Polyfluorinated heterocyclic compounds

The treatment of 2-phenyl-4-carbomethoxy-6,7,8,9-tetrafluorobenz[f]oxazepin-1,3 (I), 3-benzamido-5,6,7,8-tetrafluorocoumarin (V), and α-benzamido-β-(2-hydroxy-3,4,5,6-tetrafluorophenyl)-acrylic acid (III) with a mixture of glacial acetic acid and a mineral acid gave (IV), the π-complex of 3-hydroxy-5,6,7,8-tetrafluorocoumarin (VII) and benzoic acid. Treatment of (IV) with acetic anhydride gave 3-acetoxy-5,6,7,8-tetrafluorocoumarin (VI) and benzoic acid. Treatment with diazomethane gave 3-methoxy-5,6,7,8-tetrafluorocoumarin (VIII) and methyl benzoate. IV was also obtained from an equimolar mixture of its components. A mechanism for the formation of IV from I is proposed.     

Synthesen von Heterocyclen, 68. Mitt.: ÜberMannich-Basen heterocyclischer β-Dicarbonylverbindungen

Zusammenfassung Durch Variation der Versuchsbedingungen konntenMannich-Basen vom 6-Methyl-2,4-pyronon, 2-Äthoxy-4-hydroxy-[1,3-thiazinon-(6)] und von verschiedenen 2-Phenyl-4-hydroxy-[1,3-thiazinonen-(6)] sowie vom 4-Hydroxy-5,6,7,8-tetrahydrocumarin, Malonyl--aminopyridin und -Oxo--hydroxy-julolin hergestellt werden. Auch Barbitursäure und Thiobarbitursäure lassen sich unter gewissen Bedingungen aminoalkylieren.

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Mannich bases have been obtained from 6-methyl-2,4-pyronon, 2-ethoxy-4-hydroxy-1,3-thiazinon-(6), 2-phenyl-4-hydroxy-1,3-thiazinones-(6), 4-hydroxy-5,6,7,8-tetrahydrocoumarin, malonyl--aminopyridin and -oxo--hydroxy-julolin by appropriate variation of the reaction conditions. Also barbituric acid and thiobarbituric acid have been aminoalkylated under certain conditions.

     

Reaction of 2,2-bis(4′-hydroxy-3′-N,N-diethylaminomethylphenyl) propane with triethyl phosphite

Conclusions The reaction of 2,2-bis(4-hydroxy-3-N,N-diethylaminomethylphenyl)propane with triethyl phosphite gave 2,2-bis(4-ethoxy-3-diethylphosphonomethylphenyl)propane via the intermediate formation of a compound with a pentacovalent phosphorus atom. In the presence of acetic acid the reaction leads to 2,2-bis(4-hydroxy-3-diethylphosphonomethylphenyl)propane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1621–1624, July, 1978.     

Esters of (1,2, 5-trimethyl-4-hydroxy-4-piperedyl)- and phenyl-(1,2, 5-trimethyl-4-hydroxy-4-piperidyl) acetic acids

The methyl ester of a new hydroxy acid of the piperidine series (-phenyl--(1,2, 5-trimethyl-4-hydroxy 4-piperidyl)acetic acid) has been prepared. Ethyl -(1,2, 5-trimethyl-4-hydroxy-4-piperidyl)acetate has been converted into the substituted pyridine, 1,1-diphenyl-2-(2-5-dimethyl-4-pyridyl)ethylene.     

Flotations-spektrophotometrische Methode zur Bestimmung von Zirkonium mittels Eriochromazurol B

Zusammenfassung Eine flotations-spektrophotometrische Methode zur Bestimmung des Zirkoniums in Stählen mittels des Dinatriumsalzes der 2,6-Dichlor-4-hydroxy-3, 3-dimethylfuchson-5,5-dicarbonsäure (CAB) wurde ausgearbeitet. Der molare Extinktionskoeffizient beträgt 3,3×10⁴, die spezifische Absorptiona=0,33. Der Vorteil der bearbeiteten Methode ist die Möglichkeit, Zirkonium (IV) neben der hundertfachen Menge Hf(IV) zu bestimmen.

