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.

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.

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

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.

Organometallic oxides: preparation of the cluster [(η-C5Me5)Mo]4O7 by reduction of [(η-C5Me5)MoCl(O)]2(μ-O) or (η-C5Me5)MoCl2(O)

2000 ◽  
Vol 78 (3) ◽  
pp. 383-394
Author(s):  
Frank Bottomley ◽  
Victor Sanchez ◽  
Robert C Thompson ◽  
Olusola O Womiloju ◽  
Zhiqiang Xu
Keyword(s):  
Nmr Spectra ◽  
Chloroform Solution ◽  
X Ray Diffraction ◽  
Broad Resonance ◽  
Nmr Spectrum ◽  
X Ray ◽  
Temperature Range ◽  
H Nmr ◽  
Tributyltin Hydride ◽  
Effective Moment

Reduction of [(η-C5Me5)MoCl(O)]2(μ-O) or (η-C5Me5)MoCl2(O) with sodium or magnesium amalgam, magnesium turnings, or tributyltin hydride produced [(η-C5Me5)Mo]4O7, with [(η-C5Me5)Mo(O)(μ-O)]2 as a co-product. [(η-C5Me5)Mo]4O7 was characterized by X-ray diffraction, mass spectrometry, 1H NMR and IR spectroscopies, and magnetism. Crystals of [(η-C5Me5)Mo]4O7 contained a tetrahedral [(η-C5Me5)Mo]4 unit (Mo-Mo = 2.909 (3) Å) with the Mo4O7 core having the structure Mo4(μ2-O(b))3(µ2-O(c))3(µ3-O(a)) (3). Microcrystalline samples of [(η-C5Me5)Mo]4O7 were paramagnetic over the temperature range 2-300 K, with an effective moment of 1.26 μB at 300 K. [(η-C5Me5)Mo]4O7 was also paramagnetic in chloroform solution, over the temperature range 223-298 K, with an effective moment of 1.43 µB at 298 K. The 1H NMR spectrum showed a broad resonance at 16.3 ppm (Δν 1/2 = 113 Hz) and two narrow resonances at 1.89 ppm and 1.69 ppm (Δν 1/2 = 5 Hz). The magnetism and NMR spectra showed that [(η-C5Me5)Mo]4O7 existed in two forms which were in equilibrium in solution. One form was paramagnetic (S = 1), with the Mo4O7 core having the geometry 3, and the other was diamagnetic (S = 0), with the Mo4O7 core having the geometry 4.Key words: cluster, cyclopentadienyl, molybdenum, oxide, paramagnetism.

scholarly journals Darstellung und Charakterisiening der Spezies R-C7H7Mo(CO)3 und die Röntgenstrukturanalyse von / Synthesis and Characterisation of the Species R-C7H7Mo(CO)3 and the X-ray Structure Determination of

1978 ◽  
Vol 33 (4) ◽  
pp. 361-365 ◽  
Author(s):  
Margret Sommer ◽  
Klaus Weidenhammer ◽  
Henning Wienand ◽  
Manfred L. Ziegler
Keyword(s):  
Carbon Atom ◽  
Structure Determination ◽  
Nmr Spectra ◽  
X Ray ◽  
Ethyl Group ◽  
H Nmr

The species R−C7H7Mo(CO)3 (R=−CH2COCH3,−CH(CH3)COCH3,−CH(CH)(CH3)2COCH3) have been synthesized by electrolysing [η7-C7H7Mo(CO)3]+, η7-C7H7Mo(CO)2Br and the dimers [C7H7Mo(CO)3]2 and (C7H7)2Mo(CO)3, respectively, in suitable ketones and HBr. 1H NMR spectra and the X-ray structure determination of (CH3−CO−CH(CH3)−C7H7)Mo(CO)3 revealed the CH3−CO−CH(CH3)-group being bonded to the cycloheptatriene ligand via the α-carbon atom of the ethyl group.

Zinc Complexes of Dimethyl(phthalimidomethyl)phosphine Oxide

1994 ◽  
Vol 49 (2) ◽  
pp. 258-262
Author(s):  
Sabi Varbanov ◽  
Elena Russeva ◽  
Andrei Ganchev
Keyword(s):  
Oxygen Atom ◽  
Phosphine Oxide ◽  
Nmr Spectra ◽  
Zinc Complexes ◽  
X Ray ◽  
H Nmr ◽  
Infrared Spectral ◽  
Phosphoryl Oxygen ◽  
Halide Complexes ◽  
Powder Analysis

A series o f zinc complexes of dimethyl(phthalimidomethyl)phosphine oxide (DPPO, L) have been synthesized: ZnX2L2, where X = Cl, Br, I or NO3. The complexes are characterized by elemental analysis, infrared and 1H NMR spectra and X-ray powder analysis. Infrared spectral data show that L is coordinated to zinc via the phosphoryl oxygen atom. The zinc halide complexes are found to be isostructural, while the pattern o f Zn(NO3)2L2 differs considerably from those o f halide complexes.

scholarly journals Atran-analoge Verbindungen des Typs / Atrane Analogous Compounds of the Type

1984 ◽  
Vol 39 (3) ◽  
pp. 341-351 ◽  
Author(s):  
Joseph Grobe ◽  
Gerald Henkel ◽  
Bernt Krebs ◽  
Nikolaos Voulgarakis
Keyword(s):  
Structure Analysis ◽  
Nmr Spectra ◽  
Room Temperature ◽  
Trigonal Bipyramid ◽  
Angular Distortion ◽  
Type I ◽  
Tetrahedral Coordination ◽  
Cage Compounds ◽  
X Ray ◽  
H Nmr

