phenyl- und 2-Methyl-2,3-dihydro-1,4-dithiin-5,6-dicarbonsäureimids

Derivatives of 2-Phenyl- and 2-Methyl-2,3-dihydro-1,4-dithiine-5,6-dicarboxylic Acid Imide The reaction between 2-phenyl- ( A ) and 2-methyl-2,3-dihydro-1,4-dithiine-5,6-dicarboxylic acid imide ( B ), respectively, and primary aromatic amines or diamines in the presence of formaldehyde or acetaldehyde yields the α-aminoalkyl- and bis-α-aminoalkyl derivatives 1—26 . Interaction of A and B with disulfides, sulfochlorides, sulfuryl chloride, acetanhydride, acid chlorides and chloroformic acid esters affords the N-substituted compounds 27—32, 33—38, 39—40 and 41—48 , respectively. The IR spectra of the products are discussed.     

8种新型7胺-基取代的1,4二-氢-3H-2,3苯-并噁嗪-3甲-酸乙酯衍生物的合成

1,4二-氢-3H-2,3苯-并口恶嗪-3甲-酸乙酯经过硝化、还原和重氮化溴代得到了7溴--1,4二-氢-3H-2,3苯-并口恶嗪-3甲-酸乙酯(C)。以Pd(OAc)2/R(+)B INAP(2,2′-二苯膦-1,1′-联萘)为催化体系,C与苯胺、N-甲基苯胺、对氟苯胺、对乙氧基苯胺、环己胺、吗啡、四氢吡咯及六氢吡啶等8种有机胺类化合物(Am ine1~8),在氮气保护下,以碳酸铯为碱于干燥的甲苯中100℃反应16~24 h,生成了相应的8种新的7胺-基取代的1,4二-氢-3H-2,3苯-并口恶嗪-3甲-酸乙酯类化合物(D1~8),反应收率分别为83%、85%、71%、90%、72%、63%、75%和83%。通过1HNMR、质谱和元素分析对这些化合物的结构进行了表征。     

6-羟基-2,3-二氢-4-喹啉酮的合成方法

6-羟基-2,3-二氢-4-喹啉酮是一种重要的医药中间体,介绍了以4-甲氧基苯胺为起始原料制备6-羟基-2,3-二氢-4-喹啉酮的方法:加成或缩合、环合、脱烷基。总结了不同方法得到的不同结果,比较了各种方法的可行性。     

Synthesis and anticancer activity of (R,S)-9-(2,3-dihydro-1,4-benzoxathiin-3-ylmethyl)-9H-purines

A series of eleven 2- and 6-substituted (R,S)-9-(2,3-dihydro-1,4-benzoxathiin-3-ylmethyl)-9H-purine derivatives was obtained by applying a standard Mitsunobu protocol that led to a six-membered ring contraction from (R,S)-3,4-dihydro-2H-1,5-benzoxathiepin-3-ol via an episulfonium intermediate. The signal approximately delta=151 ppm, which corresponds to the C4' carbon atom, is unequivocal proof of the N9' regioisomer. The potential of the target molecules as anticancer agents is reflected in their activity against the MCF-7 cancer cell line. The most active compounds have IC(50) values of (6.18+/-1.70) and (8.97+/-0.83) microM. The results indicate that the anticancer activity for the most active compounds is correlated with their capacity to induce apoptosis.     

A 3-D silver(I) polymer with 5,6-dihydro-1,4-dithiin-2,3-dicarboxylate ligand,showing an unusual 6-connected (412.63)2(49.66) topology

The in situ reaction of AgClO₄·6H₂O with 5,6-dihydro-1,4-dithiin-2,3-dicarboxylic anhydride in the presence of lithium hydroxide afforded a photoluminescent three-dimensional (3-D) Ag^I coordination polymer, [Ag₂(L)]_∞ (1), which exhibited an unusual trinodal 6-connected (4¹².6³)₂(4⁹.6⁶) topological net (L = 5,6-dihydro-1,4-dithiin-2,3-dicarboxylate). Moreover, the luminescent/thermal properties of 1 have also been briefly investigated.     

The base-mediated cyclization of selected benzyl alkynyl sulfones with aromatic aldehydes: novel synthetic access to aryl-substituted 5,6-dihydro-1,4-oxathiin S,S-dioxides

Based on an unexpected product isolated during the LDA-mediated intramolecular cyclization of a benzyl alkynyl sulfones, a conceptually new cyclization method for the formation of 5,6-dihydro-1,4-oxathiin S,S-dioxides is demonstrated. The reaction affords products with (het)aryl groups at the 5- and 6-positions in 7–54% yield.     

