Synthesis and Crystal Structure of 2-Ethoxy-3-n-butyl-benzofuro[2,3-d]pyrimidin-4（3H）-one

The crystal structure of the new title compound 2-ethoxy-3-n-butyl- benzofuro[2,3d]pyrimidin-4（3H）-one （C16H18N2O3, Mr = 286.32） has been prepared and determined by singlecrystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 13.7167（14）, b = 13.113（1）, c = 8.378（1） A, β = 98.992（2）^o, V = 1488.4（3） A^3, Z = 4, Dc = 1.278, F（000） = 608, μ = 0.089 mm^-1, MoKa radiation （2 = 0.71073）, R = 0.0498, wR = 0.1238 for 2336 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that all ring atoms in the benzo[4, 5]furo [2,3-d] pyrimi- dinone moieties are almost coplanar.     

Efficient synthesis of 5,6-dihydrothieno[3′,2′:4,5]-thieno[2,3-d]pyrimidin-4(3H)-ones via an iminophosphorane

5,6-Dihydrothieno[3′,2′:4,5]thieno[2,3-d]pyrimidin-4(3H)-ones 6 were synthesized in yields of 71-87%by a consecutive method,which includes aza-Wittig reaction of iminophosphorane 3 with aromatic isocynate to give carbodiimide 4 and subsequent reaction of 4 with various amines,phenols or alcohols in the presence of catalytic amount of sodium ethoxide or solid potassium carbonate.     

Efficient Synthesis of 3,5,6,8-Tetrahydro-4H-thiopyrano[4′,3′:4,5]· thieno[2,3-d]pyrimidin-4-ones via an Iminophosphorane

3,5,6,8-Tetrahydro-4H-thiopyrano[4′,3′:4,5]thieno[2,3-d]pyrimidin-4-ones(7) were synthesized via the base catalytic reactions of amines or phenols with carbodiimides(5), which were obtained from the aza-Wittig reactions of iminophosphoranes(4) with aromatic isocyanates.     

A new route to the synthesis of thieno[2,3-d]pyrimidin-4（3H）-one derivatives catalyzed by 12-tungstophosphoric acid （H3PW12040）

Heteropoly acid H3PW12040 （PW） has been used as an effective catalyst for the synthesis of thieno[2,3-d]pyrimidin-4（3H）-one derivatives. The present methodology offers several advantages, such as high yields, short reaction times, mild reaction condition and a recyclable catalyst with a very easy work up.     

A Selective Synthesis of 2-Alkylamino-5, 6, 7, 8-tetrahydrobenzothieno[2, 3-d]pyrimidin-4（3H）-ones

2-Alkylamino-5, 6, 7, 8-tetrahydrobenzothieno [2,3-d] pyrimidin-4(3H)-ones 7 were synthesized by a new selective synthetic method, which includes aza-Wittig reaction of iminophosphorane 4 with aromatic isocynate to give carbodiimide 5 and subsequent reaction of 5 with various aliphatic primary amine in the presence of EtO^-Na^ .     

7-Deazapurines:Synthesis of new pyrrolo[2,3d]pyrimidin-4-onescatalyzed by a Brφnsted-acidic ionic liquid as a green and reusable catalyst

<正>Some new 2-aryl-3,7-dihydro-4H-pyrrolo[2,3-d]pyrimidin-4-ones have been prepared through cyclocondensation of 2-amino 1H-pyrrole-3-carboxamides with aromatic aldehydes followed by air oxidation in the presence of 3-methyl-1-(4-sulfonic acid)butylimidazolium hydrogen sulfate[(CH_2)_4SO_3HMIM][HSO_4],a Br(?)nsted-acidic ionic liquid,as a green and reusable catalyst in solvent-free conditions.     

Studies on the esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one with acid chlorides under different conditions

The esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one （4） with acid chlorides afforded normal oxime-esters 3a-e in 35-78% yields in presence of excessive 4-dimethylaminopyridine as the acid scavenger, whereas the reactions gave unexpected 8-substituted products N-（8-chloro-4-methyl-2-oxo-2H-furo-[2,3-h]chromen-9-yl）amides （5a-c） and 4-methyl-2,9-dioxo-8,9-dihydro-2H-furo[2,3-h]chromen-8-ylcarboxyloates （6d-e） by using excessive acid chlorides. The structures of 10 new compounds were determined by 1H NMR, 13C NMR, MS and HRMS, and the possible mechanism for the formation of unexpected products 5a--c and 6d-e was also proposed.     

