Oxidation von 3,3-dimethyl-1-phenyl-1,2,4-triazolidin-5-thion

3.3-Dimethyl-1-phenyl-1.2.4-triazolidine-5-thione (3) is oxidized with HgO or KMnO₄ to 2-phenylazo-2-propyl-isothiocyanate (5) which is converted to O-alkyl-N-(2-phenylazo-2-propyl)-thiocarbamates (6) and 3-substituted 1-(2-phenylazo-2-propyl)-thioureas (7). The¹H-NMR spectra of the thiono urethanes (6) reveal that at room temperature these compounds exist as a mixture of isomers s-cis-6 and s-trans-6 due to an increased rotational barrier about the thiocarbamide bond (C–N) resulting from its partial double bond character.

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Oxidationsprodukte von Arylhydrazon-Verbindungen, 12. Mitt. (11. Mitt.¹).     

1-Methyl-3-phenyl-4-aminodekahydrochinolin

Zusammenfassung Phenacetylcyclohexen wurde in dieMannichbase (II) und diese mittels Methylamin unter Umaminierung und Ringschluß in 1-Methyl-3-phenyldekahydrochinolon-(4) (III) übergeführt. Von den aus III erhaltenen 4 stereoisomeren Oximen (IV a-d) wurde IV c mit LiAlH₄ zu dem Amin V reduziert.     

Diene autocondensation of 3,3-dimethyl-2-phenyl- and 3,3-dimethyl-2-(2-thienyl)-3H-pyrroles

Chemistry of Heterocyclic Compounds -     

Addition of carboxylic acids and cyclic 1,3-diketones to 2-dimethylamino-3,3-dimethyl-1-azirine

The reaction of 2 - dimethylamino - 3,3 - dimethyl - 1 - azirine 1 with carboxylic acids 2a-e at room temperature in inert solvents generates rearranged 1:1 adducts in 65–92% yields. These adducts are N-acyl derivatives of 2-amino, -N,N dimethyl-isobutyramide 3a-e resulting from 1,2 addition of the acid followed by 1,2 ring cleavage and transfer of an acyl group. Cyclic enolizable 1,3 diketones 4a-c react similarly with 1 to yield the corresponding rearranged 1:1 adducts 5a-c, whereas acyclic diketones or ethyl acetoacetate are inert under comparable experimental conditions.     

Infrared spectrometric study of the interaction between 2-dimethylamino-3,3-dimethyl-1 azirine and some phenol derivatives

The H-bonded complexes between 2-dimethylamino-3,3-dimethyl-1-azirine (TMAAZ) and some phenol derivatives have been studied by IR spectrometry in carbon tetrachloride. The equilibrium constants at 300, 315 and 328 K and the ? ΔH°, ? Δν_OH and Δν_CN values have been determined. The comparison with previously studied OH … N complexes shows that TMAAZ forms stronger complexes than would be expected from the pK_a value. These facts are discussed in terms of steric, hybridization, solvation and charge transfer effects. From a pK_a of 8, the IR spectrum shows the appearance of ion pairs N⁺-H …^?O. A predominance of protonated species can be calculated for a pK_a of 6. This can explain why 1,2-ring cleavage whose first step is probably the formation of an azirinium cation, occurs for acids characterized by pK_a values lower than 5 but not for enolizable ketones having pK_a values higher than 9.     

1-Methyl-2-phenyl-4-aminopiperidin

Ohne Zusammenfassung     

Synthesis of 6-Aryl-3,3-dimethyl-5-phenyl-2,3,5,6-tetrahydropyran-2,4-diones

Zinc enolates obtained from methyl 4-bromo-2,2-dimethyl-3-oxo-4-phenylbutanoates and zinc react with aromatic aldehydes to form 6-aryl-3,3-dimethyl-5-phenyl-2,3,5,6-tetrahydropyran-2,4-diones as a single geometric isomer.     

Structure of 1-phenyl-1-thioxo-2,5-dimethyl-3-morpholinomethyl-phosphorinan-4-one

Chemical Sciences Institute, Kazakh Academy of Sciences. Institute for Heteroorganic Compounds, USSR Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 1, pp. 184–186, January–February, 1990.     

