Novel Reaction of Some Azoles with Dimethyl Sulfoxid

The compounds 4a～4j were prepared by 3a～3j which were prepared from 1a～1j through 2a～2j. The compounds 6a～6j were prepared by the reaction of the products of 4a～4j with dimethyl sulfoxid via Dimroth rearrangement.[1] The compounds ethyl 5-arylamino-1H-1,2,3-triazol-4-carbonates (5a～5d) and ethyl 2-methylthiamethylene-5-arylamino-2H-1,2,3-triazol-4-carbonates (6a～6j) are established by MS, IR, elemental analysis and 1H NMR spectral data. The route of syntheses is shown in Scheme 1.     

Synthesis of dimethyl 3-perfluoroalkyl-4-(3-oxo-2-triphenyl-phosphoranylidenbutanylidene)-pent-2-enedioate and its cyclization

The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroal-kynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0℃. Intramolecular elimination of Ph3PO took place when compound 5 was heated in aqueous methanol at 115-120℃ in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, 1H NMR, 19F NMR and 13C NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.     

4-芳基-6-芳氧甲基吗啉-3-酮衍生物的合成及其对A549肺癌细胞生长抑止活性的评价

A series of 4-aryl-6-aryloxymethylmorpholin-3-one derivatives were synthesized very efficiently from readily available starting compounds in two steps. Ring opening reactions of epoxides with aniline compounds on alumina gave corresponding β-aminoalcohols （3）. The resulting β-aminoalcohols were reacted with 2-chloroacetyl chloride to yield the desired 4-aryl-6-aryloxymethylmorpholin-3-one derivatives （5）. All compounds 5 were assayed for inhibitory activity against A549 lung cancer cell growth, and the inhibitory effect of the novel morpholin-3-ones on cell viability was dose-dependent.     

Synthesis of Some Novel Phenyl Substituted Oxothiazolidin- 1’’,3’’,4’’-thiadiazolo-[3’,4’-b]thiazoline of 3β-Substituted Cholestane

Three title compounds 4a—4c have been synthesized by the cyclodehydration of 1’-benzylidine-4’-(3β-substituted-5α-cholestane-6-yl)thiosemicarbazones 2a—2c with thioglycolic acid followed by the treatment with cold conc. H2SO4 in dioxane. The compounds 2a—2c were prepared by condensation of 3β-substituted-5α-cholestan- 6-one-thiosemicarbazones 1a—1c with benzaldehyde. These thiosemicarbazones 1a—1c were obtained by the reaction of corresponding 3β-substituted-5α-cholestan-6-ones with thiosemicarbazide in the presence of few drops of conc. HCl in methanol. The structures of the products have been established on the basis of their elemental, analytical and spectral data.     

Phosphonium and arsonium ylides(?)——ⅩⅦ.A facile synthesis of methyl 2,6-bisperfluoroalkylbenzoates via acyclic precursors

The title compounds 6a—6f were prepared with high yield via intramolecular Wittigreaction of methyl 3-perfluoroalkyl-6-perfluoroacyl-2-triphenylphosphoranylidenehex-3,5-dienoates(5a—5i)which were obtained from the reaciton of 3-perfluoroacylprop-2-enylidenetriphenylphos-phoranes(3a—3c)with methyl perfluoroalkynoates(4a—4c).     

Synthesis and Application of Some Azo and Azomethine Dyes Containing Pyrazolone Moiety

3-Amino-1-phenyl-4,5-dihydro-1H-pyrazol-5-one (1) was used as starting material for the synthesis of a number of azo compounds 3a—3c and azomethine derivative 4. The deblocking of 3a—3c and 4 gave rise to 5a—5c and 6 in which a free amino was revealed. The diazonium salts of 5a—5c and 6 were coupled with several phenols to produce a number of bis azo compounds 7a—7c and 8a—8c with azomethine in position 4 and azoic group in position 3. The prepared dyes were structurally confirmed by elemental analysis, spectral methods and applied to different fibers (wool, polyester and blend of wool/polyester) as disperse dyes and their fastness properties were measured.     

Synthesis of Tetrahydropyridinyltriazolothiadiazines as Possible Muscarinic Agonists

4-Amino-5-(pyridin-3-yl)-4H-l,2,4-triazole-3-thiol 1 were condensed with 2-bromo-l-(substituted phenyl)ethanone to give pyridinyltriazolothiadiazines 2a-c, which were quaternarized with methyl iodide and oxidized with 30 % hydrogen peroxide to afford the corresponding methyl pyridinium salts 3a-c and pyridine- 1 -oxides 4a-c, respectively. The redtiction of compounds 3 and 4 with NaBH4 in methanol produced the target compounds 1-methyl- 1.2.5.6-tetrahydropyridin-3-yl)-6-aryl-s-triazolothiadiazines 5a-c and 3-( l-hydroxyl- 1, 2, 5, 6-tetrahydropyridin -3-yl)-6-aryl-s-triazolothiadiazines 6a-c, respectively. The endothelium vascular relaxing activity of the target compounds was screened.     

Crystal Structure,Photoluminescence, and Theoretical Studies of Dihydropyran Derivatives

Two novel dihydropyran compounds(1 and 2) containing a triphenylamine group were synthesized and characterized. The structure of compound 2 was verified by single-crystal X-ray crystallography. It crystallizes in triclinic, space group P1 with a = 6.9943(4), b = 8.1360(4), c = 23.9274(14) , α = 87.692(4), β = 88.940(5), γ = 85.223(4)o, V = 1355.62(13) 3, Z = 2, F(000) = 520, Dc = 1.199 Mg/m3, Mr = 489.24 and μ = 0.075 mm-1. The UV-vis absorption and fluorescence of the two compounds were discussed. The two compounds exhibited strong blue emissions under ultraviolet light excitation. The molecular structure and HOMO and LUMO levels of compound 2 were calculated by density functional theory(DFT) at the B3LYP/6-31G(d) level.     

Fimbrialtols K–M,highly functionalized ent-kaurane diterpenoids from traditional Chinese plant Flickingeria fimbriata(B1.) Hawkes

Three new ent-kaurane diterpenoids fimbrialtols K–M(3–5) with highly substituted functionalities were isolated from the extract of Flickingeria fimbriata(B1.) Hawkes. The structures of these new compounds were determined by NMR and HR-ESIMS. The relative configurations of these compounds were determined by analysis of NOESY correlations. The absolute configurations of these new compounds were established by CD methods together with considering the biosynthetic pathway. Compounds 3 and4 contain a cinnamic carboxyl group, whereas compound 5 possesses a benzoic carboxyl group representing the first report in more than known 600 ent-kaurane diterpenoids.     

Synthesis of N-Aryl-2- （1＇, 6＇-dihydro-6＇-pyridazinone-3＇-carbonyl） Thiosemicarbazides and Their Related Heterocyclic Compounds

1,6-Dihydro-3-hydrozinocarbonyl-6-pyridazinone (compound 2) were prepared from α-ketoglutaric acid and hydrazine hydrate. A series of N-aryl-2-(1‘,6‘-dihydro-6‘-pyridazinone-3‘-carbonyl) thiosemicarbazides 3a-3f were synthesized from the reaction of aryl isothiocyanates with compound 2. The terminal compounds 1,3, 4-thiadiazole, 1,3,4-oxadiazole and 1,2, 4-triazol-5-thione derivatives were cyclized from compounds 3a-3f. Their structures were confirmed by IR,^1H NMR, MS and elemental analyses.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.