New Nitrogenous Bisabolene‐Type Sesquiterpenes from a Hainan Sponge Axinyssa aff. variabilis

Two new uncommon nitrogenous sesquiterpenes, 11‐ethoxy‐3‐formamidotheonellin ( 1 ) and 7‐ethoxy‐3‐formamidobisabolane‐8,10‐diene ( 2 ), together with two known related sesquiterpenes, 3‐formamidotheonellin (=theonellin formamide; 3 ) and theonellin isothiocyanate ( 4 ), were isolated from the Hainan sponge Axinyssa aff. variabilis. Their structures were determined on the basis of extensive spectroscopic analysis and by comparison of their NMR data with those of known compounds.     

Activity of γ-Al2O3 modified by NaOH in disproportionation of methanethiol

Na⁺/Al₂O₃ catalysts in disproportionation of methanethiol are highly selective towards dimethyl sulfide but less active compared to -Al₂O₃. Their activity falls with increasing Na⁺ in the sample. This decrease is due to the neutralization of Brönsted acid centers on the catalyst.

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Na⁺/Al₂O₃ , , -Al₂O₃. Na⁺ . .

     

ESR investigation of Ti3+ compounds supported on inorganic gels

CpTiCl₂-M-surface complexes (M=Al, Si, Mg, Cp=cyclopentadienyl) supported on Al₂O₃, SiO₂, MgO gels are reduced by Et₃Al, C₃H₅MgBr and BuLi to Ti³⁺ surface compounds which exhibit ESR signals. The g and g values and asymmetry of these signals depend on the kind of gel and reducing agent.

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CpTiCl₂-M ( M=Al, Si, Mg Cp=), Al₂O₃, SiO₂ MgO, Et₃Al, C₃H₅MgBr, BuLi (Et=–C₂H₅ Bu=–C₄H₉) Ti⁺³, . g g .

     

Alkaloids ofStephania hernandifolia. III

Summary 1. A new alkaloid hernandoline with the composition C₂₀H₂₅O₅N has been isolated from the herbStephania herandifolia Walp.2. The Hofmann degradation of the methiodide of the O-methyl ether of hernandoline has given a des base acetolysis of which led to the formation of a dimethoxydiacetoxyphenanthrene.3. It has been suggested that hernandoline is similar to alkaloids related to sinomenine and hasubanonine.Khimiya Prirodnykh Soedinenii, Vol. 3, No. 2, pp. 106–108, 1967     

The estimation of the iodine number in edible and industrial oils by radioiodine

Summary The iodine number of twenty-two samples of different fats and oils is determined by ¹³¹I, according to the radiometric method. The values obtained for such samples lie between 7.2 and 154.9. The method is applicable with reproducible results and is recommended to cover any stage of unsaturation.

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Zusammenfassung Die Jodzahl von 22 Proben verschiedener Öle und Fette wird radiometrisch unter Benutzung von Jod-131 bestimmt. Die erhaltenen Werte liegen zwischen 7,2 und 154,9. Das Verfahren liefert reproduzierbare Ergebnisse und ist für jeden Grad von Ungesättigtheit anwendbar.

     

Palladium-catalyzed ring expansion reaction of 1-alkynylcyclobutanols with aryl iodides: an efficient route to 2-disubstituted methylenecyclopentanones

The reaction of 1-alkynylcyclobutanols with aryl iodides in the presence of Pd(OAc)₂ and Et₃N in acetonitrile at 80°C for 24 h gives 2-disubstituted methylenecyclopentan-1-ones in modest to good yields. The tandem insertion-ring expansion process proceeds via the formation of an alkynyl π-complex, followed by migration of a carbon-carbon bond of the tert-alkanol to form the cyclopentanones stereoselectively.     

Synthesis and stereochemical assignment of 7-arylidene and 7-heteroarylidene morphinan-6-ones

A number of (E)-7-arylidenenaltrexones were synthesized by azeotropic distillation of water from a benzene solution of naltrexone and an aromatic aldehyde (benzaldehyde, 4-chloro- and 4-fluorobenzaldehyde, 3-and 4-pyridinecarboxaldehyde and 1-methyl-2-imidazolecarboxaldehyde) using piperidine as a catalyst. In addition, (E)-7-benzylidenenaloxone was prepared by the previously published Claisen-Schmidt condensation using sodium hydroxide in methanol. The stereochemistry of these arylidene derivatives 3–9 was determined to be (E) by means of nuclear Overhauser enhancement experiments. The ¹³C nmr spectra of (E)- 3–9 are recorded in deuteriochloroform and those of the hydrochlorides in deuteriodimethyl sulfoxide.     

Decomposition of hydrotrioxides catalyzed by carboxylic acids

Carboxylic acids (HCOOH, CH₃COOH, CH₂ClCOOH, CCl₃COOH, CF₃COOH and C₄H₉COOH) are shown to increase the firstorder effective rate constant of chemiluminescence quenching (k_q) in the decomposition of hydroxides Me₂C(OH)OOOH and Me₂CHOC(OOOH)Me₂. With decreasing pK_a of an acid, its catalytic effect on k_q grows.

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, HCOOH, CH₃COOH, CH₂ClCOOH, CCl₃COOH, CF₃COOH, C₄H₉COOH () Me₂C(OH)OOOH Me₂CHOC(OOOH)Me₂. .