Synthesis of asymmetric secondary and tertiary amines from a primary amine and alcohol over the methanol synthesis industrial catalyst SNM-1

Vapor-phase reactions ofn-pentan-1-ol with 2-ethylhexyiamine and ofn-heptan-1-ol with cyclohexylamine occurring in the presence of an industrial oxide copper-zinc-aluminum catalyst SNM-1 at 175–185°C have been found to afford the corresponding asymmetric secondary and tertiary amines in yields of 59–99 % and 5–49 %, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 799–800, April, 1993.     

Isomorphous substitution effects on the thermally induced interlayer reaction inN-hexylammonium layered aluminosilicates

It was found that the variation in the thermally evolved gases obtained by decomposition ofn-hexylammonium layered aluminosilicates is mainly due to the difference between octahedral and tetrahedral coordination of aluminium in the lattice and also to the contribution of the excess negative layer charges.ESCA, TG-DSC, GC and MS results indicate that the layer charge originated from the octahedral substitution induces only desintercalation ofn-hexylamine around 250–360°C, whereas that from the tetrahedral substitution induces the catalytic decomposition reaction involving the cleavage of C–N and C–C bonds at 350–450°C with the evolution of ammonia, ethylene, pentene and hexene.It is therefore concluded that the former reaction step is a simple desintercalation, but for the latter one a Brönsted acid catalytic mechanism is proposed.Presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986.     

The aggregation ofn-dodecanephosphonic acid in water

Several techniques were employed to study the aggregation ofn-Dodecanephosphonic Acid (DPA) in water. At 22°C, the solubillity of DPA increases, probably due to the formation of small premicellar aggregates. The CMC is (5.4±2.4) ×10^–4 mol·dm^–3 and the solubility reaches the CMC value at 26°C. At 30°C and at a concentration of about 9×10^–3 mol·dm^–3, a lamellar mesophase appears. Both micelles and liquid crystal lamellae are almost uncharged. Their polar heads have strong hydrogen bonds between them. The ionization of DPA molecules in micelles and mesophase structures is strongly reduced in comparison with monomerically dissolved molecules.     

Peroxide-initiated condensation of carboranes-12 with 1,2-dichloroethylene

The interaction of carboranes-12 with 1,2-dichloroethylene was investigated at 150–200°C in the presence oftert-butyl peroxide as an initiator.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 1017–1019, April, 1992.     

Synthesis and spectral properties of cyclopropyl-substituted phosphaalkenes

Cyclopropanecarboxylic acid chlorides5a-d react with tris(trimethylsilyl)phosphane6 in benzene at –2 °C to form cyclopropylcarbonyl-bis(trimethylsilyl)phosphanes7. These products undergo silylic rearrangement at 25 °C to yield phosphaalkenes8. Compounds 8a,b,d are formed as mixtures ofZ- andE-isomers where the latter predominate. In the case of8c, theZ-isomer is formed exclusively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 684–689, April, 1994.The authors are grateful to the Fonds der Chemischen Industrie (Germany) for financial support of this work. A. B. Kostitsyn is also grateful to the Deutscher Akademischer Austauschdienst for a grant to carry out this study. For a preliminary communicationcf. Ref. 1.     

Alkaloids ofAndrachne rotundifolia

Summary 1. The content of total alkaloids in the hypogeal parts ofAndrachne rotundifolia C. A. Mey. (family Euphorbicease) is 0.2–0.3% and in the epigeal parts 0.06–0.08%.The total alkaloids in both the hypogeal and the epigeal parts ofAndrachne rotundifolia consist of five or six non-phenolic bases.2. Three individual substances have been isolated: andrachnine C₁₁H₁₇NO₂, which is a new alkaloid; base (II), giving a perchlorate with mp 139°–140° C; and base (III) with mp 135°–136° C.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 4, pp. 257–260, 1966     

Lactones ofFerula gigantea

The following substances have been isolated from an acetone extract ofFerula gigantea B. Fedtsch.: a coumarin — umbelliferone, C₉H₆O₂, mp 230–233°C; and sesquiterpene lactones — talassin A, C₂₅H₃₀O₇, mp 188–191°C; malaphyllinin, C₂₄H₂₄O₇, mp 231–235°C; malaphyll, C₂₉H₃₂O₉, mp 212–213°C; and malaphyllin, C₂₆H₂₈O₉, mp 216–218°C. Structures have been proposed for three new sesquiterpene lactones on the basis of an analysis of their spectral characteristics.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov Moscow State University, Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 490–495, July–August, 1979.     

