Some Diels–Alder adducts of 6-vinyl-1-oxa-4-thiaspiro[4.5]dec-6-ene

6-Vinyl-1-oxa-4-thia­spiro­[4.5]­dec-6-ene has been reacted with dienophiles, such as N-phenyl­male­imide (NPM), N-methyl­triazoline-2,5-dione (MTAD) and di­methyl­acetyl­ene di­carboxyl­ate (DMAD), to assess the 1,3-diastereofacial selection caused by the acetal function. In each case, a mixture of two diastereoisomers was produced. The crystal structures of the products of the addition of NPM and MTAD syn to the acetal oxy­gen, 2-phenyl-2,3,3a,4,5,5a,6,7,8,9,9a,9b-dodeca­hydro-1H-benz­[e]­iso­indole-6-spiro-2′-[1′,3′]­oxa­thiol­ane-1,3-dione, C₂₀H₂₁NO₃S, (IIa), and 2-methyl-5,7,8,9,10,10a-hexa­hydro-1H-1,2,4-triazolo­[1,2-a]­cinnoline-7-spiro-2′-[1′,3′]­oxa­thiol­ane-1,3-dione, C₁₃H₁₇N₃O₃S, (IIIa), respectively, and the product of the addition of DMAD syn to the acetal sulfur, di­methyl 1,2,3,4,4a,7-hexa­hydro­naphthalene-1-spiro-2′-[1′,3′]­oxa­thiol­ane-5,6-di­carboxyl­ate, C₁₆H₂₀O₅S, (IVb), have been determined. All three structures are composed of independent mol­ecules separated by normal van der Waals distances. The 1-oxa-4-thia heterocyclic ring has an envelope conformation in the three structures and the S—Csp³ bond distances differ significantly from each other, as observed in comparable structures; the remaining molecular dimensions are as expected.     

Synthesis and Antimycobacterial Activity of New 2-Hydroxy-N-(3-oxo-1-thia-4-azaspiro[4.4]non-4-yl)/(3-oxo-1-thia-4-azaspiro[4.5]dec-4-yl)-2,2-diphenylacetamide Derivatives

Summary. 2-Hydroxy-2,2-diphenylacetohydrazide (2), cyclic ketones, and mercaptoalkanoic acids were converted into 2-hydroxy-N-(3-oxo-1-thia-4-azaspiro[4.4]non/[4.5]dec-4-yl)-2,2-diphenylacetamide derivatives (3, 4) in a one pot procedure. Compounds 3 and 4 were tested for in vitro antimycobacterial activity against M. tuberculosis H37Rv. The compounds were found to provide 0–86% inhibition of mycobacterial growth in the primary screen conducted at 6.25 μg/cm³.     

Tandem Prins cyclization for the synthesis of 1,8-dioxa-3-azaspiro[4.5]dec-2-ene derivatives

A tandem Prins strategy has been developed for the synthesis of 1,8-dioxa 3-azaspiro[4.5]dec-2-ene derivatives using 5?mol% Cu(OTf)₂ in dichloromethane at 0?°C under mild reaction conditions in short reaction times. This method provides the products in good yields with a diverse substitution pattern.     

Synthesis and Antimycobacterial Activity of New 2-Hydroxy- N -(3-oxo-1-thia-4-azaspiro[4.4]non-4-yl)/(3-oxo-1-thia-4-azaspiro[4.5]dec-4-yl)-2,2-diphenylacetamide Derivatives

2-Hydroxy-2,2-diphenylacetohydrazide (2), cyclic ketones, and mercaptoalkanoic acids were converted into 2-hydroxy-N-(3-oxo-1-thia-4-azaspiro[4.4]non/[4.5]dec-4-yl)-2,2-diphenylacetamide derivatives (3, 4) in a one pot procedure. Compounds 3 and 4 were tested for in vitro antimycobacterial activity against M. tuberculosis H37Rv. The compounds were found to provide 0–86% inhibition of mycobacterial growth in the primary screen conducted at 6.25 μg/cm³.     

Conversion of trans,trans-1-methoxy-3,5-diaryl-2-oxabicyclo[4.4.0]dec-3-enes into hemidithioacetals and 4H-thiopyrans. Structure of trans,trans-1-mercapto-3-phenyl-5-(4-methoxyphenyl)-2-thiabicyclo[4.4.0] dec-3-ene

The conversion of trans,trans-1-methoxy-3,5-diaryl-2-oxabicyclo[4.4.0]dec-3-enes into trans,trans-1-mercapto-3,5-diaryl-thiabicyclo[4.4,0]dec-3-enes or 2,4-diaryl-5,6-tetramethylene-4H-thiopyrans, which takes place when hydrogen Sulfide is reacted with the acetals in acetic acid with the use of gaseous hydrogen chloride as a catalyst, has been described. A mechanism for the reaction has been proposed. The structure and confirmations of the molecules have been determined by x-ray diffraction analysis and ¹³C NMR.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 28–33, January, 1986.     

4-Oxo-3-oxa-6,7-diazabicyclo[3.3.0]oct-6-ene and its isomerization

A product of addition of diazomethane to the double bond of crotonolactone — ¹-pyrazolinolactone — was obtained, and its isomerization to ²-pyrazolino-lactone in dry chloroform in the presence of triethylamine was studied. The structures of the compounds were confirmed by elementary analysis and the IR, UV, and PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1610–1612, December, 1977.     

