Fused Nitrogen-Containing Heterocycles: IV. 3-Benzoyl-2-oxo-1,2-dihydroquinoxaline Hydrazones and Flavazoles Derived Therefrom

3-Benzoyl-1,2-dihydroquinoxalin-2-one reacts with hydrazine and thiosemicarbazide to give the corresponding hydrazone and thiosemicarbazone. The reaction with arylhydrazines yields 3-(-arylazobenzylidene)-1,2,3,4-tetrahydroquinoxalin-2-ones which are tautomeric to the respective arylhydrazones. On heating in boiling acetic acid, the products of both types undergo intramolecular cyclocondensation with formation of 3-phenylpyrazolo[3,4-b]quinoxalines (3-phenylflavazoles). 3-Benzoyl-1,2-dihydroquinoxalin-2-one thiosemicarbazone gives rise to flavazole structure only in the presence of methyl 3-chloro-2-oxo-3-phenylpropionate as a trap of thiocarbamoyl moiety. The cyclization of 3-(-hydrazonobenzyl)-1,2-dihydroquinoxalin-2-one is accompanied by formation of quinoxalyl ketone azine.     

Fused Nitrogen-Containing Heterocycles: III. 4-Oxo-1-phenyl-4,5-dihydroimidazo[1,5-a]quinoxalines. A Retrosynthetic Approach

Retrosynthetic analysis of the structure of imidazo[1,5-a]quinoxalines made it possible to develop new convenient procedures for preparation of these compounds by reaction of 3-(-chlorobenzyl)-1,2-dihydroquinoxalin-2-one with potassium thiocyanate or isocyanate as synthetic equivalent of the two-membered N^-ÍC⁺ building blocks and by reaction of 3-(-aminobenzyl)-1,2-dihydroquinoxalin-2-one with carbon disulfide, triethoxymethane, aromatic aldehydes, or acetic anhydride as synthetic equivalent of the one-membered RC^{3 +} synthon.     

Tiegelkonstruktionen für die Differenzthermoanalytische Untersuchung ternärer intermetallischer Verbindungen mit leichtflüchtigen Komponenten

Zusammenfassung Zur differenzthermoanalytischen Untersuchung von ternären intermetallischen Verbindungen wie Li₂ZnGe, Li₂ZnSi, LiMgAs, TlZnSb und TlCdSb wurden gasdicht verschraubbare Tiegel aus Tantal, Molybdän und Titan konstruiert, die den besonderen Eigenschaften dieser Verbindungen, insbesondere der leichten Flüchtigkeit von Lithium, Magnesium, Zink und Cadmium sowie der großen Korrosivität der Schmelzen Rechnung tragen mußten. Außer diesen »Metallautoklaven« wurden geschlossene, in einer Metallhülse gelagerte Quarzampullen eingesetzt. Die kalorimetrischen Eigenschaften dieser Tiegel wurden in verschiedenen Temperaturbereichen untersucht und miteinander verglichen.

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For DTA measurements on ternary intermetallic compounds such as Li₂ZnGe, Li₂ZnSi, LiMgAs, TlZnSb and TlCdSb, gastight screwable crucibles were constructed from tantalum, molybdenum and titanium. They had to be suited to the special properties of these compounds, particularly the high volatility of lithium, magnesium, zinc and cadmium and the corroding characteristic of their melts. Besides these metallic autoclaves, closed quartz glass ampules were used, which were supported in a metallic hull. The calorimetric properties of these crucibles were investigated in different regions of temperature and compared with one another.

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Li₂ZnGe, Li₂ZnSi, LiMgAs, TlZnSb TlCdSb , , . , , , , , . « », , . .

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Teilweise vorgetragen auf dem TA-Symposium der GEFTA, Aachen, Deutschland, Oktober 1981.

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Der Deutschen Forschungsgemeinschaft und dem Verband der Chemischen Industrie danken wir für die Förderung unserer Arbeiten.     