Carbonylation reaction

Conclusions The butyl ester of-butoxypropionic acid was synthesized by the carbonylation of-butoxyethylmercury acetate at 150–250° and 50–150 atm, in which connection the maximum yield was obtained at 200° and 100 atm.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1751–1753, August, 1972.     

Application of a simple and sensitive GC–MS method for determination of morphine in the hair of opium abusers

Thirty hair samples were collected from male opioid abusers for whom the presence of morphine in their urine samples was confirmed by thin layer chromatography (TLC). The hair samples were decontaminated by washing with isopropanol, deionized water, and isopropanol, dried at room temperature, and cut into small pieces. Samples of the latter (30 mg ) were digested by incubation in a mixture of methanol–trifluoroacetic acid (9:1) for 18 h at 45 °C and sonicated to improve the extraction process. The methanolic phase was evaporated to dryness under a stream of nitrogen at 50 °C. The sample was derivatized by addition of N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA) and 1% trimethyliodosilane (TMIS) at 70 °C for 20 min, with sonication. Derivatized samples (1 L) were injected into a gas chromatograph–mass spectrometer (GC–MS) system fitted with a capillary column; the Finnigan MS was operated in SIM mode. Naltrexone was used as internal standard (IS). The masses of the ions selected for morphine and naltrexone were 429 and 557, respectively. The limit of quantitation was set at 0.03 ng mg^–1 hair. By using the above procedure we detected morphine in all the samples examined, in the concentration range 0.26–10.31 ng mg^–1 hair.     

Ionization constants of aqueous ammonia from 25 to 250°C and to 2000 bar

The ionization constant of ammonia has been determined by conductivity measurements and found to vary from 1.77×10^–5 at 25°C to 1.3×10^–6mol-kg^–1 at 250°C. The pressure effect to 2000 bar has been measured and the ratio K₂₀₀₀/K₁ is 6.8 at 25°C and 11 at 250°C. The standard molar volume change for the ionization at 1 bar, V ₁ ^o , changes from –28.8 at 25°C to –67 cm³-mol^–1 at 250°C.     

A study of some properties of the lipase from the seeds ofNigella damascena

Summary 1. A lipase isolated from the seeds ofNigella damascena L. showed a pH optimum of 8, a temperature optimum of 37–40°C, a pH stability with an exposure of 30 min in the pH range from 3 to 12 and with exposures of 60 and 120 min in the pH range from 7 to 10. Complete inactivation of the lipase takes place at 80°C.2. The lipase hydrolyzes a number of plant oils and animal fats well, but has no action on fatty acid esters, ethyl oleate, ethyl acetate, and isopropyl myristate.Khar'kov Scientific-Research Institute of Pharmaceutical Chemistry. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 645–648, September–October, 1975.     

Beitrag zur Kenntnis der Systeme Titan—Chrom—Stickstoff,Zirkonium—Chrom—Stickstoff und Hafnium—Chrom—Stickstoff

