4-Hydroxyquinol-2-ones. 86. Synthesis of Methyl (Ethyl) Esters of 1-Substituted 4-Amino-2-oxoquinoline-3-carboxylic Acids

Several variants of the synthesis of esters of 1-N-substituted 4-amino-2-oxoquinoline-3-carboxylic acids have been studied, one of which is recommended as preparative. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1355–1361, September, 2005.     

Reaction of 3-Arylmethylidene-3H-furan-2-ones with 3-Amino-1,2,4-triazole as a Convenient Technique to Synthesize Condensed Diazepinones

The interaction of the arylmethylidene derivatives of 3H-furan-2-ones with 3-amino-1,2,4-triazole was studied. The structure of the final products depends on reaction conditions and reagent ratio.

Reaction of 1-Aryl-1H-1,2,3-Triazole-4-Carbonyl Chlorides/Isothiocyanates with 3-Amino-5-Methylisoxazole

Abstract

1-Aryl-1H-1,2,3-triazole-4-carbonyl chlorides were selected as starting materials for the Boulton–Katritzky rearrangement. When 3-amino-5-methylisoxazole was acylated by 1-aryl-1H-1,2,3-triazole-4-carbonyl chlorides, 1-aryl-5-methyl-N-(5-methylisoxazol-3-yl)-1H-1,2,3-triazole-4-carboxamides 5 were obtained and no further rearrangement occurred. On the other hand, when 1-aryl-1H-1,2,3-triazole-4-carbonyl chlorides were first converted into isothiocyanates by the reaction with KSCN and then were allowed to react with 3-amino-5-methylisoxazole 4 in one pot, intermediate thioureas were formed and spontaneously transformed in statu nascendi into 1,2,4-thiadiazole derivatives 6.

GRAPHICAL ABSTRACT      

微波促进下3-(2-苯并呋喃基)-4-氨基-5-巯基-1,2,4-三唑

微波辐射条件下, 首先由2-苯并呋喃甲酰肼依次与二硫化碳和水合肼反应合成3-(2-苯并呋喃基)-4-氨基-5-巯基- 1,2,4-三唑, 进一步在微波辐射条件下由4-氨基-5-巯基-1,2,4-三唑分别与芳甲酸/芳氧基乙酸、α-溴代苯乙酮及芳醛反应以较高产率制得了相应的1,2,4-三唑并[3,4-b]-1,3,4-噻二唑、1,2,4-三唑并[3,4-b]-1,3,4-噻二嗪及4-芳亚甲基亚胺基-5-巯基-1,2,4-三唑. 产物结构经IR, ¹H NMR, MS及元素分析进行了表征.     

3-氨基-6/8取代-1H-吡唑[4,3-c]喹啉类化合物的合成

研究了合成3-氨基-6/8取代-1H-吡唑[4,3-c]喹啉类化合物的简易方法.通过3-芳基-4-氨基-5-巯基-1,2,4-三唑与6-/8-取代-4-羟基喹啉羧酸在三氯氧磷催化下的缩合反应及所生成的3-芳基-6-(6-/8-取代-4-氯喹啉-3-基)-1,2,4-三唑[3,4-b]-1,3,4-噻二唑类化合物与水合肼在乙醇中的肼解反应,合成了6个3-氨基-6/8取代-1H-吡唑[4,3-c]喹啉类化合物,并对活泼的氨基进行了初步研究,新化合物通过元素分析,IR,¹HNMR和MS确定结构,并讨论了其波谱性质.     

2-芳酰氨基-5-(5-苄基四唑-2-亚甲基)-1,3,4-噻二唑的合成

1,3,4噻二唑环类衍生物具有抗菌,杀虫,除草,调节植物生长,消炎止疼等广泛的生理活性。本文在浓硫酸催化下将1-(5-苄基四唑-2-乙酰基)-4-芳酰基氨基硫脲(1)环化为2-芳酰氨基-5-(5-芳基四唑-2-亚甲基-1,3,4-噻二(2)。2 的结构经元素分析、红外、核磁振波谱以及质谱方法确定。     

Synthesis and Preliminary Anticancer Activity Assessment of N-Glycosides of 2-Amino-1,3,4-thiadiazoles

The addition of 2-amino-1,3,4-thiadiazole derivatives with parallel iodination of differently protected glycals has been achieved using a double molar excess of molecular iodine under mild conditions. The corresponding thiadiazole derivatives of N-glycosides were obtained in good yields and anomeric selectivity. The usage of iodine as a catalyst makes this method easy, inexpensive, and successfully useable in reactions with sugars. Thiadiazole derivatives were tested in a panel of three tumor cell lines, MCF-7, HCT116, and HeLa. These compounds initiated biological response in investigated tumor models in a different rate. The MCF-7 is resistant to the tested compounds, and the cytometry assay indicated low increase in cell numbers in the sub- G1 phase. The most sensitive are HCT-116 and HeLa cells. The thiadiazole derivatives have a pro-apoptotic effect on HCT-116 cells. In the case of the HeLa cells, an increase in the number of cells in the sub-G1- phase and the induction of apoptosis was observed.     