Sulfur heterocycles. 13. Oxidative chlorination of β-thiolactones. A novel synthesis of β-(chlorosulfinyl)alkanoyl chlorides and 1,2-oxathiolan-5-one 2-oxides

Chlorination of -thiolactones with chlorine or sulfuryl chloride in acetic anhydride at a reactant ratio (RR) of 1:2:1 gives -(chlorosulfinyl)alkanoyl chlorides in 75–89% yields. Oxidative chlorination of -thiolactones with RR of 1:3:2 affords -(chlorosulfinyl)alkanoyl chlorides and cyclic sulfinic anhydrides (1,2-oxathiolan-5-one 2-oxides). The optimum RR for the preparation of 1,2-oxathiolan-5-one 2-oxides is 1:2:2. Hydrolysis of -chloro--(chlorosulfinyl)carbonyl chlorides has given novel -chlorinated sulfinocarboxylic acids.For communication 12, see [1].A. N. Nesmeyanov Institute of Heteroorganic Chemistry, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2153–2158, September, 1992.     

Syntheses in the field of 5-nitro-2-furylpolyalkenals and 5-nitro-2-furylpolyalkenones

A series of, -bis(5-nitro-2-furyl)poryalkenones has been synthesized by the condensation of 5-nitro-2-furylalkenones with 5-nitrofuran aldehydes in acetic acid (concentrated sulfuric acid catalyst). In the , -bis(5-nitro-2-furyl)polyalkenone series, the keto group acts as a partial insulator of conjugation, which is shown most clearly in the case of 1,3-bis(5-nitro-2-furyl)prop-2-en-1-one and 1,5-bis(5-nitro-2-furyl)-penta-2,4-dien-1-one, i.e. compounds having the keto group directly linked to a 5-nitrofuran ring. The electronic spectra of the semicarbazones of the, -bis(5-nitro-2-furyl)polyalkenones exhibit a stronger disturbing effect of the conjugation in the molecule than in the case of the ketones, which may be connected with a disturbance of coplanarity. In a number of cases, the infrared spectra of the, -bis(5-nitro-2-furyl)polyalkenones exhibit splitting of the symmetrical and antisymmetrical vibrations of the nitro group.For part VII, see [1].Preliminary results of the present investigation were given for the first time at the 2-nd All-union Scientific Conference on the Chemistry of Furan Compounds, Saratov, 23–26 January, 1962, see [2].     

Fluoroalkyl-containing β,β'-tricarbonyl compounds: Tautomerism and reaction with N-nucleophiles

The tautomeric composition of -polyfluoroacyl derivatives of acetylacetone and malonic ester has been established and it has been shown that with N-nu-cleophiles (ammonia, 1,2-ethylenediamine, o-phenylenediamine) these compounds undergo acid decomposition with the elimination of the polyfluoroacyl group. With hydrazines, malonic ester derivatives react similarly but acetylacetone derivatives undergo cyclization into pyrazoles. The regiodirectivity of the interaction of fluoroalkyl-containing ,-tricarbonyl compounds with N-nucleophiles does not depend on their tautomeric composition and is determined by orbital control.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 376–382, February, 1990.     

Thermal analysis of composites based on crystalline polymers and metals

Differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and infrared (IR) spectroscopy have been used to examine the chemical and physical changes (crystallinity, accumulation of oxygen-containing groups, etc.) during thermal oxidation of polyethylene, polypropylene and Penton contained in coatings and metalfilled films, taking into account the thickness of the polymer layer and catalytic activity of the metal.

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Zusammenfassung DSC, thermogravimetrische Analyse (TG) und infrarot (IR) Spektroskopie wurden zur Untersuchung der während der thermischen Oxidation von in Belägen und metallgefüllten Filmen enthaltenem Polyäthylen, Polypropylen und Penton stattfindenden chemischen und physikalischen Veränderungen (Kristallinität, Anhäufung stickstoffhaltiger Gruppen usw.) eingesetzt. Hierbei wurden die Stärke der Polymerschicht und die katalytische Aktivität des Metalls in Betracht genommen.

