三种新型二苯砜氮杂环蕃N,N’-二对甲苯磺酰基-1,m-二氮杂[m.1]对环蕃-n-砜的合成与表征(m＝8,10,12; n＝15,17,19)

以N,N’-二对甲苯磺酰基-4,4’-二氨基二苯砜与二溴代烷为原料, 高度稀释条件下合成了三种新型有硫原子桥连的氮杂环蕃N,N’-二对甲苯磺酰基-1,8-二氮杂[8.1]对环蕃-15-砜(C); N,N’-二对甲苯磺酰基-1,10-二氮杂[10.1]对环蕃-17-砜(D); N,N’-二对甲苯磺酰基-1,12-二氮杂[12.1]对环蕃-19-砜(E). 提供了三种环蕃化合物的合成方法. 用IR, 1H NMR和元素分析证实了新化合物结构. 分析了化合物D的单晶结构数据, 为环蕃化合物的空间结构研究提供了晶体学依据.     

氮杂冠醚的研究VII.2,3-苯并-10-氮杂-1,4,7,13-四氧杂-环十五-2-烯合成方法的改进

本文报道合成2,3-苯并-10氮杂-1,4,7,13-四氧杂-环十五-2-烯(3)的改进方法,1,2-二(2'-对甲苯磺酰基乙氧基)-苯(2)在无水叔丁醇中,以叔丁醇钠为缩合剂,与二乙醇胺缩合,在 50-55℃下反应4小时,得到(3)。化合物(2)和(3)均经元素分析,IR和1H NMR等鉴定。改进的缩合方法条件温和,操作简便,收率较好。     

苯并单氮杂15-冠-5-与α, β-不饱和羰基化合物的 Michael加成

本文报道借Michael加成使苯并单氮杂15-冠-5与α,β-不饱和羰基化合物反应,合成了氮支套索冠醚(1,2)和酯型双冠醚(3,4)。并提供了合成酯型双冠醚的一种方法,该法条件温和,操作简便,收率高。产物均经IR,^1HNMR和MS鉴定。     

含吡啶环氮(王)冠的合成

本文报道了新的含吡啶环的氮(王)冠的合成。以活泼双功能团化合物2,6-二(溴四基)-吡啶和N-对甲苯磺酰基取代的多乙撑基多胺(二乙撑三胺,三乙撑四胺)二钠盐直接缩合成环,得到含吡啶环的氮(王)冠化合物:3,6,9-三对甲苯磺酰基-3,6,9,15-四氮双环[9.3.1]十五环-1(15),11,13-三烯(A)和3,6,9,12-四对甲苯磺酰基-3,6,9,12,18-五氮双环[12.3.1]十八环-1(18),14,16-三烯(B)。(A)和(B)经用30%的HBr-CH_3COOH溶液处理,得到3,6,9,15-四氮双环[9.3.1]十五环-1(15),11,13-三烯(C)和3,6,9,12,18-五氮双环[12.3.1]十八环-1(18),14,16-三烯(D)。以上化合物均经元素分析、IR和1~H NMR.等鉴定。这种直接缩合的方法,具有反应条件温和、设备简单、操作简便等优点。     

N-(2-苦胺基乙基)单氮杂冠醚的合成

研究并比较了氮支套索型生色冠醚1a和1b两条不同的合成路线, 结果表明, 由N-苦基乙二胺(2)与1,11-二碘-3,6,9-三氧杂十一烷进行N-烷基化环化反应, 可方便地制备N-(2-苦胺基乙基)单氮杂-12-冠-4(1a), 但按此法未能获得更大环的-15-冠-5(1b);若从N-对甲苯磺酰基乙二胺(6)或N-(2-对甲苯磺酰胺基乙基)二乙醇胺(7)出发, 经环化, 脱除对甲苯磺酰基而制得的N-(2-氨基乙基)单氮杂冠醚5a和5b分别与苦基氯反应, 则可获得高产率的生色生色冠醚11a和1b.     

