Converting 9-Methyldipyrrinones to 9-H and 9-CHO Dipyrrinones

Yellow 9-methyldipyrrinones can be converted readily and in high yields to symmetric linear tetrapyrroles, blue biliverdinoids, which are cleaved in half, smoothly at room temperature to afford yellow 9-H dipyrrinones, and 9-CHO dipyrrinones as their violet to orange colored adducts with the carbon acid used for the scission: thiobarbituric acid (TBA), N,N′-diethylthiobarbituric acid, barbituric acid, N,N′-dimethylbarbituric acid, and Meldrum's acid. The adducts, usually only of passing interest, are formally Knövenagel condensation products of a 9-CHO dipyrrinone with TBA and other carbon acids of this work, and a reverse Knövenagel reaction of such adducts leads to 9-CHO dipyrrinones. Under a set of improved reaction conditions the sequence thus efficiently converts 9-CH₃ dipyrrinones to 9-H and 9-CHO dipyrrinones.     

Preparation of 9-vinyl-and 9-ethynyl-o-and m-carboranes

Conclusions The previously unknown 9-vinyl- and 9-ethynyl-o- and m-carboranes were obtained by the reaction of vinyl- and ethynylmagnesium halides with 9-iodo-o- and 9-iodo-m-carboranes, catalyzed by palladium complexes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 888–892, April, 1985.     

Synthesis of 9-Alkyl- and 9-Arylthiophenanthrenes

A simple method for the preparation of 9-alkyl- and 9-arylthio-phenanthrenes from 9-bromophenanthrene and a thiol is described.     

9-Alkylideneazafluorenes

A number of tertiary aza-9-fluorenols were obtained from 4- and 2-azafluofenones and were subjected to dehydration in order to synthesize the previously unknown 9-methyleneazafluorenes. The corresponding 9-methyleneazafluorenes and their polymers were obtained simultaneously in relatively stable form from both pyridine-ring-substituted and -unsubstituted 4-aza-9-fluorenols and from 1,3-diphenyl-2-aza-9-fluorenol. On the basis of an analysis of the mass spectrum of the polymer obtained from 9-methylene-4-azafluorene it was concluded that it is evidently isolated in the form of two dimers — dispiro [bis (4-aza-9-fluorene)-1, 3-cyclobutane] and the analogous product of dispiro addition with a 1,2-substituted cyclobutane ring. Condensation of the corresponding azafluorenes with benzaldehyde gave their 9-benzylidene derivatives in the form of geometrical isomers, the structures of which were established on the basis of the PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1234–1240, September, 1978.     

Aromatic nucleophilic substitution. Part 3. Preparation of novel 9-oxo-9H-thioxanthene- and 9-oxo-9H-xanthenedicarboximides and -dicarboxylates

By aromatic nucleophilic substitution followed by intramolecular acylation, 9-oxo-9H-thioxanthene- and 9-oxo-9H-xanthene-dicarboximides were prepared from nitro- or chlorophthalimides and the dianions of thiosalicylic and salicylic acids (Scheme). The 9-oxo-9H-thioxanthene-3,4-dicarboximides were converted to 9-oxo-9H-thioxanthene-3,4-dicarboxylic-acid derivatives such as anhydride, esters, and further imides. Some of these derivatives proved to be excellent photosensitizers with special properties such as liquid aggregation form, H₂O solubility, solubility in lipophilic organic solvents and polymers, or bathochromic shifts of the absorption wavelengths.     

Préparation de la 8,14-diméthyl 18-nor-testostérone

Les sécrétions de 4 espèces de Dipterocarpus Viêt-Namiens ont fourni un triterpène tétracyclique, identifié au diptérocarpol de van Itallie et à l'hydroxy-dammarénone-II (I) de Mills. Le diptérocarpol est dégradé (chaîne latérale) et modifié (cycle A) en un analogue de la testostérone (XXX). Sa stéréochimie est discutée.     

