AN EFFICIENT SYNTHESIS OF SOME BIS-(2-ALKYLTHIO-5-FURFURYLIDENE-4H-IMIDAZOL-4-ONE) DERIVATIVES BEARING POTENTIAL FUNGICIDAL ACTIVITIES

Some bis-(2-alkylthio-furfurylidene-4H-imidazol-4-one) derivatives 4 were synthesized by S-alkylation of bis-(2-thioxo-5-furfurylidene-4- imidazolidinone) 3, which was obtained via tandem aza-Wittig reaction of vinyliminophosphorane 1, carbon disulfide, and ethylenediamine.     

SYNTHESIS AND FUNGICIDAL ACTIVITIES OF 2-BENZOTHIAZOLYLTHIO-SUBSTITUTED 4H-IMIDAZOL-4-ONES AND 4(3H)-QUINAZOLINONES

4H-Imidazol-4-ones 4 or 4(3H)-quinazolinones 8 were synthesized by base catalytic reactions of 2-mercaptobenzothiazole with carbodiimides 2 or 6, respectively, which were obtained via aza-Wittig reaction of iminophosphorane 1 or 5 with aromatic isocyanates. 4 and 8 exhibited fungicidal activity.     

VERSATILE SYNTHESIS AND FUNGICIDAL ACTIVITIES OF 6-AMINO-3- ALKYLTHIO-1,5-DIHYDRO-1-PHENYL-PYRAZOLO [3,4-D]PYRIMIDIN-4-ONE DERIVATIVES

A series of new 6-alkylamino-3-alkylthio-1-phenyl-1H-pyrazolo[3,4-d] pyrimidin-4(5H)-one derivatives 5 and 6 have been rapidly synthesized by a novel solution-phase regioselective synthetic method. Treatment of pyrazole o-aminoester 1 with dibromotriphenylphosphorane gave iminophosphorane 2, which underwent a aza-Wittig reaction with phenyl ioscyanate to provide the carbodiimide 3. The latter intermediate reacted with alkylamines and regioselectively provided the 1,5-dihydro-pyrazolo[3,4-d]pyrimidin-4-one derivatives 5 and 6, some of which exhibited good fungicidal activity.     

2-烷氧基-3H-喹唑啉-4-酮的合成与杀菌活性

研究了合成2-烷氧基-3H-喹唑啉-4-酮衍生物4的方法,该方法应用膦亚胺1与芳基异氰酸酯的氮杂Wittig反应,得到的碳二亚胺2再与醇在醇钠催化下反应,合成了12种未见文献报道的喹唑啉酮衍生物4.所得产物4的结构由NMR,MS,IR所确证.探讨了成环反应的条件以及所合成的新型杂环化合物的杀菌活性,结果表明部分化合物表现出较好的抑菌活性,如41在50 mg/L浓度时,对水稻纹枯菌的抑制率为89%.     

SYNTHESIS AND REACTIONS OF HALO DERIVATIVES OF 4-ISOPROPYL-2H-1,4-THIAZIN-3-ONE

Abstract

Reaction of 4-isopropyl-2H-1,4-thiazin-3-one 1 (R [dbnd] i-Pr) with N-chloro- and N-bromosuccinimide occurred exclusively at the 6-position to give 6-chloro and 6-bromo derivatives of 1 (R [dbnd] i-Pr), respectively, in high yield, in sharp contrast to the 2-aroyloxylation by benzoyl peroxide or m-chloroperbenzoic acid reported earlier.² Reaction of 1 (R [dbnd] i-Pr) with methanesulfonyl chloride in the presence of aluminum chloride afforded an addition compound, 4-isopropyl-5,6-dichloro-1,4-tetrahydrothiazin-3-one. The 2-chloro derivative 6 of 1 (R [dbnd] i-Pr) was successfully prepared by hydrolysis of the 2-m-chloroben-zoyloxy derivative of 1 (R [dbnd] i-Pr) followed by treatment with thionyl chloride. Derivative 6 reacted readily under mild conditions with water, alcohols, thiols, ammonia and amines to give various 2-substituted compounds of 1 (R [dbnd] i-Pr). With phenol as a nucleophile, 1 (R [dbnd] i-Pr) reacted exclusively at the para position. Reaction at carbon atoms also occurred with N,N-dimethylaniline and 2,6-xylidine.     

A NOVEL SYNTHESIS OF 2-SUBSTITUTED-4H-THIENO [2,3-d][1,3] OXAZIN-4-ONE AND 2,3-DISUBSTITUTED THIENO [2,3-d]PYRIMIDIN-4(3H)-ONE DERIVATIVES

