Synthesis of compounds related to muscarine

Conclusions A method was developed for obtaining muscarine analogs, and 2-methyl-5-(N-dimethylaminomethyl)-2,3-dihydro-3-furanone- the starting product for obtaining muscarine- was synthesized.     

Zur Biogenese des Muscarins in Mycelkulturen von Clitocybe rivulosa

Studies on the biosynthesis of muscarine in mycelial cultures of Clitocybe rivulosa The incorporation and distribution of several ¹⁴C-labelled simple compounds into muscarine has been investigated with mycelial cultures of Clitocybe rivulosa. Specifically, the carbon atoms 1, 2 and 3 of pyruvate are incorporated into CH₃-C(2), C(2) and C(3), and the carbon atoms 2, 3 and 4 of glutamate into C(4), C(5) and CH₂-C(5) of muscarine. The carbon atoms 1 and 5 of glutamate are lost during the biosynthesis. Therefore, muscarine can be regarded as a derivative of glutamate.     

Muscarine and Muscarine Isomers in Selected Inocybe Species

The distribution and relative concentrations of muscarine and its isomers in Inocybe species were determined. Notable was the finding that I. cinnamomea A. H. Smith, I. geophylla Karst, and I. lacera (Fr.) Quél. contained concentrations of epi-muscarine equal to or-higher than muscarine itself.     

Efficient mild oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2(5H)-furanone,a versatile chemical intermediate

Research on Chemical Intermediates - The 5-hydroxymethyl-2(5H)-furanone is a versatile chemical intermediate used to produce a variety of products such as unsaturated (+) muscarine, microbial...     

Divergent synthesis of two novel muscarine analogues from D-glucose

A divergent synthesis of two new muscarine analogues bearing the (5S)-dioxolanyl isosteric group was achieved starting from d-glucose, enabling access to libraries of potential muscarinic agonists or antagonists. The key step of the synthesis involved a regioselective epoxide ring opening in 2,5:3,4-dianhydro derivatives 5 and 15 with LiAlH₄, whereby the natural stereochemistry of (+)-muscarine (1) and (−)-allo-muscarine (2) was efficiently established.     

A novel short convergent entry into himbacine derivatives

[reaction: see text]. The IMDA reaction of 9 leads with good stereoselectivity to exo-adduct 10b. The functionalized ABC-ring core in 10 is well suited for the convergent synthesis of analogues of himbacine, a naturally occurring M2 selective muscarine receptor antagonist, as illustrated with the further synthesis of the dehydro-derivative 5.     

Experimental observation of the transition between gas-phase and aqueous solution structures for acetylcholine, nicotine, and muscarine ions

Structural information on acetylcholine and its two agonists, nicotine, and muscarine has been obtained from the interpretation of infrared spectra recorded in the gas-phase or in low pH aqueous solutions. Simulated IR spectra have been obtained using explicit water molecules or a polarization continuum model. The conformational space of the very flexible acetylcholine ions is modified by the presence of the solvent. Distances between its pharmacophoric groups cover a lower range in hydrated species than in isolated species. A clear signature of the shift of protonation site in nicotine ions is provided by the striking change of their infrared spectrum induced by hydration. On the contrary, structures of muscarine ions are only slightly influenced by the presence of water.     

Stereoselective synthesis of tetrahydrofurans via formal [3+2]-cycloaddition of aldehydes and allylsilanes. Formal total synthesis of the muscarine alkaloids (-)-allomuscarine and (+)-epimuscarine

The stereoselective synthesis of tetrahydrofurans was achieved by formal [3+2]-cycloaddition of allyl and crotylsilanes with alpha-triethylsilyloxy aldehydes. The scope of the reaction was examined by using different alpha-substituted aldehydes and different substituents on the silicon. Tamao oxidation of the products resulted in formation of diols that are easily functionalized allowing an entry to natural products synthesis. The formal total synthesis of the muscarine alkaloids (-)-allomuscarine and (+)-epimuscarine was achieved.     