Differentiation of Constitutional Isomer of 2,2a,3,4-Tetrahydro- 4-methyl-2a-phenyl-2- （thiophen-2-yl）- 1H-azeto [-2,1-d] [- 1,51benzothiazepin-1-one-5-oxide and Fragmentations of 2,3-Dihydro-2,4-diphenyl-1,5-benzothiazepine-l-oxide／- 1,1-d

Mass spectrometric behaviour of 2,2a, 3,4-tetrahydro-4-methyl-2a-phenyl-2- (thiophen-2-yl)- 1H-azeto [-2,1-d-J1-1,5-]benzothiazepin-l-one-5-oxide and 2,3-dihydro-2,4-diphenyl-1,5-benzothiazepine-l-oxide/-1,1-dioxide have been studied with the aid of mass-analyzed ion kinetic energy spectrometry and accurate mass measurements under electron impact ionization. The monooxide derivatives showed a tendency to eliminate an alkene or an oxygen atom. 1H-Azeto[-2,1-d][1,5]benzothiazepin-1-one-5-oxide could also eliminate the thiophen- 2-ylketene molecule via a reverse [-2 q- 2 ~ cycloaddition. 2,3-Dihydro-2,4-diphenyl- 1,5-benzothiazepine-1-oxide/-1, 1-dioxide could eliminate SO2 or SO, respectively. The structure of 2,2a, 3, 4-tetrahydro-4-methyl-2a-phenyl-2- (thiophen-2-yl)-1H-azeto 1-2,1-d-] [1,5 -] benzothiazepin-1-one-5-oxide was identified on the basis of its fragmentation. The identification was supported by the fragmentations of model compound, 2,3-dihydro-2,4-diphenyl-1,5-benzothiazepine-1-oxide/-1,1-dioxide.     

One-pot synthesis of novel pyrido[2,3-d]pyrimidines using HAp-encapsulated-γ-Fe2O3 supported sulfonic acid nanocatalyst under solvent-free conditions

Novel pyrido[2,3-d]pyrimidine derivatives were synthesized through a one-pot three-component approach using HAp-encapsulated-γ-Fe2O3[γ-Fe2O3@HAp-SO3H]catalyzed condensation of 6-arnino-2-（methylthio or ethylthio）pyrimidin-4（3H）-one,Meldrum＇s acid and aryl aldehydes at 60 ℃ and under solvent-free conditions.In this protocol the use of nanocatalyst provided a green,useful and rapid method to generate the products in short reaction times and excellent yields（88%-94%）.     

Synthesis and Crystal Structure of 1-（4-Fluorophenyl）-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H）-one

The crystal structure of the title compound 1-(4-fluorophenyl) -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H) -one(C23H21FN4O2S,Mr = 436.5) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854(3) ,b = 17.2678(4) ,c = 18.1828(5) ,β = 99.364(2) °,V = 4332.58(18) 3,Z = 4,Dc = 1.338,F(000) =1824,μ = 0.185 mm-1,MoKa radiation(λ = 0.71073) ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I > 2σ(I) . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5(1H) -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.     

Synthesis of 5-glycopyranosylamino-pyrano[2,3-d]pyrimidin-2-one derivatives

Summary Three series of 3-substituted 5-glycopyranosylamino pyrano[2,3-d]pyrimidin-2-one derivatives,3 a–c,4 a–c, and5 a–c have been prepared by treatment of the corresponding 1,4-dihydro-6-glycopyranosylamino pyrimidin-4-ones1 a–c with malonic, methyl malonic and ethyl malonic acids, respectively.

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Synthese von Derivaten des 5-Glucopyranosylaminopyrano[2,3-d]pyrimidin-2-on

Zusammenfassung Es wurden drei Serien von 3-substituierten 5-Glucopyranosylaminopyrano[2,3-d]pyrimidin-2-onen (3 a–c,4 a–c und5 a–c) mittels Behandlung der entsprechenden 1,4-Dihydro-6-glucopyranosylamino-pyrimidin-4-one (1 a–c) mit Malon-, Methylmalon- bzw. Ethylmalonsäure dargestellt.

