2, 6-dicyan-1, 5-dimethyl-semibullvalen

The synthesis of the title compound $\text{8}$ is reported. According to the NMR data the semibullvalene $\text{8}$ undergoes a degenerate Cope rearrangement.     

Oxidation and nitrosation of 4-(3-alkylureido)-2, 2, 6, 6-tetramethylpiperidine-1-oxyls to 4-(3-alkyl-3-nitrosoureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium salts

4-(3-Alkylureido)-2, 2, 6, 6-tetramethylpiperidine-1-oxyls are rapidly oxidized by N₂O₄ or NOCl to 4-(3-alkylureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium nitrates and chlorides, which are then nitrosated to 4-(3-alkyl-3-nitrosoureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium salts. The perchlorates of the latter were prepared by an exchange reaction with HClO₄. The nitrosation of alkylureidooxoammonium salts is the first example of chemical modification of oxoammonium derivatives in which the highly reactive >N⁺=O group is inert toward the reagent.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 542–547, March, 1993.     

Diels-alder reactions of 3, 6-diphenyl-1, 2, 4, 5-tetrazine and 3, 6-di(2-pyridyl)-1, 2, 4, 5-tetrazine with some 1-morpholinocycloalkenes

The reactions of 3, 6-diphenyl-1, 2, 4, 5-tetrazine 1 and 3, 6-di(2-pyridyl)-1, 2, 4, 5-tetrazine 2 with the enamines 3a-d derived from morpholine and the 5-,6-,7- and 8-membered cyclic ketones have been investigated. A number of pyridazine derivatives 4–7 most of which are new have been reported. Moreover, a novel procedure for the aromatization of pyridazines 5a-d to the corresponding pyridazine 7b-d via oxidative elimination using hydrogen peroxide is described. The structures of products 4–7 were confirmed by spectral methods and elemental analysis.     

Synthesis of 2, 6-derivatives of 1, 4-dioxane

Stereoisomers of 6-halomethyl-2-hydroxymethyl-1, 4-dioxanes have been obtained via the cyclization of the monoallyl ether of glycerol. The stereoisomeric bromides differ considerably in their physical properties. The bromine atoms of the stereoisomers differ in their reactivity towards thiourea.     

Über 1, 5-Diphenyl-2, 3, 6, 7-tetrahydro-1H, 5H-pyrazolo[1, 2-a]pyrazole(2, 6-Diphenyl-1, 5-diazabicyclo[3, 3, 0]octane)

The synthesis of a 1, 5-diphenyl perhydro-pyrazolo-[1, 2-a] pyrazole (IV) (m. p. = 170–171°) by LiAlH₄-reduction of its 3, 7-dioxo derivative Va, one of the stereoisomers of V, is described. Va was obtained in small yield by the reaction of cinnamic acid with its hydrazide or with hydrazine. It proved to be identical with the compound obtained previously by interaction of cinnamic acid hydrazide with iodine which in the literature erroneously had been described as N, N′-dicinnamoyl hydrazine. This hydrazine now was obtained by bis-acylation of hydrazine with cinnamoyl chloride. In Va the extremely low NMR. absorption of the tertiary protons at ρ = 4,6 ppm is probably due to the spatial grouping with the proton situated in the deshielding region of the carbonyl group. Previously, another tertiary proton with a very low NMR. absorption at ρ = 4,85 ppm has been observed in the «bisimide M», the main criss-cross addition product of one mole benzaldazine and two moles of N-(n-butyl)-maleinimide. A stereostructure for bisimide M is now proposed, which is a hybrid between those of the bisimides L and H.     

KEu2Cl6 und K1, 6Eu1, 4Cl5: Zwei neue gemischtvalente Europiumchloride

KEu₂Cl₆ and K_1.6Eu_1.4Cl₅: Two New Mixed‐Valent Europium Chlorides The reaction of the binary chlorides EuCl₃, EuCl₂ and KCl yields the mixed‐valent compounds KEu₂Cl₆ and K_1.6Eu_1.4Cl₅. KEu₂Cl₆ (hexagonal, P6₃/m, Z = 1, a = 788.87(13), c = 411.41(6) pm, R₁ = 5.40 %) crystallizes with an addition‐variant of the UCl₃‐type of structure with tricapped trigonal prismatic coordination for the europium cations. The K⁺ ions reside in channels along [001] and exhibit extremely large displacement parameters U₃₃. The crystal structure of K_1.6Eu_1.4Cl₅ (orthorhombic, Pnma, Z = 4, a = 1260.49(12), b = 871.05(9), c = 787.18(10) pm, R₁ = 4.77 %) is closely related to that one of K₂EuCl₅ if the K⁺ and the Eu³⁺ ions are partly substituted for Eu²⁺. Absorption spectra show transitions, which can be assigned to Eu²⁺ and Eu³⁺ ions, and additional transitions due to interaction of both cations occupying common positions.     

