Synthesis and Stereochemistry of 1<Emphasis Type="Italic">H</Emphasis>,5<Emphasis Type="Italic">H</Emphasis>-Naphtho[1,8-<Emphasis Type="Italic">ef</Emphasis>][1,3]dithiocine 2-Oxides

3-Substituted 1H,5H-naphtho[1,8-ef][1,3]dithiocines (R = H, Me, Ph, t-Bu) were oxidized with m-chloroperoxybenzoic acid to the corresponding 2-oxides having trans configuration (R ≠ H). According to the ¹H and ¹³C NMR data (including NOESY experiments), the disubstituted compounds at room temperature exist in a boat conformation with equatorial orientation of the substituent on C³ and oxygen atom on S². The compound with no substituent on C³ gives rise to a mixture of boat conformers with axial and equatorial sulfoxide oxygen atoms at a ratio of 83:17.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1109–1112.Original Russian Text Copyright © 2005 by Kikilo, Khairutdinov, Shtyrlin, Klochkov, Klimovitskii.     

Synthesis of new 1<Emphasis Type="Italic">H</Emphasis>-pyridazine derivatives <Emphasis Type="Italic">peri</Emphasis>-annelated with acenaphthene and acenaphthylene

The reaction of 6-acetyl-5-hydroxyacenaphthene with methylhydrazine afforded 1,3-dimethyl-1H-6,7-dihydroacenaphtho[5,6-de]pyridazine. Its dehydrogenation with chloranil gave 1,3-dimethyl-1H-acenaphtho[5,6-de]pyridazine, which is a heteroaromatic compound with an essentially new topology of the ρsystem. The reaction of 3-methyl-1H-6,7-dihydroacenaphtho[5,6-de]pyridazine with 3,5-di-tert-butyl-1,2-benzoquinone yielded a dimer containing the acenaphthene and acenaphthylene moieties of peri-annelated 1H-1,2-diazines connected in positions 1′ and 9.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 777–780, March, 2005.     

<Emphasis Type="Italic">peri</Emphasis>-Naphthylenediamines: XXXIX. Synthesis and Structure of <Emphasis Type="Italic">N,N′,N′</Emphasis>-Trimethyl-<Emphasis Type="Italic">N</Emphasis>-nitrosonaphthalene-1,8-diamine Derivatives

The corresponding N-nitroso derivatives were synthesized by the action of nitrous acid on N,N,N′-trimethylnaphthalene-1,8-diamine, N,N,N′-trimethyl-5-nitronaphthalene-1,8-diamine, and N,N,N′-trimethylacenaphthene-5,6-diamine, and molecular structure of the products was studied.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1020–1027.Original Russian Text Copyright © 2005 by Koroleva, Dyablo, Pozharskii, Sennikova, Starikova.     

Structure and photochromism of 2-(<Emphasis Type="Italic">N</Emphasis>-acyl-<Emphasis Type="Italic">N</Emphasis>-arylaminomethylene)benzo[<Emphasis Type="Italic">b</Emphasis>]thiophen-3(2<Emphasis Type="Italic">H</Emphasis>)-ones

It was shown by electron absorption spectroscopy and X-ray diffraction analysis that steric strains in photochromic 2-(N-acyl-N-arylaminomethylene) benzo[b]thiophen-3(2H)-one molecules ortho-substituted in the N-phenyl ring increase the quantum yield of the N→O photoinduced rearrangement in accord with an increase in the steric constant of the ortho-substituent.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2151–2155, October, 2004.     

Ionic Liquid Promoted One-Pot Synthesis of Furo[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidine-2,4(1<Emphasis Type="Italic">H</Emphasis>,3<Emphasis Type="Italic">H</Emphasis>)-diones

Summary. The three-component condensation of aldehyde, N,N′-dimethylbarbituric acid and alkyl or aryl isocyanide afforded the corresponding furo[2,3-d]pyrimidine-2,4(1H,3H)-diones in 1-butyl-3-methylimidazolium bromide as an ionic liquid in high yields at room temperature within several minutes.     