5-氯-2,3-二氢-1-茚酮的合成研究

以3-氯丙酰氯、氯苯、三氯化铝、浓硫酸为原料合成5-氯-2,3-二氢-1-茚酮,对影响反应的主要因素进行了研究,优化了条件,优化后的反应条件为:氯代酮合成:n(三氯化铝)∶n(氯苯)∶n(3-氯丙酰氯)=1.1∶4∶1,滴加温度为5℃,滴加时间2h,保温温度60℃,保温时间3h;5-氯茚酮合成:搅拌速度小于100r/min,n(H2SO4)∶n(氯代酮)=36.8∶1,滴加时间4h,溶剂为石油醚(90-120℃)。此工艺原料价廉易得,产品纯度高,总收率达50.6%,产品纯度达98%。     

An unusual route to 1,4-diphenyl-2,3-dimethylbutadiene-1,3

Summary Treatment of 2,3-dimethyl-2,3-diphenylbutanediol-1,4-ditosylate with tetra-n-butylammonium bromide in dimethyl-acetamide did not give the expected 2,3-dimethyl-2,3-diphenyl-1,4-dibromobutane but, rather, by a double phenonium ion rearrangement, 1,4-diphenyl-2,3-dimethylbutadiene-1,3. 2,3-Dimethyl-2, 3-diphenyl-1,4-dibromobutane was required as starting material for the synthesis of head to head poly(-methyl-styrene) by Grignard coupling.This communication is Part XXX of Head to Head Polymers. Part XXIX: M.Malanga and O. Vogl, Acta Polymerica, in press.     

Reaction of 5-Amino-2,3-dicyano-1,4-naphthoquinone with Arylamines

The reaction of 5-amino-2,3-dicyano-1,4-naphthoquinone (1) with arylamines gave 5-amino-8-arylamino- (2), 5,8-bis(arylamino)- (3), and 5-hydroxy-8-arylamino-2,3-dicyano-1,4-naphthoquinone (4) together with 5-amino-2-arylamino-3-cyano- (5) and 5-amino-2-cyano-3-aryl-amino-1,4-naphthoquinone (6). It is proposed that the initial quinone-quinoneimine tautomerism of 1 to 4-hydroxy-2,3-dicyano-5-imino-1,5-naphthoquinone 7 facilitates the 8-arylamination. Some derivatives of 2 have good properties as dyes for optical information-recording media for semiconductor lasers.     

6-(4-甲基-3-戊烯基)-2,3-环氧基-2,3-二氢萘-1,4-二醌的合成

6-(4-甲基-3-戊烯基)-2,3-环氧基-2,3-二氢萘-1,4-二醌对肿瘤细胞有一定的抑制作用,研究其新的合成方法具有较重要的理论和实践意义。本文以6-(4-甲基-3-戊烯基)萘-1,4-二醌为原料,过氧化氢为氧化剂,通过环氧化反应制备了目标产物6-(4-甲基-3-戊烯基)-2,3-环氧基-2,3-二氢萘-1,4-二醌。采用FT-IR、GC-MS和¹H NMR等手段对产物进行了表征,确定了产物结构。探讨了氧化剂用量、反应时间、溶剂种类和无水碳酸钠用量对反应转化率和得率的影响,得到适宜的工艺条件为:以过氧化氢为氧化剂,n(萘二醌):n(过氧化氢):n(无水碳酸钠)=1:8:0.5,溶剂为乙醇,反应温度为30℃,反应时间为2h。在上述条件下,产物得率为83.9%。     

硝基-3-氧-3，4-二氢-2H-[1，4]苯并噁嗪-6-羧酸的合成

以4-羟基-3-硝基苯甲酸为原料,经酯化、醚化、还原合环、硝化、水解等5步反应,合成了两个未见文献报导的化合物7-硝基-3-氧-3,4-二氢-2H-[1,4]苯并噁嗪-6-羧酸和8-硝基-3-氧-3,4-二氢-2H-[1,4]苯并嗪-6-羧酸,其结构经IR、LC/MS、1HNMR和元素分析确证。     

1,4-Dihydroxyanthraquinone-2-carboxamides and 2,3-dicarboximides. Orange dyes for synthetic polymer fibres

Hydrolysis of 1,4-dihydroxy-2,3-dicyanoanthraquinone gives 1,4-dihydroxyanthraquinone-2,3-dicarboxylic anhydride, reaction of which with alkylamines and arylamines gives either the 2-carboxamide or 2,3-dicarboximide derivatives. These compounds colour polyester in brownish-orange hues having good light fastness. The colour of the dyes is discussed in relation to other 2-substituted derivatives of 1,4-dihydroxyanthraquinone.     

