2-(芳氧基苯基硫代膦酰基)-1,2,3σ^2-二氮磷杂环戊二烯的合成

研究了芳氧基苯基硫代膦酰基酮腙与三氯化磷的环化反应, 成功地合成了2-N上带有硫代膦酰基的3-氯1,2,3-二氮磷杂环戊烯(3)及二配位磷化物2-硫代膦酰基1,2,3σ^2-二氮磷杂环戊二烯(4)。     

2-(芳氧基苯基硫代膦酰基)-1,2,3σ~2-二氮磷杂环戊二烯的合成

芳香氮磷杂五元环是环状二配位磷化合物中的一类,近年来已有综述报道。1,2,3σ~2-二氮磷杂环戊二烯首先由Ignatova提出。本文研究了芳氧基苯基硫代膦酰基酮腙与三氯化     

1-对甲苯磺酰基-2-苯氧基-3-烷基-4-苯基-1,4-二氮-2-磷酰杂环戊-5-酮的合成及除草活性

我们已报道了1-对甲苯磺酰基-2-苯氧基-3-芳基-4-苯基-1,4,2-二氮磷酰杂环戊-5-酮的合成及除草活性[1],为了进一步探讨3-位取代基的变化对这类1,4,2-二氮磷酰杂环戊-5-酮的除草活性的影响,按如下方法合成了相应的3-位烷基取代的1-对甲苯磺酰基-4-苯基-1,4-二氮-2-磷酰杂环戊-5-酮（2）,并对脂肪醛与1及亚磷酸酯的酸催化反应机理进行了初步探讨．用元素分析、NMR、MS证实了化合物2的结构．初步除草活性测定结果表明,2具有一定的除草活性;其除草活性比相应的3-位芳基取代类化合物的低[1]．R：2a,H;2b,Me;2c,Et;2d,n－Pr…     

1,2,3—二氮磷杂环戊二烯类化合物的合成及性质

合成了2-乙酰基-1,2,3-二氮磷杂环戊二烯类系列化合物,用~1H、~(13)C、~(31)P NMR和MS确定了其结构,讨论了结构和NMR谱间的关系。     

1-芳基-2-苯基-3-甲基-3-异丙基-2-氧代-1,4,2-二氮磷杂环戊-5-酮的合成及除草活性

利用取代苯基脲与苯基二氯化膦和3-甲基-2-丁酮进行的类Mannich反应合成了15种新的1,4,2-二氮磷杂环戊-5-酮类化合物(2a_2o), 其结构经     

3,4-二苯基-4-氧(硫)代-1,3,4-二氮磷杂环戊-2-硫酮的合成、结构及其反应机理研究

本文研究了苯基硫脲、苯基二氯化膦与脂肪醛(酮)在无水苯中进行的类Mannich反应,在分离产物时发现,除了生成3,4-二苯基-4-氧代-1,3,4-二氮磷杂环戊-2-硫酮(Ⅰ)外,还得到了少量3,4-二苯基-4硫代-1,3,4-二氮磷杂环戊-2-硫酮(Ⅱ).根据化合物Ⅱ的生成及³¹PNMR跟踪反应的结果,得出反应机理为P-H键对亚胺衍生物的加成.通过X射线衍射分析发现,化合物Ⅰ和Ⅱ的五元杂环均为平面结构,其平面性受4位氧代或硫代的影响较大.     

1-单取代-1,2,3-三唑环的构建进展

随着1,2,3-三唑衍生物应用范围的扩大,该类化合物的合成在近几年引起了广泛关注并获得了快速发展.1-单取代-1,2,3-三唑衍生物比其他类型三唑的杂环构建难度大,主要原因是合成该类产物"炔源"的结构要求独特,并需要相应特殊的反应条件.综述了该类杂环的构建研究进展,按照"炔源"的种类不同分别阐述了各种构建方法,主要包括乙炔、取代乙炔、乙烯化物等,并对部分重要的反应机理进行了分析.     

