Chlorination of 2,3,6-trialkyl-5,8-dihydroxy-1,4-naphthoquinones with HCl-MnO<Subscript>2</Subscript> in acetic acid. effective transformation of 2,3,6-trialkyl-2,3,7-trichloro-1,2,3,4-tetrahydronaphthalene-1,4-diones into 7-chloro-2,3,6-trialkyl-5,8-dihydroxy-1,4-naphthoquinones

Chlorination of 2,3,6-trialkyl-5,8-dihydroxy-1,4-naphthoquinones with HCl-MnO₂ in acetic acid gave a mixture of 7-chloro-2,3,6-trialkyl-5,8-dihydroxy-1,4-naphthoquinones and 2,3,7-trichloro-2,3,6-trialkyl-1,2,3,4-tetrahydronaphthalene-1,4-diones, the latter being formed via addition of the second chlorine molecule to monochloro derivatives. The reduction of 2,3,7-trichloro-2,3,6-trialkyl-1,2,3,4-tetrahydronaphthalene-1,4-diones with sodium dithionite in alkaline medium resulted in the formation of 7-chloro-2,3,6-trialkyl-5,8-dihydroxy-1,4-naphthoquinones in high yield.     

Isomeric ammonio derivatives of nido-carborane 3- and 10-H3N-7,8-C2B9H11

Abstract

Structure of 3-ammonio derivative of nido-carborane 3-NH₃-7,8-C₂B₉H₁₁ was determined by single crystal X-ray diffraction. The isomeric 10-ammonio derivative 10-NH₃-7,8-C₂B₉H₁₁ was prepared by the treatment of the corresponding ethylnitrilium derivative 10-EtC≡N-7,8-C₂B₉H₁₁ with hydrazine hydrate in acetonitrile.     

Catalytic Activity of Diethylene Glycol Dimethyl Ethers in Conversion of 6,7-Dichloro-3-ethyl-2-ethoxynaphthazarine into Echinochrome Trimethyl Ether

The nucleophilic substitution of halogen by methoxy groups in 5,8-dihydroxy-2,3-dichloro-1,4-naphthoquinones effected by complex reagent KF-MeOH-Al2O3 is considerably accelerated in the presence of electron-donor solvents.     

Spinazarin and ethylspinazarin,pigments of the sea urchin <Emphasis Type="Italic">Scaphechinus mirabilis</Emphasis>

2,3,5,8-Tetrahydroxy-1,4-naphthoquinone (spinazarin) and 6-ethyl-2,3,5,8-tetrahydroxy-1,4-naphthoquinone (ethylspinazarin) were first isolated from the sea urchin Scaphechinus mirabilis. The structures of spinazarins were established based on analysis of spectroscopic data. A preparative synthetic route to ethylspinazarin was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 788–791, April, 2007.     

Chemistry of naphthazarin derivatives. Transetherification selectivity of naphthazarin methoxy derivatives

Transetherification of naphthazarin methoxy derivatives in basic conditions occurs only with primary monohydric alcohols. 1,3-Butanediol due to the assistance of the hydroxy group at the C¹ atom gives rise to a mixture of transetherification products at the primary and secondary hydroxy groups in a ratio 3: 1. The reaction with methyl α-D-glucopyranoside affords predominantly methyl 6-O-(5,8-dihydroxy-1,4-dioxonaphthalen-2-yl)-α-D-glucopyranoside, previously unknown water-soluble naphthoquinone-carbohydrate conjugate.     

The chemistry of naphthazarin derivatives

The 7,7′-dideoxy analog of islandoquinone, binaphthazarin of a new structural type, bearing a 2-oxo-2,3-dihydro-1,4-naphthoquinone moiety was synthesized. The carbonyl group at the C(2) atom of this binaphthazarin easily adds water to give the correspondinggem-diol. Comparison of the spectral characteristics of the prepared diol and islandoquinone made it possible to elucidate more precisely the structure of the latter.     

High-resolution mass spectra of the residual gas in a metallic vacuum system

The mass spectra of the residual gas in a metallic vacuum chamber of capacity 3 l are studied with an MI-9303 high-resolution magnetic resonance mass spectrometer in the mass range 1–140 u. The experiments are carried out under four evacuation conditions in the pressure range P = 10⁻⁸–10⁻¹⁰ Torr, and almost all the mass peaks forming multiplets are resolved. It is shown that the multiplets with mass numbers M≤80 have, as a rule, a multicomponent structure and hydrogen is the basic component responsible for the total pressure in the chamber irrespective of evacuation conditions. Next in order of intensity in the mass spectra are, CH ₄ ⁺ , H²O⁺, CO⁺, and CO ₂ ⁺ peaks. Other lines in the residual gas spectra are largely due to various C-, H-, N-, and O-based compounds. In addition, the background mass spectrum involves Cl-and F-based compounds and noble gas isotopes. The multiplets with M > 80 often degenerate into a single hydrocarbon line.     

Spiro[4H-chromene-4,5′-isoxazolines] and related compounds: Synthesis and reactivities

Reactions of chromones with methyl ketoximes in the presence of lithium diisopropylamide follow the nucleophilic 1,2-addition mechanism to give spiro[4H-chromene-4,5′-isoxazolines] in good yields. The isoxazoline ring in spiro[4H-chromene-4,5′-isoxazolines] undergoes opening under the action of conc. H₂SO₄, yielding α,β-unsaturated oximes. Their nitrosation and bromination lead to the corresponding spiroisoxazolines, while the Beckmann rearrangement, to α,β-unsaturated amides. The latter are also formed directly from spiro[4H-chromene-4,5′-isoxazolines] under the action of PCl₅. N-Substituted acetophenone hydrazones in the presence of lithium diisopropylamide react at the C(4) atom of 2-trifluoromethylchromone, while acetophenone anil under the same conditions, at the C(2) atom. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 516–522, March, 2006.