A NOVEL AND EFFICIENT SYNTHESIS OF 3-ARYL AND 3-HETEROARYL SUBSTITUTED-1H-INDAZOLES AND THEIR MANNICH DERIVATIVES

ABSTRACT

A general and highly convenient procedure for the synthesis of 3-heteroaryl and 3-aryl substituted-1H-indazoles has been developed. These compounds (3a–f) were synthesized in good yield by refluxing the NaHSO₃ adduct of heteroaromatic and aromatic aldehyde and phenyl hydrazine in DMF. This procedure is more general and shorter than earlier methods. Five new 3-hetero-aryl substituted-1H-indazoles were synthesized and characterized. New Mannich derivatives of 3-(1H-pyrrol-2-yl)-1H-indazole (3a) and 3-(1H-indol-3-yl)-1H-indazole (3b) were prepared from morpholine and formaldehyde.     

THE CRYSTAL AND MOLECULAR STRUCTURE OF Ru3(CO)9(PPh3)3

Abstract

The synthesis of tertiary phosphine and phosphite substituted derivatives of M₃(CO)₁₂ {M = Ru(1a) Os(1b)} is discussed and the X-ray crystal and molecular structure of the tris-triphenylphosphine substituted ruthenium cluster Ru₃(CO)₉(PPh₃)₃ (2a) is reported. Complex 2a crystallises in the monoclinic space group P2₁/n with cell parameters a = 14.180(9), b = 21.644(14), c = 18.248(10) Å, β = 92.52(5)°, V = 5595(6) Å ³, Z = 4. The structure was solved by full-matrix least-squares methods based on F ². The refinement converged at R1 = 0.0564, wR2 = 0.2125 for 4857 observed data [F > 4σ(F)].     

SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF THE CHLORIDE-BRIDGED FACE-SHARING BIOCTAHEDRAL DIRHODIUM COMPLEX [HP-i-Pr3][Rh2Cl7(P-i-Pr3)2]

Abstract

The reaction of an ethanolic suspension of [NH₄]₃RhCl₆] and P-i′-Pr₃, in the presence of concentrated HC1, for 24h, gives [HP-i-Pr₃][Rh₂Cl₇(P-i-Pr₃)₂], 1, in 18.5% yeild and a small amount of Rh(H)(Cl)₂(P-i-Pr₃)₂, 2. The dinuclear complex 1 was characterized by elemental analyses, IR, ¹H, ³¹P NMR spectroscopy, and single crystal X-ray analysis. However, when the above reaction is continued for 48 h one obtains only 2, in good yield. It is proposed that complex 1 is a reaction intermediate leading to 2. Crystallographic data for 1 (at 298 K) are a = 15.944(3), b = 22.413(4), c= 11.500(4) Å, space group Pna2_x (Z = 4).     

THE REACTIONS OF [MoCl(GeCl3)(CO)3(NCMe)2] WITH NEUTRAL BI- AND TERDENTATE DONOR LIGANDS

Abstract

The reaction of [MoCl(GeCl₃)(CO)₃(NCMe)₂] with an equimolar quantity of L?L {L?L = 2,2′-bipy, 1,10-phen, Ph₂P(CH₂)_nPPh₂ (n = 1 or 2)} in CH₂Cl₂ at room temperature gave either [MoCl(GeCl₃)(CO)₃(L?L)] (L?L = 2,2′-bipy or 1,10-phen) (1 and 2) or [MoCl(GeCl₃)(CO)₂ (NCMe)(L?L)]{L?L = Ph₂P(CH₂)_nPPh₂ (n = 1 or 2) (3 or 4), respectively. Equimolar quantities of [MoCl(GeCl₃)(CO)₂(NCMe){Ph₂P(CH₂)PPh₂}] (3) and L?L {L?L = 2,2′-bipy or Ph₂P(CH)₂PPh₂} react in CH₂Cl₂ at room temperature to afford the cationic complexes [Mo(GeCl₃)(CO)₂{Ph₂P(CH₂) PPh₂}(L?L)]Cl (5 and 6) in good yield. The cationic nature of 6 was established by chloride exchange by reacting Na[BPh₄] with 6 in acetonitrile to give the tetraphenylborate complex [Mo(GeCl₃)(CO)₂{Ph₂P(CH₂)PPh₂}₂][BPh₄] (7). Reaction of equimolar quantities of [MoCl(GeCl₃) (CO)₃(NCMe)₂] and PhP(CH₂CH₂PPh₂)₂ in CH₂Cl₂ at room temperature afforded the dicarbonyl complex [MoCl(GeCl₃)(CO)₂{PhP(CH₂CH₂PPh₂)₂}] (8) in good yield.     