类Mannich反应合成2,5-二苯基-3,3-二取代-2,3-二氢-1,4,2-氧氮磷杂环戊烯-2-氧化物

本文报道了以苯甲酰胺,醛(或酮)苯基二氯化膦为原料进行的Mannich反应,其产物经部分水解合成了α-(N-苯甲酰氨基)二取代甲基苯基膦酸(Ⅰ),此化合物脱水关环得2,5-二苯基-3,3-二取代-2,3-二氢-1,4,2-氧氮磷杂环戊烯-2-氧化物(Ⅱ).经¹HNMR及元素分析证明了Ⅰ和Ⅱ的结构,并对反应机理进行了探讨。     

1,3,5,7-四乙酰基-1,3,5,7-四氮杂环辛烷合成反应中间体的制备分离

1,3,5,7-四乙酰基-1,3,5,7-四氮杂环辛烷(TAT)是高能炸药奥克托今(HMX)重要的合成反应前体之一,1,5-二乙酰基-1,3,5,7-四氮杂环辛烷(DAPT)醋酐酰解法和乙腈甲醛小分子缩合法均能制备得到TAT.采用半制备高效液相色谱制备分离了上述两种制备方法反应原液中的六种中间体,分别是1-乙酰氧甲基-3,5,7-三乙酰基-1,3,5,7-四氮杂环辛烷、1,3,5-三乙酰基-1,3,5,7-四氮杂环辛烷、1-乙酰氧甲基-3,5,7-三乙酰基-1,3,5,7-四氮杂环辛烷、N,N’-亚甲基二乙酰胺、三乙酰胺二亚甲基三胺和四乙酰胺三亚甲基四胺,为反应机理研究提供了有力的证据.DAPT醋酐酰解法反应原液样品的最佳制备色谱条件为:正相硅胶柱(20 mm×250 mm,10～20μm),流动相:V(乙腈)∶V(甲醇)=95∶5,流速为10 mL·min-1,检测波长为215 nm,进样量为1 mL,样品浓度30 mg/mL.乙腈甲醛小分子缩合法反应原液样品的最佳制备色谱条件为:正相硅胶柱(20 mm×250 mm,10～20μm),流动相:V(乙腈)∶V(水)=90∶10,流速为10 mL·min-1,检测波长为215 nm,进样量为1 mL,样品浓度30 mg/mL.制备得到的中间体经HPLC分析知纯度均在97%以上,可直接作为结构鉴定的标准样品.     

1,3,2-二氮磷杂环戊-4-酮-2-硒(硫)代化合物的合成及生物活性

五元磷杂环;1;3;2-二氮磷杂环戊-4-酮-2-硒(硫)代化合物的合成及生物活性;烟草花叶病毒;除草活性;杀菌活性;抗药草花叶病毒活性     

Synthesis of 2-alkylthio-5-acetyl-2-oxazolines

The reaction of 2-acetyloxiranes with alkyl thiocyanates in the presence of Lewis acids (BF₃, AlCl₃) has given 2-alkylthio-5-acetyl-2-oxazolines (yields 40–60%). It has been shown that the reaction of trans-2-acetyl-3-methyloxirane and of trans-2-acetyl-3-methyloxirane and of trans-2-acetyl-2,3-dimethyloxirane with alkyl thiocyanates takes place stereospecifically and leads to cis-2-alkylthio-5-acetyl-2-oxazolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 468–471, April, 1980.     

Formation of carbon-carbon single bonds from isocyanates and cyclic pentaoxyphosphoranes—VI : Synthesis of 4-oxazolones and 4-thiazolones,and a new type of chapman rearrangement

The reaction of 4,5-dimethyl-2,2,2-trimethoxy-2,2-dihydro-1,3,2-dioxaphospholene with carbomethoxy, carbopropoxy and N,N-diphenylcarbamyl isocyanates yields, respectively, 2-methoxy-, 2-propoxy- and 2- diphenylamino-5-acetyl-5-methyl-2-oxazolin-4-one. The reaction with carbophenoxy isocyanate gives two products in a proportion which depends on experimental conditions: 2-phenoxy-5-acetyl-5-methyl-2-oxalin-4-one (1:1 stoichiometry) and 1,3-dicarbophenoxy-5-acetyl-5-methyl-hydantoin (1:2 stoichiometry). The 2-substituted 4- oxazolones are hydrolyzed to 5-acetyl-5-methyl-oxazolidin-2,4-dione. The alkyl group of the 2-alkoxy-4-oxazolones migrates to the adjacent nitrogen to give 3-alkyl-5-acetyl-5-methyl-oxazolidin-2,4-diones. The dioxaphospholene reacts with 2-substituted 2-thiazolin-4,5-diones to give 2-substituted 5-acetyl-5-methyl-2-thiazolin-4-ones, including rhodanine derivatives.     