N-三甲基硅基对甲苯磺酰胺与对甲苯磺酸酯的反应

报道了3-氧杂-1,5-二戊醇二对甲苯磺酸酯及1,4-丁二醇二对甲苯磺酸酯与N-三甲基硅基对甲苯磺酰胺在碱存在下反应分别得到N-对甲苯磺酰基吗啡啉和N-对甲苯磺酰基四氢吡咯这一新的有机硅胺与磺酸酯的反应,在相同条件下N-三甲基硅基-对甲苯磺酰胺与对甲苯磺酸甲酯反应后仅得到N-甲基对甲苯磺酰胺,对此反应提出了可能的反应途径。     

2-O-苄基-3,5-内醚-α和β-D-木呋喃甲基甙的合成

本文报导一对具有2,6-二氧杂双环[3.2.0]庚烷骨架的四元环内醚型戊糖甙差向异构体的合成.其关键化合物2-O-苯甲基-3,5-二-O-对甲苯磺酰基-α-和β-D-木呋喃甲基甙(S)、2-O-苯甲基-5-O-对甲苯磺酰基-α-D-木呋喃甲基甙及其3-O-乙酰基衍生物均以结晶形固体制得,由这些结晶分别制得标题化合物.     

内醚糖的研究Ⅴ.2,3-内醚-5-去羟-β-D-核糖甲基甙

自木糖经过五步反应合成了2,3-内醚-5-去羟-β-D-核糖甲基甙(Ⅵ)。这五步反应是:D-木糖(Ⅰ)→D-木糖甲基呋喃甙(Ⅱ,α-和β-端基差向异构体混合物)→2,3,5-三-O-对甲苯磺酰基-β-D-木糖甲基呋喃甙(Ⅲ)→2,3-二-O-对甲苯磺酰基-5-去羟-5-碘代-β-D-木糖甲基呋喃甙(Ⅳ)→2,3-二-O-对甲苯磺酰基-5-去羟-β-D-木糖甲基甙(Ⅴ)→2,3-内醚-5-去羟-β-D-核糖甲基甙(Ⅵ)。总产率是18%。将已知的结晶的2-O-对甲苯磺酰基-β-D-木糖甲基呋喃甙(Ⅶ)进行对甲苯磺酰化,得到与上述完全相同的Ⅲ,这样就证明了Ⅲ的端基的构型。同时,也从β-D-木糖甲基吡喃甙(Ⅷ)制备了2,3,4-三-O-对甲苯磺酰基-β-D-木糖甲基吡喃甙(Ⅸ)。根据现有的知识肯定了合成的内醚糖的结构。     

桥连双-(三氮杂环壬烷)化合物的合成

利用无水碳酸钾作缩合剂,在精制乙腈中使N,N'-二对甲苯磺酰基-1,4,7-三氮杂环壬烷3与双溴甲基化合物4a-4c缩合得到N-对甲苯磺酰基取代的桥连双-(三氮杂环壬烷)5a-5c,经浓硫酸脱去氮原子上的保护基团得到桥连双-(三氮杂环壬烷)6a-6c。化合物5a-5c和6a-6c均经元素分析、IR、^1HNMR、^1^3CNMR、MS等测试手段证实其结构和组成。     

氮杂冠醚的研究 Ⅶ.2,3-苯并-10-氮杂-1,4,7,13-四氧杂-环十五-2-烯合成方法的改进

本文报道合成2,3-苯并-10-氮杂-1,4,7,13-四氧杂-环十五-2-烯(3)的改进方法。1,2-二(2＇-对甲苯磺酰基乙氧基)-苯(2)在无水叔丁醇中,以叔丁醇钠为缩合剂,与二乙醇胺缩合,在50—55℃下反应4小时,得到(3)。化合物(2)和(3)均经元素分析,IR和~1HNMR等鉴定。改进的缩合方法条件温和,操作简便,收率较好。     

Synthesis of lateral macrobicyclic cryptand

This paper deals with the synthesis of a new lateral macrobicyclic cryptand 10. Condensation of 2.6-di(bromomethyl)pyridine with 3-(n-tosylamino) methyl propionate in the presence of anhydrous K₂CO₃ at room temperature gave 5 which was hydrolyzed to 6. Reaction of the latter with excess sulfonyl chloride afforded 2,6-di(4′-chloroformyl-2′-tosyl-2′-azabutyl)pyridine (7). Pentaaza-1,5,13,17,28-dithia-20,25-tricyclo [15,5,5,1^7,11]-octacosa-7,9,11 (28)-triene(10) has been synthesized by the following sequence of reactions: Condensation of 7 with 1,7-diaza-4,10-dithia-dodecane (3) by high dilution technique in toluene-THF at room temperature afforded 8 which was reduced by diborane in THF solution to give 9. Treatment of 9 with sodium anthracene in monoglyme produced 10.     

