Some features of RuCl3-catalyzed periodate oxidation of 3-N-substituted 5-allenyl-2,5-dichloro-4,4-dimethoxycyclopent-2-en-1-ones

3-N-Substituted 5-(1Z-carboxymethylene)-2-chloro-4,4-dimethoxycyclopent-2-en-1-ones have been prepared from the corresponding 3-N-substituted 5-allenyl-2,5-dichloro-4,4-dimethoxycyclopent-2-en-1-ones using selective oxidative cleavage of their allene bond by the RuCl₃−NaIO₄ system. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1646–1648, September, 1997.     

Synthesis and crystal structure of 5-amino-4,6-dicyano-3-dicyanomethylene-1, 8,8-trimethyl-2-azabicyclo[2.2.2]oct-5-ene

5-Amino-4,6-dicyano-3-dicyanomethylene-1,8,8-trimethyl-2-azabicyclo[2.2.2]oct-5-ene has been synthesized. The molecular and crystal structure of this compound has been determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 169–172, January, 1996.     

Synthesis of 5H-thiazolo[3,2-a]pyrimidine derivatives from 6-methyl-2-thiouracil and 1-acyl-2-bromoacetylenes. X-ray structural study of 3-benzoyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-one

3-Acyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-ones were synthesized by the reaction of 1-acyl-2-bromoacetylenes with 6-methyl-2-thiouracil, carried out with heating in DMF, dioxane, or acetonitrile in the presence of triethylamine. The structure of 3-benzoyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-one was established by X-ray structural analysis.Deceased in 1995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2306–2308, September, 1996.     

Molecular,crystal, and electronic structure of 3-aminocarbonyl-1-phenyl-5-chloro-2-iminopyridone

Riga Polytechnical Institute. Institute of Organic Synthesis, Academy of Sciences of the Latvian SSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 29, No. 5, pp. 169–172, September–October, 1988.     

Specificity of the reaction of 2,3-dichloro-4,4-dimethoxy-5-(2-methylfuran-3-yl)cyclopent-2-en-1-one with amines

2,3-Dichloro-4,4-dimethoxy-5-(2-methylfuran-3-yl)cyclopent-2-en-1-one reacted with diethyl-and dipropylamines to give products of Ad_NE replacement of the chlorine atom at the vinylic C³ atom and substitutive opening of the furan ring with simultaneous deprotection of the dimethyl acetal moiety in the 2,3-dichlorocyclopentenone fragment.     

Synthesis and structure of 2-amino- 5-azolyl-3-cyano-4H-pyrans

Previously unknown 5-azolylpyrans were obtained by reactions ofN-acetonyl- andN-phenacylimidazoles, -triazoles, and -tetrazoles with arylmethylenemalononitriles. The structure of 2-amino-3-cyano-6-methyl-5-(5-nitrotetrazol-2-yl)-4-phenyl-4H-pyran was established by X-ray structural analysis.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2050–2055, August, 1996.     

Molecular and crystal structure of 1,2-dihydro-3H-1,3,4-benzotriazepines

Three novel 1,2-dihydro-3H-1,3,4-benzotriazepines have been synthesized: 7-bromo-5-phenyl-3-phenylcarbamoyl-1,2-dihydro-3H-1,3,4-benzotriazepin-2-one, 7-bromo-5-phenyl-1,2-dihydro-3H-1,3,4-benzotriazepin-2-thione, and 7-methyl-5-phenyl-1,2-dihydro-3H-1,3,4-benzotriazepin-2-one. Their crystal structures have been determined using X-ray analysis. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1048–1056, July, 2006.     

Crystal and molecular structure ofN-phenyl-4-nitrobenzamidoxime

N-Phenyl-4-nitrobenzamidoxime has been studied by X-ray structural analysis. In two crystallographically independent molecules1A and1B, amidoxime groups adopt a planarZ configuration, and these fragments are in ans-trans conformation with respect to the =N-O and C-N(H) bonds; an intramolecular NH...O bond occurs. The nitrophenyl and phenyl groups are rotated with respect to the amidoxime plane [ONCN] by –57 and –32° in1A and –38 and –22° in1B, respectively. The rotation of the fragments about the C(1)-N(2) bond is –28 (1A) and –35° (1B). In crystals, molecules1A and1B are linked in oxime dimers through two intermolecular =N...(HO) hydrogen bonds; dimers form double chains through two NH...(O₂N) hydrogen bonds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1516–1519, August, 1995.The work was supported by the Russian Foundation for Basic Research (Project No. 93-03-05069).     

