Indole derivatives. 138. Synthesis of α-(5-indolyl)ethylamine and 5-(2-aminoethoxy)- and 5-(aminoethylthio)tryptamines

The reaction of 5-acetylindole with hydroxylamine with subsequent reduction of the resulting oxime gave -(5-indolyl)ethylamine. Coupling of 4-(2-phthalimidoethoxy)- and 4-(2-phthalimidoethylthio)phenyldiazonium chlorides with ethyl -acetyl--phthalimidovalerate, subsequent cyclization of the resulting hydrazones, hydrolysis, decarboxylation, and removal of the phthalyl protecting group led to the formation of 5-(2-aminoethoxy)- and 5-(2-aminoethylthio)tryptamines, respectively.For Communication 137, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 46–48, January, 1992.     

Crystal Structure and Spectra Characters of 2-Benzoly-3-(4-(1,2,4-triazole)-5-anilino-thiophene and 2-(4-Methyl-benzoly)-3-(4- chlrolphenyl)-3-(1,2,4-triazole)-5-anilino-thiophene

Triazole derivatives are widely studied, because they represent the largest group of modern fungicides and are widely used both in human and veterinary therapy and in agriculture. We synthesized the title compound in which the thiophene ring was substituted by a 1,2,4-triazole group, a phenacyl group, a phenylaminol group and a benzene ring.     

Studies on Acylthiosemicarbazides and Related Heterocycles(ⅪⅤ)——Synthesis and Bactericidal Activity of 1-(5-(3-Pyridyl)-2H-Tetrazol-2-ylacetyl) -4-Arylthiosemicarbazides and 3- (5- (3-Pyridyl)-2H-Tetrazol-2-ylmethyl)-4-Aryl-1,2 ,4-Triazole-5-Thiones

Introduction In the preceding paper it was described that various 1-acyl-4-substituted thiosemicarbazides and their derivatives exhibited a broad spectrum of antibacterial activities. Kothari pointed out that some heterocycles linked with tetrazole and 1,2,4-triazole can be used as antiinflammatory agent. We have also demonstrated that both 3-(5-a- naphthyl)-2H-tetrazol-2-ylmethyl)-4-aryl-1,2,4-triazole-5-thiones and 3-(3-pyridyl)-     

Regiospecific substitution of carbonyl by phosphine ligands in hydrocarbyl-substituted carbonyl clusters. Synthesis and spectroscopic characterization of Fe3(CO)8(PPh3)(μ3-η2- ⊥ -EtC2Et) and (η5-C5H5)NiFe2(CO)5(PPh3)(η3-η2- ⊥-C2But)

The complexes Fe₃(CO)₈(PPh₃)(μ₃-η²- ⊥ -EtC₂Et) and (η⁵-C₅H₅)NiFe₂(CO)₅(PPh₃)(η₃-η²- ⊥-C₂Bu^t) have been obtained by treating Fe₃(CO)₉(C₂Et₂) or (Cp)NiFe₂(CO)₆(C₂Bu^t) with PPh₃ under mild conditions; the substituted clustes have been characterized spectroscopically. Structures are proposed in which the phosphine is on the unique metalatom σ-bonded to the alkyne or acetylide moiety. Replacement of CO by PPh₃ ligands rather than by addition, is observed for the formally unsaturated Fe₃(CO)₉(C₂Et₂). Reorientation of the acetylide was expected for (Cp)NiFe₂(CO)₆(C₂Bu^t) upon substitution, but was not observed.     

Aurated tungsten-triosmium cluster compounds. Synthesis and characterization ofLWOs3(CO)12(AuPPh3) and related hydrogenation productsLWOs3(CO)11(μ-H)2(AuPPh3),L = C5 H5 and C5 Me5

Two heterometallic compoundsLWOs₃(CO)₁₂(AuPPh₃),L = Cp (6);L = Cp* (7), were prepared byin-situ generation of clusters [LWOs₃(CO)₁₂][PPh₄] from Os₃(CO)₁₀(NCMe)₂ and [LW(CO)₃][PPh₄], followed by addition of Ph₃ PAuCl. These derivatives possess a tetrahedral Os₃W core in which the AuPPh₃ unit bridges an Os-Os edge and the unique bridging CO ligand spans the opposite Os-W edge. Crystal data for6: space group P;a = 9.328(3),b = 13.745(3),c = 16.231(3) Á, = 115.00(2), = 97.27(2), = 90.17(2)°,Z = 2; finalR _F = 0 045,R _W = 0.044 for 4049 reflections withI > 2(I). Crystal data for7: space group P2₁/n;a = 9.775(2),b = 17.106(4),c = 25.074(3) Á, = 91.10(1)°,Z = 4; finalR _F = 0 035,R _W = 0.028 for 4196 reflections with I > 2(I). Hydrogenation of6 and7 afforded the respective dihydride complexesLWOs₃(CO)₁₁(-H)₂(AuPPh₃), (8)L = Cp; (9),L = Cp* in moderate yields. Their dynamic processes in solution were also established by¹H,¹³C and,³¹P NMR spectroscopies.     

