Reactions of 14-hydroxy-14-azadispiro[5.1.5.2]pentadec-9-ene-7,15-dione and related compounds. II

3 When 11-diethyl- and 3, 11-di-n-propyl-14-hydroxy-14-azadispiro[5.1. 5.2]pentadec-9-ene-7, 15-dione (E-IV and n-Pr-IV) are heated with polyphosphoric acid at 55–65°, the 14-hydroxyl group cyclizes at the 11-carbon to form E-VI and n-Pr-VI, the structures of which have been established. Compounds P-IV, i-Pr-IV and t-B-IV do not cyclize under these conditions. The Beckmann rearrangement of 12-hydroxy-12-azadispiro[4.1.4.2]tridec-8-ene-6, 13-dione-6-oxime (P-I) with polyphosphoric acid at 40–50° formed only the normal product, P-II, which could not be cyclized. Compound P-IV was the only ketone of this series which would add hydrogen cyanide to form a cyanohydrin.     

Syntheses of 11-hydroxy and 11-hydroxy-11-methyl-14-methoxy-14-azadispiro[5.1.5.2]pentadec-9-ene-7,15-diones

A facile synthesis, which permits regioselective incorporation of hydroxy and/or methyl substituents at position 11 of 14-methoxy-14-azadispiro[5.1.5.2]pentadec-9-ene-7,15-dione, has been described.     

Reaktionen in organischen kristalen. II dispiro [5.1.5.2] pentadecane durch asymmetrische festkörper-photodimerisierung des cyclohexyliden-phenyl-5(4h)oxazolons

The asymmetric solid-state photodimerization of the oxazolone $\text{1}$ leads to the trispirodimer $\text{2}$; its structure is elucidated by chemical reactions combined with PSR symmetry considerations.     

Spirocyclohexadienones: X. Three-component condesation of 1,2,3- and 1,2,4-trimethoxybenzenes with cyclohexanecarbaldehyde and nitriles. Synthesis of 1,2- and 1,4-dimethoxy-14-azadispiro[5.1.5.2]pentadeca-1,4-dien-3-ones

Substituted 1,2- and 1,4-dimethoxy-14-azadispiro[5.1.5.2]pentadeca-1,4-dien-3-ones and 1,2(1,4)-dimethoxy-14-azadispiro[5.1.5.2]pentadeca-1,4,14-trien-3-ones were synthesized by three-component condensation of cyclohexanecarbaldehyde with 1,2,3- or 1,2,4-trimethoxybenzene and the corresponding nitriles in the presence of concentrated sulfuric acid.     

Synthesis of 6, 7-dimethoxybenzo[b]quinuclidine

6,7-Dimethoxybenzo[b]quinuclidine was synthesized from ethyl veratrylidenecyanoacetate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1413–1415, October, 1971. Original     

Synthesis and Characterization of S-Methylspiro[4.5]-dec-7-en-6-one and 6-methylspiro[4.5]dec-6-en-8-one

In connection with another problem, we required authentic samples of 8-methylsiro[4.5]dec-7-en-6-one (1) and 6-methyl-spire[4.5]dec-6-en-8-one (2). The former compound is not reported in the literature. Although there are two reports of the latter material,^1,2 the physical data ascribed to it do not agree. In this communication, we report the synthesis and characterization of the two isomers.     

6-萘氧甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸衍生物的合成（英文）

介绍了通过6-氯甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯与1-和2-萘酚的Williamson醚合成反应及其随后的酯水解反应,"一锅法"高收率的合成了结构新颖的含有萘环结构的喹啉化合物,即2-(萘氧甲基)喹啉-3-羧酸.这种新合成的化合物可以为开发有用的药物活性先导化合物提供很好的底物.     

