Isovaleric Aldehyde in the Synthesis of 4-Isobutyl-Substituted Pyridine-2(1H)-thiones, 4H-Pyrans, and 1,3-Cyclohexadiene

Cyclocondensation of isovaleric aldehyde with various CH acids [benzoylacetonitrile, malononitrile, cyanothioacetamide, 4-hydroxycoumarin, resorcinol, 3-phenylpyrazol-5(1H)-one, 3-morpholinocrotonanilide] in the presence of amines yields isobutyl-substituted 4H-pyrans, 1,3-cyclohexadiene, and pyridine-2(1H)-thiones. The latter compounds were used in the synthesis of substituted 2-pyridino thioethers and thieno[2,3-b]pyridine.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 476–482.Original Russian Text Copyright © 2005 by Dyachenko.     

新型1,2,4-三取代-1,2,3-三氮唑盐的合成

以邻溴苄醇(1)和水杨醛(2)为原料,经5步反应合成了一种分子内同时具有羟基和1,2,3-三氮唑环的新型类卡宾前体盐中间化合物(7),在三氟甲磺酸酐的催化下,分子内六元环化反应得到一种新型的1,2,4-三取代-1,2,3-三氮唑并三环体系类卡宾前体盐(8),其结构经1H NMR,13C NMR和MS(ESI)表征。     

Simple and Efficient Method for Synthesis of Novel 4-Substituted 1-Acylthiosemicarbazides via One-Pot Multicomponent Reactions

A new one-pot, multicomponent condensation reaction of aldehydes, 2-naphthol, and 1-acylthiosemicarbazides is described as an efficient method for the synthesis of novel 4-substituted 1-acylthiosemicarbazides in the presence of p-toluenesulfonic acid (p-TSA) as a catalyst under two conditions: organic solvent and solvent-free media. The present procedure offers several advantages, such as good yields, low cost, and very easy workup.     

A Novel Synthesis of Aporphines via 3-Phenylphenethylamines

rac-1,2,10-Trimethoxy-aporphine ( 14 ) and rac-2-ethoxy-10,11-dimethoxyaporphine ( 27 ) have been synthesized from the 3-phenylphenethylamines 9 and 22 by a new route. The 8-phenyl-3,4-dihydroisoquinolines 11 and 24 , the oxo-aporphines 12 and 25 and the rac-nor-aporphines 13 and 26 were obtained as intermediates.     

新型紫外线吸收剂1,4-二芳基-1,3-丁二炔类化合物的合成及其性能研究

本文以含有端基炔的芳硫醚为原料，碘苯二乙酯为氧化剂，氯化亚铜为催化剂，室温下反应30 min，合成了1，4-二（2-芳硫基苯基）-1，3-丁二炔化合物。通过¹HNMR、¹³CNMR等对其进行了结构表征，并研究了其光学性质，以及作为紫外线吸收剂在紫外光固化涂料中的应用。结果表明：该类化合物能够有效吸收270~360 nm的紫外光，且光降解程度小，并具有与树脂、单体相容性好、无气味等特点。同时，合成的目标化合物在光固化过程中不参与自由基体系的固化，且增强了涂料及固化涂层的光稳定性，有益于紫外光固化涂料的存储，是一类具有发展前景的紫外光吸收剂。     

A Novel Synthesis of 1-Aminoalkylphosphonates

A nover route has been devised ofr the preparation of a series of 1-aminoalkylphosphonate deisters, precursors to analogues of a-amino acids. The route involves a ficile bromine subsititution at the 1-position of alkylphonate diesters using N-bromisuccinimide, followed by azide ion displacement and catalytic hydrogenolysis.     

Multicomponent Reaction in Ionic Liquid： A Novel and Green Synthesis of 1, 4-Dihydropyridine Derivatives

1, 4-Dihydropyridine (DHP) heterocyclic ring is a common feature of various bioactivecompounds such as vasodilator, bronchodilator and antiatherosclerotic, antitumor, andantidiabetic agents1. Due to their important pharmacological activities, many methods…     

A Novel Synthesis of Vinyl Dithiocarbamates via Phosphonium Ylides

In the presence of potassium carbonate, N, N-dimethylamino thio-carbonyl thiomethyl triphenylphosphonium bromide can form the corresponding ylide in situ, which can undergo Wittig reaction with aldehydes to give vinyl dithiocarbamates in high yields. If the esters were hydrolysized in the presence of mercuric chloride, a new method to lengthen aldehydes by one carbon atom was accomplished.     

A Novel Synthesis of 3-O-Allyl-4, 5, 6-tri-O-benzyl-1-O-（p-methoxybenzyl）-D-myo-inositol

Highly efficient synthesis of the entitled compound was achieved from a readily available myo-inositol derivative. The key step involved a desymmetrization with ( )-camphor dimethyl ketal to give two diastereomers. The two diastereomers could be used to synthesize the same compound by changing the orders to introduce the protective groups.     

Synthesis of isocoumarin, 1-isoquinolone and 4(1H)-quinolone derivatives via seleno-intermediates

The reaction of 2-styrylbenzoic acids 2 with N-phenylselenosuccinimide (N-PSS) affords 3-phenyl-iso-coumarin derivatives 3 and 3,4-dihydro-3-phenyl-4-(phenylseleno)isocoumarins 4 via selenolactonization. The reaction of 2-styrylbenzamides 5 and 1-(2-aminophenyl)-3-phenyl-2-peropen-1-one derivatives 11 with N-PSS also resulted in the formation of 1-isoquinolone 6 and 4(1H)-quinolone derivatives 12 , respectively.     

