1,3-二苄基-4-(4-甲氧羰基丁基)-噻吩并[3,4-d]-咪唑-2-酮的合成

1,3-二苄基-4-(4-甲氧羰基丁基)-噻吩并[3,4-d]-咪唑-2-酮(Ⅰ)是合成生物素的一个关键中间体.在超声波促进下,用低价钛试剂对(4 aR)-1,3-二苄基-4-(1-己二酸单甲酯酰基硫甲基)-咪唑-2,5-二酮(Ⅱ)进行还原偶联,即生成1,3-二苄基-4-(4-甲氧羰基丁基)-噻吩并[3,4-d]咪唑-2-酮(Ⅰ).超声反应1.5 h,收率71%.     

5,6,7,8-四氢吡啶并[3,4-d]嘧啶衍生物的合成

以苄胺为原料,经过取代,缩合,水解,脱保护等步骤,设计合成了一系列新型的5,6,7,8-四氢吡啶并[3,4-d]嘧啶类化合物。通过1H NMR,13C NMR,MS和元素分析确证了其结构。并且对其体外抗肿瘤活性进行了研究,发现该类化合物对乳腺癌细胞MCF-7具有一定的抑制活性,其中化合物10a和10d的抑制活性达到了中效水平。     

3,4-二氢-3-甲基-4-氧代咪唑[5,1-d]并[1,2,3,5]四嗪-8-甲酸苯磺酰基呋咱氮氧基酯的合成

以3,4-二氢-3-甲基-4-氧代咪唑[5,1-d]并[1,2,3,5]四嗪-8-甲酰胺和苯磺酰基呋咱氮氧化物为原料,通过肖滕-鲍曼法合成了5种新的咪唑四嗪衍生物——3,4-二氢-3-甲基-4-氧代咪唑[5,1-d]并[1,2,3,5]四嗪-8-甲酸苯磺酰基呋咱氮氧基酯,其结构经1H NMR,IR,MS和元素分析确证。     

选择性合成双[噻吩并[2,3-d]嘧啶-4(3H)-酮]

以2-氨基-4-三氟甲基-5-甲基-噻吩-3-羧酸乙酯(1)为起始原料制得膦亚胺2.在碳酸钾的催化下,膦亚胺2与芳基异氰酸酯和伯二胺的氮杂Wittig反应制得嘧啶环上2,2’取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]3;膦亚胺2与烷基异氰酸酯和伯二胺的氮杂Wittig反应制得嘧啶环上3,3’取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]4.化合物3的核磁共振氢谱表明关环反应在嘧啶环的2,2’位;化合物4的核磁共振氢谱表明关环反应在嘧啶环的3,3’位.对合成反应机理的推导及目标产物核磁共振氢谱数据的分析解释了此合成反应的选择性.     

新型4-芳氧基吡啶并[3′,2′∶4,5]噻吩并[3,2-d]嘧啶衍生物的合成

2-氯-3-氰基吡啶与巯基乙酸乙酯经闭环反应制得3-氨基吡啶并[3,′2′∶4,5]噻吩-2-甲酸乙酯(1);1与甲酰胺第二次成环生成吡啶并[3,′2′∶4,5]噻吩并[3,2-d]嘧啶-4-酮(2);2经氯化后与取代苯酚反应合成了12个新型的4-芳氧基吡啶并[3,′2′∶4,5]噻吩并[3,2-d]嘧啶衍生物,其结构经1H NMR,13C NMR,IR和元素分析表征。     

2-芳氧基-3-对氟苯基-3,5,6,7-四氢-4H-环戊二烯并[4,5]噻吩并[2,3-d]-嘧啶-4-酮衍生物的合成及其抑菌活性

利用三组分氮杂Wittig反应, 以三氢环戊二烯并噻吩基三苯基膦亚胺、对氟苯基异氰酸酯和酚, 合成了13个未见文献报道的2-芳氧基-3-对氟苯基-3,5,6,7-四氢-4H-环戊二烯并[4,5]噻吩并[2,3-d]-嘧啶-4-酮衍生物, 产率58%～73%. 通过IR, 1H NMR, MS 和元素分析对目标化合物的结构进行了表征. 初步探讨了所合成化合物的抑菌活性, 结果显示所合成的化合物对真菌(桔青霉菌)的抑制活性优于对细菌的抑制活性.     

用聚乙二醇简便合成3-取代-1, 2, 3, 4-四氢吡啶并[3, 2-d]嘧啶-2, 4-二酮

用聚乙二醇作为可溶性聚合物载体和相转移催化剂高效简单的合成了1, 2, 3, 4-四氢吡啶并[3, 2-d]嘧啶类化合物。该合成路线为聚乙二醇与2, 3-吡啶二酸酐反应生成聚乙二醇支载的单酯1,接着1被转化成相应的聚乙二醇支载的酰基叠氮2,2经Curtius重排,与胺加成并同时关环给出目标产物,其总产率为84%-88%。     

四氢咪唑并[2',1':2,3]噻吩并[5,4-c]哌啶衍生物的合成及抗肿瘤活性

以4-哌啶酮为原料,经过胺基保护、缩合、环合、脱保护等步骤,设计合成了一系列新型的5,6,7,8-四氢咪唑并[2',1':2-3]噻吩并[5,4-c]哌啶类化合物。通过核磁共振波谱仪(~1H NMR、~(13)C NMR)、质谱(MS)和元素分析确证了其结构。对其体外活性研究发现,该类化合物对乳腺癌细胞MCF-7具有一定的抑制活性,其中化合物5a的抑制活性最为显著,半数抑制浓度(IC_(50))值达到了8.6μmol/L。为此类化合物的抗肿瘤活性研究提供了参考。     