Crystal Structure of Methyl 3- (2-chlorophenyl )-3- (5, 5-dimethyl-3-hydroxy-2-cyclohexene- 1-one-2-yl) propionate

1INTRODUCTIONInorganicsolidsupportsascatalystshavebeenwellstudied,becauseoftheirap-plicationsinorganicsynthese('~".Recently,wehavereportedtheKnoevenagelcon-densationcatalysedbyKF-Al,O,['i.Inthispaper,wediscussedthecrystalstruc-tureofthetitlecomPoundsynthesizedbythereactionof2-chlorobenzaldehydey5,5-dimethyl-1,3-cyclohexanedioneandisopropylidenemalonateinmethanolcatalyzedbyKF-Alzo,'Inordertoconfirmthestructureofthetitlecompound,theX-raycrys-tallOgraphicstudywascarriedout.2EXPER1MEN…     

Fluorinated tris(pyrazolyl)borates. Syntheses and characterization of sodium and copper complexes of [HB(3-(CF3),5-(Ph)Pz)3]−

Sodium salt of the fluorinated tris(pyrazolyl)borate ligand [HB(3-(CF₃),5-(Ph)Pz)₃]⁻ has been synthesized from the corresponding pyrazole and NaBH₄ in high yield. It forms stable adducts with oxygen-based donors like THF and water. [HB(3-(CF₃),5-(Ph)Pz)₃]Na(THF) is monomeric in the solid state whereas {[HB(3-(CF₃),5-(Ph)Pz)₃]Na(H₂O)}_n forms a polymeric chain structure. These tris(pyrazolyl)boratosodium adducts show intra and/or inter-molecular sodium–fluorine interactions. X-ray crystal structures of [HB(3,5-(CF₃)₂Pz)₃]Na(OEt₂) and {[HB(3-(CF₃),5-(CH₃)Pz)₃]Na(H₂O)}₂ also display similar CF⋯Na contacts. The copper carbon monoxide complex [HB(3-(CF₃),5-(Ph)Pz)₃]CuCO was prepared by treating [HB(3-(CF₃),5-(Ph)Pz)₃]Na(THF) with CuOTf in the presence of CO. The infra-red stretching frequency data show relatively high ν_CO value (2103 cm⁻¹) indicating the presence of highly electrophilic copper site on [HB(3-(CF₃),5-(Ph)Pz)₃]CuCO. Crystal structure of 3-(CF₃),5-(Ph)PzH is also reported. It forms “tub” shaped tetramers in the solid state.     

Triphospha-Ferrocenes as Ligands. Crystal Structures of [Fe(η5-C5Me5)(η5-C2 TBu2P3)M(CO)5)], (M= Cr,MO, W) and the Novel ruthenium and Nickel Complexes [Fe(η5-C5Me5) (η5-C2 TBu2P3)Ru3(CO)9] and [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(Co)2]2

Abstract

Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently¹. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η⁵-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η⁵-C₅Me₅) (η⁵-C₂ ^tBu₂P₃]. In the ruthenium complex [Fe(η⁵-C₅Me₅)(η⁵-C₂ ^tBu₂P₃) Ru₃(CO)₉] ² two adjacent phosphorus atoms of the η⁵-C₂ ^tBu₂P₃ ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η⁵-C₅Me₅)(η⁵-C₂ ^tBu₂P₃)Ni(CO)₂]₂ ³ represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres.     

Oxiranyl β-aminovinyl ketones. 5. Transformation of 2-methyl-2-(1-halogenoalkyl)-3(2h)-furanones into oxiranyl β-aminovinyl ketones

In reaction with amines 2-methyl-2-(1-halogenoalkyl)-3(2H) furanones form S-amino-1-halogeno-3-hydroxy-2-methyl-4 penten-3-ones and 6-amino-2-halogeno-3-hydroxy-3-methyl-5-hexen-3-ones, which are converted by the action of bases into the corresponding oxiranyl -aminovinyl ketones.Belorussian State University, Department of Organic Chemistry and Chemistry of High-Molecular Compounds, Minsk. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 609-612, May, 1995. Original article submitted April 11, 1995.     