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Flotation spectrophotometric method for determination of zirconium by means of eriochrome azurol B

Summary A flotation spectrophotometric method for determining zirconium in steels by means of the disodium salt of 2, 6-dichloro-4-hydroxy-3,3-dimethylfuchsone-5, 5-dicarbonic acid (CAB) was worked out. The molar extinction coefficient is 3.3×10⁴. The specific absorption wasa=0.33. The advantage of the method is the possibility of determining zirconium(IV) besides the hundredfold amount of Hf(IV).

     

Reactions of 1,2,4-Triazines with Nucleophiles. 6. Use of SNH Methodology for the Direct Introduction of Cyclic Diketone Residue into the 1,2,4-Triazine Ring FORENAME = D. N.

3-R-6-Phenyl-1,2,4-triazine 4-oxides react with cyclic -diketones (dimethylbarbituric acid, dimedone, and indan) in both acidic (substrate activation) and basic conditions (nucleophile activation) with formation of ^H-adducts, intermediates in the nucleophilic substitution of hydrogen (S_N ^H) in 3-R-5-Nu-4-hydroxy-6-phenyl-4,5-dihydro-1,2,4-triazines. Oxidative aromatisation of these intermediates or auto-aromatisation of acylated (benzoyl chloride) at the NOH -adducts with elimination of benzoic acid gave the corresponding substituted 1,2,4-triazine 4-oxides or 1,2,4-triazines.     

Silylation of hydroxyketones by silicon chlorine derivatives

The reaction of 3-methyl-3-hydroxy-2-butanone (an-hydroxyketone) with dimethyl-dichlorosilane gave 2,2,4,4-tetramethyl-5-methylene-1,3,2-dioxasilolane. The silylation of-hydroxyketones leads to acyclic mono- and bis(-ketoalkoxy)silanes.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2153–2155, September, 1990.     

Nitration,amination, and halogenation of Di-O-methylphloracetophenone

Chlorination of the title compound gave 5- and 3-chloro-2-hydroxy-4,6-dimethoxyacetophenone. The nitration of its acetate, followed successively by reduction, diazotization, and reaction with cuprous chloride, gave the 3-substituted series, 2-acetoxy-4,6-dimethoxy-3-nitroacetophenone, 3-amino-2-hydroxy-4,6-dimethoxyacetophenone, and 3-chloro-2-hydroxy-4,6-methoxyacetophenone, respectively. The orientation of substituents in the products was proved. The amino and chloro members of the isomeric 5-substituted series were availablevia 2-hydroxy-4,6-dimethoxy-5-phenylazoacetophenone, the product of the reaction of the title compound with benzenediazonium chloride.

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Nitrierung, Aminierung und Halogenierung von Di-O-methylphloracetophenon

Zusammenfassung Chlorierung der Titelverbindung gab 5- und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Nitrierung des Acetats, gefolgt von Reduktion, Diazotierung und Reaktion mit CuCl ergab die 3-substituierte Reihe: 2-Acetoxy-4,6-dimethoxy-3-nitroacetophenon, 3-Amino-2-hydroxy-4,6-dimethoxyacetophenon und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Orientierung der Substituenten wird diskutiert. Die Amino- und Chlorderivate der isomeren 5-substituierten Reihe sind über 2-Hydroxy-4,6-dimethoxy-5-phenylacetophenon zugängig, dem Produkt der Reaktion der Titelverbindung mit Phenyldiazoniumchlorid.

     

Some effective solvents for rapid and reliable characterization of phenylthiohydantoin-amino acids

Summary One-dimensional chromatography with internal standards permits reliable identification of the phenylthiohydantoins from all the common amino acids with the following TLC systems: silica gel — chloroform/n-butyl acetate (9010), di-isopropylether/ethanol (955), dichloromethane/ethanol/acetic acid (9082) ortrans-dichloroethylene/ethanol/acetic acid (88102); and cellulose with 25% formic acid — heptane/isobutanol/75% fromic acid (40309) or silica gel — chloroform/ ethanol/acetic acid/water (50470.52.5).Abbreviations: PTH=phenylthiohydantoin, TLC=thin-layer chromatography, HPTLC=high-performance TLC; other abbreviations: see end of text. Proportions in solvent mixtures are v/v except where otherwise indicated.     