Synthesis of 3,3-dimethyl-2-phenyl-3H-pyrrole from Isopropyl Phenyl Ketoxime and Acetylene: A Side Formation of 4,4-dimethyl-5-phenyl-1-vinyl-2-pyrrolidinone as Clue to the Reaction Mechanism

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Cis-und Trans-1-Methyl-3-phenyl-4-aminopiperidin und Derivate der Aminofunktion

Zusammenfassung 1-Methyl-3-phenyl-5-carbäthoxylpiperidon-(4)¹ (I) wurde zum 1-Methyl-3-phenylpiperidon-(4) (II) decarboxyliert und dieses nach verschiedenen Methoden in die beiden stereomeren Verbindungen IV a und IV b übergeführt. Die Konfigurationszuordnungcis undtrans bei IV a und IV b erfolgte auf Grund der Regel vonAuwers undSkita und auf Grund des Ergebnisses der Na-Alkohol-reduktion des Oxims III, bei welcher fast ausschließlich dieTrans-verbindung IV b erhalten wurde, während die LiAlH₄-Reduktion von III dieCis-verbindung IV a als Hauptprodukt ergab. Einige an der Aminogruppe substituierte Abkömmlinge von IV a und IV b wurden hergestellt und die Base IV a selbst in die optischen Antipoden gespalten.

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1-Methyl-3-phenyl-5-carbethoxy-4-piperidone¹ (I) on decarboxylation yielded 1-methyl-3-phenyl-4-piperidone (II) which was converted by various methods into the two stereoisomeric compounds IV a and IV b.Cis andtrans configurations have been assigned to IV a and IV b, respectively, according to theAuwers-Skita rule and on the evidence of sodium-ethanol reduction of the oxime III, which yielded almost exclusively thetrans-compound IV b, while LiAlH₄ reduction led principally to thecis-compound IV a. Several N-substituted derivatives of IV a and IV b have been prepared and the base IV a resolved into its optical antipodes.

     

3-羟基4，4-二甲基-1-苯基-2-吡咯烷酮的不对称合成

乙醛酸苄酯与异丁醛间在L-脯氨酰胺催化下发生不对称交叉羟醛缩合反应,以93%的产率得到e.e.值为52%的3-甲酰基-2-羟基-3-甲基丁酸苄酯(1).经过一步还原氨解关环,1很容易转化成3-羟基-4,4-二甲基-1-苯基-2-吡咯烷酮.     

Benzyl 2-cyano-3,3-dimethyl-1-pyrrolidinecarboxylate, a versatile intermediate for the synthesis of 3,3-dimethylproline derivatives

The synthesis of racemic nitrile (+/-)-9 was accomplished in four steps and 58% overall yield from the known pyrrolidinone 5. Nitrile (+/-)-9 was resolved via preparative chiral HPLC to afford optically pure nitriles (+)-9 and (-)-9, from which 3,3-dimethylprolines (+)-1 and (-)-1 and 3,3-dimethylprolinamides (+)-2 and (-)-2 could be accessed in nearly quantitative yield, without loss of optical purity. The absolute configurations of the resolved prolines and prolinamides were determined by correlation with an intermediate of known absolute stereochemistry.     

Synthesis of 1-substituted-3,3-dimethyl-3,4-dihydroisoquinolines

The Ritter reaction between -substituted propionitriles and dimethylbenzylcarbinols gives 3,3-dimethyl-3,4-dihydroisoquinolines containing substituents in the 1-position corresponding to those in the starting nitrile.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 657–659, May, 1991.     

Structure and Extractive Ability of 1-Alkyl- and 3-Methyl-1-phenyl-2-pyrazolin-5-ones

Extractive ability of 1-substituted 3-methylpyrazol-5-ones (LH) is studied. From acidic chloride complexes, ionic thallium(III) associates (LH₂)[TlCl₄] are extracted; from trichloroacetate, coordination scandium complexes Sc(LH)₄(CCl₃COO)₃; and from ammine, copper(II) complexes CuL₂. The extractive ability decreases in the order R = C₇H₁₅ > C₆H₁₃ > C₅H₁₁ > C₆H₅ > C₄H₉.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005, pp. 326–330.Original Russian Text Copyright © 2005 by Lesnov, Sazonova, Pavlov.     

Enantioseparation of 1-phenyl-1-propanol by supercritical fluid-simulated moving bed chromatography

The enantioseparation of 1-phenyl-1-propanol through the supercritical fluid-simulated moving bed (SF-SMB) process is studied. Non-linear isotherms were measured on an analytical column, and used together with the triangle theory for SMB design to select operating conditions for the SF-SMB. Experiments were carried out on a pilot-scale SF-SMB plant at conditions that corresponded to the non-linear range of the isotherm. Under conditions of low feed concentration, complete separation (extract purity = 99.5%; raffinate purity = 98.4%) was achieved. Under conditions of larger feed concentration, the best separation corresponded to an extract purity of 98.0% and a raffinate purity of 94.0%, and yielded a productivity of 110 g of racemate per kg stationary phase per day.