Organometalloidal derivatives of the transition metals: XI. Synthesis and crystal structures of Ph3GeSiMe3 and Ph3GeSiMe2Fe(CO)2(η5-C5H5)

Ph₃GeSiMe₃ and Ph₃GeSiMe₂Fe(CO)₂(η⁵-C₅H₅) have been synthesized and their crystal structures determined. The GeSi bond in iron (2.405(2) Å) is longer by 0.021 Å than in the simple germylsilane (2.384(1) Å). The significant shortening of the SiFe bond (2.328(1) Å) in the iron complex compared to that in the analogous Ph₃SiSiMe₂Fe(CO)₂(η⁵-C₅H₅) (2.346(1) Å) and spectroscopic data indicate an enhanced SiFe interaction.     

3-ethyl-3-phenylazetidinone-2—I. Synthesis of (R)-, (S)- and (RS)-monomer,polymerization and properties of polymers

Synthesis and optical resolution of 3-ethyl-3-phenylazetidinone-2 were improved to obtain (RS)-, (R)- and (S)-monomers having optical purities up to 98%, which could successfully be determined by ¹H-NMR 250 MHz using tris[3-(2,2,2-trifluoro-l-hydroxymethylidene)d-camphorato]europium III as a shift reagent. These monomers were polymerized anionically in HMPT using potassium salt as a catalyst and by the addition of 1-acetyl-4,4-dimethylazetidinone-2 as a chain initiator. Optical purity of the starting monomer seemed to be maintained in the resulting polymers, the thermal properties of which were found to depend on the mean length of the stereoblocks contained in the chain. While the reactivity, in particular the case of polymerization, of monomer increased with the optical purity, no evidence could be obtained for stereoregulation by a preferential incorporation of a monomer enantiomer according to the configuration of the growing chain end unit.     

Synthesis of (3S,5R)-cis- and (3S,5S)-trans-3,5-Dimethylvalerolactones and Their Conversion to Biotransformation Products of (S)-5-Ethyl-5-(2′-pentyl)barbituric Acid

(R,S)-5-Ethyl-5-(2′-pentyl)barbituric acid (I)^1,2 is metabolized in vivo to give all four possible optical isomers of 5-ethyl-5-(3′-hydroxy-1′-methylbutyl)barbituric acid (II). ^3,4 From metabolism studies of pure (1′S)- I and (1′3)-I, Palmer and co-workers^4,5 were able to determine the relative amounts of each of the four isomers formed. These studies showed that (1′S)-I gave mainly one enantiomer of (1′S)-II, whereas (1′R)-I gave approximately equal amounts of both (1′R)-II enantiomers.     

Synthesis and properties of 5-furyl(aryl)-Δ2-1,2,4-triazolines and -Δ2-1,3,4-thiadiazolines. Molecular and crystal structure of 2-acetylamino-5-phenyl-Δ2-1,3,4-thiadiazoline

We show that upon acylation of arylidene amidrazones of 5-nitro-2-furancarboxylic acid, 3-(5-nitro-2-furyl)-²-1,2,4-triazolines or 5-(5-nitro-2-furyl)-1,2,4-triazole are formed (depending on the structure of the arylidene moiety). ²-1,3,4-thiadiazolines are obtained by reaction of thiosemicarbazones of aromatic and furaldehydes and furan ketones. We discuss schemes for closure of the triazolidine, triazole, and thiadiazoline rings. We describe the molecular structure of 2-acetylamino-4-acetyl-5-phenyl-²-1,3,4-thiadiazoline.Kuban State Technological University, Krasnodar 350072. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1337–1344, October, 1994. Original article submitted October 11, 1994.     

Crystal and molecular structures of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones

An X-ray study of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones is reported. The bond lengths inside the H ring are equalized due to the classical N-H...O hydrogen bond between the carbonyl oxygen and the amino group. In the 4-(2′-hydroxyethyl)amino-pent-3-en-2-one crystal, due to the classical N-H...O bonds, infinite zigzag chains are formed along the 0b axis and arranged into a layered structure due to the weak C-H...O interactions. In (±)-4-(2′-hydroxypropyl)aminopent-3-en-2-one crystal, however, centrosymmetric dimers are formed, which are then linked by weak C-H...O intermolecular interactions to form a layered structure along the a0b plane.     

