6π-Tricarbonyl-Komplexe von Pyridin-Derivaten, Synthesen und Reaktionen / 6π-Tricarbonyl-Chromium Complexes of Pyridine Derivatives, Syntheses and Reactions

1984 ◽  
Vol 39 (2) ◽  
pp. 207-212 ◽  
Author(s):  
Karl Dimroth ◽  
Rüdiger Thamm ◽  
Hans Kaletsch
Keyword(s):  
Hydrogen Atom ◽  
Phosphorus Atom ◽  
Nmr Spectra ◽  
Pyridine Derivatives ◽  
Chromium Complexes ◽  
X Ray ◽  
Chromium Hexacarbonyl ◽  
Allyl Rearrangement ◽  
Tricarbonylchromium Complexes ◽  
C Nmr

New 6π-tricarbonylchromiumpyrnftne complexes 5c and 5d could be synthesized from 2,6-di-rbutyl- and 2,4,6-tri-f-butylpyridines (3c and 3d) with chromium hexacarbonyl. They are characterized by their 1H and 13C NMR Spectra and their CO-frequencies which are rather similar to those of 6π-tricarbonylchromium-2,4 ,6-triphenyl [1] or 2,4,6-trw-butyl- [2] λ3-phosphorins. When 5d is reacted with lithiumphenyl, the phenyl residue adds to C-4, giving probably compound 7, which by methanolysis and allyl rearrangement of the hydrogen atom from position 4 to position 2 affords tricarbonylchromium-2,6-di-f-butyl-4-phenyl-1,2-dihydropyridine (8) in 56% yield. The 6π-tricarbonylchromium complexes of 2,4,6-triphenyl- or 2,4,6-tn-t-butyl-λ3-phosphorins react with lithiumorganic compounds by addition only to the phosphorus atom whose reaction with methyliodide lead to tricarbonylchromium-λ5-phosphorin-ylid complexes [2], 5 d is a well crystallized compound, the X-ray analysis of the first 6π-tricarbonylchromium pyridine derivate could be performed [3] and compared with the results of the X-ray analysis of 6π-tricarbonylchromiumx 2,4,6-triphenyl-λ3-phosphorin [4]

Reactivity of Sodium Hexaethyl-2,4-dicarba-nido-hexaborate(1-)

1999 ◽  
Vol 64 (6) ◽  
pp. 977-985 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Hans-Jörg Schanz ◽  
Wolfgang Milius ◽  
Catherine McCammon
Keyword(s):  
Mössbauer Spectroscopy ◽  
Nmr Spectroscopy ◽  
Structural Analysis ◽  
Hydrogen Atom ◽  
Mossbauer Spectroscopy ◽  
Sandwich Complex ◽  
X Ray ◽  
Bromo Derivative ◽  
Boron Tribromide ◽  
C Nmr

Sodium hexaethyl-2,4-dicarba-nido-hexaborate(1-) (6), available from hexaethyl-2,4-dicarba- nido-hexaborane(8) (4) by deprotonation, reacts with deuterated methanol, CD3OD, to give back 4 without H/D exchange of the B-H-B hydrogen atom. The reaction of 6 with diethylboron chloride, Et2BCl, affords hexaethyl-2,4-dicarba-closo-hexaborane(6) (7), the first example of a peralkylated carborane of this type. In contrast, the reaction of 6 with boron tribromide, BBr3, leads mainly to 2,3,4,5,6,7-hexaethyl-2,4-dicarba-closo-heptaborane(7) (8), together with the corresponding 1-bromo derivative (9) and the closo-carborane 7 as side products. The reaction of two equivalents of 6 with FeCl2 gives the air-stable sandwich complex bis[hexaethyl-2,4-dicarba-nido-hexaborate(1-)]iron 10 which was characterised by X-ray structural analysis. All products were characterised by 1H, 11B and 13C NMR spectroscopy, and 57Fe Mössbauer spectroscopy was used to study 10.

Bis[dicarbonyl(cyclopentadienyl)ruthenium(I)] Komplexe / Bis[dicarbonyl(cyclopentadienyl)ruthenium(I)] Complexes

2002 ◽  
Vol 57 (9) ◽  
pp. 1017-1026 ◽  
Author(s):  
Herbert Schumann ◽  
Susanne Stenz ◽  
Frank Girgsdies ◽  
Stefan H. Mühle
Keyword(s):  
Single Crystal ◽  
Nmr Spectra ◽  
X Ray ◽  
Tert Butyl ◽  
New Compounds ◽  
C Nmr

Ru3(CO)12 reacts with 1-tert-butyl-2,4-cyclopentadiene (1), 1-trimethylsilyl-2,4-cyclopentadiene (2), 1-tert-butyl-3-methyl-2,4-cyclopentadiene (3), 1,3-di(tert-butyl)-2,4-cyclopentadiene (4), 1-iso-propyl-2,3,4,5-tetramethyl-2,4-cyclopentadiene (5), 1-tert-butyl-2,3,4,5-tetramethyl- 2,4-cyclopentadiene (6), 1-phenyl-2,3,4,5-tetramethyl-2,4-cyclopentadiene (7), 2,5- diphenyl-2,4-cyclopentadiene (8), or 2,3,4,5-tetraphenyl-2,4-cyclopentadiene (9) with formation of the corresponding bis[dicarbonyl(cyclopentadienyl) ruthenium(I)] complexes [RuCp# (CO)2]2 1a to 9a. The 1H and 13C NMR spectra of the new compounds 3a and 5a to 9a as well as the single crystal X-ray structures of 1a, 4a, 5a, 7a, 8a, and 9a are reported and discussed

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.

