Facile Synthesis of Spiro Oxindoles,Azaoxindoles, and Dihydroisoquinolone

Formation of 1-aryl-4-oxo-cyclohexa(e)nonecarboxylates from the Diels–Alder cycloaddition of 2-trimethylsilyloxy-1,3-butadiene and Danishefsky diene with aryl- and pyridylacrylates and further conversion thereof to spirocycles is described. This provides an efficient method for spiro oxindoles, azaoxindoles, and dihydroisoquinolones.

Synthesis of Novel Spiro Tetrahydrothiapyrano-Isoxazolines and Pyrazolines

Cis 2,6-Diphenyltetrahydrothiapyranone (1) was subjected to Wittig reaction to generate exocyclic double bond (2a-c). Cycloaddition of nitrile oxides and nitrile imines to the latter led to a novel spiro tetrahydrothiapyranoisoxazolines (3a-f) and spiro tetrahydrothiapyranopyrazolines (4a-f)     

Synthesis and Reaction of Novel Spiro Pyrimidine Derivatives

2‐Mercapto‐6‐[(pyridin‐4‐ylmethylene)‐amino]‐3H‐pyrimidin‐4‐one 1 was synthesized from Schiff base reaction of 6‐amino‐2‐thiouracil with isonicotinaldehyde. The reaction of 1 with hydrazonyl chloride 2a , 2b , 2c , 2d afforded the novel pyrimidin‐4‐one 3a , 3b , 3c , 3d . Compounds 3a , 3b , 3c , 3d reacted with methyl iodide to give 4a , 4b , 4c , 4d . Subsequently, reaction of 4a , 4b , 4c , 4d with triethylamine as a catalyst in dry chloroform yielded tetraaza‐spiro[4.5]deca‐2, 8‐dien‐7‐one 5a , 5b , 5c , 5d . In addition, reaction of 1 with acrylonitrile gave pyrimidin‐propionitrile 6 . The cyclization of 6 by reacting with sodium ethoxide to give pyrimido [2, 1‐b] [1,3] thiazin‐6‐one 7 . The refluxing of 1 with bromine in acetic acid yielded 2‐bromo‐pyrimidin‐4‐one 8 . The latter compound 8 reacted with sodium azide gave tetrazolo‐pyrimidine 10 . The chemical structures of the newly synthesized compounds were characterized by IR, ¹H NMR, ¹³C NMR, and mass spectral analysis.     

环丙基螺环硫巴比妥衍生物的合成、表征及抗惊厥活性

设计合成了2个刚性很强的结构对称性巴比妥酸类化合物———环丙基螺环硫巴比妥酸化合物。通过红外、核磁对其结构进行了表征。其中化合物1a和1b活泼氢(N—H)的化学位移有明显区别。利用二维氢氢相关谱观察到了化合物1a结构中,环丙烷上氢质子与酰胺环上氢质子由于螺环刚性屏蔽影响使其2个环上同侧较近质子之间存在相关性,异侧较远质子之间无相关性。初步测试了2个化合物的抗小鼠电击惊厥活性:化合物1a和1b的惊厥抑制率分别为50%和70%。     

Facile One-Pot Method for the Synthesis of Novel N-Dichloroacetyl-1,3-oxazolidines

A short and efficient route to synthesis and structural characterization of a series of novel N-dichloroacetyl-5-ethyl-1,3-oxazolidine derivatives has been developed. These new compounds, characterized by the substitution at position 2 by alkyls, cycloalkanes, benzyls, or aryls, have been synthesized in good yields via a sequential procedure involving cycloaddition, condensation, and acylation. All the compounds are characterized by infrared, ¹H NMR, and ¹³C NMR.     

Benzotriazole-Mediated Facile Synthesis of Novel Glycosyl Tetrazole

A facile, simple, and high-yielding synthetic protocol for novel glycosyl tetrazoles has been devised from different carbohydrate-containing amides using benzotriazole methodology under mild reaction condition.     