THERMAL DEHYDRATION OF BARIUM AND CALCIUM TRIMETAPHOSPHATE HEXAHYDRATES: Ba3(P3O9)26H2O AND Ca3(P3O9)26H2O

Abstract

Ba₃(P₃O₉)₂6H₂O and Ca₃(P₃O₉)₂6H₂O have mobile H₂O's which, under a dynamic vacuum of about 0.133 Pa, leave the lattice without disrupting it. Under water-vapor pressure, dehydration is accompanied by hydrolysis of P₃O₉ ^3- rings. The final product of dehydration is the β polyphosphate.     

SYNTHESIS OF NEW 3-SUBSTITUTED AND SPIRO 1,5-BENZODIAZEPIN-2-ONES UNDER PHASE-TRANSFER CATALYSIS CONDITIONS

1,3-Dihydro-4-phenyl-1,5-benzodiazepin-2-one 1 was treated with bromine in 1:1 molar ratio to get the corresponding 3-bromo derivative 2 which in turn reacted with different nucleophiles to get the corresponding 3-substituted derivatives 3–11. The cyclized compounds 4_a , 5_a , 7_a,b , and 9_a–c were achieved on refluxing compounds 4, 5, 6_a,b , or 8 _a–c respectively in diphenyl ether. Compound 1 was benzoylated with benzoyl chloride to give the corresponding 1-benzoyl derivative 12 which reacted with bromine in 1:2 molar ratio to yield the corresponding 3,3-dibromo derivative 13. Spiro benzodiazepines 14_a–d–16 were obtained by reacting compound 13 with the proper bidentates. Compound 1 was treated with formaldehyde and secondary amines or thiols to give Mannich bases or sulphides 17–21, respectively.     

THE RELATIVE DONOR CAPACITIES OF CH3 O AND CH3S BY ROTATIONAL BARRIER MEASUREMENTS

Abstract

In most aromatic or unsaturated systems the donor capacity of CH₃O surpassses that of CH₃S, but the latter group becomes a successively better donor with increasing electron-attracting capacity of the attached delocalized system. Rotational barriers of RX.C:Y.NMe₂, where X = 0 or S and Y is 0, S, or NR₂, are convenient probes for the donor capacity of RX. A crossover in donor capacity has been found when going from Y = 0 to Y = S.     

VIBRATIONAL SPECTRA AND STRUCTURE OF ALKOXY AND CHLOROALKOXY DERIVATIVES OF ANTIMONY(V)

Abstract

Vibrational spectra of (CH₃O) _n SbCl_5–n . n = 1: 1; n = 2: 2: n = 3: 3: n = 4: 4; n = 5: 5; have been recorded. According to ir and Raman data 1–5 are centrosymmetrical bridged dimers. The Raman spectra of 3–5 exhibit v(Sb–O) doublets of terminal CH₃O at 530–541 and 550–570 cm^?1; vibrations of the 4-membered Sb₂O₂ ring, observed in the 500–517 cm^?1 region of the ir spectra of 1–5, are absent. The v(C–O) bands of bridged and terminal CH₃O are shifted to higher wave numbers (60 and 31 cm^?1, respectively) in the series 1 → 5. The stability of the dimers increases in the series 1 < 2 < 3 < 4 ? 5. At 100–120°C and in CH₃CN solutions dimers of 1–3 dissociate to monomers (v(Sb–O) 537–540 cm^?1, ir data). The monochloride, 4, is partially dissociated in CH₃CN. On solution of the tetrachloride, 1, in benzene a dimer-monomer equilibrium has been observed, with the dimeric form being predominant.     