Zur Darstellung und Struktur des 1.3-Dichloro-5-N.N-dimethylamino-1.3-dithia-2.4.6-triazins / Synthesis and Structure of 1,3-Dichloro-5-N,N-dimethylamino-1,3-dithia-2,4,6-triazine

1983 ◽  
Vol 38 (3) ◽  
pp. 347-349 ◽  
Author(s):  
Herbert W. Roesky ◽  
Pierre Schäfer ◽  
Mathias Noltemeyer ◽  
George M. Sheldrick
Keyword(s):  
Structure Analysis ◽  
Nmr Spectra ◽  
Membered Ring ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cl Atoms ◽  
C Nmr

Abstract The six membered ring of composition (CH3)2NCN3S2Cl2 3 a was prepared from N,N-dimethylguanidinhydrochloride and trithiadiazindichloride. 3 a was characterized on the basis of mass, 1H, 13C NMR spectra and X-ray structure analysis. Crystals of 3 a are monoclinic, space group P21/c, with a = 660.3(6), b = 834.5(7), c = 1774.7(15) pm, β = 112.83(6)° and Z = 4. The C2N unit lies approximately in the plane of the [-CNSNSN-] ring, with both Cl atoms on the same side of the ring.

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.

Selenium coronands. A novel conformational pair

1988 ◽  
Vol 66 (11) ◽  
pp. 2956-2958 ◽  
Author(s):  
B. Mario Pinto ◽  
Blair D. Johnston ◽  
Raymond J. Batchelor ◽  
Frederick W. B. Einstein ◽  
Ian D. Gay
Keyword(s):  
Nmr Spectra ◽  
Crystallographic Analysis ◽  
The Novel ◽  
Torsion Angles ◽  
X Ray ◽  
Structure Formula ◽  
Independent Molecules ◽  
Similar Conformation ◽  
C Nmr

The synthesis and characterization of the novel selenium coronands, 1,3,7,9-tetraselenacyclododecane 1a, 1,3,7,9,13,15-hexaselenacyclooctadecane 2a, the corresponding β-gem-dimethyl derivatives 1b, 2b, and 1,5,9,13-tetraselenacyclohexadecane 3, and 1,5,9,13,17,21-hexaselenacyclotetracosane 4 are described. X-ray crystallographic analysis of 1a reveals three independent molecules that exist in two distinct conformations, one molecule having approximate two-fold symmetry together with two molecules (of similar conformation) each having crystallographic [Formula: see text] symmetry. The conformations are denoted as [3333] or [66]. Whereas one resembles that of cyclododecane and tetrathia-12-crown-4 with respect to torsion angles, the other resembles that of tetraoxa-12-crown-4. The solid state CP-MAS 77Se and 13C nmr spectra are interpreted in light of the crystallographic information. Crystal structure: formula Se4C8H16; fw = 428.05; monoclinic, P21/c; Z = 8; a = 15.823(2) Å, b = 5.534(1) Å, c = 27.962(5) Å, β = 92.26(1)°; V = 2446.6 Å3; T = 200 K; R = 0.027 for 2162 observed data (I ≥ 2.5σ(I)).

The relative stabilities of PhE(NH-t-Bu)2 and PhE(μ-N-t-Bu)2EPh (E = As, Sb, and Bi): X-ray structures of {Li2[PhAs(N-t-Bu)2]}2 and PhE(μ-N-t-Bu)2EPh (E = Sb, Bi)

2003 ◽  
Vol 81 (2) ◽  
pp. 169-174 ◽  
Author(s):  
Glen G Briand ◽  
Tristram Chivers ◽  
Masood Parvez
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Phenyl Group ◽  
Synthetic Approach ◽  
Relative Stabilities ◽  
X Ray ◽  
X Ray Crystallography ◽  
In Trans ◽  
C Nmr