新型熊果酸单糖苷的简便合成

以熊果酸为原料,经苄基化反应制得熊果酸苄酯(2); 2与三氯乙酰亚胺酯经糖苷化反应制得酯保护的熊果酸-3-糖苷（4a~4d）;4a~4d依次脱去苄基和苯甲酰基合成了4个熊果酸-3-糖苷(6a～6d,其中6c为新化合物),其结构经¹H NMR, ¹³C NMR和MS(ESI)表征。     

A Facile Synthesis of Novel Benzofuranyl Benzimidazole Derivatives

In this article, we report a facile route for the synthesis of novel benzofuranyl benzimidazole derivatives. The methodology involves the Sonagashira reaction of 2‐(3‐iodo‐4‐methoxyphenyl)‐1H‐benzimidazole ( 3 ) with variety of terminal alkynes to have novel benzimidazole alkynyl derivatives followed by iodo‐cyclisation to give novel iodo benzofuranyl benzimidazole derivatives. The resulting iodo benzofuranyl benzimidazoles were functionalized further via palladium mediated carbon–carbon bond formation for molecular diversity generating novel heterocyclic compounds.     

Cycloaddition of Porphyrins to Isatin: Synthesis of Novel Spiro Porphyrin Derivatives

Isatin undergoes regioselective 1,3‐dipolar cycloaddition reactions with porphyrin azomethine ylides derived from Ni(II) β‐formyl‐meso‐tetraphenylporphyrins in the presence of N‐methylglycine to afford novel spiro porphyrin derivatives.     

Facile Synthesis,Characterization, and Fluorescence Studies of Novel Porphyrin Appended Thiazoles

A facile and high yielding synthesis of porphyrin appended thiazoles 5 from the reaction of 5‐(4‐thiocarboxamidophenyl)‐10,15,20‐triphenylporphyrin with α‐bromo ketones has been described. The fluorescence studies of synthesized porphyrin appended thiazoles 5 in chloroform indicate that porphyrin π system is not greatly perturbed by substitution of a thiazole moiety at meso‐phenyl ring even in the excited state.     

Synthesis of Novel Spiro Pyrrolidine and Pyrrolizine Derivatives by 1,3-Dipolar Cycloaddition

The 1,3‐dipolar cycloaddition of azomethine ylides derived from isatin and amino acids viz. sarcosine and proline to 2‐arylmethylidene‐5,6‐dihydroimidazo[2,1‐b]thiazol‐3(2H)‐ones afforded novel spiro pyrrolidines and pyrrolizidines regio‐ and stereoselectively in moderate yields. The products were characterized thoroughly by IR, MS, NMR together with elementary analysis.     

新型色满酮并环己烷螺环氧化吲哚类化合物的合成

以色酮 氧化吲哚合成子与硝基苯乙烯,在催化剂DBU作用下,在二氯甲烷中发生Michael/Michael加成环化反应,合成了9个未见文献报道的新型色满酮并环己烷螺环氧化吲哚类化合物3a~3i产率72%~87%, dr值4/1~2/1, 其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征确定。     

Facile Synthesis and Crystal Structure of a Novel Cyanopyridine

The title compound 2-amino-4-(4-hydroxy-3,5-dimethoxyphenyl)-5-methyl-6-phenyl nicotinonitrile,C 21 H 19 N 3 O 3,was synthesized via four-component reactions between propio-phenone,malononitrile,syringaldehyde and ammonium acetate in ethanol under reflux without catalyst and characterized by IR,1 H NMR,13 C NMR,MS,EA and single-crystal X-ray diffraction.Single-crystal X-ray diffraction analysis shows that the compound is of monoclinic system,space group P2 1 /n with a=8.4600(17),b=17.139(3),c=13.408(3),β=107.06(3)°,V=1858.6(6)3,Z=4,M r=361.39,F(000)=760,μ(MoKα)=0.088 mm-1,D c=1.292 g/cm 3,λ=0.71073,the final R=0.0751 and wR=0.0938 for 3333 observed reflections with I > 2σ(I).The crystal packing of the title compound is stabilized by intermolecular hydrogen bonds.     

