Verbindungen mit dem 5,6-Benzo-l,3,2-diazaphosphorinan-4-on-Ringsystem: Synthese von 2-Chlor-, 2-N,N-dimethylamino-und 2-Bis-(2-chlorethyl)amino- substituierten Derivaten mit drei-und vierfach koordiniertem Phosphor / Compounds Involving the 5,6-Benzo-l,3,2-diazaphosphorinane-4-one Ring System: Synthesis of 2-Chloro-, 2-N,N-dimethylamino-and 2-Bis-(2-chloroethyl)amino- Substituted Derivatives with Three-and Four-Coordinated Phosphorus

1994 ◽  
Vol 49 (6) ◽  
pp. 788-800 ◽  
Author(s):  
Ralf Sonnenburg ◽  
Ion Neda ◽  
Axel Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Nitrogen Atom ◽  
Mass Spectra ◽  
Nmr Spectra ◽  
Ring System ◽  
Phosphorus Trichloride ◽  
Amine Hydrochloride ◽  
Nmr Studies ◽  
X Ray ◽  
H Nmr ◽  
Structure Determinations

The reaction of methylisatoic anhydride with 2-(aminomethyl)pyridine, 3-(aminomethyl)- pyridine, 3-dimethylamino-1-propylamine, 3-diethylamino-1-propylamine and 3-dibutylamino- 1-propylamine furnished the N-substituted N'-methylanthranilic amides 1-5. In the reaction of 1-5 with phosphorus trichloride the 3-substituted 5,6-benzo-1-m ethyl-1,3,2-diazaphosphorinane- 4-one derivatives 6 to 10 were obtained. The possibility of intramolecular donoracceptor interaction between the nitrogen atom of the R2N group and the λ3P atom is suggested on the basis of 1H NMR studies. The reaction of 9 with dimethylamino-trimethylsilane furnished the 2-dimethylamino-substituted product 11. In the reaction of 6, 7 and 10 with bis-(2-chloroethyl)amine hydrochloride/triethylamine the expected substitution products 12 to 14 were obtained. 5,6-Benzo-2-[bis-(2-chloroethyl)amino]-1-methyl-3-(3-picolyl)-1,3,2-diazaphosphorinan- 4-one 13 reacted with (COD)PtCl2 to give the czs-dichloro-platinum(II) complex 15. The characterisation of 1-15 is based on the 1H-, 13C-, and 31P-NMR spectra, mass spectra and X-ray structure determinations of the precursor compounds 1 and 3

scholarly journals Zur Chemie der 4,6-Dioxo-1,3,5,2-triazaphosphinane, Teil III. Darstellung von 4,6-Dioxo-1,3,5,2 λ3-, 4,6-Dioxo-1,3,5,2 λ4- und 4,6-Dioxo-1,3,5,2 λ5-triazaphosphinanen / Chemistry of the 4,6-Dioxo-1,3,5,2 λ3-triazaphosphinanes, Part III. Synthesis of 4,6-Dioxo-1,3,5,2 λ3-, 4,6-Dioxo-1,3,5,2 λ4-, and 4,6-Dioxo- 1,3,5,2 λ5-triazaphosphinanes

1993 ◽  
Vol 48 (4) ◽  
pp. 443-451 ◽  
Author(s):  
Ion Neda ◽  
Michael Farkens ◽  
Axel Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Mass Spectra ◽  
Nmr Spectra ◽  
Amine Hydrochloride ◽  
X Ray ◽  
Structure Determinations

In the reaction of 2-chloro-1,3,5-trimethyl-4,6-dioxo-1,3,5,2 λ3-triazaphosphinane (1) with β-chloroethylamine hydrochloride and bis-(β-chloroethyl)amine hydrochloride, 1,3,5-trimethyl-2-(β-chloroethyl)amino-4,6-dioxo-1,3,5,2 λ3-triazaphosphinane (4) and 1,3,5-trimethyl-2-bis-(β-chloroethyl)amino-4,6-dioxo-1,3,5,2 λ3-triazaphosphinane (5) were obtained. The reaction of 4 and 5 with sulfur, hexafluoroacetone, tetrachloroorthobenzoquinone and 4-nitrobenzoyl azide gave the 1,3,5-trimethy1-4,6-dioxo-1,3,5,2 λ4-triazaphosphinanes 6 and 9 and the 1,3,5-trimethyl-4,6-dioxo-1,3,5,2 λ5-triazaphosphinanes 7 and 8. The characterization of 4-9 rests, especially, on their 1H, 13C and 31P NMR spectra, mass spectra and X-ray structure determinations of 4 and 5.