     

Synthesis of functionalized 2,3-dihydrothieno[2,3-d]pyrimidin-4(1H)-ones and their recyclization to 2,3-dihydrothieno[3,4-d]pyrimidin-4(1H)-ones

By the reaction of 6-aryl(alkyl)amino-5-cyano-2,3-dihydro-1,3-thiazin-4(10)-ones with α-halogenoketones in the presence of triethylamine, 2,3-dihydrothieno[2,3-d]pyrimidin-4(1H)-ones have been synthesized and their acid-catalyzed recyclization to 2,3-dihydrothieno[3,4-d]pyrimidin-4(1H)-ones has been found and studied. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:104–111, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20181     

选择性合成双[噻吩并[2,3-d]嘧啶-4(3H)-酮]

以2-氨基-4-三氟甲基-5-甲基-噻吩-3-羧酸乙酯(1)为起始原料制得膦亚胺2.在碳酸钾的催化下,膦亚胺2与芳基异氰酸酯和伯二胺的氮杂Wittig反应制得嘧啶环上2,2’取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]3;膦亚胺2与烷基异氰酸酯和伯二胺的氮杂Wittig反应制得嘧啶环上3,3’取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]4.化合物3的核磁共振氢谱表明关环反应在嘧啶环的2,2’位;化合物4的核磁共振氢谱表明关环反应在嘧啶环的3,3’位.对合成反应机理的推导及目标产物核磁共振氢谱数据的分析解释了此合成反应的选择性.     

Regioselectivity of Intramolecular Electrophilic Cyclization of 2-(Alkenylsulfanyl)thieno[2,3-d]pyrimidin-4(3H)-ones with p-Methoxyphenyltellurium Trichloride

Russian Journal of Organic Chemistry - 3-Phenyl-2-(prop-2-en-1-ylsulfanyl)-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4(3H)-one reacted with 4-methoxyphenyltellurium trichloride in a...     

Transformations of 5-methyl-6-carbethoxy-3,4-dihydrothieno-[2,3-d]pyrimidine for synthesis of 4-methoxy-, 4-alkylamino-, and other derivatives of thieno[2,3-d]pyrimidine

4-Chloro derivatives of thieno[2,3-d]pyrimidine are formed by the action of phosphorus oxychloride on 5-methyl- and 5-methyl-6-carbethoxythieno[2,3-d]pyrimidin-4-ones. Action of nucleophilic reagents (methanol, sodium methylate, primary and secondary amines) on these chloro derivatives gave 4-methoxy-, 4-alkylamino-, and 4-dialkylamino substituted thieno[2,3-d]pyrimidines. It was found that 4-methoxy derivatives of thieno[2,3-d]pyrimidines undergo a thermal rearrangement into 3-methyl-substituted thieno[2,3-d]pyrimid-4-ones. In the bromination of 5-methyl-4-chloro- and 5-methyl-4-methoxy-substituted thieno[2,3-d]pyrimidines by N-bromosuccinimide, 5-bromomethyl derivatives of thieno[2,3-d]pyrimidine are formed, from which, by the action of primary and secondary amines, 5-aminomethyl-substituted thieno[2,3-d]pyrimidines were obtained. A synthesis of 1,2,3,4-tetrahydro-1,3-diazepino[4a,10-d,e] thieno[2,3-d]pyrimidines was also carried out.Deceased.Translated from Khimiya Geterotsilicheskikh Soedinenii, No. 7, pp. 925–928, July, 1985.     

Efficient Synthesis of 6-(1H-1,2,4-Triazol-1-yl)-thieno[2,3-d]pyrimidin-4(3H)-ones via an Iminophosphorane

Ethyl 2-amino-4-methyl-5-(1H-1,2,4-triazol-1-yl)thiophene-3-carboxylate 2, obtained from Gewald reaction of 1-(1H-1,2,4-triazol-1-yl)acetone 1 with ethyl cyanoacetate and sulfur, was transferred into iminophosphorane 3. Further reaction of 3 with aromatic isocyanates gave carbodiimides 4, which were treated subsequently with a secondary amine to give 6-(1H-1,2,4-triazol-1-yl)-thieno[2,3-d]pyrimidin-4(3H)-ones 6 in good yields in the presence of a catalytic amount of sodium ethoxide.     