A new procedure for fusion of a five-membered ring. Building up of the naphtho[1,8-<Emphasis Type="Italic">bc</Emphasis>]furan system

Reactions of 2,6-di-tert-butylnaphthalene-1,5-diol with aminals derived from aromatic aldehydes afforded 2-aryl-4,8-di-tert-butyl-2H-naphtho[1,8-bc]furan-5-ols and 2-aryl-4,8-di-tert-butylnaphtho[1,8-bc]-furan-5-ones.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004, pp. 1349–1351.Original Russian Text Copyright © 2004 by Tyurin, Minyaeva, Mezheritskii.     

Acylation of 6,7,8,9-tetrahydro-5<Emphasis Type="Italic">H</Emphasis>-[1,2,4]triazolo-[4,3-<Emphasis Type="Italic">a</Emphasis>]azepin-3-ylacetonitrile

6,7,8,9-Tetrahydro-5H-[1,2,4]triazolo[4,3-a]azepin-3-ylacetonitrile reacts with carboxylic acid anhydrides and chlorides to afford acylation products at the nitrogen atom in the heteroring or methylene carbon atom, depending on the conditions and nature of the acylating agent. Heating of the N-acyl derivatives leads to migration of the acyl group with formation of C-acyl derivatives.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004, pp. 1858–1860.Original Russian Text Copyright © 2004 by Makei, Volovenko, Nazarenko, Tolmachev.     

Synthesis and some transformations of <Emphasis Type="Italic">N</Emphasis>,2,2-trimethyltetrahydro-2<Emphasis Type="Italic">H</Emphasis>-pyran-4-amine

Reaction of 2,2-dimethyltetrahydro-2H-pyran-4-one with aqueous methanamine, followed by reduction of the Schiff base thus obtained with sodium tetrahydridoborate gave N,2,2-trimethyltetrahydro-2H-pyran-4-amine which was subjected to cyanoethylation with acrylonitrile. The resulting 3-(2,2-dimethyltetrahydro-2H-pyran-4-ylmethylamino)propanenitrile was reduced with lithium tetrahydridoaluminate to N-(2,2-dimethyltetrahydro-2H-pyran-4-yl)-N-methylpropane-1,3-diamine, and some chemical transformations of the latter were studied.     

Synthesis of substituted octahydrochromeno[3,2-<Emphasis Type="Italic">i</Emphasis>]quinazoline-2(1<Emphasis Type="Italic">H</Emphasis>)-thiones

Condensation of 8-arylidenehexahydroquinazoline-2-thiones with di- and trihydroxybenzenes affords the new heterocyclic system, viz., octahydrochromeno[3,2-i]quinazoline-2(1H)-thiones, in which the substituents in both the chromane and quinazoline rings can be varied over a wide range. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1456–1460, June, 2005.     

Efficient <Emphasis Type="Italic">Baylis-Hillman</Emphasis> Reaction <Emphasis Type="Italic">via</Emphasis> a 1,4-Diazabicyclo[2.2.2]octane-based Ionic Catalyst

Summary. A novel ionic catalyst, 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride based on 1,4-diazabicyclo[2.2.2]octane was synthesized and applied in the Baylis-Hillman reaction, which occurred readily at room temperature to afford the corresponding adducts in good yield. The ionic catalyst could be recycled for seven runs without diminution in its catalytic activity.     

A one-pot synthesis of 8-amino-1-methoxy-6<Emphasis Type="Italic">H</Emphasis>-dibenzo[<Emphasis Type="Italic">b,d</Emphasis>]pyran-6-one

8-Amino-1-methoxy-6H-dibenzo[b,d]pyran-6-one was synthesized in a one-pot reaction of 2′,6′-dimethoxy-4-nitro-1,1′-biphenyl-2-carboxylic acid methyl ester using hydroiodic acid as a reagent to effect O-demethylation, lactonization, and nitro reduction to amine. This new reaction represents an improved alternative to the previously reported three-step reactions for this transformation.