Die Position 5 im Oxotremorin-Gerüst: Eine zentrale Stelle für die Steuerung der Aktivität am muscarinischen Rezeptor

Position 5 at the Oxotremorine Skeleton as the Stearing Position for Activity at the Muscarinic Receptors Substitution of the Ch₂ group at position 5 of oxotremorine ( 2 ) by electronegative atoms like O- or N-atom, or by sterically bulkier groups like methyl, N-formyl, or N-acetyl Changes the pharmacological profile of oxotremorine drastically. The O- and N-analogues were potent but unselective (M₁/M₂) muscarinic agonists. The methyl analogue ((R)-BOK-1) is a muscarine antagonist which is 10 times more potent on the ganglion cervical superius (pA₂ = 9.3) than pirenzepine and is able to distinguish between the ileal and ganglion receptor by a factor of 100. The N-formyl derivative differentiates between the two receptors by a factor of 500 with a potency comparable to pirenzepine. The two M₁-selective antagonists have higher affinity to the rat-ganglion receptors compared to the affinity to rat-cortex homogenate. The synthesis and the pharmacological activity of several new oxotremorine analogues are discussed.     

Muscarine, imidazole, oxazole, and thiazole alkaloids

The occurrence, structure determination, biological activities, as well as total syntheses of muscarine, imidazole, oxazole and thiazole alkaloids have been reviewed. The literature covers from the middle of 2001 to the end of 2002, and 149 references are cited.     

Synthesis of functionalized tetrahydrofurans

A novel cyclization reaction is described which affords readily manipulable 3(2H)-dihydrofuranone ethylene ketals, useful in the total synthesis of an ascofuranone model, bullatenone, and muscarine analogs.     

Synthesis and study of properties of the sulfonaphthylazophenoxyphthalonitrile and related phthalocyanine

The 4-[4′-(5-sulfonaphthylazo)phenoxy]phthalonitrile potassium salt was synthesized by the reaction of 4-chlorophthalonitrile with 5-(4′-hydroxyphenylazo)-1-naphthalenesulfonic acid, and on its basis was obtained tetra-4-[4′-(5-sulfonaphthylazo)phenoxy]phthalocyanine. The products were characterized by elemental analysis, IR and electron spectroscopy. The effect of the introduced substituent on the spectral and other properties of the synthesized compounds was demonstrated.     

Muscarine, imidazole, oxazole and thiazole alkaloids

Novel and structurally diverse natural products containing imidazol-, oxazole-, or thiazole-unit(s) display a wide variety of biological activities. The isolation, biological activity and total synthesis of naturally occurring muscarine, imidazole, oxazole and thiazole alkaloids have been reviewed. The literature covers from January 2003 to June 2004.     

新型5-[10-(9-羧基蒽基)]-间苯二甲酸的合成及荧光性质

以5-氨基-间苯二甲酸二甲酯为原料,经重氮化溴取代、Miyaura硼酸酯化反应生成3,5-二甲氧羰基苯硼酸频哪醇酯(3)。此外,以9-蒽甲酸为原料,经溴化、酯化反应生成10-溴-9-蒽甲酸甲酯(6)。最后以化合物3和6为原料,经Suzuki偶联、水解反应得到目标化合物5-[10-(9-羧基蒽基)]-间苯二甲酸。其结构经1H NMR、13C NMR和高分辨质谱表征。研究结果表明,该化合物钠盐水溶液具有发蓝光的性质,最大发射波长为425nm,同时也有较好的荧光量子效率。     

Muscarine,imidazole, oxazole,thiazole, Amaryllidaceae and Sceletium alkaloids

A review with 136 references covers the literature from July 2000 to June 2001 on the isolation, bioactivities, and synthetic highlights of complex natural products including muscarine, imidazole, oxazole, thiazole, Amaryllidaceae and Sceletium alkaloids.     

短命辐射示踪剂的合成

正电子激发断层成象(PET)是体内基本生物和生理过程研究的有力工具.合成短命放射示踪剂的目的是发展PET探针,本文综述了各种类型的短命放射示踪剂的合成.     