HALIDE EXCHANGE REACTIONS BETWEEN CpW(CO)3 − AND CpMo(CO)3X

Abstract

Halogen atom transfer from CpMo(CO)₃X (X = Cl, Br and I) to CpW(CO)₃ ^? forming CpMo(CO)₃ ^? and CpW(CO)₃X occurs with a first-order dependence on the oxidant and the reductant. The rate constants show a very small dependence on the identity of X, suggesting a mechanism involving nucleophilic attack by CpW(CO)₃ ^? on a carbonyl of CpMo(CO)₃X.     

REACTIONS OF CARBONYLSULPHIDE WITH [Rh(PPh3)3CI] AND [Pt(PPh3)3]

Abstract

Activation of small inorganic molecules (H₂, N₂, O₂, CO, NO, CO₂, SO₂, CS₂) by the complexes of transition metal ions like Rh(I), Ir(I), Pt(O) and Ru(II) have gained considerable interest during the last decade.^1–8 Because of the similarity of CO₂ and CS₂ molecules with COS, one would expect COS to form complexes with the transition metal ions analogous to those of CO₂ and CS₂. In addition, COS being susceptible to decomposition into CO and S, could also form carbonyl complexes. Until now, the only reaction of COS that has been successfully carried out is with [Pt(PPh₃)₃] which resulted in the formation of [Pt(COS)(PPh₃)₂] and [Pt₂S(CO) (PPh₃)₃]. ^8,9 It will, therefore, be interesting to study further the reactions of COS with the complexes of transition metal ions. The results of a preliminary study of such reactions with [Rh(PPh₃)₃Cl] and [Pt(PPh₃)₃] are reported in this communication.     

MIXED ANHYDRIDES OF DIALKYLPHOSPHINOUS ACIDS AND DIALKYL HYDROGEN PHOSPHITES,AND THE ISOMERIC MONOXIDES

Abstract

The three isomers possible for oxidized 1,1-dialkyl-2,2-dialkoxydiphosphines, R₂(O)P–P(OR')₂ 1, R₂P–O–P(OR')₂ 2, and R₂P–P(O)(OR')₂ 3, have been synthesized. Irreversible transformations of 1 to 2 and 2 to 3 have been found and the rearrangement patterns, the role of electrophilic and nucleophilic catalysts are discussed. The fact that 3 is more stable than 1 is attributed to higher donor activity of the ligands attached to the four-coordinate phosphorus in 3. Acid chlorides have been shown to attack the phosphorus atom of ambident anions of trivalent phosphorus acids (the products are 1 and 3) whereas the acids proper react with the acid halides at the oxygen atom, to give 2.     

SYNTHESIS AND SOLUTION NMR-STUDIES OF THE TRIS(3,5-DIMETHYLPYRAZOL-1-YL) HYDROBORATOPALLADIUM(II) COMPLEX,Pd{(pz*)3BH}(PPh3)CI

Abstract

The sterically hindered tris(3, 5-dimethylpyrazol-l-yl)hydroborate complex of palladium, Pd{(pz*)₃BH}(PPh₃)Cl (1) has been prepared by the stepwise reaction of (CH₃CN)₂PdCl₂ with K{(pz*)₃BH}, and then PPh₃. The complex 1 has been fully characterized by microanalysis and various spectroscopic methods. A solution NMR study of 1 revealed that two pz* groups of the {(pz*)₃BH} ligand coordinate to palladium in cis positions, while the remaining group is not coordinated. VT NMR experiments have been performed to determine that signal broadening of the phenyl proton resonances in the ¹H-NMR spectrum is likely attributed to restricted rotation of the coordinated PPh₃ within the congested complex on the NMR time scale. Complex 1 was metastable in solution towards reaction with water to decompose into several uncharacterized species, in which a facile hydrolytic cleavage of the B-H bond proceeded as judged by IR and ¹H-NMR spectra of the products. Reaction of 1 with PPh₃ in CDCl₃ exclusively yielded cis-PdCl₂(PPh₃)₂, implicating a chlorine abstraction from the solvent.     