Heterocyclic cage compounds of type I (compounds 8-10) have been prepared by condensation reactions of 1,2,2-trifunctional disilanes Me(R)XSiSiMeX2 (R = Me, Ph, OEt; X = NMe2, OEt) with triethanolamine using the “Dilution Principle”. The starting compounds are obtained by Si-Me cleavage of Si2Me6 with acetylchloride/AlCl3 followed by either aminolysis with HNMe2 or alcoholysis with EtOH. 1H NMR spectra indicate N→Si(1) intraction with the more acidic Si atom in 8 and 9. This result is proved by the X-ray structure analysis of 8 (monoclinic, P21/c; a = 7,088(2), b = 15,070(4), c = 12,701(4) Å, β = 104,96(2) at -130 °C, Z = 4); the Si(1)···N distance is found to be 2,768 Å , connected with a significant angular distortion of the tetrahedral coordination around Si(1) towards a trigonal bipyramid. In compound 10, too, N→Si(1) coordination is observed at room temperature in spite of almost equal acidity for both Si atoms. This can be explained by the preference of 5- over 6-membered chelating ring systems. At higher temperatures the 1H NMR spectra show a fluctuation of the N-donor between the two Si centres.

scholarly journals Reactions of 3-(p-substituted-phenyl)-5-chloromethyl-1,2,4-oxadiazoles with KCN leading to acetonitriles and alkanes via a non-reductive decyanation pathway

2018 ◽  
Vol 14 ◽  
pp. 3011-3017
Author(s):  
Akın Sağırlı ◽  
Yaşar Dürüst
Keyword(s):  
Nmr Spectra ◽  
2D Nmr ◽  
Synthetic Route ◽  
X Ray ◽  
H Nmr ◽  
2D Nmr Spectra ◽  
Tof Ms ◽  
C Nmr

The present work describes an unfamiliar reaction of 5-(chloromethyl)-3-substituted-phenyl-1,2,4-oxadiazoles with KCN affording trisubstituted 1,2,4-oxadiazol-5-ylacetonitriles and their parent alkanes, namely, 1,2,3-trisubstituted-1,2,4-oxadiazol-5-ylpropanes. To the best of our knowledge, the current synthetic route leading to decyanated products will be the first in terms of a decyanation process which allows the transformation of trisubstituted acetonitriles into alkanes by the incorporation of KCN with the association of in situ-formed HCN and most likely through the extrusion of cyanogen which could not be detected or isolated. In addition, the plausible mechanisms were proposed for both transformations. The structures of the title compounds were identified by means of IR, 1H NMR, 13C NMR, 2D NMR spectra, TOF–MS and X-ray measurements.

On the atomic interdiffusion in Co/Pt superlattices

1992 ◽  
Vol 7 (6) ◽  
pp. 1309-1312 ◽  
Author(s):  
X. Yan ◽  
T. Egami ◽  
E.E. Marinero ◽  
R.F.C. Farrow ◽  
C.H. Lee
Keyword(s):  
Minor Component ◽  
Diffraction Experiment ◽  
X Ray Diffraction ◽  
X Ray ◽  
Diffraction Peaks ◽  
Large Width ◽  
A Minor ◽  
Component Parallel

We have performed x-ray diffraction experiments on MBE grown 〈111〉 and 〈001〉 oriented Co (3 Å)/Pt (18 Å) superlattices with the scattering vector Q covering a plane that includes a major component perpendicular and a minor component parallel to the plane of the sample. The superlattice diffraction peaks were found to have a large width parallel to the plane of the film, indicating that there is strong in-plane disorder. These broad peaks were integrated to evaluate more accurately the amount of interdiffusion at the interface, which was found to be similar in both films, contrary to what the conventional x-ray diffraction experiment suggests.

scholarly journals New Synthetic Routes for 1-Benzyl-1,4,7,10-tetraazacyclododecane and 1,4,7,10-Tetraazacyclododecane-1-acetic Acid Ethyl Ester, Important Starting Materials for Metal-coded DOTA-Based Affinity Tags

2007 ◽  
Vol 62 (3) ◽  
pp. 397-406 ◽  
Author(s):  
Stephan W. Kohl ◽  
Katharina Kuse ◽  
Markus Hummert ◽  
Herbert Schumann ◽  
Clemens Mügge ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Ethyl Ester ◽  
Nmr Spectra ◽  
Acid Ethyl Ester ◽  
Affinity Tags ◽  
X Ray ◽  
H Nmr ◽  
Synthetic Routes ◽  
New Compounds ◽  
C Nmr

Two improved routes to synthesize 1-benzyl-1,4,7,10-tetraazacyclododecane (6) and 1,4,7,10- tetraazacyclododecane-1-acetic acid ethyl ester (11) are described as well as the synthesis of 1-{2-[4-(maleimido-N-propylacetamidobutyl)amino]-2-oxoethyl}-1,4,7,10-tetraazacyclododecane- 4,7,10-triacetic acid (17) and its Y, Ho, Tm, and Lu complexes. The 1H and 13C NMR spectra of the new compounds as well as the single crystal X-ray structure analyses of the intermediates 4-benzyl-1,7-bis(p-toluenesulfonyl)diethylenetriamine (3) and 1,4,7-tris(p-toluenesulfonyl)diethylenetriamine (7) are reported and discussed. The rare earth complexes of 17 have been characterized by 1H NMR spectroscopy and MALDI-TOF mass spectrometry.

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