Umsetzungen von 0,3-Dialkyl-1,3-diaza-2-chloro-5,6-benzo-1,3,2-phosphorinan-4-onen; Darstellung von P(III)-Derivaten / Reactions of 1,3-Dialkyl-1,3-diaza-2-chloro-5,6-benzo-1,3,2-phosphorinan-4-ones; Preparation of P(III) Derivatives

1993 ◽  
Vol 48 (3) ◽  
pp. 333-340 ◽  
Author(s):  
Ion Neda ◽  
Hans-Jürgen Plinta ◽  
Reinhard Schmutzler
Keyword(s):  
Sodium Fluoride ◽  
Intermediate Product ◽  
Mass Spectra ◽  
Nmr Spectra ◽  
Ring System ◽  
Phosphorus Trichloride ◽  
Unusual Reaction ◽  
Mechanism Of Formation

The reaction of 1,3-dimethyl-1,3-diaza-2-chloro-5,6-benzo-1,3,2-phosphorinan-4-one 1 with N-trimethylsilylacetamide 2 and 2-methylpiperidine hydrochloride furnished the P-substituted derivatives 3 and 4. The reaction of 1 with trimethylbromo- and trimethyliodosilane yielded the 2-bromo- and 2-iodo- substituted compounds 5 and 6. 1-Methyl-3-(2-chloroethyl)-1,3-diaza-2-chloro-5,6-benzo-1,3,2-phosphorinan-4-one 8 was prepared in the reaction of N-methyl-N'-(2-chloroethyl)-anthranilamide 7 with phosphorus trichloride. The reaction of 8 with N-trifluoromethyl-3-nitrophenylamine 9 or with sodium fluoride led to the 2-fluorosubstituted product 11. From the unusual reaction of 8 with 9 in the presence of triethylamine N-difluoromethylene-3-nitrophenylimine 10 and the intermediate product, triethylamine hydrofluoride, were isolated. A mechanism of formation of 11 is proposed. The reaction of 8 with N-trimethylsilylacetamide 2 and bis-2-chloroethylamine hydrochloride furnished the expected substitution products 14 and 15, involving the 5,6-benzo-1,3,2-phosphorinan-4-one ring system. The characterization of 3-6, 8, 11, 14 and 15 rests, especially, on their 1H-, 13Cand 31P-NMR spectra, and their mass spectra.

X-Ray Structure Analysis and Spectroscopic Data of the Antibiotic 8-(Dichloroacetyl)-5-hydroxy-2,7-dimethyl-1,4-naphthoquinone from the Fungus Mollisia sp.*

1987 ◽  
Vol 42 (1-2) ◽  
pp. 1-3 ◽  
Author(s):  
Gabriela Weber ◽  
Thomas Hübner ◽  
Alfred Gieren ◽  
Johann Sonnenbichler ◽  
Tadeusz Kowalski ◽  
...  
Keyword(s):  
High Resolution ◽  
Structure Analysis ◽  
Spectroscopic Data ◽  
Mass Spectra ◽  
Nmr Spectra ◽  
X Ray ◽  
H Nmr

Abstract Mass spectra, X-ray data and high resolution 13C and 1H NMR spectra of 8-(dichloroacetyl)-5-hydroxy-2,7-dim ethyl-1,4-naphthoquinone are reported. The antibiotic active com pound was isolated from the fungus Mollisia sp.

Fastigiatine, a lycopodium alkaloid with a new ring system

1986 ◽  
Vol 64 (5) ◽  
pp. 943-949 ◽  
Author(s):  
Robert V. Gerard ◽  
David B. MacLean ◽  
Romolo Fagianni ◽  
Colin J. Lock
Keyword(s):  
Mass Spectrum ◽  
Nmr Spectra ◽  
Minor Component ◽  
Ring System ◽  
Free Base ◽  
Relative Configuration ◽  
X Ray ◽  
H Nmr ◽  
Lycopodium Alkaloid ◽  
A Minor

Fastigiatine, C19H28N2O, is a minor component of the alkaloids of Lycopodiumfastigiatum R•Br•collected in New Zealand. Its structure and relative configuration have been resolved by an X-ray analysis of the free base. The pentacyclic ring system of fastigiatine has not been previously observed in the Lycopodium family of alkaloids or elsewhere. A proposal is presented for its derivation from the tetracyclic flabellidane ring system that is widely distributed among Lycopodium species. The mass spectrum and the 13C and 1H nmr spectra of fastigiatine are discussed.

