3-O-乙酰基-4,6-二-O-苄基-1,2-环丙烷葡萄糖的合成

以葡萄糖为起始原料制得苄基葡萄烯糖,再经Ferrier重排、双羟化反应、选择性磺酰化、羟基保护和在碱性条件下关环反应合成了3-O-乙酰基-4,6-二-O-苄基-1,2-环丙烷葡萄糖.其中5个中间体为新化合物,其结构经1H NMR,13C NMR和HR-MS表征.     

Synthesis and Properties of 4,6-Dimethyl-5-pentyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile and 3-Amino-4,6-dimethyl-5-pentylthieno[2,3-b]pyridines

The reaction of 3-pentylpentane-2,4-dione with cyanothioacetamide afforded 4,6-dimethyl-5-pentyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile. Alkylation of the latter led to the formation of 2-alkylsulfanyl-4,6-dimethyl-5-pentylpyridine-3-carbonitriles or 3-amino-4,6-dimethyl-5-pentylthieno[2,3-b]pyridines, depending on the alkylating agent and reaction conditions. The structures of the key compounds were proved by 2D NMR spectroscopy and X-ray analysis. Biological activity of the synthesized compounds was evaluated in silico. Some compounds were experimentally found to stimulate growth of sunflower seedlings.

     

The Formation of Thioacylthioketenes by Flash Vacuum Pyrolysis of 1,2-Dithiole Derivatives

Abstract

The formation of thioacylthioketenes has been observed in Flash Vacuum Pyrolysis of various 1,2-dithiole derivatives. In some cases C₃S₂, 1,2-propadiene-1,3-dithione is formed too.     

A New Version of Multicomponent Synthesis of 4,6-Diaryl-2-sulfanylidene-1,2-dihydropyridine-3-carbonitrile Derivatives

Multicomponent condensation of aromatic aldehydes with acetophenones, cyanothioacetamide, and alkylating agents has been shown to provide synthetic routes to various pyridine and thienopyridine derivatives. The structure of some of the synthesized heterocycles has been confirmed by X-ray analysis.     

Synthetic utilization of polynitroaromatic compounds. 2. Synthesis Of 4,6-dinitro-1,2-benzisothiazol-3-ones and 4,6-dinitro-1, 2-benzisothiazoles from 2-benzylthio-4,6-dinitrobenzamides

Cyclization of 2-benzylthio-4,6-dinitrobenzamides to 4,6-dinitro-1, 2-benzisothiazol-3-ones was achieved using SO(2)Cl(2) in CH(2)Cl(2) at room temperature. Alkylation of these heterocycles proceeded in a nonregioselective manner to yield a mixture of corresponding O- and N-alkylated products. Oxidation of 4,6-dinitro-1,2-benzisothiazoles (50% H(2)O(2) in AcOH) afforded the corresponding S-oxides and S, S-dioxides, depending on oxidation conditions. Unexpectedly, oxidation of a 3-methoxy derivative resulted in ring opening with the formation of the corresponding sulfamide. Chlorination of these 4,6-dinitro-1,2-benzisothiazol-3-ones (PCl(5)-POCl(3)) gave the expected 3-chloroisothiazoles.     

The Formation of Heterocumulenes from 1,2-Dithiole Derivatives upon Flash Vacuum Pyrolysis

Abstract

1,2-Dithiole derivatives such as alkylthio substituted 1,2-dithiole-3-thiones, 1,6,6aλ⁴-tritiapentalenes and 1,2-dithiolo[4,3-c]-[1,2]dithiole-3,6-dithiole gives rise to C₃S₂, :C₄S and thioketenes upon flash vacuum pyrolysis in the temperature range 800-1000°C.     

Synthesis and properties of 2-amino-4,6-dimethylnicotinic acid arylamides

It is shown that on boiling 2-amino-4,6-dimethylnicotinic acid arylamides with triethyl orthoformate in acetic anhydride, derivatives of 3-aryl-5,7-dimethyl-4-oxo-3,4-dihydropyrido[2,3-d]pyrimidine are formed. The same compounds are obtained by ternary condensation of ethyl 2-amino-4,6-dimethylnicotinate with triethyl orthoformate and alrylamines. On reaction with urea or ammonium thiocyanate, the ethyl ester or anilides of 2-amino-4,6-dimethylnicothinic acid are converted to 2,4-dioxo- or 4-oxo-2-thio-pyrido[2,3-d]pyrimidines respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1384–1386, October, 1992.     

Synthesis of 4,6-Disubstituted 2-Thioxo-1,2-dihydropyridine-3-carbonitriles by the Reaction of Acetylenic Ketones with Cyanothioacetamide

Russian Journal of General Chemistry - The reaction of acetylenic ketones with cyanothioacetamide in the presence of morpholine yields 4,6-disubstituted...     

Synthesis and properties of 4,6-diamino-3-cyano-2(1H)-pyridineselenone: Molecular and crystal structure of 2-allylseleno-4,6-diamino-3-cyanopyridine

Self-condensation of cyanoselenoacetamide gives 4,6-diamino-3-cyano-2(1H)pyridineselenone, which is regioselectively alkylated at the exocyclic heteroatom. The cisoid position of the Se-C bonds of the selenoallyl substituent relative to the N-C bond of the pyridine ring in the N¹C²SeC⁸ fragment favors cyclization into selenazolo[3,2-a]pyridinium salts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2585–2590, November, 1989.     