Zusammenfassung Das ternäre System Ti–Cr–N wurde bei 1000° C und 1200° C mit Hilfe von metallographischen und röntgenographischen Methoden untersucht. Die Mononitride TiN und CrN bilden eine lückenlose Reihe von Mischkristallen; dieVegardsche Kurve weicht schwach negativ von der Geraden ab. Es konnte keine ternäre Verbindung gefunden werden. Für 1000° C wird ein Vorschlag für einen isothermen Schnitt durch das System Ti–Cr–N entworfen.Die Untersuchungen in den Systemen Zr–Cr–N und Hf–Cr–N beschränkten sich auf den Bereich der pseudobinären Schnitte ZrN/CrN und HfN/CrN. Um die Stabilität des weniger stabilen CrN sicherzustellen, wurden bei den Versuchstemperaturen folgende Stickstoffdruck-Bedingungen gewählt: 1 at N₂ bei 1000° C, 30 at N₂ bei 1200° C und 250 at N₂ bei 1400° C.Die isotypen Phasen ZrN und CrN zeigen eine Mischungslücke; aus dem Temperaturverlauf der Mischungslücke kann angenommen werden, daß sie sich bei 1440° C und 50 Mol% ZrN schließt.Im pseudobinären System HfN–CrN konnte im untersuchten Temperaturbereich lückenlose Mischbarkeit zwischen den Komponenten festgestellt werden. Eine Entmischung tritt, wenn überhaupt, nur bei Temperaturen unterhalb 1000° C auf. DieVegardkurve der Gitterparameter der Mischkristalle zeigt eine schwach positive Abweichung von der Geraden.

---

About the ternary systems titanium—chromium—nitrogen, zirconium—chromium—nitrogen and hafnium—chromium—nitrogen

The ternary system Ti–Cr–N has been investigated by X-ray powder technique and by metallographic methods in two isothermic sections at 1000° C and 1200° C. The isotypic mononitrides TiN and CrN form a complete series of solid solutions, theVegard's curve shows a slight negative deviation from linearity. No ternary compound could be observed. A tentative phase diagram for an isothermic section at 1000° C is given.Investigation of the systems Zr–Cr–N and Hf–Cr–N was restricted to the pseudobinary sections ZrN–CrN and HfN–CrN. To ensure the stability of the less stable component (CrN) the following pressure conditions were chosen: 1 atm N₂ at 1000° C, 30 atm N₂ at 1200° C, 250 atm N₂ at 1400° C. The isotypic compounds ZrN and CrN exhibit a miscibility gap, which diminishes with increasing temperature. The cirtical point can be estimated to be at 1440° C and 50 mol% ZrN. In the pseudobinary system HfN–CrN a complete series of solid solutions could be observed. A miscibility gap should occur, if ever, at temperatures below 1000° C.Vegard's curve for the lattice parameters of the solid solutions (Hf, Cr)N shows a slight positive deviation from linearity.

---

---

Mit 6 Abbildungen

---

Herrn Prof. Dr.H. Nowotny gewidmet.

---

Auszug aus der von der Fakultät für Naturwissenschaften der T. H. Wien approbierten Doktor-Dissertation des Herrn Dipl.-Ing.F. Petter.     

Ruthenium catalysts of liquid-phase hydrocracking ofn-alkanes

Catalysts of liquid-phase hydrocracking ofn-alkanes with higher activity than Ru-black were obtained by decomposition of Ru₃(CO)₁₂ and Ru₃(CO)₁₂ +i-Bu₂AlH in alkanes at 180–200°C and 5 MPa H₂ and (benzene)(1,3-cyclohexadiene)ruthenium at 20°C and 0.1 MPa H₂. The system based on Ru₃(CO)₁₂ +i-Bu₂AlH is x-ray amorphous, and the remainder have a 30–60 Å particle size.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1211–1213, May, 1992.     

Potentiometric Determination of the First Hydrolysis Constant of Gallium(III) in NaCl Solution to 100°C

The hydrolysis equilibrum of gallium (III) solutions in aqueous 1 mol-kg^–1 NaCl over a range of low pH was measured potentiometrically with a hydrogen ion concentration cell at temperatures from 25 to 100°C at 25°C intervals. Potentials at temperatures above 100°C increased gradually because of further hydrolysis of the gallium(III) ion, followed by precipitation. The results were treated with a nonlinear least-squares computer program to determine the equilibrium constants for gallium(III)–hydroxo complexes using the Debye–Hückel equation. The log K (mol-kg^–1) values of the first hydrolysis constant for the reaction, Ga³⁺ + H₂O GaOH²⁺ + H⁺ were –2.85 ± 0.03 at 25°C, –2.36 ± 0.03 at 50°C, –1.98 ± 0.01 at 75°C, and –1.45 ± 0.02 at 100°C. The computed standard enthalpy and entropy changes for the hydrolysis reaction are presented over the range of experimental temperatures.     