Gomphacil — A cardenolide glycoside ofGomphocarpus fruticosus

The leaves ofGomphocarpus fruticosus (L.) R.Br. have yielded the new acetylated glycoside gomphacil, which is (3-O-1,2-O-2)-(3-acetoxy-2-hydroxy-4,6-dideoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide.State Scientific Center for Drugs, Ukraine, 310085, Kharkov, ul. Astronomicheskaya, 33. Ukrainian Pharmaceutical Academy, 310002, Kharkov, ul. Pushkinskaya, 53. Translated from Khimiya Prirodnykh Soedinenii, Vol. 33, No. 1, pp. 71–73, January–February, 1997.     

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.     

New derivatives of 4-quinaldinol

The reactions of 1, 1, 3-trichloro-1-propene and also 1, 1, 1-trichloro-2-propene with acetoacetic ester gave -(, -dichlorallyl)acetoacetic ester (I). In the reactions with aniline and o- and p-toluidines, the corresponding -(, -dichloroallyl)--arylamino-crotonic esters were produced, thermal cyclization of which gave 2-methyl-3-(, -dichloroallyl)-4-hydroxyquinoline (II) and its 6CH₃- (III) and 8CH₃- (IV) homologs. With phosphorus oxychloride, II–IV gave the corresponding 4-chloro-substituted quinolines (V–VII); with concentrated sulfuric acid, II–VII were converted into the corresponding -quinolinylpropionic acids VIII–XIII.For part XI, see [5].     

Optisch aktive aromatische Spirane, 18. Mitt.: Darstellung von optisch aktiven 4,4′-disubstituierten 2,2′-Spirobi-s-hydrindacenen

Summary All optically active title compounds were obtained from the 4,4-diacetyl-spiro compound2; (+)- and (–)-2 were accessible by chromatography on triacetyl cellulose in ethanol. The enantiomeric purities were established from chromatographic data. The chirality (–)-(2R) was deduced for all new compounds on the basis of the CD spectra of (–)-2 and (–)-2,2-spirobi-(5,6,7,8-tetrahydrobenzo[f]indane). From the molar rotations of these 4,4-disubstituted 2,2-spirobiindanes (empirical) ligand parameters were determined (using the so-called shortened approach). Generally, the values of in these compounds are higher than those of the analogous tetrahydrobenzoindane derivatives.

Herrn Prof. Dr.F. Sauter mit besten Wünschen zum 65. Geburtstag gewidmet     

Radiation-induced reactions of cholesterol in an aqueous medium

⁶⁰Co -ray radiolysis of cholesterol /3-hydroxy-5-cholestene/ /I/ in the two-phase system /water-ethyl acetate/ and in the presence of air has been studied using TLC and GC methods. The following products were observed in the irradiated mixture: 3, 7-dihydroxy-5-cholestene /II/, G O. 36, 3-hydroxy-7-keto-5-cholestene /III/, G 1.48, 3-hydroxy-7-keto-5-cholestane /IV/, G 0.22, 3,5,6-trihydroxy-5-cholestane /V/, G 0.83, 5,6-epoxy-3-hydroxy-5-cholestane /VIa/, G 0.26, 5,6-epoxy-3-hydroxy-5-cholestane /VIb/, G 0.24, and 2, 3-dihydroxy-5-cholestene /VII/, G 0.22. The dose dependence of the formation of these products shows that the cholesterol derivatives substituted in the position 7 /II–IV/ are formed from a common precursor — the radical Ia. On the other hand, the products of the 5–C=C double bond reactions /V and VI/ are formed independently. Also the product VII is formed independently. A reaction scheme that is in agreement with these results is proposed.     

