Studies on the Cyclisation of 4-[2′-Cyclohexenyl]-3-hydroxy[1]benzopyran-2-one

The bicyclic coumarin derivative-1, 3 propano-2-bromo-1,2-dihydro-3H-pyrano [2, 3-c] [1]benzo-pyran-5-one (8) was synthesised by a sequence of reaction viz. acetylation of 4-[2′-cyclohexenyl] -3-hydroxy [1] benzopyran-2-one (4), addition of bromine to cyclohexenyl double bond and treating the resulting acetyldi-bromo derivative (7) with 4% alcoholic KOH. Benzofuro [2, 3-c] [1] -benzopyran-6-one (10) was synthesised from 4 via oxymercuration with mercuric acetate in methanol followed by dehydrogenative damercuration with Pd-C in refluxing diphenyl ether.     

Catalyst-free glycerol-mediated green synthesis of 5′-thioxospiro[indoline-3,3′-[1,2,4]triazolidin]-2-ones/spiro[indoline-3,3′-[1,2,4]triazolidine]-2,5′-diones

The development of new catalyst-free green and efficient protocol to access 5′-thioxospiro[indoline-3,3′-[1,2,4]triazolidin]-2-ones/spiro[indoline-3,3′-[1,2,4]triazolidine]-2,5′-diones, potential privileged scaffolds for drug discovery, is disclosed. Key feature of this methodology is the dual use of glycerol—a recyclable, bioorganic compound, as a solvent cum promoter. Other highlights include use of inexpensive reagents, mild reaction conditions, operational simplicity, short reaction time, no need for chromatographic purification, and high yields.     

One Pot Synthesis of Some New Spiro[3H-Indol-3,5′(4′H)-[1,2,4] Oxadiazol]-2-Ones and Bis[Spiro[3H-Indol-3,5′(4′H)-[1,2,4] Oxadiazol]-2-Ones]

A facile preparation of the title compound by 1,3-dipolar cycloaddition reaction of benzonitrile oxides with isatin imines or isatin diimines, in excellent yield, are reported.     

Synthesis of 4′-alkyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-ones

N-Boc-protected 8-azaspiro[bicyclo[3.2.1]octane-3,2′-oxirane] reacted with primary aliphatic amines through opening of the epoxide ring with formation of the corresponding amino alcohols which were converted into N-chloroacetyl derivatives. The latter underwent cyclization to N-Boc-protected 4′-alkyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-ones by the action of sodium hydride in DMF, and subsequent treatment with hydrogen chloride in ethyl acetate afforded 8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-one hydrochlorides.     

Synthesis of 4′-[3-methyl-5-thioxo-1H-1,2,4-triazol-4(5H)-yl]-2′,5′-diphenyl-2′,4′-dihydro spiro[indolin-3,3′[1,2,4]triazol]-2-one derivatives

In this paper 1,3-dipolar cycloaddition reaction has been studied. An efficient synthesis of 4′-[3-methyl-5-thioxo-1H-1,2,4-triazol-4(5H)-yl]-2′,5′-diphenyl-2′,4′-dihydro spiro(indolin-3,3′[1,2,4]triazol)-2-one derivatives using triethylamine in MeCN at room temperature is reported. The structures of the obtained compounds were confirmed by means of elemental analysis, MS and spectral (IR, ¹H, and ¹³C NMR) methods.     

Stereoselective [4+2] cycloadditions of tetrazines to 3-oxo- and 3-arylimino-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furans]

Stereoselective inverse-demand [4+2] cycloadditions of 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine and dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate to 4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furans] and 4′-methylene-1′-(4-nitrophenyl)spiro[bicyclo[2.2.1]heptane-3,2′-pyrrolidine] were studied. Cycloadditions took place stereoselectively at the exocyclic CC double bonds to give novel 11:14-isopropylidene-14-methyl-2,3-diaza-8-oxadispiro[5.1.5.2]pentadecane and 11:14-isopropylidene-11-methyl-2,3,8-triazadispiro[5.1.5.2]pentadecane derivatives in 50–98% de. The structures of the novel dispiro compounds were determined by NMR techniques, NOESY spectroscopy and X-ray diffraction.     