Introduction stéréosélective du groupement difluorométhylène en position allylique

The regio- and stereo-selective introduction of a difluoromethylene group in an allylic position is described. The key step is the treatment of 1,1-difluoro-1-alken-3-acetates with Grignard reagents in the presence of copper and lithium salts.

Résumé

Nous décrivons ici une méthode régio- et stéréo-sélective permettant l'introduction du groupement difluorométhylène en position allylique. L'étape principale est la réaction des 3-acétoxy-1,1-difluoro-1-alcènes avec les réactifs de Grignard en présence de sels de cuivre et de lithium.     

Mixed-crystal packing calculations. 9-methoxyanthracene in host 9-cyanoanthracene

Packing calculations by the atom-atom interaction method are reported for 9-methoxyanthracene (9MeOA) as a guest in host crystalline 9-cyanoanthracene (9CNA). The lower-energy local packing has approximately parallel anthracene nuclei, and substituents in head-to-head (“cis”) registry, in agreement with the structure found experimentally for the photochemical 9MeOA-9CNA complex. Electronic excitation of a host 9CNA adjacent to the guest 9MeOA causes an impulsive, short-lived, displacement of 9CNA*, giving dynamic preformation of either (9CNA)₂ excimer, or 9CNA-9MeOA exciplex. Over longer times, the structural response to excitation is followed by calculations including the successive relaxation of neighbour molecules, converging to an equilibrium structure for the locally excited crystal.     

Reactions of the 9-mesityl-9-boraanthracene anion

The synthesis of 9-mesityl-9,10-dihydro-9-boraanthracene is described. Proton abstraction with organolithium reagents gave the title anion, which was converted with various electrophiles into derivatives substituted at C-10. UV spectra indicated the absence of intramolecular coordination of oxygen-containing substituents at C-10 to the Lewis acidic boron centre. The preparation and some properties of the fulvenoid 9-mesityl-10-methylene-9,10-dihydro-9-bora-anthracene and its reaction with tert-butyllithium are reported.     

9-Trimethylsilylphenanthrene and 9-Trimethylsilyl-9,10-Dihydroanthracene

9-Trimethylsilylphenanthrene and 9-trimethylsilyl-9,10-dihydroanthracene were synthesized, the latter being photosensitive and oxidizable in exposure to air. When pulverized, the latter electrically charged negative.     

9-alkenylcarbazoles

A number of 9-alkenylcarbazoles were obtained in good yields by elimination of alcohols from 9-(l-alkoxyalkyl)carbazoles by heat treatment and under the influence of catalysts. The method makes it possible to obtain both pure trans isomers and mixtures of cis-trans isomers of disubstituted 9-alkenylcarbazoles. The trans isomers of N-propenyl derivatives of pyrrolidone and caprolactam were similarly obtained. The fact of the catalysis of the electrophilic addition of alcohols to 9-alkenylcarbazoles by carbon tetrachloride was observed.See [1] for communication 4.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 497–502, April, 1979.     

9-Acyl- and 9-aroyl-3-methyl-2-azafluorenes

The condensation of 3-methyl-2-azafluorene with esters of aromatic and aliphatic acids has given 9-aroyl and 9-acyl derivatives of 2-azafluorene. They are stable in the enolic form. The 9-benzoyl derivative (II) has also been isolated in the oxo form. The transition from (II) to the cis-trans isomers of 9-benzylidene-3-methyl-2-azafluorene has been effected.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 986–989, July, 1973.     

9-羟基-9-呫吨羧酸甲酯和中间体的合成

9-羟基-9-咕吨羧酸甲酯是合成咕吨类抗胆碱能药物的一种重要的中间体.本文以9-咕吨羧酸为原料,通过微波催化先合成了中间体9-咕吨羧酸甲酯,然后很简便地得到了9-羟基-9-咕吨羧酸甲酯.在中间体的合成中,利用正交设计,探讨了微波辐射时间、功率以及催化剂用量对反应的影响,实验结果表明微波辐射时间的影响最为显著.     

