Variants of the complete synthesis of d,l-19-nortestosterone, d,l-19-norandrost-4-ene-3, 17-dione, and their stereoisomers

Summary The complete synthesis of d,l-19-nortestosterone (I) and its 8-iso- and 9, 10-iso- stereoisomers, and also the synthesis of d,l-19-norandrosten-4-ene-3, 17-dione (VI) and its 9, 10-iso-stereoisomer (IX), has been carried out.The stereodirectivity of the simultaneous reduction of the ⁸⁽⁹⁾ double bond and the aromatic ring conjugated with it by means of alkali metals and alcohol in liquid ammonia, both under Birch's conditions and Wilds and Nelson's conditions, depends on the nature of the substituent at C₁₇; in the case of the 17-ketone (III) and the carbinol (VIII), considerable amounts of the 9- isomers are formed.Compounds (I), (Ia), (Ib), (V), and (VI) possess anabolic activity, but to a smaller extent than the analogous compounds in the d,l-D-homo series.Khimiya Prirodnykh Soedinenii, Vol. 1, No. 3, pp. 180–188, 1965     

Synthetic studies on mitomycins. 1. A regiospecific Michael addition of 2-methylcyclopentane-1,3-dione to p-toluquinonesulfonimides.

A Michael addition of 2-methylcyclopentane-1,3-dione to various p-toluquinone imides exclusively afforded the sole products in a regiospecific manner. Acid treatment of these adducts gave indole or benzofuran derivatives, which could be the key intermediates for synthesis of mitosane skeleton.     

Free-radical addition of phenyl- and diphenylphosphines to 2-vinyl-1,3-dioxa-6-aza-2-silacyclooctanes

Conclusions Phenyl- and diphenylphosphines add to 2,6-dimethyl-2-vinyl-1,3-dioxa-6-aza-2-silacyclooctane upon the action of UV irradiation to form 2,6-dimethyl-2-[(2-phenylphosphino)ethyl)]-1,3-dioxa-6-aza-2-silacyclooctane and 2,6-dimethyl-2-[(2-diphenylphosphino)ethyl]-1,3-dioxa-6-aza-2-silacyclooctane, respectively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2615–2616, November, 1985.     

Diastereoselective synthesis of spiro-functionalized tetraalkyl benzoisoquinopyrrolonaphthyridine-tetracarboxylates from isoquinoline, dialkyl acetylenedicarboxylates, and indane-1,3-dione

An effective route to spiro-functionalized fused polycyclic derivatives of isoquinoline is described via tandem reaction of isoquinoline, dialkyl acetylenedicarboxylates, and indane-1,3-dione.     

Synthesis of Pyrimidine Annelated Heterocycles [1]. Regioselective Heterocyclization of 6-Cyclopent-2-enyl-5-hydroxy-1,3-dimethyl-pyrimidine-2,4( 1H, 3H)-dione and 5-Cyclopent-2-enyl-6-hydroxy-1,3-dimethylpyrimidine-2,4( 1H, 3H)-dione

Summary. Two hitherto unreported pyrimidine annelated heterocycles were synthesized from 6-cyclopent-2-enyl-5-hydroxy-1,3-dimethylpyrimidine-2,4(1H,3H)-dione and 5-cyclopent-2-enyl-6-hydroxy-1,3-dimethylpyrimidine-2,4(1H,3H)-dione by reaction with pyridine hydrotribromide or hexamethylenetetramine hydrotribromide. The first one was also obtained by reaction with concentrated sulfuric acid.Received October 28, 2002; accepted October 30, 2002 Published online June 2, 2003     

Synthesis of Pyrimidine Annelated Heterocycles [1]. Regioselective Heterocyclization of 6-Cyclopent-2-enyl-5-hydroxy-1,3-dimethyl-pyrimidine-2,4( 1H, 3H)-dione and 5-Cyclopent-2-enyl-6-hydroxy-1,3-dimethylpyrimidine-2,4( 1H, 3H)-dione

Two hitherto unreported pyrimidine annelated heterocycles were synthesized from 6-cyclopent-2-enyl-5-hydroxy-1,3-dimethylpyrimidine-2,4(1H,3H)-dione and 5-cyclopent-2-enyl-6-hydroxy-1,3-dimethylpyrimidine-2,4(1H,3H)-dione by reaction with pyridine hydrotribromide or hexamethylenetetramine hydrotribromide. The first one was also obtained by reaction with concentrated sulfuric acid.     