New captodative polyheterofunctionalized cyclopentenones from 2,3,5-Trichloro-4,4-dimethoxy-5-(2-methylfuran-3-yl)cyclopent-2-en-1-one and secondary amines

2,3,5-Trichloro-4,4-dimethoxy-5-(2-methylfuran-3-yl)cyclopent-2-en-1-one reacted with secondary amines to give unusual Ad_NE-substitution-fragmentation products, 5-[(1Z,2E)-1-acetyl-3-dialkylaminoprop-2-en-1-ylidene]-3-dialkylamino-2-chloro-4,4-dimethoxycyclopent-2-en-1-ones.     

One-step synthesis of 5-acetyl-2-amino-4-aryl-3-cyano-4H-pyrano[3,2-b]indoles. Molecular and crystal structure of 5-acetyl-2-amino-4-(4"-chloro-3"-nitrophenyl)-3-cyano-4H-pyrano[3,2-b]indole

A one-step procedure was developed for the synthesis of 5-acetyl-2-amino-4-aryl-3-cyano-4H-pyrano[3,2-b]indoles involving the three-component reaction of 1-acetylindol-3(2H)-one with aromatic aldehydes and malononitrile in ethanol in the presence of triethylamine as the catalyst. The structure of 5-acetyl-2-amino-4-(4"-chloro-3"-nitrophenyl)-3-cyano-4H-pyrano[3,2-b]indole was established by X-ray diffraction analysis.     

The molecular and crystal structure of stable 5-methyl-2-methylsulfonyl-3-thiophenecarbonitrile oxide

A stable thiophene derivative, 5-methyi-2-methylsulfonyl-3-thiophenecarbonitrile oxide, which is active in reactions with dipolarophiles, was studied by means of X-ray structural analysis. In the crystalline state the structure includes two independent molecules with similar values of geometric and conformation parameters. The bond angle at the C atom of the nitrile oxide group is significantly different from 180°. The intramolecular distances between the C and S atoms in the nitrile oxide and sulfonyl groups are well below the equilibrium distance. The stability of the molecule is thought to be increased by electrostatic or donor-acceptor interactions between the atoms of these groups. The mutual orientation of the two independent molecules in the crystal is nearly orthogonal.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 725–727, April, 1993.     

Molecular and crystal structure of 4,4,4-trifluoro-3,3-dihydroxy-1-thiophene-2-yl-butane-1-one

An X-ray diffraction analysis and quantum chemical calculations of hydrated 2-thenoyltrifluoroacetone show that the planar diketone, form of TTA found in its metal complexes, does not occur in the free ligand. Hydrated TTA with two geminal hydroxo groups has a non-planar structure stabilized by an intramolecular hydrogen bond.     

Synthesis,structure, and configuration of new spirooxyndol compound

Structure of a new spirooxyndol compound, [indoline-3,2′(3′H)-[3′-acetyl-2′-acetamide-[1,3,4]-thiodiazoline]-1-benzyl]-2, has been determined by X-ray diffraction analysis. Crystal is monoclinic, unit cell parameters are: a = 12.097(1) Å, b = 10.172(1) Å, c = 32.987(1) Å; β = 97.731(3)°, space group P2₁/n, Z = 4, compound C₄₂H₄₄N₈O₇S₂. Independent part of the unit cell is formed by two crystallographically independent molecules, practically equal in composition and configuration. Two independent molecules are united by the exosphere molecule of ethanol. Phenyl and pyrol rings are located virtually in one plane, dihedral angle formed by mean-square planes of these rings vary within 1.5(2)–3.3(2)°. In both molecules thiodiazoline and pyrol rings are spiro-joint over carbon atom, the dihedral angle formed by the latter is 89.1(1)° and 88.5(1)°, sulfur and nitrogen atoms in the molecules A and B being on different sides of pyrol ring keeping identical configuration of carbon node. Crystal structure is composed due to branched system of intermolecular hydrogen bonds.     

Furylcyclohexenones. 3. Synthesis and properties of 6-acetyl-3(5)-furylcyclohex-2-enones. Molecular and crystal structure of 6-acetyl-3-(2-furyl)-5-phenylcyclohex-2-enone

6-Acetyl-3(5)-furylcyclohex-2-enones were prepared by condensation of furan-containing chalcones with acetylacetone. Acetylcyclohex-2-enones were subjected to C-methylation. Studies by IR and ¹H NMR spectroscopy demonstrated that the resulting compounds occur predominantly in the enol form both in solutions and in the crystalline state. The molecular structure of 6-acetyl-3-(2-furyl)-5-phenylcyclohex-2-enone was established by X-ray diffraction analysis.     