Sur les dérivés de la fluorénone VI Les acides bromo-3-fluorénonecarboxylique-2 et bromo-2-fluorénonecarboxylique-3 et la bromo-3-méthyl-4-fluorénone

Starting from 2-amino-3-bromo-9-oxofluorene and from 3-methylfluorene respectively the preparation of 3-bromo-9-oxofluorene-2-carboxylic acid and of 2-bromo-9-oxofluorene-3-carboxylic acid is described. A synthesis of 3-bromo-4-methyl-9-oxofluorene is also given.     

9-Substituted acridines. Demethoxylation of 9-methoxyacridine and dechlorination of 9-chloroacridine in hydroxylic solvents

In methanol-water mixtures containing sodium or potassium hydroxide (up to 2.00M) the demethoxylation of 9-methoxyacridine to 9-acridone is of first order in both the free form of 9-methoxyacridine and the hydroxyl ion. The rate of the reaction is increased with an increase in the concentration of water. Sodium perchlorate has a small retarding effect on the reaction. In methanol-water mixtures containing perchloric or hydrochloric acid (up to 3.45M) the demethoxylation is of first order with respect to the protonated form of 9-methoxyacridine. The rate of the reaction decreases with an increase in the concentration of the acid or of sodium perchlorate, but when the concentration of water is increased (≈?1.7 to 50M) and that of the acid is not changed, it reaches a maximum value in mixtures containing 8 to 10M-water. The dechlorination of 9-chloroacridine to 9-methoxyacridine in methanol containing sodium hydroxide or methoxide (up to 0.31 M) is of first order in both the 9-chloroacridine and the hydroxyl or methoxyl ions.     

Synthèse de polyéthers polycycliques. 1 Stéréosélectivité de l'hétérocyclisation d'alcools tétrahydrofurfuryliques γ,δ-éthyléniques par les sels mercuriques

The intramolecular oxymercuration of the l-(2-tetrahydrofuryl)4-penten-1-ols (5) by merruric salts followed by reductive demercuration affords the 2-methyl-5-tetrahydrofuryltetrahydrofuran (9) as a mixture of cis and trans isomers in good yields. By using mercuric acetate, each isomier threo 5a and erythro 5b gives the trans isomer, 9d and 9b, respectively, as the major products. On the other hand, cyclizations carried out with mercuric chloride are not stereoselective.     

Ge9=Ge9=Ge9=Ge9]8-: a linear tetramer of nine-atom germanium clusters,a nanorod

A tetramer of nine-atom deltahedral germanium clusters and charge 8-, [Ge9=Ge9=Ge9=Ge9]8- , has been characterized as a (Rb-18C6)(+) salt (18C6 = 18-crown-6 polyether). The clusters are connected by pairs of parallel bonds, and the electrons are delocalized over the whole anion. The size of the tetramer is of nanorod dimensions, ca. 2 nm.     

Facile synthesis of unsymmetrical 9-phospha- and 9-arsafluorenes

Unsymmetrical 9-chloro-9-phosphafluorenes (dibenzophospholes) and 9-chloro-9-arsafluorenes (dibenzoarsoles) have been obtained by simple thermolysis of m-terphenyldichlorophosphines and -arsines in close to quantitative yields. The reaction temperatures are about 200 degrees C for the phosphines and 140 degrees C for the arsine, and the reactions are complete within 5 min. Alternatively, these compounds can be synthesized through an AlCl3-catalyzed Friedel-Crafts type ring-closure reaction at low temperatures, but this method suffers from difficult workup procedures. The P(As)-Cl functionality is readily alkylated. Methylation of m-xylyl derivative 4 afforded 1-(3,5-dimethylphenyl)-6,8,9-trimethyl-9-phosphafluorene, 11. The latter compound formed the complexes 11 x Fe(CO)4, 12, and 11 x RuCl2(eta(6)-p-cymene), 13, indicating its good donor properties. The new compounds have been characterized by 1H, 13C{1H}, and 31P{1H} NMR spectroscopy; mass spectrometry; and single-crystal X-ray crystallography in the case of 11, 12, and 13.     