Synthesis and electropolymerization of 1,2-bis(thiophen-3-ylmethoxy)benzene and its electrochromic properties and electrochromic device application

A new thiophene-based monomer; 1,2-bis(thiophen-3-ylmethoxy)benzene (BTMB) has been synthesized and chemical structure of the monomer was characterized. Polymerization of BTMB and characterization of the resulting polymer P(BTMB) were performed. Spectroelectrochemical analysis of the P(BTMB) reflected electronic transitions at 400 nm, 520 nm and ～720 nm, corresponding to π–π* transition, polaron and bipolaron band formation respectively. Switching ability was evaluated by a kinetic study via measuring the transmittance (%T) at the maximum contrast. Dual type all polymer electrochromic device (ECD) based on P(BTMB) and poly(ethylene dioxythiophene) (PEDOT) was constructed. Spectroelectrochemistry and switching ability of the devices were investigated by UV–vis spectroscopy.     

Synthesis and properties of functionally substituted 1,2-azolidines

Results of investigations on the synthesis and properties of functionally substituted 1,2-azolidines are reviewed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 829–850, June, 1992.     

Synthesis of 3-cyano-4,6-dinitrobenzo[d]isoxazole and its reactions with anionic nucleophiles

The action of various anionic O-, N-, and S-nucleophiles on 3-cyano-4,6-dinitro-benzo[d]isoxazole mostly resulted in regiospecific nucleophilic substitution for the nitro group in position 4. With an excess of an nucleophilic reagent, the nitro group in position 6 was also replaced. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 523–528, March, 2006.     

The Synthesis of 1,3-Dithiole Derivatives by Using Bun3P·CS2 Adduct

The red crystalline adducts formed between trialkylphosphines and carbon disulfide were confirmed to be l,3-dipolar structure by X-ray diffraction in 1961.^[1] Despite the apparent synthetic potential of the 1,3-dipolar structure, studies on its cycloaddition have only been restricted in electron-deficient alkynes as dipolarophiles.^[2-5] However, reactions with electron-rich alkynes have received little attention.     

Synthesis of 1-phenylbut-3-ene-1,2-dione and its attempted radical polymerization

1,2-Diketone moiety-bearing monomer 1-phenylbut-3-ene-1,2-dione, an analogue of phenyl vinyl ketone, was synthesized from 4-chlorobutyryl chloride in a 29 % overall yield in five steps. Following acylation of benzene with 4-chlorobutyryl chloride, the resulting α-methylene group was oxidized to 1,2-diketone in three steps: successive bromination, substitution with lithium hydroxide, and oxidation of α-hydroxyketone with potassium dichromate. The final step was dehydrochlorination of 4-chloro-1-phenyl-butane-1,2-dione. The attempted copolymerization of this monomer with styrene, using AIBN as the initiator, was unsuccessful.     

Synthesis of 4,6-disubstituted 2-methylpyridines and their 3-carboxamides

A new one-pot synthesis of title compounds by the reactions of α,β-unsaturated carbonyl compounds with β-aminocrotononitrile in the presence of sodium hydroxide is described.     

Synthesis of 3-Acyl-1,2-benzisoxazoles

A convenient method for the synthesis of 3-acyl-1,2-benzisoxazoles, which are unstable toward bases, is described. Base-catalyzed cyclization of 2-alkyl- and aryl-1,3-dithian-2-yl o-chlorophenylketoximes 4a-1 gave 3-(2-alkyl- and aryl-1,3-dithian-2-yl)-1,2-benzisoxazoles 8a-1 , which were converted into the corresponding 3-acyl-1,2-benzisoxazoles 1a-1.     

2-氯-4,6-二(2-萘氧基)-1,3,5-三嗪的合成及性能

1,3,5-三嗪（均三嗪）衍生物一般是由三聚氯氰与-OH、-NH2、-SH、-NHR等含活泼氢的化合物反应得到。由于三聚氯氰上三个氯原子具有反应分级可控性,以及这类衍生物具有良好的热稳定性、光活性和生物活性,因此均三嗪衍生物受到了广泛关注。含萘氧基的均三嗪衍生物是其中重要的一部分。这部分衍生物中以一取代和三取代物研究得较多,王巧峰,江璐霞等合成了萘酚取代三聚氯氰上一个氯的产物,     

Synthesis and spectral properties of shielded 1,2-disubstituted imidazolines

Shielded 1,2-disubstituted imidazolines were synthesized by condensation of diethylenetriamine with 2-ethylhexanoic acid. UV, IR and¹H and¹³C NMR spectral data were discussed. The effect was studied of branching in an alkyl substituent at the 2 position of the imidazoline ring on the spectral parameters of the synthesized compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 878–882, April, 1991.     

Synthesis, structures and some chemical and electrochemical properties of E-1,2-diferrocenyl-3-methylthioprop-2-enone and its ketals

2,3-Diferrocenyl-1-methylthiocyclopropenylium iodide reacts with water, metal alkoxides, phenolates and with alcohols in the presence of Et₃N to give E-1,2-diferrocenyl-3-methylthioprop-2-enone or its ketals. Their structures were established based on data from ¹H and ¹³C NMR spectroscopy and X-ray diffraction analysis. The mechanistic aspects of these reactions are discussed. Electrochemical properties of 8 and 13b have been studied. The compounds present two oxidation processes (I-II), attributed to the oxidations of the ferrocenes groups, E^0′(I), E^0′(II), ΔE^0′(II-I) and comproportionation constant K_com are reported.