Synthesis of Tri-O-acetyl-d-allal from Levoglucosenone

Tri-O-acetyl-d-allal has been enantiospecifically synthesized in six steps from levoglucosenone in 55% overall yield. A key step in the synthesis is the anhydro bridge ring-opening with concomitant formation of a 1,3-oxathiolane-2-thione ring.     

Synthesis of Pyrazolines Based on Levoglucosenone

The 1,3-dipolar cycloaddition of diazomethane to levoglucosenone was found to occur regio- and stereoselectively to form optically active 9,11-dioxa-4,5-diazatricyclo[6.2.1.0^2,6]undec-4-en-7-one. Levoglucosenone was found to react with methyldiazoacetate to give the 2:1 adduct.     

Synthesis of Thiochroman 1,1-Dioxide Derivatives on the Basis of 2,4,6-Trinitrotoluene

Treatment of 2,4,6-trinitrotoluene with -mercaptocarboxylic acid esters and subsequent oxidation gave 2-(alkoxycarbonyl-R-methylsulfonyl)-4-X-6-nitrotoluenes which were brought into Knoevenagel condensation with aromatic aldehydes (heating in benzene in the presence of secondary amine acetates). As a result of intramolecular cyclization, 2-alkoxycarbonyl-3-aryl-2-R-5-X-7-nitrothiochroman 1,1-dioxides (R = H, Me; X = NO₂, R'SO₂) were obtained. The developed procedure opens the way to hitherto unknown thiochroman 1,1-dioxide derivatives.     

Synthesis of Magnesium Octa-4,5-phenoxyphthalocyanine and Sulfo- and Alkylsulfamoyl Derivatives on Its Basis

By the reaction of nucleophilic substitution of bromine atom and the nitro group of 4-bromo-5- nitrophthalonitrile 4,5-diphenoxyphthalonitrile was obtained and on its basis new derivatives of octa-4,5- phenoxyphthalocyanine were synthesized soluble in water- and organic solvents. The spectral properties and thermodestruction of the products were investigated.     

Green Synthesis of UV-Reactive Polycarbonates from Levoglucosenone and 5-Hydroxymethyl Furfural

This study focuses on the synthesis of fully renewable polycarbonates (PCs) starting from cellulose-based platform molecules levoglucosenone (LGO) and 2,5-bis(hydroxymethyl)furan (BHMF). These unique bio-based PCs are obtained through the reaction of a citronellol-containing triol (Triol-citro) derived from LGO, with a dimethyl carbonate derivative of BHMF (BHMF-DC). Solvent-free polymerizations are targeted to minimize waste generation and promote an eco-friendly approach with a favorable environmental factor (E-factor). The choice of metal catalyst during polymerization significantly influences the polymer properties, resulting in high molecular weight (up to 755 kDa) when Na₂CO₃ is employed as an inexpensive catalyst. Characterization using nuclear magnetic resonance confirms the successful incorporation of the furan ring and the retention of the terminal double bond of the citronellol pendant chain. Furthermore, under UV irradiation, the presence of both citronellol and furanic moieties induces singular structural changes, triggering the formation of three distinct structures within the polymer network, a phenomenon herein occurs for the first time in this type of polymer. These findings pave the way to new functional materials prepared from renewable monomers with tunable properties.     

Transformation of C4-Methyl Derivatives of Levoglucosenone to 2,5-Dihydrofurans. An Unexpected Intramolecular Oxacyclization

Russian Journal of Organic Chemistry - The acid-catalyzed reaction of C4-methyl derivatives of levoglucosenone with ethanethiol and propane-1,3-dithiol was studied. The reaction takes a nontrivial...     

Cyclopentane Ring Fusion to α-Iodo and α-Bromo Levoglucosenone Derivatives with 2,2-Dimethyl-1,3-dinitropropane

Russian Journal of Organic Chemistry -     

Synthesis of New 5-Mercapto-1,3-oxazole Derivatives on the Basis of 2-Acylamino-3,3-dichloroacrylonitriles and Their Analogs

Enamides of the general formula Cl₂CÍC(X)NHCOR¹, where X = CN, COOAlk, CONH₂, P(O)(OEt)₂, P(O)Ph₂, +PPh₃ Cl^-, were treated in succession with alkane- or arenethiols and silver carbonate to obtain 5-alkyl(aryl)thio-2-R¹-4-X-1,3-oxazoles with high selectivity. The latter were converted into the corresponding sulfonyl derivatives. Unlike 2-acylamino-3,3-dichloroacrylonitriles which react with sodium hydrogen sulfide in a nonselective fashion, reactions of derivatives like Cl(ArS)CÍC(CN)NHCOR¹ with NaHS lead to hitherto unknown 5-arylthio-4-thiocarbamoyl-2-R¹-1,3-oxazoles whose structure was confirmed both by spectral methods and by cyclocondensation with bromoacetophenone according to Hantzsch. Heating of some 2-aryl-5-mercapto-4-X-1,3-oxazoles with benzenethiols results in recyclization into the corresponding 2,4-disubstituted 5-arylthio-1,3-thiazoles, presumably due to prototropic tautomerism in the 5-mercaptooxazole fragment.     