Preparation and Structure Characterization of 4-Amino-1,2,4-triazol-5-one Hydrate

4-Amino-1,2,4-triazol-5-one hydrate (ATO·H₂O) was prepared and its structure was analyzed by four-circle diffraction measurement. The obtained results show that the crystal belongs to the triclinic crystal system, space group P 1 with crystal parameters a = 6.432(1), b = 6.551(1), c = 6.740(1) ; = 68.04(1), = 82.18(1), = 81.90(1)°, V = 259.7(7) ³; Z = 2; Dc = 1.510 g/cm³; = 0.131 mm^-1; F(000) = 124. ATO·H₂O was characterized by FT-IR analysis, X-ray diffraction analysis, and single crystal diffraction analysis.     

Quantum-chemical Studies of Pyrimidin-4-ones. 2. Stability in the Gas Phase of Tautomers of Pyrimidin-2,4-dione, 2-Thioxo-, 2-Selenoxo-, 2-Amino-, and 2-Acetylaminopyrimidin-4-ones, and Their 6-Methyl- and 6-Phenyl Derivatives

The relative stability in the gas phase and the most probable reaction centers for electrophilic attack for the tautomers of pyrimidin-2,4-dione, 2-thioxo-, 2-selenoxo-, 2-amino-, and 2-acetylaminopyrimidin-4-ones, and their 6-methyl- and 6-phenyl derivatives have been investigated on the basis of the results of quantum-chemical calculations, using the semi-empirical PM3 method, without taking solvent effects into account.     

5-芳酰氨基-2-苯基-2H-1, 2, 4-噻二唑-3-酮的合成

用1-芳酰基-5-苯基-2-硫代双脲与溴进行氧化成环反应制备了九个新的5-芳酰氨基-2-苯基-2H-1, 2, 4-噻二唑-3-酮, 相应的1-芳酰基-5-苯基-2-硫代双脲可以通过苯基脲与酰基异硫氰酸酯加成制得。     

2-氨基-5-取代-1,3,4-噻二唑与2-氯代-1-(2,4-二氯苯基)乙酮的反应研究

2-氨基-5-烷基/芳基1,3,4-噻二唑与2-氯代-1-(2′,4′-二氯苯基)乙酮在热乙醇中反应生成一系列2-烷基/芳基-6-(4,4-二氯)苯基咪唑并[2-1-b]-1,3,4-噻二唑.产物通过元素分析, IR, 1H NMR, 13C NMR及MS分析,化合物5g的X衍射晶体结构分析表明,产物的芳基是在咪唑并[2-2-b]-1,3,4-噻二唑的6-位而不在5-位.     

Heteroannulated Quinazoline and Quinazolinone Derivatives from (Z)-2-[1-Benzamido-2-(3,4,5-trimethoxyphenyl)]vinyl-3,1-benzoxazin-4(3H)-one

The title compound 1 was prepared and allowed to react with a series of nitrogen nucleophiles to afford the quinazoline and quinazolinone derivatives 2–12 and tetrazole derivative 13. The IR, ¹H NMR, ¹³C NMR, and mass spectra of all the synthesized compounds were discussed.     

Oxidative Addition of N-Aminophthalimide and 3-Amino-2-methylquinazolin-4(3H)-one to Conjugated Azocyclopentenes and Azocyclohexenes

The oxidation of N-aminophthalimide and 3-amino-2-methylquinazolin-4(3H)-one in the presence of conjugated azocyclopentenes, azocyclohexenes, and 3-arylazocyclohexen-2-ones gives adducts at the carbon-carbon double bond corresponding to C-azoaziridines and/or bicyclic 2H-1,2,3-triazoles.     