Synthesis of Derivatives of 1, 2, 6-Trisubstttuted-4-Piperidones

Robinson-Schöpf cyclisation was used to prepare several 1, 2, 6-trisubstituted-4-piperidones: 1, 2, 6-trimethyl-4-piperidone, tricyclic ketones 2 and 3 derivatives of coccinelline. In the case of 1, 2, 6-trimethyl-4-piperidone, a mixture of the trans and cis compounds 4 and 1 was obtained. The pure cis compound was prepared by another route.     

哌啶酮催化氢化制备哌啶醇催化剂的研究

研究了2,2,6,6-四甲基-哌啶酮-4-催化氢化合成2,2,6,6-四甲基-哌啶醇-4。重点研究催化剂种类对催化反应的影响。确定RaneyNi(4)为最适宜催化剂,并对其最佳用量进行了研究。对哌啶酮催化氢化的反应历程进行了探讨。选用常压塔式反应器进行氢化。对其它有关工艺参数进行研究,确定最佳条件:哌啶酮浓度为30%,20%异丙醇水溶液为溶剂、催化剂用量为20%、温度为80℃、时间为2h,哌啶醇产率97.3%,m.p.130.0-131.0℃。     

Molecular and crystal structures of stereoisomeric2R,3R,6S-2-(1′S-hydroxy-1′-biphenylyl)- and2R,3R,6S-2-(1′R-hydroxy-1′-biphenylyl)methyl-3-methyl-6-isopropylcyclohexanones

It was established by X-ray diffraction analysis that 2-(1′-hydroxy-1′-biphenylyl)methyl-3-methyl-6-isopropylcyclohexanone, one of the minor products of the directed aldol reaction of (−)-menthone bromomagnesium enolate with 4-phenylbenzaldehyde, has the2R,3R,6S, 1′R configuration. The characteristic features of the spatial structure of this β-hydroxyketone were compared with those of the major stereoisomeric product of the above-mentioned reaction. The latter has the2R,3R,6S,1′S configuration. In the crystals, both stereoisomers have the cyclohexanone ring in a chair-like conformation with the three substituents in equatorial positions and are characterized by the presence of the annelated (cis-fused) pseudoring with an −OH…O=C< intramolecular hydrogen bond. The structures of the stereoisomers differ in the orientation of the aryl group and the hydrogen atom at the C(1′) chiral center with respect to the cyclohexanone ring. The results of X-ray diffraction analysis were compared with the data of molecular mechanics calculation for the energetically most favorable conformations of the isolated molecules of β-hydroxyketones under study. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2251–2257, November, 1998.     

Synthesis and properties of salts of 2-substituted derivatives of 1, 6-dimethyl-7-chloro-1, 6-diazaphenalenium salts,III

A series of 2-substituted 1,6-diazaphenalene derivatives, the subsequent alkylation of which give 1,6-dimethyl-2-R-7-chloro-1,6-diazaphenalenium salts, was obtained by cyclization of acyl derivatives of 5-amino- and 5-methylamino-8-chlorolepidines. A study of the absorption spectra of the salts attests to the fact that, as in cyanine dyes, electron-donor substituents heighten the color, while electron-acceptor substituents deepen it.See [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1391–1395, October, 1972.     

吩噻嗪与四甲基哌啶氧铵正离子的电子转移反应动力学研究

以Marcus半经典电子转移理论为基本框架, 改进了重组能的计算方法, 建立了一套研究自交换和交叉电子转移反应的理论方案。用密度泛函理论和半经验分子轨道理论具体研究了四甲基哌啶氧铵正离子与吩噻嗪在乙腈溶液中的交叉电子转移反应以及相应的2个自交换反应的动力学性质, 计算了反应的活化能、重组能、耦合矩阵元等有关参数,获得了和实验结果相一致的电子转移速率常数。     

The Synthesis of 12-Methyl-1, 2, 3, 4, 6, 7, 12, 12B-Octahydroindolo [2,3-A]Quinolizine (1), 1-Benzoyl-1, 2, 3, 4, 6, 7, 12, 12B-Octahydroindolo[2, 3-A]Quinolizine (2), and 1-Phenylcarbinol-1, 2, 3, 4, 6, 7, 12, 12B-Octahydroindolo[2, 3-A]Quinolizine (3)

12-Methyl-l, 2, 3, 4, 6, 7, 12, 12b-octahydroindolo[2, 3-a]quinolizine (1) is synthesized through a new route developed in our laboratory. The most important step in this synthesis is the condensation of I-methyltryptophyl bromide (4) with 2-piperidone (5) to give N -(2-(1-methylidol)-3-ylethyl)-2-piperidone (6) in good yield (70%). The synthesis of 1-benzoyl-1, 2, 3, 4, 6, 7, 12, 12b-octahydroindolo(2, 3-a]quinolizine (2) and 1-phenylcarbinol-1, 2, 3, 4, 6, 7, 12, 12b-octahydroindolo[2, 3-a]quinolizine (3) follow the method developed by Wenkert. But the yield of tetrahydropyridine 9 from partial hydrogenation of pyridinum bromide 8 with 10% palladium-charcoal is 84% which is much higher than the best yield (40%) in the literature, since the phenyl group contribute additional stability.