Synthese eines Propellans ausTetrakis(ethoxycarbonyl)norbornen: 8,11-Dioxa-2,5-methano[4.3.3]propella-3-en

Summary The synthesis of the title propellane3, derived from norbornene, is reported.3 was synthesized by dehydratation of tetraalkohol2. On the basis of NMR and mass spectra, the possibility of the formation of polycyclic ethers (4) is discussed.

     

Synthesen und Stereochemie des 3,6,10,13-Tetrathia[6.6.1]propellans

3,6,10,13-Tetrathia[6.6.1]propellane (1) has been prepared by two independent syntheses.1 exists as an equilibrium of two conformers with C₂ and C_s symmetry, respectively. The heterocyclic rings adopt a twist-tub conformation. The multistage synthesis of1 makes also 1,5-cyclooctadiene (5) accessible, as the result of [4_s+4_s]-cycloaddition. The formation of [6.6.1]propellanes of the isomeric [6.0.6.1]dispiranes depends on the nature of the hetero atom.

     

Synthesis of 3,6,10,13-tetrathia[6.6.2]propellanes from 1,1,2,2-Tetrakis-(bromomethyl)cyclobutane

Summary A synthesis of two new tetrathia[6.6.2]propellane systems, each containing one cyclobutane ring, is described. On the basis of¹HNMR, UV/Vis and mass spectra, the possibility of the formation of an isomeric bispirane is discussed.

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Synthese von 3,6,10,13-Tetrathia[6.6.2]propellanen aus 1,1,2,2-Tetrakis(brommethyl)cyclobutan

Zusammenfassung Es werden die Synthesen zweier neuer Tetrathia[6.6.2]propellansysteme beschrieben, die jeweils einen Cyclobutanring enthalten. Auf der Grundlage von NMR-, UV/Vis- und Massenspektroskopie wird die Möglichkeit der Bildung isomerer Bispirane diskutiert.

     

Propellane, 11. Mitt.: Synthese von Dioxa[4.3.3]propellanen aus vicinalen Tetrakis(hydroxymethyl)cycloalkanen

Summary The synthesis of two new [4.3.3]propellanes is described. The structure of the compounds was determined by chemical and spectroscopic methods. Some aspects of the conformation of the propellanes were studied using¹H NMR.

     

Synthese von Propellanen aus 1,8-Dihydroxynaphthalin: 3,7,11,15-Tetraoxa[4,5,6-12,13,14-dinaphtho(1′,8′)]-(7.7.1)propellan

Condensation of 1,1,2,2,-tetrabromomethylcyclopropane with 1,8-dihydroxynaphthalene yielded the (7.7.1)-type propellane. The peri effect on the reaction and the product conformation is discussed. As a result condensation of 1,1-dibromomethylcyclopropane withperi-dihydroxynaphthalene gives the diether-type compound2 instead of the expected spirane2.

Jamrozik, J., Propellanes III. J. für prakt. Chemie, im Druck (1980).     

Basicities and structures of 2-(N-arylaminomethylene)-3(2H)-benzo[b]thiophenones,-benzo[b]furanones,and -benzo[b]selenophenones

The ionization constants of the conjugate acids of the reaction series 2-(N-arylaminomethylene)-3(2H)-benzo[b]thiophenones,-benzo[b]furanones, and -benzo[b]selenophenones were determined by potentiometric titration in anhydrous acetonitrile. The electronic and vibrational spectroscopic data showed that the protonation center in the molecules of these compounds is the carbonyl oxygen atom. It was established by correlation analysis that N-aryl substituents affect the protonation center primarily via an induction mechanism.Communication XVIII from the series Basicities and structures of azomethines and their structural analogs. See [1] for communication XVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. pp. 619–623, May, 1977.     

异苯并二氢吡喃并吡唑类化合物的合成

本文通过异苯并二氢吡喃酮-4的克莱森缩合反应得β-二酮衍生物,并由此合成出一系列标题化合物。所合成的新杂环化合物均经核磁共振光谱,红外光谱及无素分析证明其分子结构。     

Conversion from (-)-delta-6,1-3,4-trans-tetrahydrocannabinol in (-)-delta-1,2-3,4-trans-tetrahydrocannabinol

Successive treatment of (?)-Δ^6,1-3,4-trans-tetrahydrocannabinol with hydrochloric acid/zinc chloride and potassium-t-amylate gives (?)-Δ^1,2-3,4-trans-tetrahydrocannabinol in quantitative yield.     

An access to 3,4-(aminomethano)proline in racemic and enantiomerically pure form

Protected racemic and enantiomerically pure 3,4-(aminomethano)prolines rac-9 and (2S,2'R,3R,4R)-9 have been prepared applying a titanium-mediated reductive cyclopropanation as a key step. Thus, cyclopropanations of N,N-dibenzylformamide with titanacyclopropanes generated in situ from racemic or enantiomerically pure tert-butyl N-Boc-3,4-dehydroprolinates rac-8 or (S)-8 proceed diastereoselectively, and furnish the protected racemic and enantiomerically pure diamino acid 9. The latter was incorporated into three tripeptides containing glycyl, alanyl and phenylalanyl moieties.     

Structural studies on (3,4,8,9)-dibenzo-2,7-dioxa-5,10-diaza[4.4.4]propellanes (DDDP)

The methyl and nitro derivatives of (3,4,8,9)-dibenzo-2,7-dioxa-5,10-diaza[4.4.4]propellanes P2, P3, P7 and P9 were synthesized. The X-ray diffraction studies showed that 16,20-dinitro derivative (P7) crystallizes in non-centrosymmetric Pcn2 space group making this crystal to be promising in non-linear optics. The geometry of molecules is discussed in relation to the intramolecular interaction and charge distribution. Very helpful appeared from this point of view the ¹³C NMR spectra. In packing of molecules an important role play the N-H?O and C-H?O hydrogen bonds reflected both in the crystal structures and IR spectra.     