Trihapto cycloheptatrienyl molybdenum and tungsten dicarbonyl compounds incorporating tridentate chelating dimethyl(1-pyrazolyl)(ethanolamine)gallate ligands

1980 ◽  
Vol 58 (21) ◽  
pp. 2278-2285 ◽  
Author(s):  
Kenneth S. Chong ◽  
Alan Storr
Keyword(s):  
Nitrogen Atom ◽  
Low Temperature ◽  
Physical Properties ◽  
Nmr Spectra ◽  
Room Temperature ◽  
Amino Nitrogen ◽  
Nmr Studies ◽  
Dicarbonyl Compounds ◽  
H Nmr ◽  
And Tungsten

The synthesis and physical properties of a series of cycloheptatrienyl molybdenum and tungsten dicarbonyl compounds incorporating dimethyl(1-pyrazolyl)(ethanolamine)gallate ligands have been investigated. The monomeric, pseudo octahedral, complexes have the organogallate ligand occupying a set of facial positions with the cycloheptatrienyl ring situated opposite to the amino nitrogen atom. Proton nmr studies have shown the η3-C7H7 ligand of the complexes to be fluxional in solution at room temperature. In the low temperature limiting 1H nmr spectra of the complexes in solution, however, it is possible to distinguish ail seven protons of the static η3-C7H7 ring owing to the asymmetric nature of the octahedral molecules.

scholarly journals Zur Koordination unterschiedlicher Hauptgruppenmetalle mit einem speziellen, chelatisierenden Silazan / On the Coordination of Different Main Group Metals with a Special, Chelating Silazane

1988 ◽  
Vol 43 (7) ◽  
pp. 846-856 ◽  
Author(s):  
M. Veith ◽  
F. Goffing ◽  
V. Huch
Keyword(s):  
Nmr Spectra ◽  
Main Group ◽  
High Symmetry ◽  
Hydrogen Atoms ◽  
X Ray ◽  
Main Group Metals ◽  
H Nmr ◽  
Structure Determinations ◽  
Cis Isomer

Abstract The cis-isomer of the silazane H2L (1) (L = [NtBu][Me]Si(NtBu)2Si[Me][NtBu]) has been used as a ligand to main group metals. By displacing the hydrogen atoms of 1 the compounds L(MgMe)2 (4), L(MgCl)2 (5) and L(Li)(InMe2) (6) have been obtained. According to the 1H NMR spectra the structures of 4-6 are very similar: a polycyclic, cubane-like Si2N4M2 framework results from the special atomic arrangements and from intramolecular Lewis acid-base interactions between the metals M and the nitrogen atoms. Divalent metals and metal-centered groups can also be incorporated into 1. In the latter case a seco norcubane-like polycycle Si2N4M is produced as confirmed by X-ray structure determinations of LGaMe (8) and LSb+ InCl4- (11). LInMe (7) and LSn (9) seem to adopt the same tricyclic structure as 8, although the 1H NMR spectra are not consistent with a rigid molecule (low symmetry), but rather with a fluxional behaviour (high symmetry). When 5 is allowed to react with sodium/naphthalene in THF part of the magnesium is reduced and LMg(THF)2 (12) is formed. An X-ray structure determination of 12 reveals the compound to be only bicyclic with the magnesium atom coordinated by two nitrogen and two THF oxygen atoms.

scholarly journals Chemie polyfunktioneller Moleküle, 106. Kupfer(I)halogenid — Komplexe des Bis(diphenylphosphino)amins / Chemistry of Polyfunctional Molecules, 106. Copper(I) Halide Complexes of Bis(diphenylphosphino)amine

1990 ◽  
Vol 45 (12) ◽  
pp. 1657-1668 ◽  
Author(s):  
Jochen Ellermann ◽  
Falk A. Knoch ◽  
Klaus J. Meier
Keyword(s):  
Crystal Structure ◽  
Mass Spectra ◽  
Nmr Spectra ◽  
Conductivity Data ◽  
Triclinic Space Group ◽  
X Ray ◽  
Lattice Constants ◽  
H Nmr ◽  
Nmr Data ◽  
Halide Complexes

Reaction of Copper(I) halides CuX (X = Cl, Br, I) in methanol with bis(diphenylphosphino)amine (dppa, 1) yields complexes [Cu3X2(dppa)3]X (X = Cl, Br, I: 2a–c). The derivates [Cu3X2(dppa)3]PF6 (2a′–c′) have been synthesized by metatheses of 2a–c with NH4PF6. The IR, Raman, 31P{1H} NMR, 1H{31Ρ} NMR, 13C{1H} NMR spectra, and FD mass spectra as well as the conductivity data are reported and discussed together with the X-ray crystal structure of 2a · 5 CH3OH. The structure consists of the trinuclear cations [Cu3Cl2(dppa)3]+, distorted tetrahedral anions [Cl( · · · HOCH3)4]- and molecules of methanol of crystallization, hydrogen bridged to the solvated anions. The Cu3Cl2 core of the cations corresponds closely to a trigonal bipyramid with the copper atoms in the equatorial and the chlorine atoms in the axial positions. The colourless prisms of 2a · 5 CH3OH crystallize in the triclinic space group P1̅, with the lattice constants a = 1368.0(4); b = 1486.7(4); c = 2036.8(10) pm; α = 74.52(3); β = 74.73(3); γ = 82.26(2)°. Raman and 31P{1H} NMR data of the complexes [Cu(X)dppm]4 (dppm = (C6H5)2PCH2P(C6H5)2; X = Br, I) described earlier suggest that these compounds should also be formulated as [Cu3X2(dppm)3]X (4b, c).The Raman spectra of the cations of 2a–c, 2a′–c′ and 4a–c show bands at 165 (X = Cl), 145 (X = Br) and 125 (X = I) cm-1, which can be assigned to the symmetric (XCu3X) stretching mode of the XCu3X unit.

