5- and 7-substituted 2-methyl-8-quinolinols

The synthesis and characterization of the 5- and 7-monosubstituted 2-methyl-8-quinolinols where the substituents are fluorine, chlorine, bromine, iodine, nitro, amino, and sulfonic acid groups were carried out. The bischelates with copper(II) of those ligands containing hydrogen, fluorine, chlorine, bromine, iodine, and nitro are also reported.     

7-{2-[1-(8-羟基喹啉-7-亚甲基)]苯并咪唑基}-8-羟基喹啉及其金属配合物的合成与荧光性能

以7-甲酰基-8-羟基喹啉和邻苯二胺为原料,经缩合反应合成了一种新型的配体——7-{2-[1-(8-羟基喹啉-7-亚甲基)]苯并咪唑基}-8-羟基喹啉(H2L);H2L分别与醋酸锌和三氯化铝经配位反应合成了两种新型的金属配合物Zn L·H2O(1)和Al_2L_3·3H_2O(2),其结构和性能经UV-Vis,1H NMR,IR,元素分析及FL表征。1和2的λem分别为514 nm(λex=400 nm)和525 nm(λex=401 nm)。     

Synthesis of 6-Methyl-4-(1-methyl-2-buten-1-yl)-2-(2-cyclohexen-1-yl)- and 6-Methyl-4-(1-methyl-2-buten-1-yl)-2-(1-cyclohexen-1-yl)anilines

Alkenylation of 6-methyl-2-(2-cyclohexen-1-yl)- and 2-(1-cyclohexen-1-yl)anilines with piperylene in the presence of AlCl₃ and transformation of the resulting cyclohexenylanilines into carbazole structures were studied.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 441–443.Original Russian Text Copyright © 2005 by Gataullin, Ishberdina, Sotnikov, Abdrakhmanov.     

Short Synthesis of 1-(3-tert-Butyl-1-phenyl-1H-pyrazol-5-yl)-3-(5-(2-morpholinoethoxy)-2H-chromen-8-yl) Urea Derivatives

A short and efficient synthesis of 1-(3-tert-butyl-1-phenyl-1H-pyrazol-5-yl)-3-(5-(2-morpholinoethoxy)-2H-chromen-8-yl) urea derivatives (1a–c), a novel type of p38 MAPK inhibitors, is described. The Claisen thermal rearrangement of arylpropargyl ethers was employd as a key step to synthesize the chromene core. The solvent effect on the ratio of the resultant two isomers of Claisen thermal rearrangement, namely 2-methylbenzofuran and 2H-chromen, was also investigated.     

Synthesis of 1-methyl-8-(pyridin-2-yl)-3,6-diazahomoadamantane and its derivatives

Condensation of 1-(pyridin-2-yl)butan-2-one with 1,3,6,8-tetraazatricyclo[4.4.1.13, 8]dodecane gave 1-methyl-8-(pyridin-2-yl)-3,6-diazahomoadamantan-9-one as intermediate product in the synthesis of 1-methyl-8-(pyridin-2-yl)-3,6-diazahomoadamantane and its derivatives with various functional groups at the bridging carbon atom.     

Practical Synthesis of 1-(7-Fluoro-naphthalen-1-yl)piperazine Hydrochloride

A practical and scalable preparation of 1-(7-fluoronaphthalen-1-yl)-piperazine hydrochloride (1) is reported. The original route for the synthesis of this compound involved the use of 1-amino-7-fluoronaphthalene and bis(2-chloroethyl)amine hydrochloride, two highly toxic compounds. A new protocol has been developed that employs a palladium-catalyzed Buchwald–Hartwig cross-coupling reaction between 1-Boc-piperazine and 1-bromo-7-fluoronaphthalene followed by piperazine deprotection with HCl gas. In addition, an efficient palladium removal protocol allowed for the preparation of the target molecule with less than 20 ppm of this metal. This methodology has been successfully implemented to produce multigram quantities of 1 with excellent purity and low palladium content.     

New transformations involving squarate esters. Multi-channel rearrangement options available to 2-(dimethoxy-methyl)-1-cycloalken-1-yl adducts

The Vilsmeier-Haack reaction of cyclic ketones with PBr₃ and DMF is an effective means for generating β-bromo-α,β-unsaturated aldehydes, which are readily transformed into their dimethyl acetals. These bromides are conveniently amenable to halogen-metal exchange in the presence of tert-butyllithium. The resultant organometallic intermediates, when treated with an equimolar amount of diisopropyl squarate, undergo 1,2-addition to deliver α-hydroxy ketone adducts that have proven to be sensitive to different rearrangements when in the presence of silica gel or boron trifluoride etherate. Although both processes involve net ring expansion of the cyclobutene ring with loss of methanol, the similarity stops there. In the first instance, spirocyclic diketones are produced by 1,2-shift of either of two ring carbons. In the second, extensively conjugated lactones are generated. The behavior of the adduct originating from a lithiated quinone bisketal has also been scrutinized.     