The Homoconjugated Electron-Releasing Carbonyl Group of 1-Methylbicyclo[2.2.1]hept-5-en-2-one. Regioselective syntheses of 5-chloro- and 6-chloro-1-methylbicyclo[2.2.1]hept-5-en-2-one

Syntheses of (±)-2-exo-cyano-1-methyl-7-oxabicyclo[2.2.1]hept-5-en-2-endo-yl acetate ( 1 ) and of (±)-1-methyl-7-oxabicyclo[2.2.1]hept-5-en-2-one ( 2 ) are reported. The additon of PhSeCl to 1 afforded (±)-5-endo-chloro-2-exo-cyano-1-methyl-6-exo-(phenylselenenyl)-7-oxabicyclo[2.2.1]hept-2-endo-yl acetate ( 6 ), whereas 2 added to PhSeCl with the opposite regioselectivity giving (±)-6-endo-chloro-1-methyl-5-exo-(phenylselenenyl)-7-oxabicyclo[2.2.1]heptan-2-one ( 7 ). These adducts were converted into 5-chloro-1-methyl-7-oxabicyclo[2.2.1]hept-5-en-2-one ( 9 ) and 6-chloro-1-methyl-7-oxabicyclo[2.2.1]hept-5-en-2-one ( 10 ), respectively.     

New Synthesis and Molecular Structure of 2-(4'-Methoxyphenyl)-2,4-dithia-1,3,2-diazaphospholidine-5,1'-spirocyclohexane

1 INTRODUCTION Our continuous efforts to look for biologically active heterocyclic compounds led to a new and efficient synthesis of phosphoroheterocycles 1, 3, 2-diazaphospholidine-4-thione 2-sulfides in good yields by the treatment of Lawesson磗 reagent with various -aminonitriles in one-pot procedure. Many approaches to synthesize such phosphoroheterocycles have been reported[1~4]. The common pathways leading to 1, 3, 2-diazaphospho- lidine-4-thione(one) 2-sulfide(oxide) are using t…     

Reaction of 2-methyl-3-morpholino-1-phenylprop-2-en-1-one with Ru3(CO)12

The reaction of Ru₃(CO)₁₂ with 2-methyl-3-morpholino-1-phenylprop-2-en-1-one (1) produced the Ru₆(CO)₁₆(μ₄-η¹:η¹:η²:η²-PhC(O)-C(Me)=C)₂ (2), Ru₂O₂(CO)₄(η³-OC(Ph)C(Me)C(H)C(Me)₂C(Ph))₂ (3), and [Ru(CO)₂(PhCO₂)(O(CH₂-CH₂)₂NH]₂ (4) complexes, which were characterized by IR and NMR spectroscopy. The structures of the complexes were established by X-ray diffraction. The formation of the complexes is accompanied by deamination of ligand 1. Complexes 2 and 3 bearing the vinyl ketone groups contain five-membered oxaruthenacycles and dihydropyran rings. Morpholine is not removed from the reaction mixture and leads to the formation of complex 4. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2063–2068, December, 2006.     

Synthesis and crystal structure of 4,4′(1,2-ethanediyldiimino)bis(1,1,1-trichloro-3-penten-2-one)

The preparation, characterization and crystal structure of theSchiff base obtained from 1,1,1-trichloroacetylacetone and ethylenediamine is reported. The structural determination shows that the compound is 4,4(1,1-ethanediyldiimino)bis(1,1,1-trichloro-3-penten-2-one), it suggests that the electron accepting ability of the CCl₃ group induces a larger + charge on the remote carbonyl. In the solid state it occurs in two different conformations and N-H ----O hydrogen bond is present.

---

Synthese und Kristallstruktur von 4,4(1,2-Ethandiyldiimino)bis(1,1,1-Trichlor-3-penten-2-on)

Zusammenfassung Es wird über die Darstellung, Charakterisierung und Kristallstruktur derSchiff-Base berichtet, die aus 1,1,1-Trichloracetylaceton und Ethylendiamin erhalten wurde. Die Röntgenstrukturanalyse zeigte, daß es sich um 4,4(1,1-Ethandiyldiimino)bis(1,1,1-trichlor-3-penten-2-on) handelt. Dies impliziert, daß die Elektronacceptorfähgkeit der CCl₃-Gruppe eine größere Partialladung + im entfernteren Carbonyl induziert. Die Verbindung besitzt im Kristall zwei verschiedene Konformationen. Es wurde eine N-H----O-Wasserstoff-brückenbinding festgestellt.

     

Molecular and crystal structure of 2,3,4,5,6,7,8-heptachloro-2-morpholinocarbonyltricyclo[4.3.0.01,3]nona-4,7-dien-9-one

2,3,4,5,6,7,8-Heptachloro-2-morpholinocarbonyltricyclo[4.3.0.0^1,3]nona-4,7-dien-9-one was synthesized by the reaction of the tetrachlorocyclopentadienone dimer with morpholine, and its crystal and molecular structure was established by X-ray diffraction analysis.