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, (, .) , .

     

Effects of gas-phase mass transport in the pyrotechnic system red lead-silicon-potassium perchlorate

The acceleratory effect of potassium perchlorate on the reactivity of the red lead-silicon system has been studied by employing DTA and DSC. Supporting investigations on pure potassium perchlorate and the binary system red lead-potassium perchlorate suggest that the complex decomposition kinetics of potassium perchlorate drastically influences the oxidation of silicon. Further, the ternary system also undergoes a transition from exothermic smooth decomposition to ignition at a certain critical mass, as noted in the red lead-silicon and iron(III) oxide system. The criticality should be a result of the rise in temperature expressed as a perturbation of the steady-state energy conservation conditions, as postulated by Gray.

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Zusammenfassung Mitsels DTA- und DSC-Methoden wurde der Beschleunigungseffekt von Kaliumperchlorat auf die Reaktivität des Systemes Mennige-Silizium untersucht. Ergänzende Untersuchungen an reinem Kaliumperchlorat und am binären System Mennige-Kaliumperchlorat lassen darauf schliessen, dass die komplexe Zersetzungskinetik des Kaliumperchlorates die Oxidation des Siliziums erheblich beeinflusst. Weiterhin kann im Deeikomponentensystem bei einem bestimmten kritischen Massenwert ein Übergang von einer leicht exothermen Zersetzung bis zur Entzündung stattfinden, wie dies im System Mennige-Silizium-Eisen(III)oxid beobachtet wird. Wie von Gray vorasugesetzt, sei die Kritikalität ein Ergebnis der Temperaturerhöhung, einer Veränderung der Bedingungen zur Erhaltung des stationären Energiezustandes.

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-. , - , , . , -- . , .

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The author thanks the Management of IDL Chemicals Ltd., for permission to publish this paper, and Mr. Sudhir Achar and Dr. O. S. Josyulu for help in the experimental work.     

The thermal analysis of “argentic oxynitrate” and silver oxides

The precise stoichiometry of argentic oxynitrate has been elucidated by analytical and thermal analytical techniques. A decomposition path of the oxynitrate has been proposed and values of the enthalpy changes obtained. TG has been used as the criterion of purity of silver(II) oxide and new values for the heat of formation of silver(I) and silver(II) oxide are reported.

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Zusammenfassung Die genaue Stöchiometrie des Silberoxynitrats wurde durch analytische und thermoanalytische Prüfung geklärt. Der Zersetzungsvorgang des Oxynitrats wurde verfolgt und die Enthalpieänderungen beobachtet. Die Reinheit von Silber(II)oxyd läßt sich thermogravimetrisch kontrollieren. Es wurden neue Werte für die Bildungswärmen des Silber(II)oxyds und Silber(I)oxyds gefunden.

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Résumé Etude de la stoechiométrie précise de l'oxynitrate argentique par les techniques analytiques et thermoanalytiques. On propose un schéma de décomposition de l'oxynitrate et l'on évalue les variations d'enthalpie. Emploi de la TG comme critère de pureté de l'oxyde d'argent(II). Communication de nouvelles valeurs pour les chaleurs de formation des oxydes d'argent (I) et d'argent (II).

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. . (II) . (I) (II).

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The authors wish to thank Mr. J. McEwan and Mrs. I. M. Walker for valuable practical assistance and the United Kingdom Atomic Energy Authority for financial support.     

Shape selectivity of aluminium deficient mordenites

The liquid-phase hydrogenation of isododecenes has been investigated in the presence of a 0.5% Pd–Al₂O₃ catalyst suspended in n-heptane. A kinetic equation was derived and the rate constants were determined.

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0,5% Pd–Al₂O₃, -. .