Selective and Scalable Electrosynthesis of 2H-2-(Aryl)-benzo[d]-1,2,3-triazoles and Their N-Oxides by Using Leaded Bronze Cathodes

Electrosynthesis of 2H-2-(aryl)benzo[d]-1,2,3-triazoles and their N-oxides from 2-nitroazobenzene derivatives is reported. The electrolysis is conducted in a very simple undivided cell under constant current conditions with a leaded bronze cathode and a glassy carbon anode. The product distribution between 2H-2-(aryl)benzo[d]-1,2,3-triazoles and their N-oxides can be guided by simply controlling the current density and the amount of the charge applied. The reaction tolerates several sensitive functional groups in reductive electrochemistry. The usefulness and the applicability of the synthetic method is demonstrated by a formal synthesis of an antiviral compound.     

Preparation and some reactions of 3,5:8,10-di-1,3-benzo[8](3,4)-1,2,5-thiadiazolocyclophane

Titled 1,2,5-thiadiazolometacyclophane 1 was prepared via thia[2.3]cyclophane 5 which was obtained by the reaction of di(bromomethyl) 2 with sodium sulfide under phase-transfer-catalyzed conditions. Cyclophane 1 gave the corresponding pyrene derivatives by the oxidative transannular reaction in the reaction with brominating reagent. Reduction of 1 with lithium aluminum hydride followed by acetylation with acetic anhydride gave a 4:l-mixture of cis- and trans-diamide 11 and 12 with a trace amount of cyclophane-ring-cleaved product 13 . On the other hand, 13 was obtained as a major product in the reduction with metal sodium and diisobutylaluminum hydride.     

Synthesis and X‐ray Structures of the Polycyclic Dimers {[PhB(μ‐NtBu)2AsN(tBu)H]LiI}2 and [PhB(μ‐NtBu)2AsN(tBu)Li]2

The metathesis of [PhB(μ‐NtBu)₂]AsCl and tBuN(H)Li in 1:1 molar ratio in diethyl ether produced the amido derivative [PhB(μ‐NtBu)₂AsN(tBu)H] ( 1 ) in good yield. The lithiation of 1 with one equivalent of nBuLi afforded the lithium salt [PhB(μ‐NtBu)₂AsN(tBu)Li] ( 2a ). Both 1 and 2a were characterized by multinuclear NMR spectroscopy. The crystal structure of 2a is comprised of a U‐shaped, centrosymmetric dimer in which the monomeric [PhB(μ‐NtBu)₂AsN(tBu)]^?Li⁺ units are linked by Li‐N interactions to give a six‐rung ladder. Oxidation of 2a with one‐half equivalent of I₂ in diethyl ether resulted in hydrogen abstraction from the solvent to give the dimeric lithium iodide adduct {[PhB(μ‐NtBu)₂AsN(tBu)H]LiI}₂ ( 1 ·LiI) with a central Li₂I₂ ring.     

Structures of 1-（3,4-Dihydroxyphenyl）-2-（3,4-dimethoxyphenyl） ethanone and Its Hydrate Complex

The title compounds, C16H16O5 (I) and C16H16O5·H2O (II), were structurally characterized by single-crystal X-ray diffraction. Compound I crystallizes in monoclinic space group P21/c with a = 10.5574(10), b = 8.3576(9), c = 16.5528(16) , β = 91.762(3)°, Z = 4, R = 0.0524 and wR = 0.1084. The molecules are jointed into a chain by intermolecular O-H···O and C-H···O hydrogen bonds, which form layers parallel to (001). The chains run along the [110] and [110] directions alternatively layer by layer, and are assembled into a network by intermolecular O-H···O (carboxyl) hydrogen bonds. On the other hand, the hydrate complex (II) crystallizes in the triclinic space group P1 with a = 5.1451(2), b = 10.4583(4), c = 14.8267(5) , α = 70.900(2), β = 82.478(2), γ = 81.359(2)°, Z = 2, R = 0.0393 and wR = 0.0983. The molecules are linked into infinite two-dimensional ribbons by O-H···O (carbonyl) and solvent-bridged O-H···O hydrogen bonds.     

Synthesis of heterospiranes by cyclization of dinucleophiles with 1,1-bis(tosyloxymethyl)cyclopropane and -cyclobutane

A variety of heterocyclic spiranes were prepared by cyclization of dinucleophiles with 1,1-bis(tosyloxymethyl)cyclopropane and -cyclobutane.     

Convenient Synthesis of 3,4-bis(Alkylthio) Thiophenes

A variety of symmetrically substituted 3,4-dithioether-thiophenes were prepared by the acid catalyzed nucleophilic substitution of 3,4-di(methoxy)thiophene with the appropriate thiol.     

双吲哚马来酰亚胺硫脲化合物的合成及抗肿瘤活性

基于双吲哚马来酰亚胺化合物和硫脲化合物的结构及多样的生物活性,通过1-氨基-3,4-二(吲哚-3-基)-3-吡咯啉-2,5-二酮与异硫氰酸酯反应,合成了17种新的3,4-二(吲哚-3-基)-2,5-二酮-1-吡咯亚胺硫脲类化合物,化合物的结构通过1H NMR、13C NMR、HRMS等进行了表征。该系列化合物的初步抗肿瘤活性测试表明,它们都对细胞周期分裂蛋白25B(CDC 25B)表现出良好的抑制活性(大部分化合物的抑制率在96%以上),具有潜在的抗肿瘤活性及应用价值。