(2S,3S,4R)-2-正戊基-3,4-二叠氮基四氢噻吩的合成

以（＋）－4，10－二氧杂三环[5.2.1.O^2,6]－癸－8－烯－3－醇为原料。经8步反应，对映选择性地合成出去氧维生素H的重要中间体：（2S，3S，4R）－2－正戊基－3，4－二叠氮基四氢噻吩。为对映选择性合成手性四氢噻吩类化合物提供了新的方法。     

顺式六氢-1H-呋喃并[3,4-C]吡咯的合成

以N-（甲氧甲基）-N-（三甲基硅甲基）苄胺和马来酸二甲酯为原料通过环加成、氢化铝锂还原、T_SOH催化脱水、氢氧化钯/碳催化氢化脱苄基四步反应,设计并合成了一种含氮、氧的杂环化合物--顺式六氢-1H-呋喃并[3,4-C]吡咯,其结构经¹H NMR, ¹³ C NMR和MS（ESI）表征。      

Synthesis of derivatives of 2-oxo-2,3-dihydro-1H-thieno[3,4-d]imidazole

Conclusions Derivatives of 2-oxo-2,3-dihydro-1H-thieno[3,4-d]imidazole were synthesized from 4,5-di-substituted 2-imidazolinones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2381–2383, October, 1987.     

New synthesis of 5,6,7,8-tetrahydro-4H-thieno[2,3-d]azepine

This paper describes two new access routes to 5,6,7,8-tetrahydro-4H-thieno[2,3-d]azepine from 2-(2-thienyl)ethylamine or its N-(2-chlorobenzyl) derivative. One of these two syntheses involves a new ring expansion from a 6,7-dihydro[3,2-c]pyridinium derivative, chloromethylated in position 4.     

Synthesis of 1H-thieno[3,4-c]pyrazoles,thieno[3,4-b]furans,selenolo[3,4-b]furans and pyrrolo[3,4-d]thiazoles

Starting from the readily available aryl 2-methyl-5-phenyl-3-furyl ketones, 5-methyl-1H-1-phenylpyrazole-4-yl ketones and 4-methyl-2-phenyl-5-thiazolylcarboxaldehyde, a series of 2-phenyl-4-arylthieno[3,4-b]-furan, 2-phenyl-4-(p-methoxyphenyl)selenolo[3,4-b]furan, 4-aryl-1H-1-phenylthieno[3,4-c]pyrazole and 5-benzyl-2-phenylpyrrolo[3,4-d]thiazole were prepared in high yield.     

Synthesis of cis- and trans-perhydrothieno[3,4-d]imidazole-2-thione 5,5-dioxides

It is shown that the cis and trans isomers of perhydrothieno[3,4-d]imidazole-2-thione 5,5-dioxides can be obtained in good yields from the accessible derivatives of thiolane and 2-thiolene 1,1-dioxides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 328–330, March, 1982.     

Synthesis of 3-substituted-2,3,4,5-tetrahydro-1H-naphth[1,2-d]-imidazole-2,4,5-triones and 1-Substituted-2,3,4,9-tetrahydro-1H-naphth[2,3-d]imidazole-2,4,9-triones

Tricyclic compounds with an imidazolinone ring fused to 1,2- and 1,4-naphtoquinones were synthesized by a reaction of 4-amino-1,2-naphthoquinone and 2-amino-1,4-naphthoquinone with electrophilic symmetric and non symmetric diazenes.     

Selenium heterocycles. XXXII . Synthesis of [1]benzoxepino[3,4-d]-thiazole, [1]benzothiepino[3,4-d]thiazole, [1]benzoxepino[3,4-d]selenazole,and [1]benzothiepino[3,4-d]selenazole. four novel heterocycles

Starting from the readily available ethyl 2-phenyl-4-methyl-thiazole-5-carboxylate (III), 2-phenyl-4-chloromethyl-thiazole (VIII) and 2-aryl-4-chloromethylselenazole (XIV), 2-phenyl-4,10-dihydro-10-oxo-[1]benzoxepino[3,4-d]thiazole (Ia), 2-phenyl-4,10-dihydro-10-oxo[1]benzothiepino[3,4-d]thiazole (Ib), 2-aryl-4,10-dihydro-10-oxo[1]benzoxepino[3,4-d]selenazoles (IIa-IIe) and 2-aryl-4,10-dihydro-10-oxo[1]benzothiepino[3,4-d]selenazoles (IIf-IIj) were prepared.     

Synthesis of some 3-alkenyl-4-oxo-6,7-dihydro-4H-pyrano[3,4-d]isoxazoles

A series of 3-alkenyl-4-oxo-6,7-dihydro-4H-pyrano[3,4-d]isoxazole derivatives was prepared by reaction of hydroxylamine with 4,5-dioxo-2,3,7,8-tetrahydro-4H,5H-pyrano[4,3-b]pyran derivatives.     

Synthesis of 1H-[1]benzothiopyrano[3,4-d]imidazol-4-ones

By the condensation of 3,4-diaminothiocoumarins containing primary or secondary amino groups in position 4, with formic and acetic acids (or acetic anhydrides), a number of 1H-[1]benzothiopyrano[3,4-d]imidazol-4-ones and their 2-methyl derivatives have been synthesized; the latter have also been obtained from the corresponding 3-monoacetylamino-4-aminothiocoumarins. By the acetylation of 3-4-diaminothiocoumarins with tertiary amino groups in positions 4 their 3-diacetyl derivative has been obtained, and these, under the action of bases, have been converted into 3-N-acetyl derivatives. The structures of the compounds synthesized have been confirmed by IR, PMR, and mass spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 479–483, April, 1980.