Cp′—X—Cp′-überbrückte μ-Cyclooctatetraen- und -trien-Zweikernkomplexe des Chroms sowie Vanadiums (Cp′ = η5-C5H4, X = CH2, SiMe2, GeMe2) / Binuclear Cp′–X–Cp′-Bridged μ-Cyclooctatetraene and -triene Complexes of Chromium as well as Vanadium (Cp′ = η5-C5H4, X = CH2, SiMe2, GeMe2)

1990 ◽  
Vol 45 (2) ◽  
pp. 221-238 ◽  
Author(s):  
Bernd Bachmann ◽  
Gerhard Baum ◽  
Jürgen Heck ◽  
Werner Massa ◽  
Bernd Ziegler
Keyword(s):  
Temperature Dependent ◽  
Nmr Studies ◽  
One Pot ◽  
X Ray ◽  
H Nmr ◽  
Metal Metal ◽  
Structure Determinations ◽  
Work Up ◽  
Conditions Of Work ◽  
By Products

Synfacial binuclear μ-Cot complexes of the general formula X(Cp′M)2— μ-Cot with Cp′—X—Cp′ as an additional bridging group (M = V, Cr; Cot = cyclooctatetraene) can be prepared by a one-pot reaction of the appropriate metal dichlorides with K2Cot and Li2[(C5H4)2X]. For M = V the vanadocenophanes {V(Cp'2X)}2 (X = SiMe2, GeMe2) are isolated as by-products. Depending on the conditions of work-up for M = Cr µ-(σ:η3:η2-cyclooctatriene) complexes can be obtained instead of the μ-Cot compounds. X-ray structure determinations of several μ-Cot species attest only a poor influence of the bridging group X on the metal metal bond. Low temperature 1H NMR spectra of the dichromium μ-Cot complexes show that the rapid Cotrotation can be frozen below T = 200 K. Temperature dependent 1H NMR studies indicate a diamagnetic-paramagnetic equilibrium for the binuclear μ-C8H10 compounds, wherein a Cr,Crmultiple bond must be assumed.

Homoleptische 1,4-Diazadienverbindungen elektronenarmer Übergangsmetalle. Synthese, Eigenschaften und Strukturen von (DAD)2Ti und (DAD)3Ti [1] / Homoleptic 1,4-Diazadiene Compounds of Early Transition Metals. Syntheses, Properties and Structures of (DAD)2Ti and (DAD)3Ti [1]

1994 ◽  
Vol 49 (4) ◽  
pp. 519-528 ◽  
Author(s):  
Richard Goddard ◽  
Carl Krüger ◽  
Ghassan Abdul Hadi ◽  
Karl-Heinz Thiele ◽  
Joachim Scholz
Keyword(s):  
Nmr Spectra ◽  
Room Temperature ◽  
Titanium Atom ◽  
Ring System ◽  
Temperature Dependent ◽  
X Ray ◽  
H Nmr ◽  
Tetrahedral Environment ◽  
Rigid Conformation

Syntheses and structures of homoleptic 1,4-diaza-1,3-diene (DAD) complexes of titanium are described. The spiranoid DAD complexes of formula (DAD)2Ti 3a-c are formed by reaction of TiCl4·2THF with the disodium salts Na2DAD 2a-c or by reduction of TiCl4·2TH F with magnesium in presence of two equivalents of DAD 1a-c . The endiaide complexes 3a-c are thermally stable, very sensitive to oxygen and water, and soluble in all com monorganic solvents. An X-ray crystal structure determination of 3 c reveals the titanium atom to be in a strongly distorted tetrahedral environment. The two five-membered metallacyclic rings are folded along the N,N′ axis. Temperature-dependent 1H NMR spectra of 3a-c indicate a rapid intramolecular inversion of this non-planar ring system in solution even at room temperature.Reduction of TiCl4·2THF with magnesium in presence of excess DAD 1d-f leads to the formation of the blue-violet complexes (DAD)3Ti 4d-f. At low temperatures three sterically crowded DAD ligands cause a rigid conformation as demonstrated by their unique lowtemperature 1H NMR spectra.

Preparation, properties and structure of some intermediate nido- and arachno-monocarbaboranes

1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Liquid Ammonia ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Starting Compound

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.

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