Synthesis of 2,5 -Bis(4-methyl-2-thienyl)thiophene and 2,5-Bis(4-methyl-2-thienyl)pyrrole

Syntheses of 2,5-bis(4-methyl-2-thienyl)thiophene 3 and 2,5-bis(4-methyl-2-thienyl)pyrrole 4 are described. The key step involves Stetter reaction between 4-methyl-2-thiophenecarboxaldehyde and divinyl sulfone. Cyclizaton of the resulting 1,4-bis-(4-methyl-2-thienyl)-1,4-butanedione 2 with Lawesson's reagent gives 2,5-bis(4-methyl-2-thienyl)thiophene 3, whereas condensation with ammonium acetate provides the 2,5-bis(4-methyl-2-thienyl)pyrrole 4.     

Photochromic Dihetarylethenes. 8. A Novel Route to the Synthesis of 3,4-Bis(2,5-dimethyl-3-thienyl)furan-2,5-dione as a Potential Photochrome

There is proposed, and in the case of 2,5-dimethylthiophene carried out, a novel route to the synthesis of 3,4-dithienylfuran-2,5-dione type photochromes. This is done in two stages, the first being a Friedel-Crafts reaction of the starting thiophene with the dichloride of squaric acid and the second is a Baeyer-Villiger oxidation of the 3,4-bis(2,5-dimethyl-3-thienyl)cyclobutenedione to give the target 3,4-bis(2,5-dimethyl-3-thienyl)furan-2,5-dione.     

Synthesis and Photoisomerization of 3-Cyano-6,6-dimethyl-4-(4-nitrophenylvinyl)-5,6-dihydropyran-2-one

The condensation of 4-nitrobenzaldehyde with 3-cyano-4,6,6-trimethyl-5,6-dihydropyran-2-one leads to the formation of a crotonization product and a compound of the Michael adduct type. The main product of the photochemical conversion of (E)-3-cyano-6,6-dimethyl-4-(4-nitrophenylvinyl)-5,6-dihydropyran-2-one is the Z-isomer. Investigation of the photoisomerization of 3-cyano-6,6-dimethyl-4-(4-nitrophenylvinyl)-5,6-dihydropyran-2-one by the semiempirical AM1 method showed that in the ground state the E-isomer was thermodynamically more stable than the E-isomer. E-Z-photoisomerization is effected most probably through the lowest excited singlet state S₁.     

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[(5-(2,4-dichlorophenoxy)-3-methyl-1-phenyl-1H-pyra-zol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 (C28H23Cl2N5O2, Mr = 532.41) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1 with a = 8.9438(4), b = 11.6065(5), c = 14.2215(6) , α = 112.566(1), β = 92.324(2), γ = 102.91(1)o, V = 1315.65(10) 3, Z = 2, Dc = 1.344 g/cm3, μ(MoKα) = 0.282 mm-1, λ = 0.71073 , F(000) = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections (I > 2σ(I)). X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra-and intermolecular C(12)-H(12)···O(1) and C(28)-H(28)···O(1)#1 hydrogen bonds were observed in the title compound.     

Reactions of 2,5-di(2-thienyl)pyrroles

We have studied the possible modification of 2,5-di(thienyl)pyrroles with the aim of preparing compounds which can serve as precursors of polymers and monomers showing electrical conductivity and specific photochemical properties. Dedicated to Boris Aleksandrovich Trofimov on his 70^th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1356–1365, September, 2008.     

Synthesis and Bioactivity of Novel Aminomethyl-2-（1, 2,4-triazol）-4, 4-dimethyl-3-pentanone （ol）

3, 3-Dimethyl-1-(1,2,4-triazol)-2-butanone was treated with aqueous formaldehyde to give an additional product, and subsequent elimination by acetic anhydride yielded 4,4-dimethyl-2-(1,2,4-triazol)-1-penten-3-one. Further addition with substituted amines provideda series of (1,2,4-triazol)-4,4-dimethyl-3-pentanone, which were then reduced by KBH4 to obtaina series of (1,2,4-triazol)-4,4-dimethyl-3-pentanol. Their structures were confirmed by ^1HNMR and elemental analysis. The results of bioassay showed that the title products possess good fungicidal activities.     