     

Thermoanalytical examination of orthoboric acid

The effects of the conditions of thermal analysis of the process of dehydration of orthoboric acid to boric oxide were studied. The parameters for obtaining structurally arranged boric oxide directly from orthoboric acid were determined.

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Zusammenfassung Der Einfluss der Versuchsbedingungen bei der thermischen Entwässerung von ortho-Borsäure H₃BO₃ zu B₂O₃ wird gezeigt. Die Parameter zur Darstellung von strukturell geordnetem Boroxid direkiaus ortho-Borsäure wurden bestimmt.

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. .

     

Transformed steroids

Conclusions The addition of thioacetic acid to the ⁵ bonds of 16- and 16-mercapto-3-hydroxypregn-5-en-20-one 3,16-diacetates (II) and (III) under radical conditions gives not only trans-diaxial addition products-6,16- and 6,16-dimercapto-3-hydroxy-5o;-pregnan-20-one 3,6,16-triacetates (IV) and (V) -but also cis-addition products-6,16- and 6,16-dimercapto-3-hydroxy-5-pregnan-20-one 3,6,16-triacetates (VI) and (VII).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 405–411, February, 1969.     

Promotion of the catalytic activity of zeolites by alkyl halides

The promotion of catalytic activity of zeolites by CCl₄ was studied in a pulse reactor using aromatic alkylation as model reaction. The reaction of surface OH groups with CCl₄ produced HCl which increased the catalytic activity. The maximum enhancement of activity occurred when the catalyst was weakly acidic.

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CCl₄ , . OH CCl₄ HCl, . , .

     

Indole derivatives

A series of -, -substituted -(3-indolyl) ketones was obtained by the reaction of indole with , -unsaturated ketones in the presence of perchloric acid.     

Reaction of dichlorocarbene with substituted 3,4-dihydroisoquinolines and 1-methylene-1,2,3,4-tetrahydroisoquinolines

Reaction of dichlorocarbene with 3,3-dialkyl-3,4-dihydroisoquinolines results in the formation of gemdichloroazirino[2,1-a]isoquinolines, which are in turn converted to 3-benzazepinones upon hydrolysis. Reaction of dichlorocarbene with the ethyl ester or amide of (3,3-dimethyl-1,2,3,4-tetrahydroisoquinolin-1-ylidene)acetic acid is accompanied by rearrangement of the intermediate carbene adducts at the enamine C=C bond and results in the formation of a 1-azadiene, 3-(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-3-chloroacrylic acid ethyl ester, and a spirolactam, 3,3-dimethyl-3-chlorospiro[1,2,3,4-tetrahydroisoquinoline-1,2-pyrrole]-5(2H)-one, respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1086–1091, August, 1990.     

2,3-Diferrocenylcyclopropenone in the reaction with organomagnesium compounds

The reactions of 2,3-diferrocenylcyclopropenone with ethyl- and benzylmagnesium chlorides afford 3,3-diethyl- and 3,3-dibenzyl-1,2-diferrocenylcyclopropenes along with products of nucleophilic opening of the three-membered ring: ,-unsaturated and saturated ketones (cis-1,2-diferrocenylpent-1-en-3-one and cis-1,2-diferrocenyl-4-phenylbut-1-en-3-one, 4,5-diferrocenylheptan-3-one, and 3,4-diferrocenyl-1,5-diphenylpentan-2-one). The products of insertion of intermediate diferrocenyl(vinyl)carbene at one of the -bonds of the starting 2,3-diferrocenylcyclopropenone were also isolated: 4-(2-oxo-1-ferrocenylbutyl)- and 4-(2-oxo-3-phenyl-1-ferrocenylpropyl)-2,3,4-triferrocenylcyclobutenones. 3,3-Dibenzyl-1,2-diferrocenylcyclopropene and one of the diastereomers of 4,5-diferrocenylheptan-3-one were studied by X-ray diffraction analysis.     