Abstract

The synthesis of acetic 2-{[1-methyl-2-(4-oxo-5,6,7,8-tetrahydro-4H-benzo [4,5]-thieno [2,3-d] [1,3-oxazin-2-yl)ethylidene]amino}-4,5,6,7-tetrahydrohenzo[b]thiophene ?3-carboxylic acid anhydride 5 and 2-(oxopropyl)-5,6,7,8-tetrahydro-4H-benzo-[4,5] thieno[2,3-d][1,3]oxazin-4-one 7, has been achieved in three steps from ethyl 2-amino-4,5,6,7-tetrahydrobenzo(b]thiophene-3-carboxlate 1 via the reaction with ethyl acetoacetate followed by hydrolysis and acetic anhydride-induced cyclization. The 2-substituent in compound 5 has two functional groups i.e. active methylene and acid anhydride which are suitably located for intramolecular transformation. Thermal and/or base catalyzed intramolecular cyclization of 5 afforded 2-(4-acetoxy-(hydroxyl)-2-methyl-5,6,7,8-tetrahydrobenzo[4,5] thieno[2,3-b]pyridin-3-yl)-5,6,7,8- tetrahydro-4H-benzo[4,5]thieno[2,3-d] [1,3]oxazin-4-one 10 and 9 respectively. Treatment of 5 with hydrazine hydrate, aromatic and/or heterocyclic amines induced the same intramolecular cyclization with a concomitant oxazine-pyrimidine interconversion to give 3-amino(aryl or heteryl)-2-(4-hydroxy-5,6,7,8-tetrdhydrobenzo-[4,5]thieno[2,3-b]pyridin-3-yl)-3,4,5,6,7,8-hexahydrobenzo[4,5] thieno[2,3-d] pyrimid in-4-one 11–14 respectively.     

2-(4-甲硫苯氧基)-3-(4-甲苯基)-4H-咪唑啉-4-酮衍生物的合成及杀菌活性(Ⅱ)

用烯基膦亚胺与4-甲苯基异氰酸酯、对甲硫苯酚的串联aza-Wittig反应合成了2-(4-甲硫基苯氧基)-3-(4-甲苯基)-4H-咪唑啉-4-酮衍生物.探讨了反应进行的条件和产物的波谱性质,提出了可能的环化反应机理.生成的环化产物均为新的化合物,其结构经元素分析、IR、1H NMR和MS确证.并探讨了所合成的新型杂环化合物的生物活性,结果表明部分化合物表现出良好的抑菌活性,其中3f的活性最好,在质量分数为5×10-5浓度时,对稻瘟菌和苹果轮纹菌的抑制率均达到100%.     

2-烷氧基-4H-咪唑啉-4-酮衍生物的合成与杀菌活性

应用烯基膦亚胺（1）与芳基异氰酸酯的氮杂Wittig反应，得到的碳二亚胺2再 与醇在醇钠催化下反应，合成了新的2-烷氧基-4H-咪唑啉-4-酮衍生物（3），探讨 了成环反应的条件以及所合成的新型杂环化合物的杀菌活性，结果表明部分化合物 表现出较好的抑菌活性，其中以3b活性最好，在50 mg/L浓度时，对水稻纹枯菌和 苹果轮纹菌的抑制率达81%以上。     

New Facile Synthesis of 2-Aryloxy-5-(2-furfurylidene)- 4H-imidazolin-4-ones

Many N-heterocycles including 4H-imidazolin-4-ones exhibit biological activities1-3. Some derivatives of 5-(2-furfurylidene)-4H-imidazolin-4-one were found to show good antiinflammatory activity4. They can be synthesized by condensation of furfural with 5- unsubsituted 4H-imidazolin-4-ones or from corresponding oxazolones5,6. However, no synthesis of 2-aryloxy substituted 5-(2-furfurylidene)-4H-imidazolin-4-one was reported. Recently, aza-Wittig reaction has received increased attention …     

2-烷硫基-4-芳基亚甲基-5-氢-1-苯氨基-1H-咪唑啉-5-酮的合成与杀菌活性

应用CS2与烯基膦亚胺1的氮杂Wittig反应,得到的异硫氰酸酯2再与苯肼作用得到氨基硫脲3,而后用3与卤代烷在K2CO3的作用下反应直接得到2-烷硫基-4-芳基亚甲基-5-氢-1-苯氨基-1H-咪唑啉-5-酮衍生物4.探讨了反应的条件以及合成的新型杂环化合物的生物活性,结果表明部分化合物表现出较好的杀菌活性.如4e在50 mg/L浓度时,对黄瓜灰霉菌的抑制率为87%.     

HETEROCYCLES SYNTHESIS THROUGH REACTIONS OF INDOLIN-2-ONE DERIVATIVES WITH ACTIVE METHYLENE AND AMINO REAGENTS,PART 3, NOVEL AND FACILE ONE-STEP SYNTHESIS OF SPIROTHIOPYRAN-4- YL INDOLIDENE DERIVATIVES

Abstract

New spirothiopyran-4-yl indolidene derivatives have been synthesised via a facile one-step method. Structures and reaction mechanisms are also reported and supported by another synthetic route.     

(4R,5S)-5-羟基-4-甲基-3-己酮的合成

农业害虫药材甲Stegobium panicem Linnae在我国各省区都有分布,主要危害谷类、食品、药材、图书、档案等.我国一般每年可以发2～3代,温度较高的地区可发生4代[1] .     