Acetyl ketene aminals in Nenitzescu reaction

Nenitzescu reaction of acetyl ketene aminals (N,N-acetals) was investigated. The interaction of 2-acetyl-1-amino-1-anilinoethene with benzoquinone gave 3-acetyl-2-amino-7a-hydroxy-1-phenyl-5,7a-dihydro-1H-indol-5-one, which was then transformed into 3-acetyl-2-amino-6-chloro-5-hydroxy-1-phenylindole. The reaction of benzoquinone with 2-acetyl-1-amino-1-benzoylaminoethene led to the corresponding hydroquinone-adduct which was oxidized to 4-acetylamino-5-(2,5-dihydroxyphenyl)-2-phenyloxazole. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 160–165, January, 1999.     

Synthesis of polyfunctionalized furans from 3-acetyl-1-aryl-2-pentene-1,4-diones

The BF₃-catalyzed cyclization of 3-acetyl-1-aryl-2-pentene-1,4-diones 1a-e in the presence of water in boiling tetrahydrofuran gave bis(3-acetyl-5-aryl-2-furyl)methanes 2a-e in 26-79% yields along with a small amount of 3-acetyl-5-aryl-2-methylfurans 3a-e. The exact structure of 2a was determined by X-ray crystallography. The use of a half volume of the solvent for the reaction of 1a resulted in the formation of 2,4-bis(3-acetyl-5-phenyl-2-furfuryl)-3-acetyl-5-phenylfuran (4) together with 2a and 3a. A similar reaction of 1a was carried out in the presence of 3-acetyl-5-(4-methylphenyl)-2-methylfuran (3d) to afford 4-(3-acetyl-5-phenyl-2-furfuryl)-3-acetyl-5-(4-methylphenyl)-2-methylfuran (5) in 49% yield. The BF₃-catalyzed reaction of 1a with 2,4-pentanedione in dry tetrahydrofuran at 23°C gave 3-(3-acetyl-5-phenyl-2-furfuryl)-4-hydroxy-3-penten-2-one (6a) and 3-(3-acetyl-2-methyl-4-phenyl-5-furyl)-4-hydroxy-3-penten-2-one (7a) in 66 and 24% yields, respectively. The product distribution depended on the reaction temperature. A similar reaction of 1b-e also yielded the corresponding trisubstituted furans 6b-e and tetrasubstituted furans 7b-e in good yields. These results suggested the presence of the furfuryl carbocation intermediate A during the reaction. The one-pot synthesis of 6a and 7a was also achieved by a similar reaction using phenylglyoxal. The deoxygenation of 1a with triphenylphosphine gave 3a in 88% yield, while 1a was treated with concentrated hydrochloric acid to yield 3-acetyl-2-chloromethyl-5-phenylfuran (8) which was quantitatively transformed in ethanol into 3-acetyl-2-ethoxymethyl-5-phenylfuran (9) and in water into 3-acetyl-5-phenylfurfuryl alcohol (10), respectively. In addition, the Diels-Alder reaction of cyclopantadiene with 1a gave the corresponding [4+2] cycloaddition products 11 and 12.     

