Heteroadamantanes and their derivatives. 14. Synthesis of 3,6-diazahomoadamantan-9-ols and their acetates

The reduction of 3,6-diazahomoadamantan-9-ones with metal hydrides gave 3,6-diazahomoadamantan-9-ols, which were convened to acetates by the action of acetic anhydride. The effect of the substituents in the nodal positions on the rates of reduction and acylation is demonstrated.See [1] for Communication 13.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 804–809, June, 1991.     

Synthesis of 1,8-, 1,6- and 3,6-dichloro-9H-thioxanthen-9-ones

Cyclization of 2-chloro-6-[(3-chlorophenyl)thio]benzoic acid ( 2 ) gave a mixture of 1,8-, 3 , and 1,6-dichloro-9H-thioxanthen-9-ones 4 . The mixture was converted to 1,8-diamino- 7 , and 1-amino-6-chloro-9H-thioxanthen-9-ones 8 , from which 3 and 4 were prepared separately, respectively. From a mixture of 4 and 3,6-dichloro-9H-thioxanthen-9-one ( 11 ) obtained by cyclizing 4-chloro-2-[(3-chlorophenyl)thio]benzoic acid ( 10 ) was separated 11 by conversion of 4 to 8 .     

Heteroadamantanes and their derivatives 11. Synthesis of 3,6-diazahomoadamantan-9-one and its derivatives with substituents in the angular positions

The condensation of ketones with tetramethylenediethylenediamine led to the isolation of 3,6-diazahomoadamantan-9-one and its derivatives with substituents in the angular positions; their structure was confirmed by the data of the IR, PMR, and mass spectra.For Communication 10, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 675–680, May, 1990.     

Diastereoselective synthesis of 3,6-disubstituted 3,6-dihydropyridin-2-ones

In a short sequence, 5-vinyloxazolidin-2-ones were converted into the 3,6-disubstituted 3,6-dihydropyridin-2-ones via Pd-catalysed carbonylation and enolate alkylation with high diastereoselectivity. Alkylation of 6-substituted N-methylpyridin-2-ones gives stereoselectively the 3,6-anti diastereoisomer with MeI, BuI and i-PrI. Alkylation of the corresponding N-BOC pyridinones gives the 3,6-syn diastereoisomer with high selectivity.     

Synthesis of fluoren-9-ones via palladium-catalyzed cyclocarbonylation of o-halobiaryls

The synthesis of various substituted fluoren-9-ones has been accomplished by a novel palladium-catalyzed cyclocarbonylation of o-halobiaryls. The cyclocarbonylation of 4'-substituted-2-iodobiphenyls produces very high yields of 2-substituted fluoren-9-ones bearing either electron-donating or electron-withdrawing substituents. 3'-Substituted 2-iodobiphenyls afford in excellent yields with good regioselectivity 3-substituted fluoren-9-ones. This chemistry has been successfully extended to polycyclic and heterocyclic fluorenones.     

3,6-二烷硫基-1-苯基-吡唑并[3,4-d]嘧啶-4-酮衍生物的合成与除草活性

通过3-甲硫基-1-苯基-吡唑并[3,4-d]嘧啶-6-硫酮和卤代烃RX(BrR'Br)亲核取代反应合成了16种标题化合物,其结构使用元素分析、IR,1H NMR及LC-MS进行了表征.初步的生物活性测试表明,部分化合物对单、双子叶植物根的生长具有优异的抑制作用.     

新型潜香化合物3,6-二甲基-2,5-吡嗪二甲酸二薄荷醇酯的热裂解产物

为开发新型高温释放型烟用香料,以2,3,5,6-四甲基吡嗪和薄荷醇为原料,经过酯化反应制备了3,6-二甲基-2,5-吡嗪二甲酸二薄荷醇酯(DPAME).采用在线热裂解-气相色谱-质谱联用技术(Py-GC-MS)在空气氛围和不同的温度(300、600和900 ℃)下,对DPAME进行热裂解研究,裂解产物经GC-MS进行了定性和半定量分析.结果表明,DPAME在300 ℃下裂解产生了多种有致香效果的醛类、薄荷烯和薄荷醇等;在600 ℃和900 ℃下裂解产生了烯烃类、烷基吡嗪、薄荷醇和薄荷烯等香味物质,并且吡嗪类的种类和相对含量在这两个温度下明显增加.结合DPAME的热裂解产物分析和卷烟感官评吸结果,初步推测了其可能的裂解机理.采用该方法可以方便、快速地分离鉴定物质的热裂解产物,为该物质在烟草中的加香应用提供理论依据.     