Synthesis of spiro[furan-3,3′-indolin]-2′-ones by PET-catalyzed [3+2] reactions of spiro[indoline-3,2′-oxiran]-2-ones with electron-rich olefins

An efficient procedure for the synthesis of spiro[furan-3,3′-indolin]-2-ones and dispiro[cycloalkane-1,2′-furan-3′,3″-indolin]-2″-ones has been achieved in high yields and stereoselectivity by photoinduced electron transfer-catalyzed [3+2] reactions of substituted spiro[indoline-3,2′-oxiran]-2-ones with olefins. The reactions proceed by ring opening of spiro[indoline-3,2′-oxiran]-2-ones via C_β–O bond cleavage and subsequent cycloaddition with olefins by using 2,4,6-triphenylpyrylium tetarfluoroborate (TPT) as a sensitizer.     

2,5-二[2′-(4′-氯代苯氧乙酸)基]-1,3,4-噻二唑的合成

通过对称双酰肼与P_2S_5的缩合反应合成2,5-二-羟苯基-1,3,4-噻二唑,并由此制备了2,5-二[2′-(4′-氯代苯氧乙酸)基]-1,3,4-噻二唑及其相关化合物,同时测定了它们的生物活性。     

1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑的合成

以2,4-二氟联苯为起始原料,经酰化反应制得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲酮(2);2经NaBH4还原得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲醇(3);3经氯代得2′,4′-二氟-(1,1′-联苯)-4-基苯基氯甲烷(4);4与咪唑发生亲核取代反应合成了1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑(5). 2～5为新化合物,其结构经1H NMR, IR, MS和元素分析确证.     

2-[Pyridin-2(4)-yl]-N-[ω-vinyloxyalkyl]ethanamines

Russian Journal of Organic Chemistry -     

Synthesis,Structure and Antimicrobial Activity of 2-Phenyl-4H-spiro[benzo[e][1,4,2]oxaza- phosphinine-3,3′-indolin]-2′-one 2-oxide

A novel spiro-compound(C20 H15 N2 O3 P) has been synthesized and characterized by means of IR and 1H NMR. Its crystal structure was determined by X-ray diffractometry. The crystal belongs to the monoclinic system, space group P21 /c with a = 9.1628(7), b = 12.9490(7), c = 15.7898(11), β = 103.952(8)o, Mr = 36.08, V = 1818.2(2)3, Z = 4, Dc = 1.382 g/cm3, F(000) = 788, μ = 0.179 mm-1, R = 0.0701 and wR = 0.1513. The preliminary biological test showed that the title compound has activities against Escherichia coli, S.albus, Bacillus subtilis, Staphylocc- ocusaureus and Micrococcus tetragenus with MIC to be 0.038, 0.038, 0.075, 2.48, and 0.15 mg/mL, respectively.     

Synthesis and Crystal Structure of Spiro[1-bromo-4-methoxy-5-oxa-6-oxo-bicyclo[3.1.0]hexane-2,2′-（3′- cyclohexanoxy-4′-methoxybutyrolactone]

1INTRODUCTIONThecyclopropane-containingnaturalproductshavereceivedconsiderableattentionassynthetictar-getsastheincorporationofrigidifiedcyclopropylmotifintobioactiveanaloguescanleadtoconfor-mablyconstrainedmolecules[1,.Suchmodifica-2]tionsareexpectedtohavesignificanteffectsonbio-activitieswithconcomitantmedicalimplications.Des-pitethegreatadvancesinthisfield,theefficientsyn-thesisofspiro-cyclopropanecompoundsstillremainsaconsiderablechallenge.Particularnoticeisthede-ficiencyinthepreviousm…     

Crystal Structure and Antitumor Activity of Tri[2-[N-（4′-methyl-benzylsulfonyl）amino]ethyl]-amine

The crystal structure of the title compound (C27H38N4O7S3, Mr = 626.79) has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pīwith a = 9.411(1), b = 11.645(2), c = 14.672(2) (A。), α = 91.80(1), β = 95.36(1), γ =104.56(1)o, V = 1547.0 (A。)3, Z = 2, Dc = 1.346 g/cm3, λ = 0.71073 (A。), μ(MoKα) = 0.289 mm－1 and F(000) = 664. The structure was refined to R = 0.0406 and wR = 0.1177 for 4103 observed reflections with I > 2σ(I). X-ray diffraction analysis reveals that the title compound is a practically distorted tetrahedron and each molecule contains one lattice H2O by hydrogen bond. The antitumor activity of the title compound against HL-60 human leukemia cells has also been studied by MTT method.     