甲亚胺叶立德的1,3-偶极环加成反应合成螺吲哚里西啶类化合物

通过7-芳亚甲基-6,7-二氢中氮茚-8(5H)-酮与甲亚胺叶立德(经苊醌或靛红与肌氨酸反应原位生成)进行的l,3-偶极环加成反应,合成了具有良好产率的新的1’-甲基-4’-芳基-5",6"-二氢-2H,8"H-二螺[苊烯-1,2’-吡咯烷-3’,7"-中氮茚]-2,8"-二酮类化合物和1’-甲基-4’-芳基-5",6"-二氢-1H,8"H-二螺[吲哚-3,2’-吡咯烷-3’,7"-中氮茚]-2,8"-二酮类化合物.采用NMR,IR,质谱,元素分析以及X射线单晶衍射等多种谱学技术对产物进行了结构表征.     

Facile Synthesis of Novel Aminopyrrolobenzimidazole System via Regioselective Amination

A new series of substituted pryrrolobenzimidazoles have been prepared via regioselective displacement of chlorine atom from dichloropyrrolobenzimidazoles with various amine nucleophiles. The dichloro compounds were obtained from the reaction of ortho phenylene diamine compounds with dichloromaleic anhydride.     

Facile Synthesis of Novel Selenium‐Containing Benzopyrans

4,4‐Dimethylchromeno[4,3‐d]selenadiazoles 8 with insecticide activities have been synthesized via oxidative ring closure of the corresponding semicarbazone derivatives 7 by treatment with selenium dioxide. Reaction of various alkoxy‐2,2‐dimethyl‐2H‐benzopyrans with phenylselenyl chloride was utilized to prepare different phenylselenyl‐ and 3‐chloro precocene analogs.     

A Novel Entry into a New Class of Spiro Heterocyclic Framework: A Facile Synthesis of Dispiro[oxindole-1,2,3,4-tetrahydro-naphthalen-1-one]pyrrolidines and Spiro[1,2,3,4-tetrahydro-naphthalen-1-one]pyrrolidines

Abstract

2-Arylidene-1,2,3,4-tetrahydro-naphthalen-1-ones undergo regioselective 1,3-dipolar cycloaddition reaction with the azomethine ylide derived from isatin and sarcosine by decarboxylative route affording a series of 1-N-methyl-spiro[2.3¹]oxindole-spiro[3.2¹¹]1¹¹, 2¹¹,3¹¹,4¹¹, -tetrahydro-naphthalen-1¹¹-one-4-aryl-pyrrolidines. 2-Arylidene-1,2,3,4-tetrahydro-naphthalen-1-ones also undergo cycloaddition reaction with azomethine ylide derived from paraformaldehyde and sarcosine affording a series of 1-N-methyl-spiro[3.2¹]1¹,2¹,3¹,4¹-tetrahydro-naphthalen-1¹-one-4-aryl-pyrrolidines. The structures of the compounds were established by spectroscopic techniques.     

新型螺环配体的合成及其在不对称催化氢化反应中的应用

以光学纯的S-2,2′-螺二氢茚-1,1′-二酮为原料,合成了新型螺环氧膦配体(1R,2S,1′S)-1,1′-双(二苯基膦氧)-2,2′-螺二氢茚烷(S-cis,trans-Sp iroB IP),考查了催化剂[Rh(COD)(R-cis,cis-Sp iroB IP)]BF4,[Rh(COD)(S-cis,trans-Sp iroB IP)]BF4和Ir(R-cis,cis-Sp iroB IP)(COD)C l在不对称催化氢化反应中的应用。