Thermoelectric Properties of Nano-grained Mooihoekite Cu9Fe9S16

Cu-Fe-S-based compounds gain the interest from thermoelectric community because all the consisting elements, Cu, Fe, and S, are non-toxic and earth-abundant. Comparing with CuFeS₂ and Cu₅FeS₄, the investigation on Cu₉Fe₉S₁₆ is very rare. In this work, a series of Cu_9–xFe_9+xS₁₆ samples were fabricated by means of melting-annealing process. Their phase composition, microstructure, electrical and thermal transport properties were systematically investigated. X-ray measurement confirms that all samples are phase pure. Transmission electron microscopy characterization indicates that the fabricated Cu₉Fe₉S₁₆ has a natural nanostructure. Cu₉Fe₉S₁₆ shows semiconducting-like electrical transport behavior and intrinsically low lattice thermal conductivity. Beyond the numerous boundaries between nanosized grains, the existence of low-frequency optical phonons is also responsible for the intrinsically low lattice thermal conductivity. Doping Fe at the Cu-sites in Cu₉Fe₉S₁₆ significantly alters the electrical transport properties by introducing extra carriers. A peak dimensionless figure of merit zT value of 0.21 is obtained at 800 K for pure Cu₉Fe₉S₁₆, which is comparable with that for CuFeS₂.     

Probing the limits of the Zintl concept: structure and bonding in rare-earth and alkaline-earth zinc-antimonides Yb9Zn4+xSb9 and Ca9Zn4.5Sb9

A new transition metal Zintl phase, Yb(9)Zn(4+x)Sb(9), was prepared by high-temperature flux syntheses as large single crystals, or by direct fusion of the corresponding elements in polycrystalline form. Its crystal structure was determined by single-crystal X-ray diffraction. Its Ca-counterpart, hitherto known as Ca(9)Zn(4)Sb(9), and the presence of nonstoichiometry in it were also studied. Yb(9)Zn(4+x)Sb(9) was found to exist in a narrow homogeneity range, as suggested from the crystallographic data at 90(3) K (orthorhombic, space group Pbam (No. 55), Z = 2): (1) a = 21.677(2) A, b = 12.3223(10) A, c = 4.5259(4) A, R1 = 3.09%, wR2 = 7.18% for Yb(9)Zn(4.23(2))Sb(9); (2) a = 21.706(2) A, b = 12.3381(13) A, c = 4.5297(5) A, R1 = 2.98%, wR2 = 5.63% for Yb(9)Zn(4.380(12))Sb(9); and (3) a = 21.700(2) A, b = 12.3400(9) A, c = 4.5339(4) A, R1 = 2.75%, wR2 = 5.65% for Yb(9)Zn(4.384(14))Sb(9). The isostructural Ca(9)Zn(4.478(8))Sb(9) has unit cell parameters a = 21.830(2) A, b = 12.4476(9) A, and c = 4.5414(3) A (R1 = 3.33%, wR2 = 5.83%). The structure type in which these compounds crystallize is related to the Ca(9)Mn(4)Bi(9) type, and can be considered an interstitially stabilized variant. Formal electron count suggests that the Yb or Ca cations are in the +2 oxidation state. This is supported by the virtually temperature-independent magnetization for Yb(9)Zn(4.5)Sb(9). Electrical resistivity data show that Yb(9)Zn(4.5)Sb(9) and Ca(9)Zn(4.5)Sb(9) are poor metals with room-temperature resistivity of 10.2 and 19.6 mOmega.cm, respectively.