The first synthesis and X-ray structures of polyfluorinated 1,2-, 2,3- and 2,4a-dihydro-1,3-diazafluorenes

Acetic acid-catalyzed condensation of 2-amino-3-(1-imino-2,2,2-trifluoroethyl)-1,1,4,5,6,7-hexafluoroindene (1b) with acetone and cyclopentanone gives 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene (2a) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3a) together with small amounts of 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene (2b) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3b), respectively. When acted upon by (CH₃)₂SO₄ compounds 2, 3 were converted into corresponding fluorine-containing 1-methyl-1,2-dihydro-1,3-diazafluorenes 6, 7. 4a-Chloro-5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,4a-dihydro-1,3-diazafluorene (8) has been synthesized by the interaction of compound 2 with SOCl₂. Solution of compound 2 as well as 8 in CF₃SO₃H-CD₂Cl₂ generated 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2,3,4-tetrahydro-1,3-diazafluorene-4-yl cation (2c). The structures of compounds 2, 3, 6-8 have been determined by single crystal X-ray diffraction.     

Amination of 5-hydroxy-1,4-naphthoquinone in the presence of copper acetate

The reaction of 5-hydroxy-1,4-naphthoquinone with butylamine in the presence of copper(II) acetate monohydrate on heating resulted in the formation of a mixture of regioisomeric 2,6- and 2,8-bis(butylamino)-5-hydroxy-1,4-naphthoquinones.     

Crystal structure of 4,6-dimethyl-2-nitro-and 2-nitro-5-phenylpyrimidines

The crystal structures of two substituted 2-nitropyrimidines are solved by X-ray diffraction analysis. The influence of the nitro group and the endocyclic nitrogen atoms on the geometric parameters of the 2-nitropyrimidine and related -nitroazines are discussed.Novosibirsk Institute of Organic Chemistry of the Siberian Division of the Russian Academy of Sciences, Novosibirsk 630090, Russia; e-mail: benzol@nioch.nsc.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 348–354, March, 1999.     

Oxidative transformations of labdane diols. III. Preparation of acids with a strobane skeleton from larixol

It has been shown that the oxidation of larixol with chromic acid mixture forms methyl 6-oxo-8α,13α-epoxystroban-14β-oate, methyl 6-oxo-8α,13α-epoxystroban-14α-oate, and 6,13-dioxo-14,15-bisnorlabd-7-en-17-oate.     

Triterpenoids from species ofAbies hill. II. Abiesolidic acid — A new 3,4-secolanostanoid from the oleoresin ofAbies sibirica

The oleoresin of the Siberian fir has yielded a new 3,4-secolanostanoid for which the structure of (20R,23S,25R)-3,4-seco-9β-lanosta-4(28),7-dien-26,23-olid-3-oic acid has been established by x-ray structural analysis. The pathways of the mass-spectrometric fragmentation of this acid and its esters have been investigated.     

Synthetic transformations of sesquiterpene lactones. Controllable synthesis of 11,13-dihydroisoalantolactone azides and 13-(1,2,3-triazolyl)eudesmanolides based on sesquiterpene lactones

Chemistry of Heterocyclic Compounds - Modification of eudesmane-type lactones isoalantolactone and 4,15-epoxyisoalantolactone was carried out at the active methylene group. The reaction of...     

Induced Alkene Reactions with Sulfur Dichloride. System Sulfur Dichloride-Dimethyl Sulfide as a Reagent for Polysulfonation and Conjugate Chlorination of Alkenes

In reaction of unsaturated compounds with sulfur dichloride in the presence of dimethyl sulfide radically new induced directions are realized: the reagent is involved as dimer or trimer (formation of di- and trisulfides). Alongside this process a conjugate chlorination occurred with participation of external nucleophiles, dimethyl sulfide and acetonitrile, furnishing sulfonium chlorides and N-substituted acetamides respectively. The relative importance of these alternative reactions depends on solvent, alkene structure, and order of reagents addition.     

Oxidative transformations of labdane diols. III. Preparation of acids with a strobane skeleton from larixol

It has been shown that the oxidation of larixol with chromic acid mixture forms methyl 6-oxo-8,13-epoxystroban-14-oate, methyl 6-oxo-8,13-epoxystroban-14-oate, and 6,13-dioxo-14,15-bisnorlabd-7-en-17-oate.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 697–703, November–December, 1986.