1,4-二氢吡啶衍生物的合成方法改进

采用改进的Hantzsch反应,在氮气保护下的封闭体系中回流芳香醛、乙酰乙酸乙酯和NH4HCO3,合成了1,4-二氢吡啶衍生物(1a~1d),其结构经1HNMR,IR和元素分析确认。用XRD测定了1b的晶体结构。     

合成金雀异黄素水溶性硫酸酯的研究

金雀异黄素(Genistein,4',5,7-trihydroisoflavone,G)属异黄酮类化合物,在豆类植物中广泛存在.许多关于G药理作用的研究报道显示:G具有抑制癌细胞生长、影响心血管系统的活性,对多种酶(如:TPK,TOPOⅡ,CKⅡ,PKC等)有抑制作用,且其类雌激素作用具有可能的抗骨质疏松作用[1-4],具有开发成新型药物的潜在价值.     

蒂巴茵衍生物的合成研究

The reaction of 7α-acetyl-6,14-endoethano-6,7,8,14-tetrahydrothebaine with 2-（thien-2-yl）ethylmagnesium bromide was investigated. The tertiary alcohol derivative 7α-[R-l-hydroxyl-l-methyl-3-（thien-2-yl）propyl]）-6,14- endoethano-6,7,8,14-tetrahydrothebaine （3） and a by-product 4 were isolated. The structure of 4 was elucidated by X-ray analysis. The Grignard reaction shows high degree of stereoselectivity according with Cram rule. The crystal structure of 4 indicates that dihydrofuran ring was opened to form a phenolic hydroxyl group and a three-membered ring structure. It maintains the main rigid structure of morphine and contains a C（6）-C（14） enthano bridge. The 1-hydroxyl-1-methyl-3-（thien-2-yl）propyl group at C（7） position adopted S-configuration.     

糖基化青蒿素衍生物的合成

以糖[D-葡萄糖(1a),D-木糖(1b),D-甘露糖(1c),乳糖(1d)和D-半乳糖(1e)]为原料,经溴化、乙酰化一锅法使糖基乙酰化制得相应的溴代乙酰化糖(2a～2e);2在相转移催化剂四丁基硫酸氢铵催化下分别与二氢青蒿素经醚化反应合成了五个糖基化青蒿素衍生物,其结构进行1H NMR,13C NMR,IR和LC-MS表征。     

Synthesis of Phosphorylated Cyclopropanes on the Basis of gem-Dichlorocyclopropyloxiranes

Russian Journal of General Chemistry -     

Synthesis of Spiroindolines on the Basis of Isatylidene Malononitrile

Russian Journal of Organic Chemistry - New representatives of spiroindolines are synthesized by the reaction of isatylidene malononitrile with methylene-active compounds (malononitrile,...     

Synthesis of Ethenylbenzothiazole Derivatives

Ethenylbenzothiazoles were synthesized by the Horner-Emmons reaction of benzothiazolylmethylphosphonate with aldehydes under phase transfer catalytic conditions in 60–71% yields. Not only aromatic but also aliphatic aldehydes gave the desired products under these mild conditions in 66–71% yields.     

靛红衍生物的合成

以取代苯胺或者靛红为原料,通过四条不同的路线合成了一系列苯环上卤代和N-取代的靛红衍生物,最高产率达83%.其结构经NMR确认.     

Synthesis of Isatin Derivatives

Reactions were studied of isatin sodium salt with bromocyclohexane, p-ethoxyphenyl chloroethyl ketone, 4,4'-di(chloromethyl)biphenyl, and 4,4'-(dichloromethyl)diphenylmethane. N-cyclohexylisatin, p-ethoxyphenyl N-isatinoethyl ketone, 4,4'-di(N-isatinomethyl)biphenyl, 4-chloromethyl-4'(N-isatinomethyl)biphenyl, 4,4'-di(N-isatinomethyl)diphenylmethane, 4-chloromethyl-4'(N-isatinomethyl)diphenylmethane, and 4-(N-morpholinomethyl)-4'-(N-isatinomethyl)diphenyl were synthesized.     

异色满并[4,3—d]嘧啶类衍生物的合成

利用异色满酮－４合成了一系列新的异色满并嘧啶类衍生物４ａ－ｔｆ，其结构均经元素分析，ＩＲ和ＨＮＭＲ分析予以证实。     

美金刚胺衍生物的合成

以盐酸美金刚胺为原料,分别与对硝基苯甲酰氯,苄氧羰基缬氨酸经酰基化反应和催化加氢反应,合成了两个新型的美金刚胺衍生物——N-对氨基苯甲酰基美金刚胺和缬氨酰基美金刚胺,其结构经1H NMR和IR表征。