A Novel and Cheap Synthesis of Artemisia Ketone1 (3,3,6-Trimethylhepta-L,5-Dien-4-One)

The Sequential dialkylation of dimethylaminoacetonitrile with first methallylchloride and then prenylbromide is performed at room temperature using K₂CO₃ in DMF. Subsequent hudrolysis and isomerisation offord artemisia ketone in 77% overall yield.     

Synthesis of A Novel Fulleroaziridine Carrying 4-Deoxy-4''''-demethylepipodophyllotoxin

Functionalization by cycloaddition reactions1 represents a useful strategy to modify fullerenes1,2. Stable cycloadducts are interesting in regarding to the development of new materials with unique physical properties or biological activities3. One of the typical reactions is the cycloadditions of C60 with azide compounds. Wudl and Miyata et al. reported that C60 reacted with alkyl azides4 or benzyl azides5 to give the same kind of adduct azafulleroids with an opened 6,5-ring junction by th…     

A Novel Method for Synthesis of 2, 3, 4-Trisubstituted Furans

Intermolecular addition-cyclization of 1, 3-dicarbonyl compounds with arylbromoallenes in K2CO3 mediated condition afforded 2, 3, 4-trisubstituted furans in good yield.     

1-取代-1H-1,2,3-三唑-4-甲酰胺类化合物的设计合成与生物活性

以吡唑酰胺类杀菌剂为模板,应用"生物等排原理"设计了1,2,3-三唑甲酰胺类具有等排结构的化合物,从丙炔酸出发合成内炔酰胺后,利用Cu(I)催化的1,3-偶极环加成反应,使其与叠氮化合物反应,快速合成了17个结构新颖的1-取代-1H-1,2,3-三唑-4-甲酰胺类化合物.当使用Cu/C催化时,中间体N-(3,4-二甲氧基苯基乙基)丙炔酰胺(4a)与2,2,2-三氟乙基叠氮(14)在三乙胺作添加剂的条件下,可以获得中等收率的偶联的1,2,3-三唑化合物17.所有目标化合物都通过核磁共振氢谱,元素分析或高分辨质谱的确认,并测试了其生物活性.结果表明,该类化合物虽无明显的杀菌活性,但在100μg/mL测试浓度下,化合物6a,6e,6k和61均表现出较好的除草活性.     

新型1,4-苯并二氮杂?-5-酮衍生物的合成及抗肿瘤活性初探

以邻硝基苯甲酸衍生物为底物,经3步反应并在最后一步使用了乙酰丙酮钼和三氟甲磺酸铜为催化剂,共合成了8个新型的1,4-苯并二氮杂?-5-酮衍生物（4a~4h）,其结构经¹H NMR,¹³C NMR和HR-MS(ESI)表征。并测试了4a~4h对肺癌（A549）、乳腺癌（MDA-MB-231）、宫颈癌（HeLa）等3种肿瘤细胞系的抑制活性。结果表明：目标化合物对所有肿瘤细胞系均有一定的抑制活性。其中9-氯-2-(丙-1-烯-2-基)-4-(2-(噻吩-2-基)乙基)-1,2,3,4-四氢-5H-苯并[e][1,4]二氮杂-5-酮(4e)对A549的IC₅₀可达1.7μM。而阳性对照药苯达莫司汀（Bendamustiune）和伏立诺他（SAHA）对A549没有明显的抑制作用。      

新型3-氟苯基-1H-咪唑基甲胺基衍生物的合成

以4-咪唑甲醛为原料,通过保护、格氏反应、酰化、取代、脱甲基或甲酯共5步反应合成了4种新型的3-氟苯基-1H-咪唑基甲胺基衍生物,5步总收率分别为21%、18%、22%和24%,终产物结构经1H NMR、13C NMR和HR-MS(ESI)确证。     

A Novel and Convenient Synthesis of Coenzyme Q1

Abstract

A convenient and efficient synthetic route to Coenzyme Q₁ (6) starting from 3,4,5‐trimethoxytoluene (1) is described. The key features of this synthesis include the Diels–Alder reaction of 2,3‐dimethoxy‐l,4‐benzoquinone (3) with cyclopentadiene and the introduction of a C₅ side chain to 4,5‐dimethoxy‐2‐methyltricyclo[6.2.1.0^2,7]undeca‐4,9‐diene‐3,6‐dione (4) under mild conditions, (6) was obtained in overall 60% yield.     

Synthesis of Mesoporous Silica and Ti-containing Molecular Sieves via A Novel Assembly

Although titanium silicate-1 (denoted TS-1) is an effective catalyst for the selective oxidation of organic substrates1,2, the substrates that can be oxidized by TS-1 are limited to species having kinetic diameters ( 6 ?. However, the recently discovered silica-based mesoporous molecular sieve offers new opportunities for the preparation of large-pore TS-1 analogs capable of transforming larger organic molecules. The Ti-containing mesoporous molecular sieve catalysts thus obtained, are promi…     

Synthesis of A Novel Fulleroaziridine Carrying 4-Deoxy-4′-demethylepipodophyllotoxin

A novel fulleroaziridine 2 with a closed 6,6-ring junction was synthesized from [60]fullerene and 4-azido-4-deoxy-4′-demethylepipodophyllotoxin 1 in 1, 2-dichlorobenzene at 110℃ for 45 h, in a yield of 39.3 % based on consumed C60. The structure of the product was characterized by NMR and MS.