Über einige β,β,β-Trichlor-α-[dichlor-phenyl]-äthanole

Zusammenfassung Unter Verwendung derGrignardschen Reaktion wurden aus 2,4-, 2,5-und 3,4-Dichlor-jodbenzol und Chloral die entsprechenden ,,-Trichlor--[dichlor-phenyl]-äthanole synthetisiert und als Acetate charakterisiert. Das ,,-Trichlor--[3,4-dichlor-phenyl]-äthanol (IV) läßt sich schneller und in besserer Ausbeute aus dem Produkt der Umsetzung von o-Dichlorbenzol mit Chloral in Gegenwart von Aluminiumchlorid isolieren. IV besitzt insektizide Wirksamkeit (Testtiere: Drosophila melanogaster, Blatta orientalis, Phyllodromia germanica, Calandra granaria, Acanthoscelides obtectus, Musca domestica).     

Fast Atom Bombardment Mass Spectroscopic Investigation of Inclusion Complexes of Cyclodextrins with 4-Nitrophenol and Benzoic Acid

Mixtures of -, -, and -cyclodextrins and 4-nitrophenol (or benzoic acid) were investigated by means of fast atom bombardment mass spectroscopy. In the gas phase, inclusion complexes of -, , and -cyclodextrins with 4-nitrophenolate and benzoate, which have a 1 : 1 cyclodextrin–guest stoichiometry, were observed in negative-ion mode. In addition, guest anions, clusters of two and three guest molecules, and guest–matrix complexes were observed.     

Marked differences between acetonitrile/water and methanol/water mobile phase systems on the thermodynamic behavior of benzodiazepines in reversed phase liquid chromatography

Summary Two different methods were used to determine the separation factor at different temperatures and the Gibbs-Helmholtz parameters ((H), (S)) of two adjacent benzodiazepines on a chromatogram were obtained from plots of ln versus 1/T. We first studied each factor (fraction of water in the ACN/water mixture and column temperatureT), which controls the retention mechanism, and then we examined the simultaneous variation of all these factors. The changes in (H) and (S) in relation to a volume fraction of water in an ACN/water mixture were examined. In the ACN/water system, (H) was fairly constant in the acetonitrile region of 0.52 and appears to be a roughly linear function of for 0.52. In this system (S) is approximately a parabolic function of with an optimum at 0.52. The retention mechanism of ten benzodiazepines was found to be significantly different in the methanol/water and ACN/water mixtures. The separation optimization of these ten benzodiazepines was then considered. A fraction of water of 0.43 in the ACN/water mixture and a column temperature of 44°C gave the most efficient separation conditions in the ACN/water mixture.     

Zum Thermischen Verhalten von Alkylammonium- und Kalium-N-Alkylthiocarbamaten

Zusammenfassung Es wurde das thermische Verhalten von Alkylammonium- und Kalium-N-alkylthiocarbamaten der Zusammensetzung (RNH₃) (RHNCXY) mit X=Y=S oder X= S und Y= 0; R=n-C₃H₇,i-C₃H₇,n-C₄H₉,i-C₄H₉,c-C₆H₁₁ bzw. K(RHNCOS) mit R= CH₃ C₂H₅,n-C₃H₇,i-C₃H₇,n-C₄H₉,i-C₄H₉,c-C₆H₁₁ untersucht. Die Zersetzungsmechanismen zeigen bei allen untersuchten Verbindungen einen ähnlichen Charakter. Im Verlaufe der Thermolyse entstehen symmetrische Dialkylharn- bzw. -thioharnstoffe sowie Aminé, CS₂ (bzw. COS) und H₂S. Während sich die Alkylammoniumthiocarbamate ohne Rückstand zersetzen, verbleibt bei den Kaliummonothiocarbamaten Kaliumsulfat als Rückstand. Für den Prozeß der Harn- bzw. Thioharnstoffbildung während der ersten Abbaustufe der Alkylammoniumthiocarbamate wurden die Aktivierungsenergien berechnet.

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The thermal behaviours of alkylammonium and potassium N-alkylthiocarbamates of general formula (RNH₃) (RHNCXY) (where X= Y= S or X= S and Y= 0; R=n-C₃H₃,i-C₃H₃,n-C₄H₉,i-C₄H₉ orc-C₆H₁₁) and K(RHNCOS) (where R=CH₃, C₂H₅,n-C₃H₇,i-C₃H₇,n-C₄H₉,i-C₄H₉ orc-C₆H₁₁) were investigated. The decomposition mechanisms exhibit a similar character for all studied compounds. In the course of thermolysis symmetric dialkylureas and dialkylthioureas, as well as amines, CS₂ (or COS) and H₂S are formed. The alkylammonium thiocarbamates decompose without any residue, whereas with potassium monothiocarbamates potassium sulfate is left as a residue. For the process of urea and thiourea formation during the first step of decomposition, the activation energies were computed for some compounds.