A NOVEL SYNTHESIS OF 2-SUBSTITUTED-4H-THIENO [2,3-d][1,3] OXAZIN-4-ONE AND 2,3-DISUBSTITUTED THIENO [2,3-d]PYRIMIDIN-4(3H)-ONE DERIVATIVES

Abstract

The synthesis of acetic 2-{[1-methyl-2-(4-oxo-5,6,7,8-tetrahydro-4H-benzo [4,5]-thieno [2,3-d] [1,3-oxazin-2-yl)ethylidene]amino}-4,5,6,7-tetrahydrohenzo[b]thiophene ?3-carboxylic acid anhydride 5 and 2-(oxopropyl)-5,6,7,8-tetrahydro-4H-benzo-[4,5] thieno[2,3-d][1,3]oxazin-4-one 7, has been achieved in three steps from ethyl 2-amino-4,5,6,7-tetrahydrobenzo(b]thiophene-3-carboxlate 1 via the reaction with ethyl acetoacetate followed by hydrolysis and acetic anhydride-induced cyclization. The 2-substituent in compound 5 has two functional groups i.e. active methylene and acid anhydride which are suitably located for intramolecular transformation. Thermal and/or base catalyzed intramolecular cyclization of 5 afforded 2-(4-acetoxy-(hydroxyl)-2-methyl-5,6,7,8-tetrahydrobenzo[4,5] thieno[2,3-b]pyridin-3-yl)-5,6,7,8- tetrahydro-4H-benzo[4,5]thieno[2,3-d] [1,3]oxazin-4-one 10 and 9 respectively. Treatment of 5 with hydrazine hydrate, aromatic and/or heterocyclic amines induced the same intramolecular cyclization with a concomitant oxazine-pyrimidine interconversion to give 3-amino(aryl or heteryl)-2-(4-hydroxy-5,6,7,8-tetrdhydrobenzo-[4,5]thieno[2,3-b]pyridin-3-yl)-3,4,5,6,7,8-hexahydrobenzo[4,5] thieno[2,3-d] pyrimid in-4-one 11–14 respectively.     

Derivatives of condensed thieno[2,3-d]-pyrimidines. 20. Synthesis of 2-substituted 5,6-dihydro-8H-pyrano[4′,3′:4,5]thieno[2,3-d]pyrimidin-4(3H)-ones and 5,6,7,8-tetrahydrobenzo-[b]thieno[2,3-d]pyrimidin-4-ones

We have developed a method for obtaining 2-substituted 3-amino-6,6-dimethyl-5,6-dihydro-8H-pyrano[4′,3′:4,5]-and 5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]pyrimidin-4(3H)-ones, converted by deamination to the corresponding dihydropyranothieno-3H-pyrimidinones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 441–444, March, 2006.     

吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶化合物的合成与生物活性

应用串联氮杂Wittig反应设计合成了一系列新的2-烷氨(芳氧)基-3,8-二苯基-5-芳基-6-甲基-5,8-二氢-4H-吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶-4(3H)-酮衍生物。通过氢核磁共振谱仪(1H NMR)、傅里叶变换红外光谱仪(FTIR)和元素分析等方法对所合成的化合物进行了结构表征,用X射线单晶衍射确证了化合物2-二正丙基氨基-3,8-二苯基-5-(4-甲基苯基)-6-甲基-5,8-二氢-4H-吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶-4(3H)-酮(Ⅲi)晶体结构。室内的杀菌和杀虫活性测试结果表明:目标化合物具有一定的杀菌活性,其中部分化合物对黄瓜灰霉菌(Botrytis cinereapers)在50 mg/L剂量下抑制率达到90%以上,显示了优异的杀菌活性;对水稻褐飞虱无明显的杀虫活性,但发现对粘虫具有较高的杀灭效果,大多数抑制率达到90%以上。