Synthesis of fluoren-9-ones by the palladium-catalyzed cyclocarbonylation of o-halobiaryls

The synthesis of various substituted fluoren-9-ones has been accomplished by the palladium-catalyzed cyclocarbonylation of o-halobiaryls. The cyclocarbonylation of 4'-substituted 2-iodobiphenyls produces very high yields of 2-substituted fluoren-9-ones bearing either electron-donating or electron-withdrawing substituents. 3'-Substituted 2-iodobiphenyls afford 3-substituted fluoren-9-ones in excellent yields with good regioselectivity. This chemistry has been successfully extended to polycyclic fluorenones and fluorenones containing fused isoquinoline, indole, pyrrole, thiophene, benzothiophene, and benzofuran rings.     

Synthesis of 3,6-diazahomoadamantane

Condensation of 1-phenylsulfanylpropan-2-one with 1,3,6,8-tetraazatricyclo[4.4.1.1^3,8]dodecane gave 1-phenylsulfanyl-3,6-diazahomoadamantan-9-one which was reduced to 1-phenylsulfanyl-3,6-diazahomoadamantane, and the latter was subjected to desulfurization over Raney nickel to obtain previously unknown 3,6-diazahomoadamantane. Heating of 9-phenyl-3,6-diazahomoadamantan-9-ols with Raney nickel resulted in reduction of the hydroxy group with formation of 9-phenyl-3,6-diazahomoadamantanes.     

Perchloric Acid-Catalyzed Synthesis of 9-Aryl Xanthenes-9H-3,6-diol and 1,3,6,8-Tetraol in Water

Efficient syntheses of xanthenes have been described using a catalytic amount of perchloric acid in water. The high temperature and lengthy reaction time normally required for formation of xanthenes derivatives are not necessary when using a catalytic amount of perchloric acid. The method is relatively inexpensive, easily available, nonvolatile, nonexplosive, and thermally robust to catalyze the reaction at 80 °C by simple heating with good to excellent yields. The advantages of the reaction involve simple reaction protocol, simple workup, and improved synthesis in the presence of perchloric acid as catalyst.     

Synthesis of N-arylmethyl-3-azabicyclo[3.3.1]nonan-9-ones

Russian Journal of Organic Chemistry -     

Synthesis of 1, 5- and 1, 7-dichloro-9H-thioxanthen-9-ones

1, 5-Dichloro-9H-thioxanthen-9-one ( 2 ) was prepared by cyclization of 2-chloro-6-[(2-chlorophenyl)thio]-benzoic acid ( 10 ) obtained from 2-chloro-6-iodobenzoic acid ( 9 ) and 2-chlorobenzenethiol. Similarly, 1, 7-di-chloro-9H-thioxanthen-9-one ( 6 ) was prepared from 9 via 2-chloro-6-[(4-chlorophenyl)thio]benzoic acid ( 11 ). Compound 6 was also obtained by condensation of 2-chloro-6-mercaptobenzoic acid ( 12 ) with chlorobenzene in the presence of sulfuric acid.     

Heteroadamantanes and Their Derivatives: XXV. Synthesis of 3,6-Diazahomoadamantane-9-spirothiiranes

By treating 3,6-diazahomoadamantane-9-spirooxiranes with potassium thiocyanate 3,6-diazahomoadamantane-9-spirothiiranes were obtained which further by reductive desulfuration were converted into 3-methyl- and 9-methylene-3,6-diazahomoadamantanes.     

3,6-二甲基-9-芳基-1,8-二氧代-2,7,10-三氧杂蒽的合成及晶体结构

以芳醛、6 甲基 4 羟基 2 吡喃酮为原料 ,醋酸酐为溶剂合成了一系列 3 ,6 二甲基 9 芳基 1,8 二氧代 2 ,7,10 三氧杂蒽 ,产物的结构经红外、核磁、元素分析及X射线衍射法表征 ;并对反应过程提出了可能的机理     

3,6-二氨基-N-异丁基邻苯二甲酰亚胺的合成

以3-硝基邻苯二甲酸为原料,经脱水成酐、氨解、还原酰化、硝化、水解、还原等六步反应合成了一种新型的环芳酰胺的构筑单元对苯二胺衍生物——3,6-二氨基-N-异丁基邻苯二甲酰亚胺,总收率16.4％,其结构经1H NMR,13C NMR和ESI-MS表征.