芳亚甲基丙二腈和4-羟基喹啉-2-酮反应的研究

以芳亚甲基丙二腈和4-羟基喹啉-2-酮为原料,在六氢吡啶催化下以乙醇为溶剂,80℃合成了一系列新的2-氨基-3-氰基-4-芳基5,6-二氢化-4H-吡喃并[3,2-c]喹啉-5-酮衍生物,反应条件温和,产率较高,并通过单晶X射线衍射分析确证产物的结构.     

可见光诱导邻烯基甲酰苯胺环化合成2-喹啉酮

使用廉价易得的邻烯基甲酰苯胺在可见光的诱导下发生自由基环化反应, 以良好至优秀的产率合成了15种2-喹啉酮衍生物. 该方法简单高效、 条件温和、 产率较高, 具有优异的官能团兼容性, 不仅拓展了邻烯基甲酰苯胺参与的新型有机反应, 也为光催化合成喹啉酮类化合物提供了一条新途径.     

2-(5,7-二氯/二溴-8-喹啉氧甲基)-4-苯基喹啉-3-羧酸乙酯的便捷合成(英文)

在K2CO3作为碱、乙腈作为溶剂的条件下,将2-氯甲基-4-苯基喹啉-3-羧酸乙酯(3)分别与5,7-二氯-8-羟基喹啉(4a)和5,7-二溴-8-羟基喹啉(4b)发生Williamson反应,以高收率得到结构新颖的二氯或二溴取代的双喹啉类目标化合物2-(5,7-二氯/二溴-8-喹啉氧甲基)-4-苯基喹啉-3-羧酸乙酯(2a,2b);其结构经波谱数据和元素分析证实.     

2-(2-喹啉偶氮)-1,3-二氨基苯与铜的显色反应

环境样品中铜的测定具有重要意义。我们曾合成了几个2-喹啉偶氮苯酚和2-喹啉偶氮苯甲酸试剂,并用于金属元素的测定。本文合成了2-(2-喹啉偶氮)-1,3-二氨基苯(QADAB),并研究了其与铜的显色反应,     

贝达喹啉中间体3-苄基-6-溴-2-甲氧基喹啉的合成工艺优化

贝达喹啉是本世纪初开发上市的新型二芳基喹啉类药物,而3-苄基-6-溴-2-甲氧基喹啉是合成贝达喹啉的重要中间体。本文针对此中间体合成时间长,收率低的问题,通过探讨不同的反应时间、温度、溶剂等因素对其影响,寻找到较优的反应条件,提高了反应收率,缩短了反应时间,便于工业化生产。     

Brnsted酸性离子液体催化芳香醛和2-甲基喹啉反应合成1,3-二(2-喹啉基)丙烷化合物

以Brnsted酸性离子液体1-乙基-3-丁基咪唑对甲苯磺酸盐为催化剂,将芳香醛和2-甲基喹啉类化合物在无溶剂或甲苯中于120℃反应48 h,制备了一系列的1,3-二(2-喹啉基)丙烷化合物,产率56%~92%,产物结构经核磁共振波谱和高分辨质谱确证.该方法具有简便易行、产率较高等特点.     

KF-alumina催化下2-氨基-4-芳基-5,6-二氢化-4H-P比喃[3,2-c]喹啉-5-酮-3-羧酸酯衍生物的一步合成

以芳醛、氰乙酸酯和4-羟基喹啉-2-酮为原料，乙醇为溶剂，在KF—Al2O3催化下80℃，一步合成了2-氨基-4-芳基-5，6-二氢化-4H-吡喃[3，2-c]喹啉-5-酮-3-羧酸酯衍生物，和其它方法相比，具有反应条件温和，容易操作和产率高等优点，产物4a的结构通过X单晶衍射分析确证．     

脯氨酸催化新型3-α,β-不饱和酮取代-4-羟基喹啉-2-酮简便合成及其荧光性质研究

3-乙酰-4-羟基喹啉-2-酮和芳香醛在L-脯氨酸有效催化下发生Aldol反应,生成一系列缩合产物3-α,β-不饱和酮取代-4-羟基喹啉-2-酮.该反应在甲醇溶液中进行,并且产物作为沉淀直接从溶液中析出,简单洗涤可得纯产物.研究表明芳香醛上的取代基性质对产物的产率有显著影响,其结果证实了该缩合反应经历了一个脱水中间体的反应历程.此外,对产物的荧光性质研究表明该类化合物可作为潜在应用价值的有机光学材料.     