Novel synthesis of 2-amino-3-hetaryl-4(5H)-oxothiophenes

3-Cyano-3-hetaryl-2-oxopropyl thioacetates were obtained by the acylation of hetarylacetonitriles with acetylmercaptoacetyl chloride. Their reaction with amines led to the formation of 2-amino-3-hetaryl-4(H)-oxothiophenes. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 680–685, May, 2006.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

2,5-二甲基-4-羟基-3(2H)呋喃酮的合成

以乙酰丙酮(1)为原料，经电解氧化偶联，Paal-Knorr闭环，Baeyer-Villiger氧化，水解等步骤，合成了一种重要的杂环香料，2,5-二甲基-4-羟基-3(2H)呋喃酮(6)。     

Synthesis of （S）-2-（3-Arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）ethoxy]phenyl}propanoic Acids

The synthesis of （S）-2-（3-arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR.     

Synthesis and Crystal Structure of 4,4'-(4-(1-Naphthyl)-4-phenyl-1,3-butadienylidene)-bis[N,N-diethylbenzenamine]

1 INTRODUCTION Organic photo-conductors (OPCs), due to their great advantages over inorganic ones, have been widely used in xerography and holography and aroused considerable interest in the past several de- cades. Recently, almost all OPCs are of a layered structure with a thin charge generation layer (CGL) and a charge transport layer (CTL). Current resear- ches are directed to both improving the chara- cteristics of existing OPCs and developing new ma- terials for future applicati…     

1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物的合成及抑菌活性

将邻羟苯基引入1,2,3-三唑结构中, 设计合成了10个1-(4-取代苯基)-4-苯基-5-取代-1,2,3-三唑类衍生物. 首先, 以对位取代的芳胺为原料, 经重氮化、叠氮化、闭环和缩合反应制得1-(4-取代苯基)-4-苯基-5-水杨醛亚胺-1,2,3-三唑类衍生物(3a~3e), 再用硼氢化钠还原制得1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物(4a~4e). 目标化合物的结构经核磁、IR及元素分析确认. 抑菌活性测试表明, 当质量浓度为0.1 mg/L时, 除化合物3e和4e外, 所有化合物对白色念球菌的抑菌率均达95%以上, 对大肠杆菌的抑菌率达85%以上, 具有强抑菌活性, 表明该类化合物在抗菌药物开发方面有重要应用价值.     

4－羟基－2，5－二甲基－3（2H）呋喃酮的合成

总结了食品增香剂４－羟基－２．５－二甲基－３（２Ｈ）呋喃国的合成方法，包括近期的合成研究进展，对一些合成方法的优缺点作了评述。参考文献２８篇。     

Synthesis,Crystal Structure and Antitumor Activity of 2-(3-Methyl-5-(methylthio)-4H-1,2,4-triazol-4-yl)isoindoline-1,3-dione

The title compound 2-(3-methyl-5-(methylthio)-4H-1,2,4-triazol-4-yl)isoindoline-1,3-dione(C12H10N4O2S, Mr = 274.30) has been synthesized by a three-step procedure including the cyclization, hydrazinolysis and substitution reactions, and its crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 12.264(3), b = 14.646(3), c = 14.349(4) , β = 91.69(3)°, μ = 0.255 mm-1, Mr = 274.30, V = 2576.2(10) 3, Z = 8, Dc = 1.414 g/cm3, F(000) = 1136, R = 0.0487 and w R = 0.1329 for 4048 observed reflections with Ⅰ 2σ(Ⅰ). In addition, the preliminary bioassay suggested that the title compound 6 exhibits relatively good antitumor activity against HT-29 and MCF-7.     

Synthesis of substituted 1,2-di(alkylsulfonyl)indolizines. Molecular and crystal structure of 3-(4-fluorobenzoyl)-6-methyl-1,2-di(propylsulfonyl)indolizine

The reactions of substituted pyridinium salts with E-1,2-di(alkylsulfonyl)-1,2-dichloroethenes proceed regiospecifically. Heating of these reagents in chloroform in the presence of a threefold excess of Et₃N affords substituted 1,2-di(alkylsulfonyl)indolizines in high yields. The structures of the reaction products were confirmed by physicochemical methods, including X-ray diffraction. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1205–1209, May, 2005.     

Molecular and crystal structure of <Emphasis Type="Italic">trans</Emphasis> and <Emphasis Type="Italic">cis</Emphasis> isomers of 3-cyano-4-[2-(4-methoxyphenyl)vinyl]-6,6-dimethyl-5,6-dihydro-2H-pyran

Monocrystals of the trans and cis isomers of 3-cyano-4-[2-(4-methoxyphenyl)vinyl]-6,6-dimethyl-5,6-dihydro-2H-pyran have been obtained and an X-ray structural analysis of them has been carried out. Both compounds have a molecular structure corresponding to symmetry group C₁. The heterocyclic ring is in a distorted envelope conformation. The crystals of the trans isomer are rhombic and have a fir-tree type of packing. The crystal packing of the cis isomer is formed by pairs of molecules, each of which consists of only one enantiomer. *Dedicated to deeply respected Professor Hank van der Plas in connection with his jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 535-540, April, 2009.     