6-N-烷基-6-氮杂-2-氧代-3-氧杂-4-甲氧基-双环[3.1.0]己烷的合成、立体化学及抗癌活性研究

以3-溴-5-甲氧基-2(5H)-呋喃酮和伯胺为原料,在均相中用三乙胺作碱性催化剂,可以得到一对非对映异构体(1Z,4E,5Z)-6-N-烷基-6-氮杂-2-氧代-3-氧杂-4-甲氧基-双环[3.1.0]己烷(4)和(1Z,4Z,5Z)-6-N-烷基-6-氮杂-2-氧代-3-氧杂-4-甲氧基-双环[3.1.0]己烷(5).目标分子4和5经IR,1HNMR,13CNMR,EIMS进行了表征,并做了结肠癌细胞(HCT-8)、肝癌细胞(BEL-7402)、人胃癌细胞(BGC-823)、肺腺癌细胞(A549)和人卵巢癌细胞(A2780)的抗癌活性实验,其中5c和5d对HCT-8,BGC-823,A549和A2780等癌细胞有一定的抑制作用.此研究结果不仅丰富了该领域研究的理论基础,而且对某些新型药物的研制具有一定的指导意义.     

The synthesis of 4-benzylamino-6-methyl-1H-pyrrolo[3, 2-c]pyridine and 4-benzylamino-6-methyl-1H-pyrrolo[2, 3-b]pyridine

4-Benzylamino-6-methyl-1H-pyrrolo[3,2-c]pyridine ( 2 ) and 4-benzylamino-6-methyl-1H-pyrrolo[2,3-b]pyridine ( 3 ) were synthesized as deaza analogues of the anxiolytic agent 4-benzylamino-2-methyl-7H-pyrrolo[2,3-d]pyrimidine ( 1 ). The 1-deaza analogue (2) was prepared via a multi-step procedure from a pyrrole precursor, 1-benzyl-2-formylpyrrole ( 4 ) while the 3-deaza analogue 3 was synthesized from a pyridine precursor, 2-amino-3,6-dimethylpyridine ( 12 ).     

Synthesis and Crystal Structure of 2-Oxo-3-phenyl-1-oxaspiro[4.5]dec-3-en-4-yl 4-chlorobenzoate

The title compound 2-oxo-3-phenyl-1-oxaspiro[4.5]dec-3-en-4-yl 4-chloro-benzoate 6 (C22H19ClO4, Mr = 382.82) has been synthesized by the condensation reaction of 4-hydroxy-3-phenyl-1-oxaspiro[4.5]dec-3-en-2-one 5 with 4-chlorobenzoyl chloride, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a = 10.6749(11), b = 6.0573(7), c = 29.680(2) , β = 94.073(3)o, V = 1914.3(3) 3, Z = 4, Dc = 1.328 g/cm3, F(000) = 800, μ = 0.224 mm–1, S = 1.003, the final R = 0.0605 and wR = 0.1500 for 1828 observed reflections with I > 2σ(I) and 244 variable parameters. The crystal analysis shows that the molecular structure of the title compound has one planar furan ring, one chair conformation cyclohexane ring and two benzene rings. The furan and cyclohexane rings adopt whorl conformations.     

Synthesis of a novel series of 10-oxa-3-aza-tricyclo[5.2.1.0]dec-8-en-4-ones through an intramolecular Diels-Alder reaction

The synthesis of a novel series of 10-oxa-3-aza-tricyclo[5.2.1.0^1,5]dec-8-en-4-ones through the use of the intramolecular Diels-Alder reaction is presented. The use of this reaction allows for the synthesis of functionalized polycyclic systems in a stereocontrolled manner.     

Terpenes and terpene derivatives - XV. [1 ] Synthesis of 4,8-dimethyl-2-(2-methyl-1-propenyl)--1-oxaspiro(4.5]dec-7-ene (“bisabolene oxide”)

Starting from the ketones $\text{3}$ and $\text{4}$ the synthesis of six spiro ethers with an l-oxaspiro[4.5]decane skeleton is described. Five of them, $\text{9a}$,$\text{b}$, $\text{10a}$,$\text{19}$ and $\text{19}$ represent typical partial structures of the sesquiterpenoid spiro ether $\text{1}$. The unambiguous synthesis of $\text{1}$ shows a previous assignment of “'bisabolene oxide“' to structure $\text{1}$ to be wrong.     

1, 3-dipolar cycloaddition of diazomethane to azolopyridazines. The synthesis of 8-methyl-8H- and 9-methyl-9H-pyrazolo[3, 4-d]-s-triazolo[4, 3-b]pyridazine and 1-methyl-1H- and 2-methyl-2H-imidazo[1, 2-b]pyrazolo[3, 4-b]pyridazine derivatives

The transformations of 7-methyl-7H- and 8-methyl-8H-pyrazolo[4, 3-d]tetrazolo[1, 5-b]pyridazines 1, 2, 9 and 10 into 8-methyl-8H- and 9-methyl-9H-pyrazolo[3, 4-H]-s-triazolo[4, 3-b]pyridazines 7 and 8 , and 1-methyl-1H-and 2-methyl-2H-imidazo[1, 2-b]pyrazolo[3, 4-d]pyridazines 13 and 14 are described.