Synthesis of stereoisomeric 4-(2-methylindolin-1-yl)- and 4-(2-methylindol-1-yl) derivatives of glutamic acid

The reaction of dimethyl (2S,4RS)-N-phthaloyl-4-bromoglutamate with 2-methylindoline afforded diastereomeric 4-(2-methylindolin-1-yl)-(S)-glutamic acid derivatives, whose oxidation gave rise to 4-(2-methylindol-1-yl)-(S)-glutamic acid derivatives.     

2-(2,4-二氟苯基)-1-(4-烃基派嗪-1-基)-3-(1,2,4-三唑-1-基)-2-丙醇类化合物的合成及抗真菌活性

近20年来,真菌感染特别是深部真菌感染日益引起人们的广泛关注[1]。三唑类抗真菌药物对真菌的选择性较高,代谢稳定,体内动态、安全性都较好,已成为目前抗真菌药物研究开发的重点[2]。三唑类抗真菌药物是细胞色素P450 14α 去甲基酶的抑制剂,可影响该酶所催化的真菌麦角甾醇的生物合成,导致真菌细胞膜破损而死亡[3,4]。1998年,SynPhar实验室及Taiho制药公司[5]研制开发的化合物Syn 2869采用了取代哌嗪作为侧链。体外实验表明,该化合物抗菌谱广,对多种念珠菌、隐球菌及曲莓菌均有效,体内实验中,与目前临床上治疗真菌感染的主要用药伊曲…     

Synthesis and molecular structure of 1-(pyrimidin-2-yl)-2-(4-aryl-1,3-thiazol-2-yl)hydrazines

Reactions of some 2-hydrazinopyrimidine hydrochlorides with potassium thiocyanate gave 1-(pyrimidin-2-yl)thiosemicarbazides which underwent Hantzsch condensation with aryl chloromethyl ketones to produce 1-(pyrimidin-2-yl)-2-(4-aryl-1,3-thiazol-2-yl)hydrazine hydrochlorides. The protonation was accompanied by mutually dependent tautomeric rearrangements of heterocyclic fragments.     

Synthesis and Characterization of Novel 2-(1,2,3-Triazol-4-yl)-4,5-dihydro-1H-pyrazol-1-yl)thiazoles and 2-(4,5-Dihydro-1H-pyrazol-1-yl)-4-(1H-1,2,3-triazol-4-yl)thiazoles

Reactions of 1-(5-methyl)-1H-1,2,3-triazol-4-yl)ethan-1-ones and benzaldehydes in ethanol under basic conditions gave the corresponding chalcones. Reactions of the chalcones combined with thiosemicarbazide in dry ethanol containing sodium hydroxide afforded the corresponding pyrazolin-N-thioamides. Reactions of the synthesized pyrazolin-N-thioamides and several ketones (namely, ethyl 2-chloro-3-oxobutanoate, 2-bromoacetylbenzofuran, and hydrazonoyl chloride) gave the corresponding novel 2-(1,2,3-triazol-4-yl)-4,5-dihydro-1H-pyrazol-1-yl)thiazoles in high yields (77–90%). Additionally, 2-(4,5-dihydro-1H-pyrazol-1-yl)-4-(1H-1,2,3-triazol-4-yl)thiazoles were obtained in high yields (84–87%) from reactions with N-pyrazoline-thioamides and 4-bromoacetyl-1,2,3-triazoles under basic conditions. The structures of six of the newly synthesized heterocycles were confirmed by X-ray crystallography.     

Synthesis,Crystal Structure and Antitumor Activity of (E)-1-(7-Methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl)-3-(2-methoxyphenyl)-2-(1H-1,2,4-triazol-1-yl)propenol

The title compound,(E)-1-(7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl)-3-(2-methoxyphenyl)-2-(1H-1,2,4-triazol-1-yl)propenol(3a), was synthesized by the Aldol condensation reaction of 1-(7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl)-2-(1,2,4-triazol-1-yl)ethanone with 2-methoxybenzaldehyde and then reduced with NaBH_4, and its crystal structure was determined by single-crystal X-ray diffraction: monoclinic system, space group P21 with a = 6.2002(3), b = 12.8452(7), c = 13.2257(7) ?, Z = 2, V = 1031.23(9) ?~3, M_r = 407.46, Dc = 1.312 Mg/m~3, S = 1.054, μ = 0.091 mm-1, F(000) = 432, the final R = 0.0353 and w R = 0.0769 for 3161 observed reflections(I 2σ(I)). X-ray analysis displays that the title compound adopts an E configuration for the C(7)=C(8) double bond and S configuration for the chirality center with the specific rotation of –63.75°. Furthermore, the stability of the crystal was maintained through the intermolecular hydrogen bond O(1)–H···N(3). The antitumor assay exhibits that the title compound 3a(E configuration) has a good antitumor activity against the Hela cell line with the IC50 value of 36.9 μM, which is better than that of 3b(Z configuration).     