CuBr_2催化的三组分反应合成喹啉-2,4-二羧基衍生物

以廉价的CuBr2为催化剂,发展了一种通过芳胺、乙醛酸酯与丙酮酸酯三组分反应制得喹啉-2,4-二羧基衍生物的简便有效方法.该方法具有很好的原子经济性,使用了便宜的催化剂和易得的试剂,在温和的条件下解决了以往喹啉-2,4-二羧基衍生物合成条件苛刻、产率低等问题,在生物活性分子和药物分子合成上有潜在的应用价值.     

2-(2-喹啉偶氮)-5-二甲氨基苯酚光度法测定铀的研究

铀的测定一般采用铀试剂-Ⅲ或5-Br-PADAP光度法。2-喹啉偶氮类试剂已用于一些金属离子的测定,由于其共轭体系大,比吡啶偶氮类试剂具有更高的灵敏度。我们合成了2-(2-喹啉偶氮)-5-二甲氨基苯酚(QADMAP),产品经IR,MS及^1H NMR表征(谱图略)。研究其和铀的显色反应,建立了一种测定矿石中铀的方法。     

The Stereoselective Synthesis of 2‐Aryl‐2‐hydroxybutanoic Acid via Menthyl Chiral Auxiliaries

In the presence of titanium(IV) tetraethoxide ((EtO)₄Ti), menthyl arylglyoxylates are prepared by transesterification of ethyl arylglyoxylates and natural (−)‐(1R,2S,5R)‐menthol. Using menthyl as a chiral auxiliary, the corresponding novel (R)‐menthyl 2‐aryl‐2‐hydroxybutanoates are synthesized by the addition of Et₂Zn with menthyl arylglyoxylates. The structures of the products are characterized by IR and ¹H‐ and ¹³C‐NMR spectroscopy, mass spectrometry, and elemental analysis. The diastereoselectivities are analyzed by HPLC. The addition reactions are completed with good yields and high diastereoisomeric excess (de up to 95%), and, after hydrolysis, the (R)‐2‐aryl‐2‐hydroxybutanoic acids are obtained with high optical purities.     

Nucleophilic Substitution on Porphyrin Ring： Synthesis of 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenylporphyrin

The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenyl porphyrin （5） and its Ni （Ⅱ） （6）, Cu （Ⅱ） （7）, Zn （Ⅱ） （8） complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 （70%）, 6 （34%）, 7 （54%） and 8 （50%）, the corresponding 2-（2-naphythoxy）-5, 10,15,20-tetraphenylporphyrin （9）, and its Ni （Ⅱ） （10）, Cu （Ⅱ） （11）, Zn （Ⅱ） （12） complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.     

Liquid-Phase Synthesis of Methyl （2Z）-2-Arylsulfonylmethyl-2-alkenoates from PEG-Supported a-Phenylselenopropionate

Treatment of lithio derivativ e of novel PEG-supported a-phenylselenopropionate with aldehydes, followed by oxidation-elimination with 30% hydrogen peroxide, formed Baylis-Hillman products, which were then reacted with sodium arylsulfinate. The resulting sulfonylated products were cleaved from the PEG efficiently affording methyl （2Z）-2-arylsulfonylmethyl-2-alkenoates in good yields and high purities.     

Selective Transformations of a Diprotected 2‐Oxobutanedial

The reactivity of 1,1‐diethoxy‐3‐(1,3‐dithian‐2‐yl)propan‐2‐one, a diacetal of oxobutanedial, and some of its derivatives toward selected reagents has been studied. As expected, hydride and Grignard‐type additions take place at the oxo moiety only and give the corresponding alcohols in good‐to‐excellent yields. Standard reductive amination occurs at the oxo moiety as well, but the reaction was in most cases not selective and furnished the expected amine mixed with 3‐(1,3‐dithian‐2‐yl)‐1,1‐diethoxypropan‐2‐ol. The conversion of the diethyl acetal moiety to an aldehyde group is generally an efficient transformation, but some aldehydes are unstable, making the deprotection useless. If the acetal contains a tertiary alcohol or a benzyloxy moiety, however, stable products are formed in good yields. Attempts to convert the 1,3‐dithiane substituent into an aldehyde group without concomitant decomposition of the product were totally unsuccessful. The chemical potential of this moiety, therefore, has to be utilized at an earlier stage and under different conditions.     