1,4-PENTADIEN-3-ONES. A SOURCE FOR SELENANO 1,2,3- SELENA AND THIADIAZOLES

The 4-Selenanols (2,3) and 4-selenanones (4) were obtained by the reaction of 1,4-pentadien-3-ones (1) with sodium hydrogen selenide under different conditions. The fused 1,2,3-selenadiazoles (6) and 1,2,3-thiadiazoles (7) were prepared from 4 on oxidative cyclization with SeO₂ and Hurd–Mori reaction with SOCl₂.     

SYNTHESIS AND CHARACTERIZATION OF TWO NOVEL,NEST-SHAPED Mo-Cu-S CLUSTER COMPOUNDS, [MoOS3Cu3(Py)5X] (X = Br,I), AND THE SUBSTITUTION OF Mo-Cu-S CLUSTERS

Abstract

The title compounds [MoOS₃Cu₃(Py)₅Br] (3) and [MoOS₃Cu₃(Py)₅I] (4) were obtained through the nest-shaped cluster [(n-Bu)₄N]₂[MoOS₃Cu₃BrCl₂] (1) and twin-nest-shaped cluster [Et₄N]₄[Mo₂Cu₆S₆O₂Br₂I₄](2) by reacting with pyridine. They show nest-shaped skeletons, and are characterized structurally by single-crystal X-ray analysis. These are the first neutral nest-shaped Mo(W)-Cu(Ag)-S clusters.     

SILYL- AND GERMYL-DIAZADIPHOSPHETIDINES

Abstract

Reaction of the 1,3,2,4-diazadiphosphetidine, trans-[C₆H₅N(H)P(S)NC₆H₅]₂ with LiR (R = Me, n-Bu) followed by treatment of the resulting dianions with Me₃SiCl and Me₃GeBr produced trans-[C₆H₅N(R)P(S)NC₆H₅]₂(R = Me₃Si, 2; Me₃Ge, 3). Substitution occurs without cis-trans isomerization or significant cleavage of the 1,3,2,4-diazadiphosphetidine ring. 2 and 3 have been characterized by spectral (¹H and ³¹P NMR, IR, and MS) and elemental analytical data. Analogous reactions involving Me₃SnCl yield mixtures containing [C₆H₅N(SnMe₃)P(S)NC₆H₅]₂ which could not be isolated or completely characterized.     

PREPARATION AND MULTINUCLEAR NMR STUDY OF BENZOYL METHYLENE TRIPHENYLPHOSPHORNE AND BENZOYL METHYLENE TRI-N-BUTYLPHOSPHORANE PT (0) AND PD (0) COMPLEXES

The reactions of Pd (dba)₂ (dibenzylidene acetone palladium (0)) and Pt (dba)₂ (dibenzylidene acetone platinum (0)) with BPPY (Benzoyl Methylene Triphenylphosphorane) and BBuPY (Benzoyl MethyleneTri-n-butylphosphorane) in (1:2) ratios using tetrahydrofuran as solvent have yielded Pd (dba)(BPPY)₂ (1), [Pd (dba)(C(H)COPh(PPh₂-o-C₆H₄)][PPh₃CH₂COPh](2), Pd (dba)(BBuPY)₂ (3), and Pt (dba)(BPPY)₂ (4) complexes. Upon heating complex (1) in THF, a cyclization reaction occurred to give complex (2). The products (1), (2), (3), and (4) are studied by IR, ¹H, ³¹P, and ¹³C NMR technique.     