3-氨基-1,3,4,5-四氢-2H-1-苯并氮杂革-2-酮的合成

以3-溴-1,3,4,5-四氢-2H-1-苯并氮杂--2-酮为起始原料,与苄胺反应制得3-苄氨基-1,3,4,5-四氢-2H-1-苯并氮杂(堇)-2-酮(2);2经5％ Pd/C催化加氢合成了3-氨基-1,3,4,5-四氢-2H-1-苯并氮杂——革)-2-酮(3),总收率90％.最佳氢化反应条件为:以无水乙醇为溶剂,5％ Pd/C用量为总用量的10％,于100℃/2.5 MPa条件下反应10 h,3的收率95.5％,纯度99.7％.5％ Pd/C可套用7次,收率稳定在95％左右.     

Synthesis of heierocyclic compounds from 2-phenyl-1, 2,3-triazole-4-formylhydrazine

2-Phenyl-1, 2, 3-triazole-4-formylhydrazine (2) was prepared by hydrazinolysis of the corresponding ester 1. Reaction of 2 with CS2/KOH gave the oxadiazole derivatives (3) which via, Mannich reaction with different dialkyl amines furnished 3-N, N-dialkyl derivatives (4a-c). Also, condensation of 2 with appropriate aromatic acid in POCl3 yielded oxadiazole derivatives (5a-c), or with aldehydes and ketones afforded hydrazones (6a-c). Cyclization of (6a-c) with acetic anhydride gave the desired dihydroxadiazole derivatives (7a-c). On the other hand, reaction of dithiocarbazate (8) with hydrazine hydrate gave the corresponding triazole derivative (9) which on treatment with carboxylic acids in refluxing POCl3 yielded s-triazole[3,4-b]-1, 3, 4-thiadiazole derivatives (10a-b). The structures of all the above compounds were confirmed by means of IR, 1H NMR, MS and elemental analysis.     

4-(1-硫杂-2亚氨基-3,4-二氮杂-1,4-亚丁基)-4-脱氧阿维菌素B1a的合成

以阿维菌素B1a为原料经选择性C-5羟基保护、氧化合成5-O-烯丙氧羰基-5-氧代-5-脱氧阿维菌素B1a (3), 然后与N-取代氨基硫脲偶联, 缩合产物经MnO2氧化关环、脱保护得到10个未见文献报道的4-(1-硫杂-2-亚氨基- 3,4-二氮杂-1,4-亚丁基)-4-脱氧阿维菌素B1a (7a～7j). 目标化合物结构经1H NMR, 13C NMR和MS确证.     

Efficient syntheses of 3-phosphorylquinolin-4-ones and 3-phosphoryl-1,8-naphthyridin-4-ones

A series of 3-diethoxyphosphorylquinolin-4-ones and 3-diethoxyphosphoryl-1,8-naphthyridin-4-ones containing various substituents at N-1 and C-7 was synthesized in a four-step reaction sequence starting from readily available ethyl 2-chlorobenzoates or ethyl 2-chloronicotinates and diethyl methylphosphonate. Selected quinolinone and naphthyridinone products were transformed into free mono and diacids.     

Reactivity of Amidinium Salts' Access to Benzo[4,5]imidazo[2,1-b]Thiazoles

Abstract

We present the synthesis of benzimidazole substituted at the 1 and 2 positions. The appropriate 2-thioalkyl-substituted benzimidazoles undergo intramolecular cyclization for occuring [4,5] imidazo[2,1-b] thiazoles derivatives.     

Photosynthesis and Molecular Structure of2—Amino—3H—phenoxazin—3—one

1 INTRODUCTION 2-Amino-3H-phenoxazin-3-one (APX) is related to the naturally occurring antineoplastic actinomycin D and has been used as a chemical model of actinomycin D[1]. Usually APX is synthesized from 2-aminophenol with the phenoxazinone synthase in human body[2]. A variety of artificial synthesis methods of APX via the oxidation of 2-aminophenol have also been reported, but each method needs some artificial condition such as chemical catalysis[3～7], natural enzyme[8], UV…     

新型2-胺基-1,3,4-噻二唑类化合物的合成及其抗肿瘤活性的研究

设计合成了一系列新型的N1-(5-取代基-1,3,4-噻二唑-2-基)-N3-取代苯基-脲类化合物,并测定了它们的抗肿瘤活性.标题化合物对肿瘤转移的生物活性实验是以荷Lewis肺癌小鼠为模型的.生物活性表明部分标题化合物对肿瘤的转移和肿瘤生长具有较好的抑制作用.其结构经元素分析、红外光谱及1H NMR确证.