Reactivity of "Eu(OiPr)2" with phenols: formation of linear Eu3, square pyramidal Eu5, cubic Eu8, and capped cubic Eu9 polymetallic europium complexes

The direct reaction of europium with 2-propanol and phenols has been investigated under a variety of conditions. The reaction of europium metal with 2,6-dimethylphenol and 2,6-diisopropylphenol in 2-propanol at reflux revealed that polymetallic europium complexes could be generated by this method. Hx[Eu8O6(OC6H3Me2-2,6)12(OiPr)8], 1, and H5[Eu5O5(OC6H3iPr2-2,6)6(NCCH3)8], 2, were isolated by recrystallization in the presence of hexanes and acetonitrile, respectively, and characterized by X-ray crystallography. Complex 1 has a cubic arrangement of europium ions with face-bridging mu 4-O donor atoms, edge-bridging mu-O(phenoxide/phenol) ligands, and terminal O(isopropoxide/2-propanol) ligands. Complex 2 is mixed valent and has a square pyramidal europium core with four Eu(II) ions at the basal positions and one Eu(III) ion at the apex. Since these reactions gave complicated mixtures of products from which 1 and 2 could only be obtained in low yields, direct reactions under less forcing reaction conditions were investigated. Europium reacts slowly at room temperature to form arene-soluble divalent [Eu(OiPr)2(THF)x]n, 3. Complex 3 reacts with 2,6-dimethylphenol to form the arene-insoluble complex (H[Eu(OC6H3Me2)2(OiPr)])n, 4. Recrystallization of 4 in the presence of THF results in the crystallographically characterizable divalent trimetallic complex [Eu(OC6H3Me2-2,6)2(THF)2]3, 5, which has an unusual linear metal geometry. In the presence of HOiPr at ambient conditions in the glovebox, crystals of 5 slowly convert to the mixed valent H10[Eu8O8(OC6H3Me2-2,6)10(OiPr)2(THF)6], 6, which was found to have a cubic arrangement of europium atoms similar to 1 by X-ray crystallography. Complex 4, upon heating under vacuum, followed by reaction with THF, forms the arene-soluble divalent complex H18([Eu9O8(OC6H3Me2-2,6)10(THF)7][Eu9O9(OC6H3Me2-2,6)10(THF)6]), 7, which contains two types of capped cubic arrangements of europium ions in the solid state.     

Terphenyl cyclooctatetraenyl compounds of samarium

The syntheses and molecular structures of a number of terphenyl-based compounds of the lanthanide element samarium are reported. Reaction of 2 equiv of DppLi (Dpp = 2,6-diphenylphenyl) with 1 equiv of SmCl(3) in tetrahydrofuran at room temperature yields (Dpp)(2)SmCl(micro-Cl)Li(THF)(3) (1). The one-pot reaction of 1 equiv of K(2)COT (COT(2)(-) = cyclooctatetraenyl dianion) with 1 equiv SmCl(3) in tetrahydrofuran at room temperature followed by addition of 1 equiv of terphenyllithium salt DppLi, DmpLi (Dmp = 2,6-dimesitylphenyl), or DanipLi (Danip = 2,6-di(o-anisol)phenyl) produces DppSmCOT(micro-Cl)Li(THF)(3) (2), DmpSm(THF)COT (3), and DanipSm(THF)COT (4), respectively. In the case of the Danip-based compound 4 the order of addition of reagents can be reversed producing the same compound, however, in considerably lower yield. Compound 2 can also be prepared by reaction of 1 with 1 equiv of K(2)COT in tetrahydrofuran. The molecular structure of the bis(terphenyl) compound 1 exhibits a formally four-coordinate metal atom. The molecular structures of the terphenyl COT compounds 2-4 feature monomeric complexes which are obtained either as a lithium chloride adduct (2) or as tetrahydrofuran adducts (3, 4). In 4 the Danip ligand adopts the meso form.     