Fällungsanalyse im Mikrogrammbereich: Eine neue Methode

Zusammenfassung Eine neue Methode zur Durchführung gravimetrischer Bestimmungen im Mikrogrammbereich wurde beschrieben; diese beruht im wesentlichen darauf, daß der Niederschlag nicht mehr zusammen mit dem Filter, sondern nach Überführen mit einem geeigneten Lösungsmittel in einem separaten Wägegefäß gewogen wird.Die dazu nötigen Geräte und deren Herstellung wurden beschrieben. Nach dieser Methode wurden folgende Bestimmungen mit zufriedenstellender Richtigkeit durchgeführt: 2,5–25g Al, 5–50g Cu und 5–50g Zn mit Oxin, 2,5–25g Fe(III) und 2,5–25g Ti(IV) mit N-Benzoyl-phenylhydroxylamin, 5–50g Ni und 5–50g Cu mit Salicylaldoxim, 2,5–50g Co(II) und 2,5–50g Fe(III) mit -Nitroso--naphthol sowie 5–50g Chlorid als Silberchlorid.

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Precipitation analysis in the microgram-scale: A new method

Summary A new method for gravimetric determinations in the microgram-scale is described. This method is based on the fact that the precipitate is not weighed together with the filter but is transferred to a separate weighingvessel using a suitable solvent. The necessary simple devices and their use are described. The following determinations were carried out with satisfying accuracy: 2,5–25g Al, 5–50g Cu and 5–50g Zn with Oxine, 2,5–25g Fe and 2,5–25g Ti withN-benzoylphenylhydroxylamine, 5–50g Ni and 5–50g Cu with salicylaldoxime, 2,52–50g Co and 2,5–50g Fe with -nitroso--naphthol and 5–50g chloride as silver chloride.

     

Fused Polycyclic Nitrogen-Containing Heterocycles: VII. Reaction Products of 3-(α-Chlorobenzyl)-1,2-dihydro-quinoxalin-2-one and Thioureas as Key Intermediate Compounds in the Synthesis of Thiazolo[3,4-a]quinoxalines

Products of the reactions of 3-(-chlorobenzyl)-1,2-dihydroquinoxalin-2-one with thiourea, N-phenylthiourea, N,N'-diphenylthiourea, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, and potassium thiocyanate were brought into intramolecular cyclizations. Specific features of these reactions are discussed.     

The spectra of 3-OXO-2, 3-dihydrothianaphthene and its derivatives

Condensation of isatin--anil with acetylacetone and with derivatives of malonic and acetoacetic acids in acetic anhydride has given 5 indogenides. It is observed that isatin--anil is readily acetylated by acetic anhydride. The acetyl derivative is very reactive, and is an intermediate in the condensation of isatin--anil with acetylacetone in acetic anhydride. The indogenides which have been synthesized are nonphototropic as a result of the presence of intramolecular hydrogen bonds.For part IX, see [1].     

Indole derivatives. I.β-(3-indolyl) ketones

A number of -skatyl--substituted acetoacetic esters (ethyl, tert. -butyl, and benzyl) are prepared by treating gramine with sodium derivatives of -substituted acetoacetic esters. When ethyl -alkyl--skatylacetoacetates are heated with dilute alkali, they are split into indole and a substituted acetoacetic ester, while saponification with concentrated alcoholic alkali gives -substituted-(3-indolyl)propionic acids. 3-Skatyl-heptan-2-one can be obtained by pyrolysis of 3-skatyl-3-carbo-tert. -butoxyheptan-2-one, or by hydrogenolysis of 3-skatyl-3-carbobenzoxyheptan-2-one over a palladium catalyst. Alkylation of cycloheptanone and cyclohexanone enamines by gramine gives cyclic-(3-indolyl)ketones, viz., 2-skatylcyclopentanone and 2-skatylcyclohexanone.