Crystal and molecular structure studies of 1′-Benzyl-8-(4-fluorobenzyl)-8-azaspiro[bicyclo-[3.2.1]octane-3,4′-imidazolidine]-2′,5′-dione

The title compound 1′-Benzyl-8-(4-fluorobenzyl)-8-azaspiro[bicyclo[3.2.1] octane-3,4′-imidazolidine]-2′,5′-dione, C₂₃H₂₃FN₃O₂ is synthesized and the structure is investigated by X-ray diffraction studies. The compound crystallizes in the triclinic crystal class in the P1 space group. The hydantoin ring adopts a planar conformation and is affected by the π conjugation. The pyrrolidine and piperidine rings in the bicyclo octane moiety adopt envelope and chair conformations respectively. The structure exhibits both inter- and intramolecular hydrogen bonds of the type N-H...O, C-H...O, and C-H...N. The oxygen atom in the hydantoin ring simultaneously accepts two hydrogen bonds to form a three-centered hydrogen bonding pattern.     

5-[4-amino(1,2,5)oxadiazolyl]-5H-[1,2,3]tri-azolo [4,5-c][1,2,5]oxadiazole from 4,4′-diamino-3,3′-azofurazane

4,4-Diamino-3,3-azofurazane undergoes intramolecular oxidative cyclization to give 5-[4-amino(1,2,5)oxadiazolyl]-5H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole upon heating with Pb(OAc)₄ in chlorobenzene oro-dichlorobenzene or with thionyl chloride.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 253–254, February, 1996.     

Synthesis of new pyridazino[4′,3′:4,5]-thieno[3,2-d]-1,2,3-triazine and pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine derivatives

Summary 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (2), 3-substituted 8,9-diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-ones (3a–c), 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (4), 8-chloro-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (5), 8-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazines (6a–h) and 7-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-ones(7a–c) were synthesized from 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide (1).

---

Synthese neuer Pyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-und Pyrimido[4,5:4,5]thieno[2,3-c]pyridazin-Derivate

Zusammenfassung Folgende Verbindungen wurden ausgehend von 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (1) synthetisiert: 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-on (2), 3-substituierte 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (3a–c), 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8[7H]-on (4), 8-Chlor-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin (5), 8-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (6a–h) und 7-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (7a–c).

     

Synthesis of 4′H-spiro[adamantane-2,3′-isoquinoline] derivatives

Russian Journal of Organic Chemistry -     

Synthesis of 1′-substituted 4′,4′-dimethyl-6′-methoxy-4′H-spiro[cyclohexane-1,3′-isoquinolines]

The reaction of 1-(4-methoxyphenyl)-1-(1-methylcyclohexyl)ethanol with nitriles in concentrated sulfuric acid afforded 1′-substituted 6′-methoxy-4′,4′-dimethyl-4′H-spiro[cyclohexane-1,3′-isoquinolines] as a result of consecutive Wagner-Meerwein rearrangement and Ritter reaction.     

Green Aspect for Multicomponent Synthesis of Spiro[4H-indeno[1,2-b]pyridine-4,3′-[3H]indoles]

An efficient, four-component reaction of isatin, 1,3-indanedione, ethyl acetoacetate, and ammonium acetate in ethanol/water (9:1) system furnished spiro[4H-indeno[1,2-b]pyridine-4,3′-[3H]indoles] at room temperature. Merits of the method are mild reaction conditions, simple workup procedure, and ambient temperature. The synthesized compounds exhibit excellent fluorescence properties.