Binary group 15 polyazides. structural characterization of [Bi(N3)4]-, [Bi(N3)5]2-, [bipy·Bi(N3)5]2-, [Bi(N3)6]3-, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the lone pair activation of valence electrons

The binary group 15 polyazides As(N(3))(3), Sb(N(3))(3), and Bi(N(3))(3) were stabilized by either anion or donor-acceptor adduct formation. Crystal structures are reported for [Bi(N(3))(4)](-), [Bi(N(3))(5)](2-), [bipy·Bi(N(3))(5)](2-), [Bi(N(3))(6)](3-), bipy·As(N(3))(3), bipy·Sb(N(3))(3), and [(bipy)(2)·Bi(N(3))(3)](2). The lone valence electron pair on the central atom of these pnictogen(+III) compounds can be either sterically active or inactive. The [Bi(N(3))(5)](2-) anion possesses a sterically active lone pair and a monomeric pseudo-octahedral structure with a coordination number of 6, whereas its 2,2'-bipyridine adduct exhibits a pseudo-monocapped trigonal prismatic structure with CN 7 and a sterically inactive lone pair. Because of the high oxidizing power of Bi(+V), reactions aimed at Bi(N(3))(5) and [Bi(N(3))(6)](-) resulted in the reduction to bismuth(+III) compounds by [N(3)](-). The powder X-ray diffraction pattern of Bi(N(3))(3) was recorded at 298 K and is distinct from that calculated for Sb(N(3))(3) from its single-crystal data at 223 K. The [(bipy)(2)·Bi(N(3))(3)](2) adduct is dimeric and derived from two BiN(8) square antiprisms sharing an edge consisting of two μ(1,1)-bridging N(3) ligands and with bismuth having CN 8 and a sterically inactive lone pair. The novel bipy·As(N(3))(3) and bipy·Sb(N(3))(3) adducts are monomeric and isostructural and contain a sterically active lone pair on their central atom and a CN of 6. A systematic quantum chemical analysis of the structures of these polyazides suggests that the M06-2X density functional is well suited for the prediction of the steric activity of lone pairs in main-group chemistry. Furthermore, it was found that the solid-state structures can strongly differ from those of the free gas-phase species or those in solutions and that lone pairs that are sterically inactive in a chemical surrounding can become activated in the free isolated species.     

Why are SiX5(-) and GeX5(-) (X = F, Cl) stable but not CF5(-) and CCl5(-)?

The possible existence of the CF(5)(-), CCl(5)(-), SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions has been investigated using ab initio methods. The species containing Si and Ge as central atoms were found to adopt the D(3h)-symmetry trigonal bipyramidal equilibrium structures whose thermodynamic stabilities were confirmed by examining the most probable fragmentation channels. The ab initio re-examination of the electronic stabilities of the SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions [using the OVGF(full) method with the 6-311+G(3df) basis set] led to the very large vertical electron detachment (VDE) energies of 9.316 eV (SiF(5)(-)) and 9.742 eV (GeF(5)(-)), whereas smaller VDEs of 6.196 and 6.452 eV were predicted for the SiCl(5)(-) and GeCl(5)(-) species, respectively. By contrast, the high-symmetry and structurally compact anionic CF(5)(-) and CCl(5)(-) systems cannot exist due to the strongly repulsive potential predicted for the X(-) (F(-) or Cl(-)) approaching the CX(4) (CF(4) or CCl(4)). The formation of weakly bound CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) anionic complexes (consisting of pseudotetrahedral neutral CX(4) with the weakly tethered X(-)) might be expected at low temperatures (approaching 0 K), whereas neither CX(5)(-) (CF(5)(-), CCl(5)(-)) systems nor CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) complexes can exist in the elevated temperatures (above 0K) due to their susceptibility to the fragmentation (leading to the X(-) loss).     

Synthesis and molecular structure of [1, 3-(Me3Si)2C5H3]2Lu(μ-Cl)2

Cp^* ₂Lu(-Cl)₂ (1) was isolated following the reaction of Cp^*Na (Cp^* = 1, 3-(Me₃Si)₂C₅H₃) with LuCl₃ in THF and subsequent treatment with toluene at 80°C. An X-ray structural investigation of1 was performed (MoK radiation, 2933 reflections,R = 0.020). The crystals are triclinic,a = 10.744(3) Å,b=11.821(2) Å, c=12.966(3) Å, a=71.54(1)°, =85.32(2)°, =74.83(1)°,Z = 2, space groupP-1. Two Lu atoms withdistorted tetrahedral coordination are linked by two chloride bridges with a mean Lu-Cl distance equal to 2.62 Å.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 568–570, March, 1993.