Activation of low-percentage Re-Al2O3 and Tc-Al2O3 catalysts for the dehydrogenation of paraffins

The activity and selectivity of low-percentage (0.1–1 mass. %) Re-Al₂O₃ and Tc-Al₂O₃ catalysts in the dehydrogenation ofn-dodecane is shown to increase in response to an increase in the temperature of their activation in hydrogen from 500°C to 900°C. The activities of such catalysts are comparable to those of analogous alumina-platinum systems, while the selectivity of the former catalysts inn-monoolefin production is higher than that of the latter.Deceased January 7, 1991.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 484–487, March, 1993.     

Tracer diffusion of131I− ions in a few 1–2 electrolytes in agar gel

Tracer diffusion of¹³¹I^– ions is studied at different temperatures /20°C–50°C/ in 2.5% agar gel containing sodium and potassium sulphate solutions over a wide range of concentrations. The results are in qualitative agreement with the theoretical values in the concentration range 10^–6–10^–1M. Agar gel shows an obstruction effect to diffusional flow. The activation energy for tracer diffusion was found to be of the order of 16.3 kJ mol^–1.     

Dzheiranbatanolide — A new guaianolide fromArtemisia fragrans

A new guaianolide which has been called dzheiranbatanolide (I), C₁₅H₂₀O₄, mp 186–188°C has been isolated from the epigeal part ofArtemisia fragrans Willd. The oxidation of (I) led to a keto derivative (II) with the composition C₁₅H₁₈O₄, mp 247–248°C. The structure of (I) has been established by the chemical and spectral (IR, UV, and¹³C NMR) analysis of (I) and (II).V. L. Komarov Institute of Botany, Academy of Sciences of the Azerbaijan SSR, Baku. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 595–598, September–October, 1984.     

The preparation and characterisation of chromium(III) complexes of C-meso-5, 12-dimethyl-1, 4, 8, 11-tetraazacyclotetradecane (LM). Aquation and base hydrolysis kinetics ofcis- andtrans-[CrLMCl2]+

Summary The reaction of [CrCl₃(DMF)₃] with C-meso-5, 12-dimethyl-1, 4, 8, 11-tetra-azacyclotetradecane(L_M) in DMF gives a mixture ofcis-[CrL_MCl₂]Cl (ca. 90%) andtrans-[CrL_MCl₂]Cl (ca. 10%). These complexes are readily separated, as thecis-isomer is insoluble in warm methanol while thetrans-isomer is soluble. Using the dichlorocomplexes as precursors it has been possible to prepare a range ofcis-[CrL_MX₂]⁺ complexes (X=Br^–, NO ₃ ^– , N ₃ ^– , NCS^– and X₂=bidentate oxalate) and alsotrans-[CrL_MX₂]⁺ complexes (X=Br^–, H₂O or NCS^–). The spectroscopic properties and detailed stereochemistry of the complexes are discussed.The aquation and base hydrolysis kinetics ofcis- andtrans-[CrL_MCl₂]⁺ have been studied at 25° C. Base hydrolysis of thecis-complex is extremely rapid with K_OH =1.46×10⁵ dm³ mol^–1 at 25° C. This unusual reactivity appears to be associated with thetrans II stereochemistry of thesec-NH centres of the macrocycle. Base hydrolysis of thetrans complex with thetrans III chiral nitrogen stereochemistry is quite normal with k_OH =1.1 dm³ mol^–1 s^–1 at 25° C.     