Copper(II) complexes of 2-(1,4-dihydro-2-hydroxy-1,4-dioxonaphthalen-3-ylthio) acetic acid

Selective carbon–sulphur bond cleavage reaction of (3-mercapto-1,4-dioxo-1,4-dihydro-naphthalen-2-ylsulfanyl) acetic acid by copper(II) nitrate tetrahydrate at room temperature to form copper(II) complex of 2-(1,4-dihydro-2-hydroxy-1,4-dioxonaphthalen-3-ylthio) acetic acid is described.     

Reactions of 2-arylhydrazones of 1,2,3-triketones with 1,2-diaminoethane. I. Synthesis and spectral characterization of 6-arylazo-2,3-dihydro-1H-1,4-diazepines and 3,10-diarylazo-4,9-dimethyl-5,8-diaza-3,9-dodecadiene-2,11-diones

Reactions of 3-arylhydrazones of 2,3,4-pentanetrione ( 1a–1e ) and 2-arylhydrazones of 1,3-diphenyl-1,2,3-propanetrione ( 1f–1l ) with 1,2-diaminoethane have been studied. It was found, that 3-arylhydrazones of 2,3,4-pentanetrione react with 1,2-diaminoethane with formation of 6-arylazo-2,3-dihydro-1,4-diazepines ( 2a–2e ) or the diarylazo derivatives of 4,9-dimethyl-5,8-diaza-3,9-dodecadiene-2,11-dione ( 3a–3e ). Analogous reactions of 2-arylhydrazones of 1,3-diphenyl-1,2,3-propanetrione yielded exclusively the derivatives of dihydrodiazepine. The structure of obtained products has been elucidated on the basis of i.r., m.s. and ¹H-n.m.r. spectra.     

1-环丙基-6,7-二氟-1,4-二氢-8-甲氧基-4-氧代-3-喹啉硼二乙酯的合成研究

用螯合法把化合物1-环丙基-6,7-二氟-1,4-二氢-8-甲氧基-4-氧代-3-喹啉羧酸乙酯(DFQ-Et)螯合制得硼螯合物(1-环丙基-6,7-二氟-1,4-二氢-8-甲氧基-4-氧代-3-喹啉羧硼二乙酯)[DFQ-B(OAc)2],并考察了此步反应在DMF、DMSO等不同溶媒以及不同温度和不同时间时的反应情况。筛选结果显示,此步缩合反应的溶媒采用DMSO,所得产物(粗品)的纯度可达到大于90.0%(HPLC归一法)。总收率92.4%。该工艺反应条件温和,原料易得,操作简便,产率高,成本较低,适合工业化生产。     

1,4-二碘-2,3-二乙氧基苯的合成

以邻苯二乙醚为原料,合成了新化合物1,4-二碘-2,3-二乙氧基苯.中间体和产物的结构经 1HNMR、13CNMR、IR、UV-Vis和元素分析表征.     

5-氯-2，3-二氢茚-1-酮的合成

对茚虫威关键中间体5-氯-2,3-二氢茚-1-酮的合成进行了研究。以3-氯苄基氯为原料,经亲核取代、水解、脱羧、酰氯化和付氏酰基化等5步反应生成目标产物,产率42％。     

1,4-二氨基-2,3-二氯蒽醌合成的新工艺

将1,4-二氨基蒽醌隐色体在溶剂中直接通入氯气进行氯化,可以得到色谱含量98％以上的1,4-二氨基-2,3-二氯蒽醌,收率93％左右.     

2,7-二甲基-2,3-二氢-6-氯苯并呋喃的分析方法

采用气相色谱法,选用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2,7-二甲基-2,3-二氢-6-氯苯并呋喃的含量。方法的变异系数0.18%,回收率100.02%。该方法快速、准确,可以实际应用于2,7-二甲基-2,3-二氢-6-氯苯并呋喃的生产监测和质量控制。