Synthesis and fungicidal activity of substituted 6-azolylmethyl-7-benzylidenespiro[4.5]decan-6-ols

A series of halogen substituted 6-azolylmethyl-7-benzylidenespiro[4.5]decan-6-ols were obtained from spiro[4.5]decan-6-one in three steps: Claisen—Schmidt condensation with substituted benzaldehydes, conversion of 7-benzylidenespiro[4.5]decan-6-ones to oxiranes by reaction with dimethylsulphonium methylide followed by ring opening of oxiranes with 1,2,4-triazole or imidazole. In vitro testing of fungicidal activity of synthesized compounds against seven phytopathogenic fungi showed, that a number of compounds are more active than triadimenol.     

Indolobenzo[b]furans. 3. Synthesis of unsubstituted indolo[7′,6′∶2,3]- and indolo[6′,7′∶2,3]benzo[b]pyrans

Indolo[7,62,3]- and indolo[6,72,3]benzo[b]furans have been synthesized with the aid of the Fischer reaction. The physicochemical characteristics of the compounds synthesized are considered.For communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 631–634, May, 1985.     

Synthesis of 5H-Tetrazolo[1,5-d] [1,4]benzodiazepin-6(7H)ones

Syntheses of 5H-tetrazolo [1,5-d] [1,4 ]benzodiazepin-6(7H)ones 2a-d from 5-(o-aminophenyl)-tetrazoles 1a-d and bromoacetyl bromide are described. Compounds 2a-d are representatives of a novel tricyclic ring system. Several alternate methods for the synthesis of 2a-d were attempted without success. Spectral evidence for structural assignments 2a-d is presented. Chemical evidence for these assignments includes the transformation of 2a to 6-(2,2-dimethylhydrazino)-5H-tetrazolo[1,5-d] [1,4]benzodiazepine ( 19 ) via the thione analog of 2a ( 18 ).     

Synthesis of diamantane by skeletal isomerization of pentacyclo[6.6.0.02,6.03,13.010,14]tetradecane induced by ionic liquids

Diamantane was synthesized by skeletal isomerization of a 2,6 3,13 10,14 new precursor pentacyclo[6.6.0.0^2,6.0^3,13.0^10,14]tetradecane being the hydrogenated norbornadiene dimer of an unusual structure wholly composed of five-membered rings. The isomerization was induced by ionic liquids based on aluminum, iron, nickel, manganese, zinc, tin, and copper salts, among which aluminate ionic liquids were the most efficient ensuring diamantane yields of up to 85%.     

Synthesis of 6-phenyl and 6-styrylthiazolo[3,2-b] [1,2,4]triazoles

Thiazole rings have been often encountered in the structure of antibiotic or antitumor drugs. An easy synthesis of them has revealed itself necessary in order to elucidate the mechanism of action of these naturally occurring substances. A method of preparation of conjugated b-ethylenic thiazole[3,2-b] [1,2,4]triazoles by heating a 3-thio substituted [1,2,4]triazole in the presence of polyphosphoric acid is reported here, giving the expected product in a 60% yield.     

Synthesis and isomerization of epoxides derived from 7-phenylsulfonyl-and 7-methylsulfonyl-6-methylidenebicyclo[3.1.1]heptanes

Oxidation of exo-7-phenylsulfonyl-and exo-7-methylsulfonyl-6-methylidenebicyclo[3.1.1]heptanes with m-chloroperoxybenzoic acid gave the corresponding epoxy derivatives, anti-7-phenylsulfonyl-and anti-7-methylsulfonyl-endo-2′-oxaspiro[bicyclo[3.1.1]heptane-6,2′-cyclopropanes]. Treatment of the phenylsulfonyl-substituted epoxide with potassium tert-butoxide in THF led to the 1,3-cyclization product, 7-phenylsulfonyltricyclo[4.1.0.0^2,7]hept-1-ylmethanol. anti-7-Methylsulfonyl-endo-2′-oxaspiro[bicyclo[3.1.1]heptane-6,2′-cyclopropane] under analogous conditions underwent 1,6-cyclization, being converted into 6-hydroxy-3λ⁶-thiatricyclo[4.4.0.0^2,7]decane 3,3-dioxide.