Cationic copolymerization of 2-vinyl-1,3-dioxane with styrene and 1,3-dioxolane

Copolymerization of 2-vinyl-1,3-dioxane with styrene and 1,3-dioxolane was carried out in methylene chloride at 0°C with triethyloxonium tetrafluoroborate as an initiator. Random copolymers were obtained from both of these monomer pairs, but attempted copolymerization of 2-vinyl-1,3-dioxane with 3,3-bis(chloromethyl)oxetane under similar conditions resulted in the homopolymer of the latter monomer. There were three structural units of 2-vinyl-1,3-dioxane in these copolymers as in its homopolymer: the “ester” unit, which was formed by vinyl addition with hydride shift followed by ring-opening rearrangement, the “vinyl” unit produced by ring-opening reaction, and the unit with a pendant 1,3-dioxane ring formed by simple vinyl addition. The fractions of the ester and vinyl units to the total 2-vinyl-1,3-dioxane units in the copolymer of 2-vinyl-1,3-dioxane with styrene decreased with decreasing 2-vinyl-1,3-dioxane content. On the contrary, the fraction of the vinyl unit in the copolymer of 2-vinyl-1,3-dioxane with 1,3-dioxolane increased slightly with decreasing 2-vinyl-1,3-dioxane content, while that of the ester unit decreased. The reactivities of the propagating species are discussed on the basis of these results.     

New organic nitrates. I. Synthesis of 1,3-benzoxazine-2,4-dione, 1,3-benzoxazine-2-thion-4-one, 1,3-benzothiazine-2,4-dione and quinazoline-2,4-dione derivatives

The preparation and the physico-chemical characterization of new heterocyclic organic nitrates containing 1,3-benzoxazine-2,4-dione, 1,3-benzoxazine-2-thion-4-one, 1,3-benzothiazine-2,4-dione and quinazo-line-2,4-dione moieties, are reported.     

Derivatives of 5-nitro-1H-benzo[de]isoquinoline-1,3(2H)-dione: design, synthesis, and biological activity

Abstract  

A series of mono and bis-2-(2-(dimethylamino)-ethyl)-5-nitro-1H-benzo[de]isoquinoline-1,3(2H)-diones with different amino side chains, a novel family of antitumor agents, has been designed and synthesized. Their antitumor activity was evaluated against HeLa, A549, P388, HL-60, MCF-7, HCT-8, and A375 cancer cell lines in vitro. Preliminary results showed that most of the derivatives had antitumor activity comparable with that of mitonafide, with IC ₅₀ values of 10⁻⁶–10⁻⁵ M. More importantly, the derivatives had distinct antitumor selectivity against different cancer cell lines. This work provided a novel class of mitonafide-based lead compounds with improved antitumor selectivity against cancer cell lines for further optimization.     

Solid-state structures of 2-(4-hydroxyphenyl)-substituted phenalene-1,3-dione and indan-1,3-dione

The structure of 2-(4-hydroxyphenyl)-substituted indan-1,3-dione and phenalene-1,3-dione is investigated using a combination of solid-state NMR, single crystal X-ray analyses and quantum chemical calculations. It is shown that 2-(4-hydroxyphenyl)-1,3-indandione exists as a diketo tautomer while 2-(4-hydroxyphenyl)-1,3-phenalenedione exists in the enol form.