Synthesis of 1‐Acyl‐3,4‐dihydroquinazoline‐2(1H)‐thiones by Cyclization of N‐[2‐(Isothiocyanatomethyl)phenyl] Amides Generated in situ from N‐[2‐(Azidomethyl)phenyl] Amides

An efficient method for the preparation of 1‐acyl‐3,4‐dihydroquinazoline‐2(1H)‐thiones 5 has been developed. The reaction of N‐[2‐(azidomethyl)phenyl] amides 3 , easily prepared by a three‐step sequence starting with (2‐aminophenyl)methanols, with Ph₃P, followed by CS₂, allowed generation of N‐[2‐(isothiocyanatomethyl)phenyl]‐amide intermediates 4 , which underwent cyclization on treatment with NaH to furnish the corresponding desired products in generally good yields.     

An Unexpected Result of the Reaction of Benzothioamide Derivatives with 2‐Aryl‐2‐bromoacetonitriles

Unexpectedly, in the reaction of 2‐bromo‐2‐phenylacetonitrile derivatives with 2 mol‐equiv. of benzothioamide in DMSO, 3,5‐diaryl‐1,2,4‐thiadiazoles were obtained in excellent yields (83–90%) and in short reaction times (5–10 min). It is found that, in DMF, a quite different reaction takes place and 2,5‐diaryl‐1,3‐thiazol‐4‐amines are formed as the main products.     

Radiolysis of 2-acetylfuran in 2-propanol in absence of atmospheric oxygen

Gamma radiolysis of 2-acetylfuran (AF) in 2-propanol, in absence of atmospheric oxygen, has been investigated. The radiation yields of hydrogen, methane at different doses as well as radiolytic products in solution were determined. The radiolytic products were determined by gas chromatography coupled with mass spectrometry. The mechanisms for formation of detected radiolytic products and the effect of (AF) concentration on hydrogen and methane yields are discussed.     

水相介质中碳酸钾/硫脲联合促进邻位氨基溴转变成α,β-脱氢氨的研究

建立了在水相介质中, 在碳酸钾/硫脲联合促进下, 具有邻位氨基溴的酯和邻位氨基溴的酮在室温下发生溴化氢消除反应, 高收率地制备α,β-脱氢氨(功能化烯胺)的新方法. 共考察了23种不同结构α,β-邻位氨基溴的酯和α,β-邻位氨基溴的酮的反应情况, 证明该方法具有广泛的适应性. 实验发现, 无论底物为α-氨基-β-溴结构还是α-溴-β-氨基结构, 反应过程中都要经过一个氮丙啶过程, 而氮丙啶的开环是区域专一的, 因此产物具有区域专一性(烯键上的氨基均处在羰基的α-位). 所有产物的结构均经过核磁共振波谱及高分辩率质谱确证. 克量级放大实验结果表明, 该方法具有一定的用于工业化生产的可行性.     

An Efficient Synthesis of [(Tosylamino)alkyl]naphthalenols by Nucleophilic Addition of Naphthalen‐2‐ol with N‐Tosyl Imines Using Boron Trifluoride Etherate as Catalyst

[(Tosylamino)alkyl]naphthalenols have efficiently been synthesized by nucleophilic addition of naphthalen‐2‐ol with N‐tosyl imines (derived from both aromatic and aliphatic aldehydes) in the presence of BF₃?OEt₂ as a catalyst at room temperature. The products are formed within 5–9 h in high yields (72–91%).     

ZnBr2催化合成2-噁唑烷酮类化合物

在甲苯中,以ZnBr_2为催化剂、4-二甲氨基吡啶为碱,通过N-Boc取代的炔基胺类化合物的环化反应合成了5位取代的2-噁唑烷酮类化合物。考察了催化剂种类、碱、温度等对反应的影响,在优化条件下以良好的产率得到了一系列目标产物。