The Synthesis of 2-Alkylthio-3-alkyl-5-arylmethylidene4H-imidazol-4-ones

2-alkylthio-3-alkyl-5-arylmethylidene-4H-imidazol-4-ones were synthesized by the S-alkylation and N-alkylation of 2-thioxo-5-arylmethylidene-4-imidazolidinones, which were obtained via a tandem aza-Wittig reaction of vinyliminophosphoranes, carbon disulfide, and excess ammonium hydroxide (28% NH₃ in water).     

2-氨基-4H-咪唑啉-4-酮衍生物的快速平行合成法

咪唑啉酮衍生物是一类具有良好生物活性和药理活性的杂环化合物 [1,2 ] ,尤其是一些 2 -氨基咪唑啉酮表现出良好的杀菌、抗炎及抗癌活性 [3 ,4 ] .从自然界如一些海洋生物中可分离得到含 2 -氨基咪唑啉酮结构的生物碱 [5,6] .最近 ,组合化学方法广泛地应用于有机合成 ,它包括固相合成法和液相合成法[7～ 9] .我们曾应用氮杂 Wittig反应制得 2 -氨基取代咪唑啉酮衍生物 ,部分化合物表现出一定的抑菌活性 [10 ,11] .本文进一步报道应用液相平行反应法快速合成 2 -氨基 - 4H-咪唑啉 - 4-酮衍生物 (4) .该方法应用烯基膦亚胺 1与苯基异氰酸酯的…     

2-烷(芳)氧基苯并呋喃并[3,2-d]嘧啶-4(3H)-酮衍生物的合成及杀菌活性

应用膦亚胺3与芳基异氰酸酯的氮杂Wittig反应, 生成碳二亚胺4, 4再分别与酚、醇作用, 在碳酸钾或醇钠催化下关环, 以72%～88%的产率合成了2-烷(芳)氧基取代-苯并呋喃并[3,2-d]嘧啶-4(3H)-酮衍生物5和6, 其结构经IR, 1H NMR, MS和元素分析证实. 初步生物活性测试表明该类化合物表现出温和的杀菌活性. 如5f在50 mg/L浓度时, 对黄瓜灰霉菌的抑制率为55%.     

香豆素类衍生物的合成

由人免疫缺陷病毒 ( HIV)感染引起的免疫缺陷综合症 ( AIDS)——艾滋病 ,是人类致命疾病之一。世界各国都在致力于寻找抗艾滋病药物 ,其中一个研究热点是通过大规模筛选寻找生物活性较强的小分子非肽类抑制剂 ,然后进行结构优化 ,以期找到新一代的抗艾滋病药物。香豆素类衍生物是一类具有抗病毒等许多生物活性的化合物 ,一直被人们所重视。 1 992年 ,从马来西亚热带雨林植物 Calophllum L anigerum中分离出具有抗艾滋病病毒活性的香豆素类化合物 Calanolides[1] 。同时 ,由于香豆素类化合物合成相对简单 ,生物利用度高 ,促使人们在这个…     

SYNTHESIS OF 3-(2-MERCAPTO-4-THIAZOLYL)-2H-1-BENZOPYRAN-2-ONE AND ITS DERIVATIVES

Abstract

Treatment of 3-(2-bromoacetyl)coumarins with ammonium dithiocarbamate provides 3-2-mercapto-4-thiazolyl)-2H-1-benzopyran-2-one (11) but not 4-hydroxy-4-(3-coumaririnyl) thiazolidine-2-thione (I). II undergoes smooth condensation with alkyl, aralkyl, phenacyl and acid halides to give corresponding thioethers and thioesters (III) respectively. The structures of the newly synthesized compounds were established on the basis of spectral data (IR, PMR and MS).     

含氮杂环三烃基锡衍生物的合成及其生物活性

本文合成了14个含氮杂环三烃基锡衍生物,红外光谱,核磁共振谱和质谱的研究表明三烃基锡-1,2,4-三氮唑为以氮原子作桥联的五配位聚合结构化合物,化合物的生物活性和生物选择性主要取决于锡原子上的三烃基。     

NOVEL AND FACILE SYNTHESIS OF THIOPHENE,THIAZOLE, 2H-PYRAN-2-ONE BENZIMIDAZO[1,2-a]PYRIDINE AND PYRIDINE DERIVATIVES CONTAINING ANTIPYRINE MOIETY

Several new thiophene, thiazole, 2H-pyran-2-one, benzimidazo[1,2-a]pyridine and pyridine derivatives were synthesised from active methylene reagents, 4-chloroacetylantipyrine and enaminones as starting materials.     

四氢苯并[4',5']噻吩并[3',2':5,6]吡啶并[4,3-d]嘧啶-4(3H)-酮的合成、晶体结构及杀菌活性

通过氮杂Wittig反应合成了一系列结构新颖的未见文献报道的取代四氢苯并[4',5']噻吩并[3',2':5,6]吡啶并[4,3-d]嘧啶-4(3H)-酮化合物6, 产物的结构通过核磁共振氢谱、质谱、红外光谱、元素分析的确证. 为进一步了解此类化合物的结构, 对化合物6c进行了X射线单晶衍射. 初步杀菌活性测定结果表明, 该类化合物具有较好的杀菌活性和选择性. 如6f在50 mg/L浓度时, 对黄瓜灰霉菌的抑制率为98%.