双酰胺双(3'-正十五烷基-苯并-15-冠-5)PVC膜钾离子选择电极的研究

本文合成了十个双酰胺型双(3'-正十五烷基-苯并-15-冠-5)化合物, 制成的PVC膜钾离子选择电极, 性能优良.     

Facile Synthesis of 9-Acetyl/Formyl/Cyano-Substituted Pyrano[2,3-f]flavones and Chromones Using the Baylis–Hillman Reaction

Condensation of 8-formyl-7-hydroxyflavones (2a–f) and 8-formyl-7-hydroxy-2-(2′-furyl)-3-methylchromone (2g) with methyl vinyl ketone (3), acrolein (4), and acrylonitrile (5) in the presence of diazabicyclo[2.2.2]octane (DABCO) under an N₂ atmosphere at room temperature using Baylis–Hillman reaction conditions afforded 9-acetyl/formyl/cyano-substituted pyrano2,3-f]flavones (6a–f, 7a–f, 8a–f) and chromones (6g, 7g, 8g).     

Alkylation of pyridine-3,5-dicarboxamide and pyridine-3,5-dicarbonitriles by radical substitution

Structural modification of NAD(P) model compounds, N,N,N',N'-tetramethylpyridine-3,5-dicarboxamide ( 1 ), pyridine-3,5-dicarbonitrile ( 2 ), and 4-methylpyridine-3,5-dicarbonitrile ( 3 ), have been explored by the reaction with alkyl radicals such as the 1-adamantyl, tert-butyl, and isopropyl radicals. The alkyl substitutions of compounds 1 , 2 , and 3 with the 1-adamantyl and the tert-butyl radical gave both 2-mono and 2,6-disubstitution products, whereas the reaction of compound 2 with the isopropyl radical gave 2-mono 6c , 2,4-di 7c, 2,6-di 8c , and 2,4,6-trisubstitution 9c products.     

Synthesis of 3-(2-guanidinoethyl) and 3-[2-(S-methylisothioureidoethyl)] analogs of 5-isopropyl 2,6-dimethyl-1,4-dihydro-4-(2,3-dichlorophenyl)pyridine-3,5-dicarboxylate as a respective releaser of nitric oxide and inhibitor of nitric oxide synthase

The Hantzsch condensation of 2-azidoethyl acetoacetate with 2,3-dichlorobenzaldehyde and isopropyl 3-aminocrotonate afforded 3-(2-azidoethyl) 5-isopropyl 2,6-dimethyl-1,4-dihydro-4-(2,3-dichlorophenyl)pyridine-3,5-dicarboxylate ( 7 ). Reduction of the 3-(2-azidoethyl) moiety of 7 using 5% palladium-on-calcium carbonate and hydrogen gas gave the 3-(2-aminoethyl) derivative 8 , which was subjected to guanylation using 1H-pyrazole-1-carboxamidine hydrochloride to yield the target 3-(2-guanidinoethyl) analog 9 . The 3-(2-aminoethyl) product 8 was elaborated to the title compound 3-[2-(S-methylisothioureidoethyl)] 5-isopropyl 2,6-dimethyl-1,4-dihydro-4-(2,3-dichlorophenyl)pyridine-3,5-dicarboxylate hydrochloride ( 12 ) via the intermediate 3-(2-thioureidoethyl) compound 10 . The 3-(2-guanidinoethyl 9 and 3-[2-(S-methylisothioureidoethyl)] 12 compounds were about 116- and 23-fold less potent calcium channel antagonists, respectively relative to the reference drug nifedipine.     