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Résumé On a étudié le comportement thermique des N-alcoyl-thiocarbamates d'ammonium et de potassium de composition (RNH₃) (RHNCXY), avec X=Y=S ou X=S et Y=O; R=n-C₃H₇,i-C₃H₇,n-C₄H₉,i-C₄H₉,c-C₆H₁₁ ainsi que des composés K(RHNCOS) avec R=CH₃, C₂H₅,n-C₃H₇,i-C₃H₇,n-C₄H₉,i-C₄H₉,c-C₆H₁₁. Les mécanismes de décomposition montrent un caractère similaire pour tous les composés. Au cours de la thermolyse il se forme des dialcoylcarbamides symétriques ou des thiocarbamides ainsi que des amines, CS₂ (ou COS) et H₂S. Alors que les alcoylthiocarbamates d'ammonium se décomposent sans résidu, les monothiocarbamates de potassium donnent du sulfate de potassium comme résidu. On a calculé les énergies d'activation pour la réaction de formation de la carbamide ou de la thiocarbamide pendant la première étape de la décomposition des alcoylthiocarbamates d'ammonium.

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N- (RNH₃) ((RHNCXY), X=.Y=S X=S Y=; R=-₃₇, -₃₇, -C₄H₉, -₄₉, -₆₁₁ K(RHNCOS) c R=₃, ₂₅, -₃₇, -C₃H₇, -₄₉, o-C₄H₉ -₆₁₁. . : , CS₂ ( COS) H₂S. , . , .

     

Study of thermal properties of endellite clay compound

The temperature dependence of the thermal properties (specific heat,C _p, thermal diffusivity,a, and thermal conductivity,K) of endellite clay has been investigated over the temperature rangeR·TT/280 °C using the plane temperature wave technique. The experimental results showed that in the initial stage of temperature rise botha andK diminish exponentially with increasing temperature up to 100 °C. Above 100 °C, the thermal parameters are found to reach stable values, namely,C _p=0.22±0.008 cal g^–1 deg^–1,a=(5.0±0.18)–10^–4 cm² sec^{– 1} andK=(2.2±0.16) · 10^–4 cal cm^–1 sec^–1 deg^–1. The explanation of the results was supported by using DTA and TG analysis.

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Zusammenfassung In einem Temperaturbereich zwischen Raumtemperatur und 280 °C wurde die Temperaturabhängigkeit der thermischen Eigenschaften (spezifische WärmeC _p, Temperaturleitfähigkeita, WärmeleitfähigkeitK) von Endellittonerde untersucht. Die Ergebnisse zeigen, daß sowohla als suchK im ersten Abschnitt der Temperaturzunahme mit steigender Temperatur bis 100 °C exponentiell abnehmen. Oberhalb 100 °C erreichen die Parameter stabile Werte:C _p=0,22 ±0,008 cal g^–1 deg^–1,a=(5,0±0,18)·10^–4 cm² sec^–1 undK=(2,2±0,16)·10^–4 cal cm^–1 sec^–1 deg^–1. Die Erklärung der Ergebnisse wurde unter Zuhilfenahme von DTA und TG durchgeführt.

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( _p, ) T280°. , 100° K . 100° _n=,22 ±0,008 · ^–1· ^–1, =5,0±0,18·10^{–4 2}· ^–1 K=2,2±0,16· 10^–4 · ^–1· ^–1· ^–1. .

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We wish to thank Dr. N. Afify, Phys. Dept. Assiut University, for his assistance during DTA and TGA analysis.     

Quinindines

It is shown that, together with -quinindane-9-carboxylic acid, the condensation of isatin with cyclopentanone in alkaline medium (Pfitzinger reaction) also affords , -dicyclopentylidenecyclopentanone and 3-cyclopentylidene--quinindane-9-carboxylic acid, the structure of which was confirmed by its NMR, IR, and UV spectra.