The reaction of PhECl2 with 2 equiv of LiHN-t-Bu has been studied for the series E = As, Sb, and Bi to determine the effect of the phenyl group on subsequent amine condensation processes. For PhAsCl2, the metathesis product PhAs(NH-t-Bu)2 4 was obtained as a colourless oil. Similar reactions involving PhECl2, where E = Sb or Bi, yielded the cyclodipnict(III)azanes PhE(μ-N-t-Bu)2EPh 5 (E = Sb) and 6 (E = Bi), respectively. Treatment of 4 with 2 equiv of n-BuLi produced the dilithium salt Li2[PhAs(N-t-Bu)2] 7a. Products 4, 5, 6, and 7a were characterized by 1H, 7Li (7a), and 13C NMR spectra, while 5, 6, and 7a were also structurally characterized by X-ray crystallography. Compound 7a is dimeric in the solid state via intermolecular Li···N and η6-Li···Ph interactions. The cyclodipnict(III)azanes 5 and 6 have similar structures, with the exocyclic phenyl groups in trans positions relative to the E2N2 ring. This synthetic approach provides a new route to the four-membered rings RE(μ-N-t-Bu)2ER (E = Sb, Bi) and the first example of a bis(organyl)cyclodibism(III)azane.Key words: arsenic, antimony, bismuth, amides, imides.

Article

1999 ◽  
Vol 77 (5-6) ◽  
pp. 1057-1065
Author(s):  
John T Edward ◽  
Francis L Chubb ◽  
Denis FR Gilson ◽  
Rosemary C Hynes ◽  
Françoise Sauriol ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Acidic Solution ◽  
Variable Temperature ◽  
X Ray Diffraction ◽  
Nmr Studies ◽  
Cage Compounds ◽  
Amine Nitrogen ◽  
X Ray ◽  
Bridgehead Nitrogen ◽  
C Nmr

Three new cage peroxides, 1,6-diaza-3,4,8,9-tetraoxabicyclo[4.4.2]dodecane (3a),1,6-diaza-3,4,8,9-tetraoxa-11-methylbicyclo[4.4.2]dodecane (3b), and 1,6-diaza-3,4,8,9-tetraoxatricyclo[4.4.2.411,12]hexadecane (4), have been prepared by reaction of 1,2-diaminoethane, 1,2-diaminopropane, and trans-1,2-diaminocyclohexane, respectively, with formaldehyde and hydrogen peroxide in aqueous acidic solution. Their structures have been established by X-ray diffraction, and show the bridgehead nitrogen atoms to be predominantly sp2 hybridized. The structures accord with 1H and 13C NMR spectra. Variable temperature NMR studies show that the diperoxide 3a begins to undergo rapid inversion (on the NMR time scale) at about 303 K; up to 370 K the diperoxides 3b and 4 show no conformational change.Key words: cage compounds, formaldehyde, peroxides, amine nitrogen, hybridization.

On the chemistry and high field nuclear magnetic resonance spectroscopy of rapamycin

1980 ◽  
Vol 58 (6) ◽  
pp. 579-590 ◽  
Author(s):  
John A. Findlay ◽  
Lajos Radics
Keyword(s):  
High Field ◽  
Nmr Spectra ◽  
Resonance Spectroscopy ◽  
X Ray ◽  
Conformational Isomers ◽  
H Nmr ◽  
Neutral Compounds ◽  
Complete Assignment ◽  
Hydrolysis Of ◽  
C Nmr

Base catalysed hydrolysis of rapamycin (C51H79NO13) affords six neutral compounds identified by chemical and spectroscopic means as 2a, 3b, 3d, 5, 2,4-dimethylphenol, and L(−)-piperidine-2-carboxylic acid 6, and whose generation has been plausibly rationalized. These findings as well as detailed analyses of 13C nmr and 1H nmr spectra provide independent corroboration of the X-ray derived rapamycin crystal structure 1. Structurally homogeneous in the solid state, rapamycin is found to occur in solutions as a mixture of two conformational isomers (approximately 4:1). Through nearly complete assignment of the high field 1H (400 MHz) and 13C (100.6 MHz) nmr spectra, the isomerism is shown to be associated with trans–cis rotation of an amidic bond within the 31-membered macrolide ring. The predominant form corresponds to the conformer portrayed by X-ray analysis.

Alkylated benzimidazole and benzotriazole derivatives of 3-amino-2-propenoic acid

1989 ◽  
Vol 54 (3) ◽  
pp. 713-724 ◽  
Author(s):  
Viktor Milata ◽  
Dušan Ilavský ◽  
Igor Goljer
Keyword(s):  
Hydrogen Atom ◽  
Nmr Spectra ◽  
Model Compounds ◽  
Methyl Group ◽  
Propenoic Acid ◽  
Independent Synthesis ◽  
Amino Derivatives ◽  
Derivatives Of ◽  
Benzotriazole Derivatives ◽  
C Nmr

The alkylation of unsubstituted 3-(5-benzimidazolyl- and 5-benzotriazolyl)amino derivatives of 2-propenoic acid (I) results in the replacement of hydrogen atom at the nitrogen of YZC=CH-NH- substituent (II-IV). The model compounds with a methyl group in the azole nucleus (V-VII) have been prepared by an independent synthesis. The structure of all products has been confirmed and confronted with their IR, UV, 1H and 13C NMR spectra.

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