Synthesis and chemical properties of 8-aryl-7-acyl-1-6-dimethyl-6-hydroxy-4-cyano-5,6,7,8-tetrahydro-3(2H)-isoquinolinones and isoquinolinethiones

8-Aryl-7-acetyl-1, 6-dimethyl-6-hydroxy-4-cyano-5, 6, 7, 8-tetrahydro-3(2H)-isoquinolinones and -isoquinolinethiones and their sodium salts were obtained by the reaction of cyanoacetamide and cyanothioacetamide with 3-aryl-2, 4-diacetyl-5-methyl-5-hydroxycyclohexanonesinbasicrnedium. 8-Aryl-7-acetyl-6-methoxycarbonyl-1, 6-dimethyl-4-cyano-5, 6, 7, 8-tetrahydro-3(2H)-isoquinolinones were obtained by the reaction of acetyl chloride and the above isoquinolinone sodium salts. The reaction of iodoacetamide and the above isoquinolinethione sodium salts yielded 8-aryl-7-acetyl-3-carbamoylmethylthio-1, 6-dimethyl-4-cyano-5, 6, 7, 8-tetra-hydroisoquinolines, which were cyclized into 1-amino-6-aryl-7-acetyl-2-carbamoyl-5, 8-dimethyl-8-hydroxy-6, 7, 8, 9-tetrahydrothiophene[2,3-c]isoquinolines in basic medium.     

Manganese(III) acetate oxidation of 1-acetylindole derivatives

In the presence of malonic acid, the reaction of 1-acetylindole ( 2 ) with manganese(III) acetate resulted in the formation of 4-acetyl-3,3a,4,8b-tetrahydro-2H-furo[3,2-b]indol-2-one ( 5 ). The same reaction of 1-acetyl-2,3-dimethylindole yielded a mixture of 2-acetoxymethyl-1-acetyl-3-methylindole and 4-acetyl-3a,8b-dimethyl-3,3a,4,8b-tetrahydro-2H-furo[3,2-b]indol-2-one, furthermore, the oxidation of 1-acetylindoline proceeded to the formation of 2, 5 and 1-acetylindoline-5-carboxylic acid.     

Synthesis and properties of 5-(1,2-dihaloethyl)-2′-deoxyuridines and related analogues

The regiospecific reaction of 5-vinyl-3′,5′-di-O-acetyl-2′-deoxyuridine ( 2 ) with HOX (X = Cl, Br, I) yielded the corresponding 5-(1-hydroxy-2-haloethyl)-3′,5′-di-O-acetyl-2′-deoxyuridines 3a-c . Alternatively, reaction of 2 with iodine monochloride in aqueous acetonitrile also afforded 5-(1-hydroxy-2-iodoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 3c ). Treatment of 5-(1-hydroxy-2-chloroethyl)- ( 3a ) and 5-(1-hydroxy-2-bromoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 3b ) with DAST (Et₂NSF₃) in methylene chloride at -40° gave the respective 5-(1-fluoro-2-chloroethyl)- ( 6a , 74%) and 5-(1-fluoro-2-bromoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 6b , 65%). In contrast, 5-(1-fluoro-2-iodoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 6e ) could not be isolated due to its facile reaction with methanol, ethanol or water to yield the corresponding 5-(1-methoxy-2-iodoethyl)- ( 6c ), 5-(1-ethoxy-2-iodoethyl)- ( 6d ) and 5-(1-hydroxy-2-iodoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 3c ). Treatment of 5-(1-hydroxy-2-chloroethyl)- ( 3a ) and 5-(1-hydroxy-2-bromoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 3b ) with thionyl chloride yielded the respective 5-(1,2-dichloroethyl)- ( 6f , 85%) and 5-(1-chloro-2-bromoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 6g , 50%), whereas a similar reaction employing the 5-(1-hydroxy-2-iodoethyl)- compound 3c afforded 5-(1-methoxy-2-iodoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 6c ), possibly via the unstable 5-(1-chloro-2-iodoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine intermediate 6h . The 5-(1-bromo-2-chloroethyl)- ( 6i ) and 5-(1,2-dibromoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 6j ) could not be isolated due to their facile conversion to the corresponding 5-(1-ethoxy-2-chloroethyl)- ( 6k ) and 5-(1-ethoxy-2-bromoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 61 ). Reaction of 5-(1-hydroxy-2-bromoethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 3b ) with methanolic ammonia, to remove the 3′,5′-di-O-acetyl groups, gave 2,3-dihydro-3-hydroxy-5-(2′-deoxy-β-D-ribofuranosyl)-furano[2,3-d]pyrimidine-6(5H)-one ( 8 ). In contrast, a similar reaction of 5-(1-fluoro-2-chloroethyl)-3′,5′-di-O-acetyl-2′-deoxyuridine ( 6a ) yielded (E)-5-(2-chlorovinyl)-2′-deoxyuridine ( 1b , 23%) and 5-(2′-deoxy-β-D-ribofuranosyl)furano[2,3-d]pyrimidin-6(5H)-one ( 9 , 13%). The mechanisms of the substitution and elimination reactions observed for these 5-(1,2-dihaloethyl)-3′,5′-di-O-acetyl-2′-deoxyuridines are described.     