呋喃并呫吨酮衍生物的合成与生物活性研究

以水杨酸、间苯三酚为原料合成了1,3-二羟基呫吨酮, 经醚化、环化反应得到1-羟基呋喃并呫吨酮3a和3b, 再经Mannich反应合成了10个呋喃并呫吨酮衍生物4和5, 接着通过季铵化反应得到相应的10个季铵盐6和7. 运用IR、一维和二维NMR、MS、元素分析等对化合物进行了结构表征, 考察了化合物4～7对乙酰胆碱酯酶的抑制作用及化合物6, 7的抗癌活性. 结果表明: 化合物4～7对乙酰胆碱酯酶具有较好的抑制活性, IC50＝2.0～12.4 μmol/L; 化合物6, 7对肝癌(HepG2)、肺癌(SPC-A)、口腔上皮癌(KB)、乳腺癌(MCF-7)这四种癌细胞株的增殖均有抑制作用, 其中化合物6c对癌细胞株HepG2、化合物7d对癌细胞株MCF-7的抑制作用最强, IC50分别为0.82和0.77 μmol/L.     

Synthesis of 1-(1,1-dimethylethyl)-1H-pyrazole-4-carboxylate ester derivatives

Attempts to prepare ethyl 5-cyano-1-(1,1-dimethylethyl)-1H-pyrazole-4-carboxylate ( 7 ) by the reaction of the corresponding 5-chloro derivative 1b with cyanide ion were unsuccessful. The chloro ester was synthesized from the corresponding amino ester la utilizing nonaqueous diazotization with nitrosyl chloride. An alternate process was developed which allowed the preparation of 7 from the corresponding 5-methyl ester 3 in four steps. The structure of the N-methylamide 8 synthesized from 7 was confirmed by X-ray diffraction analysis.     

A new derivative of 1,5-dihydropyrazolo[4,3-c][1,2,5]benzotriazepine

A new compound, 1,5-dihydro-3-methyl-7-nitro-propylpyrazolo[4,3-c][1,2,5]benzotriazepine, was synthesized by intramolecular cyclization of 5-amino-4-[(2-bromo-5-nitrophenyl) azo]-3-methyl-1-isopropylpyrazole, and it was established on the basis of the spectral data that the triazepine ring in the synthesized compound exists in two tautomeric forms — amino-azo- and hydrazone. The structure of the compound synthesized was confirmed by the data of the PMR, IR, electronic, and mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1136–1139, August, 1984.     

Synthesis and characterization of chelate polymers containing etheric diphenyl ring in the backbone: thermal,optical, electrochemical,and morphological properties

A novel Schiff base, 4‐bromo‐2‐[(2‐[(5‐bromo‐2‐hydroxyphenyl)methylene]amino‐5‐nitrophenyl)iminomethyl]phenol (M1) was synthesized from the reaction of 5‐brom‐salicylaldehyde with 4‐nitro‐o‐phenylenediamine. Schiff base–metal complex was synthesized from the reaction of 4‐bromo‐2‐[(2‐[(5‐bromo‐2‐ hydroxyphenyl)methylene]amino‐5‐nitrophenyl)iminomethyl]phenol (M1) with copper (II) acetate monohydrate [(CH₃COO)₂ Cu · H₂O] salt. Poly‐ (M1‐Cu‐TDP) was synthesized from the reaction of M1‐Cu with 4,4′‐dithiodiphenol (TDP). Poly(M1‐Cu‐PDP) was synthesized from the reaction of M1‐Cu with 4,4′‐propane‐2,2‐diyldiphenol (PDP). Poly(M1‐Cu‐HDP) was synthesized from the reaction of M1‐Cu with 4,4′‐(1,1,1,3,3,3‐hexafluoropropane‐2,2‐di‐yl)diphenol (HDP). The structures of the synthesized monomer and chelate polymers were confirmed by FT‐IR, UV–Vis, ¹H‐ and ¹³C‐NMR, and elemental analysis. The characterization was made by TGA‐DTA, DSC, size exclusion chromatography, cyclic voltammetry, and solubility tests. Also, surface morphologies of chelate polymers were investigated by scanning electron microscope. Copyright © 2009 John Wiley & Sons, Ltd.