X-ray Structure of 1- (3' -Phenyl-4' -morpholinyl-2' 5' - dithiole-1' - ylidene)-3, 4-biscarboethoxy-2-thionaphthalene

1INTR0DUCTIONa-Thiocarbonylthioformamideshavebeensynthesizedsince1980[l-23,however,thereisn0reP0rtofthesecomP0undsrelatedtheirpropertiesandreactivities(3).Ac-cordingtothepublishedpapers('-",adithioketone,adithioesterandadithioth-ioesteraresnitablefort4 2JcycloadditionwithalkenicandacetylenicdienophileS.Wewanttoknowwhethera-thiocarbonylthioformamideshavethesamecharacters,thereforethereactionofathiobenzoylthioformmorpholine(1)withdiethylacetylenedicarboxylate(2)wasexplored.Theredultsshowth…     

The synthesis and photoactivated cytotoxicity of novel 5-phenyl-3- （2,2＇：5＇,2″-terthien-5-yl）-4,5-dihydro-lH-pyrazolines

A series of novel 5-phenyl-3-（2,2＇：5＇,2″-terthien-5-yl）-4,5-dihydro-lH-pyrazolines were synthesized in this report. Their photoactivated cytotoxicities on the 5podoptera litura （SL） cell line were evaluated using the MTT method. It was noticed that the inhibitory activities of all the conjugates was enhanced when irradiated with UV-A light. Compounds 4, 6 and 8 were found to be most effective with inhibition rates of 88.1%, 88.0%, and 90,5%, respectively, For compound B, the inhibition rate value was only slightly enhanced under the irradiation treatment （78.3%） compared to the dark treatment （74.8%）. The relationship analysis between structure and activity showed that the middle thiophene ring played an important role on the inhibitory activities. It was shown that these compounds could be the potential candidates for new photoactivated pesticides.     

Conformational polymorphism and thermochemical analysis of 5,5' '-bis[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)ethyl]-2,2':5',2' ':5' ',2' '-quaterthiophene

The titled compound exists as two polymorphic solid phases (denoted form-I and form-II). Form-I obtained by as-synthesized material is a more stable phase. Form-II is a less stable phase. Spontaneous solid-solid transformation from form-II to form-I is observed in the temperature range between room temperature and the melting point of form-I (Tm = 156.5 degrees C), and its activation energy is estimated to be 96 kJ mol-1 by Arrhenius plot. The solid-solute-solid transformation (recrystallization from solution) from form-II to form-I is also observed. In contrast, form-II is obtained only by a solid-melt-solid transformation from form-I. Therefore, the system of two polymorphs is monotropic. The solid-state NMR measurement shows that form-I has the molecular conformation of complete S-syn-anti-syn in the oligothiophene backbone, whereas form-II has that of S-all-anti. With the solution NMR data, the polymorphism could not be observed. Therefore, the polymorphs originate from the different molecular packing involving the conformational change of the molecule. This unique property is attributed to the extra bulky terminal groups of the compounds. However, despite the extra bulky terminal groups, the mentioned polymorphism is not observed in the titled compound analogue which has S-all-anti conformation (like form-II).     

3-(2-二唑啉基)-色酮类化合物的合成研究

报道了取代的邻羟基苯乙酮(1a～1e)经Vilsmeier-Haack反应一步制得3-醛基色酮(2a～2e),2a～2e与取代的芳酰肼(3a～3c)缩合制得15个酰腙类化合物(4a～4o),4a～4o在醋酸酐作用下关环得15个3-(2-苝二唑啉基)-色酮(5a～5o),并通过元素分析,IR,~1H NMR和MS诺数据确证了上述化合物的结构。     

8-5’新木脂素类化合物的合成方法研究

对羟基桂皮酸甲酯和阿魏酸甲酯分别在氧化银催化下发生自由基仿生氧化偶联反应, 合成得苯并二氢呋喃环结构化合物1, 1经甲基化反应得2. 1a和1和2分别在无水碳酸钾、10%氢氧化钠水溶液等不同的碱性条件下进行反应, 获得了11个苯并二氢呋喃环开环产物, 即8-5’新木脂素类化合物3a～9b, 实现了由苯并二氢呋喃新木脂素向8-5’新木脂素的转变, 也为合成芪类化合物提供了一种新方法. C-8位上的吸电子基团如酯基的影响使苯并二氢呋喃环易在碱性条件下开环形成8-5’新木脂素类化合物．所合成化合物的结构由MS, IR, 1H NMR和13C NMR进行了表征.     

Unusual Recyclization of 2(1-Bromostyryl)-4-oxo-1'3-benzoxazinium Perchlorate into 2'3'4'5-Tetrahydro-1'4-benzoxazepine-4'5-dione

Russian Journal of Organic Chemistry -     

5',6',7',8'-Tetrahydro-1'H,3'H-spiro[cyclohexane-1,2'-quinazolin]-4'-one in Mannich reaction

The Mannich aminomethylation of 5',6',7,'8'-tetrahydro-1'H,3'H-spiro[cyclohexane-1,2'-quinazolin]-4'-one leads to formation of a heterocyclic system containing an annelated azabicyclic fragment. Hydrolysis of the indicated spirans gives 3-azabicyclo[3.3.1]nonanes.     

Synthesis of [ethylene-1-(eta(5)-4,5,6,7-tetrahydro-1-indenyl)-2- (eta(5)-4',5',6',7'-tetrahydro-2'-indenyl)]titanium dichloride, the elusive isomer of the Brintzinger-type ansa-titanocenes

We present a short synthesis of 1-(2-indenyl)-2-(3-indenyl)ethane (5) and a method for its conversion to the ansa-metallocene [ethylene(eta5-inden-1-yl)(eta5-inden-2-yl)]titanium dichloride (13). The synthetic strategy applied to prepare bisindene 5 relies on the efficient alkylation of 2-(phenylsulfonyl)indane followed by HMPA-assisted E1cB-elimination of phenylsulfinate. This tandem sequence circumvents the predisposition of indene to undergo C(1)-alkylation and enables access to C(2)-substituted indenes. The key step in the synthesis of the title ansa-titanocene (4) features a previously unreported equilibration step to generate the bis(indenide anion) of 5. Complexation with TiCl4.(THF)2 followed by hydrogenation of the product metallocene furnishes ansa-titanocene 4.     

Solar one-way photoisomerisation of 5',8-cyclo-2'-deoxyadenosine

Under sunlight irradiation (5'S)-5',8-cyclo-2'-deoxyadenosine 2 photoisomerises to the (5'R) isomer 1, which is the more easily repaired damage when these cyclopurine lesions are formed in DNA.