Sur l'orientation et les anomalies de l'acetylation des Bz-méthoxy nitro-2 benzofurannes

4-Methoxy-, 5-methoxy- and 7-methoxy-2-nitrobenzofurans have been acetylated via the Friedel-Crafts reaction under the same reaction conditions. 2-Nitrobenzofuran does not undergo acetylation while 6-methoxy-2-nitrobenzofuran only produces decomposition products. As a result of the positive acetylation reactions, 7-acetyl-4-methoxy-, 4-acetyl-5-methoxy- and 4-acetyl-7-methoxy-2-nitrobenzofuran have been prepared. As side products in the acetylation reactions, 4-methoxy-3-(4′-methoxy-2′-nitro-7′-benzofuranyl)-2,3-dihydrobenzofuran-2-one was isolated when 4-methoxy-2-nitrobenzofuran was the starting material and, likewise, when 5-methoxy-2-nitrobenzofuran was the starting material, 3-chloro-5-methoxy-2,3-dihydrobenzofuran-2-one was obtained. Furthermore, 5-methoxy-2-nitrobenzofuran participated in an unexpected chlorination leading to 4-chloro-5-methoxy-2-nitrobenzofuran.     

Synthesis of functional derivatives of trifluoromethylpyrimidines from acetylacetone,trifluoroacetonitrile, and aryl isocyanates

1, 1,1-Trifluoro-2-amino-3-acetyl-2-penten-4-one was obtained by the addition of acetylacetone to trifluoroacetonitrile in the presence of catalytic amounts of nickel acetylacetonate. The reaction of 1,1,1-trifluoro-2-amino-3-acetyl-2-penten-4-one with aryl isocyanates gave 1-aryl-5-acetyl-6-methyl-4-trifluoromethyl-1H-pyrimidin-2-ones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2639–2642, November, 1991.     

Synthesis of 1,8- and 2,8-dihydrocycloheptapyrazol-8-one derivatives by the reactions of 3-acetyltropolone and its methyl ethers with phenylhydrazine

3-Acetyltropolone ( 1 ) reacted with phenylhydrazine to give 3-acetyltropolone phenylhydrazone ( 3 ) and 3-methyl-1-phenyl-1,8-dihydrocycloheptapyrazol-8-one ( 4 ). The former ( 3 ) cyclized to afford the latter ( 4 ). The reaction of 3-acetyl-2-methoxytropone ( 2a ) with phenylhydrazine gave 4 , 3-methyl-2-phenyl-2,8-dihydrocyclo-heptapyrazol-8-one ( 5 ), and 3-methyl-2-phenyl-2,8-dihydrocycloheptapyrazol-8-one phenylhydrazone ( 6 ). The compound ( 5 ) reacted with phenylhydrazine to afford 6 . The reaction of 7-acetyl-2-methoxytropone ( 2b ) with phenylhydrazone gave 7-acetyl-2-methoxytropone phenylhydrazone ( 7 ), 7-acetyl-2-(N′-phenylhydrazino)-tropone phenylhydrazone ( 8 ), 3-methyl-1-phenyl-1,8-dihydrocycloheptapyrazol-8-one phenylhydrazone ( 9 ), and 6 . The compound ( 7 ) was heated to afford 4 and reacted with phenylhydrazine to afford 8 and 9 . The compound ( 8 ) was also refluxed to give 9 .