Dissociation constants of the ampholyte glycine in 50 mass % methanol-water from 5 to 55°C,with related thermodynamic quantities

The two thermodynamic dissociation constants of glycine at 11 temperatures from 5 to 55°C in 50 mass % methanol-water mixed solvent have been determined from precise emf measurements with hydrogen-silver bromide electrodes in cells without liquid junction. The first acidic dissociation constant (K ₁)for the process HG⁺H⁺+G^± is expressed as a function ofT(^oK) by the equation pK ₁ = 2043.5/T – 9.6504 + 0.019308T. At 25°C, pK ₁is 2.961 in the mixed solvent, as compared with 2.350 in water, with H°=1497 cal-mole^–1, G°=4038 cal-mole^–1, S°=–8.52 cal-°K^–1-mole^–1, and C _p ^o =–53 cal-°K^–1-mole^–1. The second acidic dissociation constant (K ₂)for the process G^±H⁺+G^– over the temperature range studied is given by the equation pK ₂ = 3627.1/T – 7.2371 + 0.015587T. At 25°C, pK ₂is 9.578 in MeOH–H₂O as compared with 9.780 in water, whereas H° is 10,257 cal-mole^–1, G° is 13,063 cal-mole^–1, S° is –9.41 cal-°K^–1-mole^–1, and C _p ^o is –43 cal-°K^–1-mole^–1. The protonated glycine becomes weaker in 50 mass % methanol-water, whereas the second dissociation process becomes stronger despite the lower dielectric constant of the mixed solvent (=56.3 at 25°C).     

Die Entwässerung von Zeolithgermanaten

Zusammenfassung Germanate des TypsM ₃HGe₇O₁₆·4H₂O (M=Alkali) bzw.M ₂Ge₇O₁₆·xH₂O (M=Ba, Pb) mit Zeolithcharakter wurden mittelsDTA, Thermogravimetrie und mit derGuinier-Lenné-Kamera im Temperaturbereich von 20 bis etwa 1000°C bei Atmosphärendruck untersucht.Die Elementarzelle der Germanate schrumpft beim Aufheizen infolge Wasserabgabe; erst nach weiterer Temperaturerhöhung macht sich eine Ausdehnung bemerkbar. Während der NH₄–Ge-Zeolith bereits bei 160°C instabil wird, bleibt das Gerüst des Rb–Ge-Zeoliths bis etwa 600°C bestehen. Die Li-und Na–Ge-Zeolithe verhalten sich wie der K–Ge-Zeolith. Si/Ge-Austausch im NH₄–Ge-Zeolith unterdrückt die Bildung der GeO₂-Cristobalit- und-Rutilform.Die bei höheren Temperaturen entstehenden wasserfreien Germanate lassen sich zum größten Teil identifizieren.

---

Dehydratation of zeolitic germanates

Germanates of typeM ₃HGe₇O₁₆·4H₂O (M=alkali metal ion) andM ₂Ge₇O₁₆·xH₂O (M=Ba, Pb) with zeolitic properties have been investigated by means ofDTA, thermogravimetry and theGuinier-Lenné-X-ray camera within the temperature range of 20 to approxim. 1000°C at atmospheric pressure.The germanates exhibit a comparatively narrow temperature region at which dehydratation occurs. Increase of temperature leads first to contraction due to the loss of water and later on to dilatation of the lattice parameters. Temperatures at which disintegration of the zeolite framework begins diverge considerably. Thus breakdown of the NH₄–Ge-zeolite lattice starts at 160°C whereas Rb–Ge-zeolite is stable up to 600°C. The observations made with Li- and Na–Ge-zeolites reveal similar properties as those of K–Ge-zeolite. Partial substitution of Ge by Si in NH₄–Ge-zeolite suppresses formation of the GeO₂-cristobalite- and rutile-modification.Identification of the dehydratated germanates originating at higher temperatures from the zeolites is possible in most cases.

---

---

Mit 6 Abbildungen