Crystal and molecular structure of organosilicon titanium(iv) derivatives: (Me3Si)3SiTi(NEt2)3 and ClTi[N(SiMe3)2]3

An X-ray structural study of two titanium-containing organosilicon compounds, (Me₃Si)₃SiTi(NEt₂)₃ (1) and ClTi[N(SiMe₃)₂]₃ (2), has been performed. The conformation of molecule1 in a crystal is staggered (approximate inherentC ₃ symmetry), the Ti-Si and Ti-N bond lengths are 2.671(2) and 1.874–1.890(5) Å, respectively. A crystal of1 consists of one type of enantiomers (the space group is P4₁2₁2; the absolute configuration has been determined). The structure of2 studied previously has been refined to the value of R=0.029 on the basis of 3442 reflections (the absolute structure has been determined), the Ti-Cl and Ti-N bond lengths are 2.260(1) and 1.926(1) Å, respectively. The strong distortions in the symmetry of the valence environment of the N atoms in the molecules of1, 2, and related structures are caused by electronic effects, in which the conformation of the relevant molecular fragments plays a determining role.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1473–1476, August, 1993.     

SYNTHESIS AND STRUCTURE OF A NOVEL MONONUCLEAR TUNGSTEN (VI) CITRATO COMPLEX, (NH4)3[Li(H2O)3WO3(C6 H4O7)]

Abstract

The first mononuclear tungsten-citrato complex, (NH₄)₃[Li (H₂O)₃WO₃(C₆H₄O₇)] (1), has been prepared by the reaction of ammonium tetrathio tungstate and lithium citrate in CH₃OH-H₂O solution at pH 8.2. There are two crystallographically independent anions in the asymmetric crystallographic unit. The crystal structure of the title compound (triclinic, space group P1, a = 6.901(1), b = 15.136(3), c = 16.107(3) Å, α = 75.85(3), β = 89.89(3), γ = 89.97(3), V = 1631.4(6) ų, R = 0.068, R _W = 0.1674 for 3878 reflections with I > 2σ(I)), reveals that in the compound a tungsten atom is coordinated to a fully deprotonated citrate as a tridentate ligand and three terminal oxygen atoms to form a distorted coordination octahedron.     

Si3S-, Si3Se-, Si3Te-Bicyclo[1.1.0]butanes and Si3S2-Bicyclo[1.1.1]pentane

The reaction of trisilirene 1 with propylene sulfide or elemental sulfur produced Si₃S-bicyclo[1.1.0]butane 2, which underwent Si–Si insertion of a second S atom forming Si₃S₂-bicyclo[1.1.1]pentane 3. Analogous reactions of 1 with elemental Se or Te resulted in the formation of heavier analogues of 2, namely, Si₃Se-bicyclo[1.1.0]butane 4 and Si₃Te-bicyclo[1.1.0]butane 5.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT     

SYNTHESIS AND NMR CHARACTERIZATION OF P-VINYL SUBSTITUTED PHOSPHAZENE PRECURSORS1

Abstract

The reactions of either PhPCl₂ or PCl₃ with (Me₃Si)₂NLi followed by H₂C[dbnd]CHMgBr were used to prepare the new P-vinyl substituted [bis(trimethylsilyl)amino]phosphines, (Me₃Si)₂NP(R)CH[dbnd]CH₂ [1: R=Ph, 2: CH[dbnd]CH₂, 3: R=Me, and 4: R=N(SiMe₃)₂]. Oxidative bromination of phosphines 3–1 afforded the P-bromo-P-vinyl-N-(trimethylsilyl)phosphoranimines, Me₃SiN[dbnd]P(CH[dbnd]CH₂)(R)Br [5: R=Ph, 6: R=CH[dbnd]CH₂, 7: R=Me], which, upon treatment with CF₃CH₂OH/Et₃N, were subsequently converted to the P-trifluoroethoxy derivatives, Me₃SiN[dbnd]P(CH[dbnd]CH₂)(R)OCH₂CF₃ [8: R=Ph, 9: R=CH[dbnd]CH₂, 10: R=Me]. Compounds 1–10, which are of interest as potential precursors to P-vinyl substituted poly(phosphazenes), were fully characterized by elemental analyses (except for the thermally unstable P-Br derivatives 5–7) and NMR spectroscopy (¹H, ¹³C, and ³¹P) including complete analysis of the vinylic proton splitting patterns via HOM2DJ experiments.