Synthesis and Structures of 1-(2-Thienylmethyl)-2-(2-thienyl)bezimidazole and Its Cu(I) and Ag(I) Complexes

N,N′-1,2-phenylenebis(2-thienylideneimine) (PTI) can be obtained via the condensation of o-phenylenediamine and thiophene-2-carboxaldhyde in cyclohexane. It isomerized to its cyclic form 1-(2-thienylmethyl)-2-(2-thienyl)benzimidazole (TMTBI) readily in the presence of Fe₂(CO)₉. Coordination reactions of PTI with cuprous iodide and silver nitrate in acetonitrile resulted in the formation of [Cu(TMTBI)I]₂ and [Ag(TMTBI)₂]NO₃, respectively, in which the PTI ligand had been isomerized to TMTBI. Both PTI, TMTBI, and complexes were characterized by NMR, IR, and Mass spectroscopies as well as elemental analysis. The crystal structures of TMTBI and [Cu(TMTBI)I]₂ were determined by single-crystal X-ray diffraction. Crystallographic details for X-ray structures are as follows. TMTBI is crystallized in the monoclinic space group P2₁/n with a = 8.953(3), b = 9.150(1), c = 17.436(2) Å, β = 93.73(2)°, and Z = 4. The final R factor was 0.050 (R_w = 0.066) for 1337 observed reflections. Complex [Cu(TMTBI)I]₂ is crystallized in the triclinic space group $ {\rm P}\bar 1 $ with a = 9.961 (2), b = 10.825(2), c = 9.184(2) Å, α = 112.98(2), β = 110.78(2), γ = 88.71 (2)°, and Z = 2. The final R factor was 0.056 (R_w = 0.057) for 2363 observed reflections.     

新型3-氧-3-芳基-2-芳基腙-丙腈衍生物的合成及其抗癌活性

以取代苯甲酸、乙腈和取代苯胺为原料,经4步反应合成了31个3-氧-3-芳基-2-芳基腙-丙腈衍生物(5a~5z和5Ⅰ~5Ⅴ),其中5a~5z为新化合物,其结构经1H NMR,13C NMR和MS表征。以STAT3抑制剂姜黄素和Stattic为对照,测试了5对人肝癌细胞、人前列腺癌细胞、人乳腺癌细胞(三株STAT3相关细胞)及小鼠胚胎细胞(STAT3低表达细胞)的抑制活性。结果表明:3-氧-3-(4'-氯苯基)-2-(4″-乙酰苯腙)-丙腈(5e)对受试细胞均有较好的抑制活性,IC50分别为6.01μmol·L-1,7.10μmol·L-1,9.00μmol·L-1和9.89μmol·L-1。     

Ultrasound promoted enantioselective transesterification of 3-hydroxy-3-(2-thienyl) propanenitrile catalyzed by lipase

(S)-3-hydroxy-3-(2-thienyl) propanenitrile, which is the key chiral building block for the synthesis of (S)-duloxetine, was successfully prepared via enantioselective transesterification catalyzed by lipase under ultrasound irradiation. Compared with conventional shaking, the enzyme activity and enantioselectivity were dramatically enhanced under ultrasound irradiation. Under optimum reaction conditions (solvent: n-hexane, ultrasound power: 150?W, a_w: 0.33, temperature: 40°C), Pseudomonas sp. lipase exhibited an excellent catalytic performance (enzyme activity: 81.5?μmol?g^?1?min^?1, E-value: 65.4). The reaction achieved its equilibrium in approximately 7?h with a conversion of 53.9% and high enantiopurity (99% ee) of (S)-3-hydroxy-3-(2-thienyl) propanenitrile could be obtained.     

Synthesis, spectroscopic and DFT investigation of dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate

Dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate has been synthesized and characterized by elemental analysis, FT-IR and ¹H, ¹³C and ³¹P NMR. The vibrational wavenumbers, gauge including atomic orbital (GIAO) ¹H and ¹³C chemical shift values of title compound in the ground state have been computed with density functional theory method (DFT) and the B3LYP functional. The basis sets used are 6-311G(d,p) and 6-31G(d). The harmonic vibrational wavenumbers have been computed and the scaled values have been compared with the experimental FT-IR spectra. The complete assignments have been performed on basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Most of the computed wavenumbers are found to be in good agreement with the observed spectrum.