Synthetic and structural study of 4-phosphacyclohexanones and 3-aza-7-phosphabicyclo[3.3.1]nonan-9-ones

The synthesis of bicyclic phosphorus–nitrogen (PN) compounds containing the rigid bicyclo[3.3.1]nonan-9-one framework was attempted using the Mannich condensation reaction of four different phosphorinanone classes with amines and aldehydes. Three different isomers of 4-tert-butyl-2,6-di(methoxycarbonyl)-3,5-bis(p-dimethylaminophenyl)-4-phosphacyclohexanone were obtained from the Michael addition reaction of tert-butylphosphine with 2,4-di(methoxycarbonyl)-1,5-bis(p-dimethylaminophenyl)penta-1,4-dien-3-one. The reaction of the all-equatorial isomer with methylamine and formaldehyde produced the bicyclic PN compound 7-tert-butyl-1,5-di(methoxycarbonyl)-6,8-bis(p-dimethylaminophenyl)-3-methyl-3-aza-7-phosphabicyclo[3.3.1]nonan-9-one. The identical Mannich reaction of the enol tautomer also yielded the same product, as well as the PN compound 4-tert-butyl-6-methoxycarbonyl-5-(p-dimethylaminophenyl)-2-methyl-2-aza-4-phosphacyclohexanone and the E/Z isomers of 3-(p-dimethylaminophenyl)methyl-2-propenoate. The newly synthesised 3-aza-7-phosphabicyclo[3.3.1]nonan-9-one PN compound adopts a chair–chair conformation both in solution and the solid state.     

Size matters: room temperature P-C bond formation through C-H activation in m-terphenyldiiodophosphines

m-Terphenyl- and biphenyl-2-diiodophosphines, TerphPI 2 and BiphPI 2, have been obtained by halide exchange from the chloro derivatives TerphPCl 2 and BiphPCl 2 and excess LiI in a benzene solution at room temperature. Whereas BiphPI 2 compounds are stable, the TerphPI 2 species undergo intramolecular C-H activation at room temperature and cyclize to form unsymmetrical 9-iodo-9-phosphafluorenes 1-(3,5-dimethylphenyl)-6,8-dimethyl-9-iodo-9-phosphafluorene, 4; 1-(4-t-butylphenyl)-7-t-butyl-9-iodo-9-phosphafluorene, 5; and 1-(2-methylphenyl)-5-methyl-9-iodo-9-phosphafluorene, 6, albeit the latter reaction is rather slow due to unfavorable steric interactions. Cyclization of the alkyl-substituted 4,4'-di- tert-butyl-biphenyl-2-diiodophosphine, 11, is slow in refluxing benzene solution, but faster than that for the parent biphenyl-2-diiodophosphine. Ab initio and density functional theory calculations are in agreement with an electrophilic aromatic substitution mechanism that is facilitated by steric strains in the terphenyl compounds 2,6-(3,5-Me2C6H3)2C6H3PI2, 1; 2,6-(4-t-BuC6H4)2C6H3PI 2, 2; and 2,6-(2-MeC6H4)2C6H3PI 2, 3. All new compounds have been characterized by multinuclear NMR spectroscopy and direct analysis in real time mass spectrometry. 9-Iodo-9-phosphafluorene, 12, was also analyzed by X-ray diffraction.     

含吡啶环系西佛碱大环配合物和氮杂大环自由配体的合成

2, 6-二羟甲基吡啶(1)经活性MnO~2氧化得到2, 6-二甲酰基吡啶(2)。邻硝基苯酚与N-取代的二(氯乙基)胺在DMF溶液中反应, 得到N-取代的1, 5-二(邻硝基苯氧基)-3-氮杂戊烷(3a～3c), 再经水合肼/Raney Ni还原, 获得N-取代的1, 5-二(邻氨基苯氧基)-3-氮杂戊烷(4a～4c)。利用Ba^2^+作为模板离子, (2)分别与(4a～4c)反应, 合成了一类新的含吡啶环系西佛碱大环配合物I-III, 配合物I、III与NaBH~4的乙醇溶液还原解络, 得到氮杂大环自由配体IV和V。所有西佛碱大环配合物和氮杂大环自由配体均经元素分析、IR、^1H NMR、MS等证实了它们的结构和组成。