Synthesis of 1-[2-Methyl-6(8)-R-quinolin-4-yl]thiosemicarbazides

1-(2-Methylquinolin-4-yl)thiocemicarbazides and S-(2-methylquinolin-4-yl)thiosemicarbazide hydrochlorides were synthesized by reaction of 6(8)-substituted 4-chloro-2-methylquinolines with thiosemicarbazide under different conditions. Alkaline hydrolysis of the hydrochlorides afforded substituted 1-(2-methylquinolin-4-yl)thiosemicarbazides.     

Synthesis and microbial screening of 8-(benzyloxy)-5-(2-[1,3-diphenyl-1H-pyrazol-4-yl]thiazol-4-yl)quinolin-2(1H)-one derivatives

The present investigation describe the synthesis of 8-(benzyloxy)-5-(2-[1,3-diphenyl-1H-pyrazol-4-yl]thiazol-4-yl)quinolin-2(1H)-one derivatives. Quinolin-8-ol was transformed by five step synthetic procedures into 8-Benzyloxy-5-(2-bromo-acetyl)-1H-quinolin-2-one. Subsequently, 8-Benzyloxy-5-(2-bromo-acetyl)-1H-quinolin-2-one condensed with 1,3-Diphenyl-1H-pyrazole-4-carbothioic acid amide in the presence of acetonitrile to afford 8-(benzyloxy)-5-(2-[1,3-diphenyl-1H-pyrazol-4-yl]thiazol-4-yl)quinolin-2(1H)-one derivatives. Synthesized compounds were screened for their antimicrobial activity against gram-positive and gram-negative bacteria. Most of the synthesized compounds are found to be active against tested bacterial strains and fungal strain.     

Synthesis,Crystal Structure and Biological Activity of 2-((2,2-Dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)-N-(3-(furan-2-yl)-1-phenyl-1H-pyrazol-5-yl)acetamide

The title compound 2-((2,2-dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)-N-(3-(furan-2-yl)-1-phenyl-1H-pyrazol-5-yl) acetamide(C25H23N3O4, Mr = 429.46) has been synthesized, and its structure was characterized by 1H-NMR, 13C-NMR, H RMS, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 20.6205(18), b = 5.2930(5), c = 18.9282(17) ?, β = 94.089(2)°, V = 2060.6(3) ?3, Z = 4, Dc = 1.384 g/cm~3, μ(Mo Ka) = 0.71073 mm~(-1), F(000) = 904, R = 0.0345 and w R = 0.0930. The intramolecular hydrogen bond at N(1)–H(1)···O(2), intermolecular weak interactions at O(3)···H(4) and weak π-π interactions connected the molecules to lead to one-dimensional tapes. Bioassay results indicated that the title compound had moderate herbicidal and fungicidal activities.     

Synthesis of substituted 2-(2-oxopyrrolidin-1-yl)acetamides

The reaction of chloroacetamide with 2 equiv of γ-aminobutyric acid potassium salts provides a convenient method for the synthesis of substituted 4-[(2-amino-2-oxoethyl)amino]butanoic acids. Alkylation products of 2-aminoacetic and 3-aminopropanoic acid with chloroacetamide were isolated. Thermal cyclization of substituted 4-[(2-amino-2-oxoethyl)amino]butanoic acids afforded 2-(2-oxopyrrolidin-1-yl)acetamides.     

X-Ray Diffraction Study of 8-(Pyridin-2-yl)- and 8-(1,2,4-Triazin-5-yl)-2H-chromen-2-ones

Russian Journal of General Chemistry - The molecular and crystal structures of 8-(3,6-diphenylpyridin-2-yl)-5,7-dimethoxy-4-phenyl-2H-chromen-2-one,...     

Synthesis and antitumor activity of 7-(triazol-1-yl)pyrroloallocolchicine derivatives

The cycloaddition of acetylene derivatives of azido-substituted pyrroloallocolchicines afforded 7-(triazol-1-yl)pyrroloallocolchicines. The synthesized compounds exhibit considerable cytotoxicity and apoptosis-inducing activity against Nalm 6 human leukemia cells.