Coordination compounds of indium. Part 44. The oxidation of indium(I) halides by tetrahalogeno-ortho-quinones

1988 ◽  
Vol 66 (11) ◽  
pp. 2935-2940 ◽  
Author(s):  
Theodore A. Annan ◽  
Dennis G. Tuck
Keyword(s):  
Coordination Compounds ◽  
Nmr Spectra ◽  
Dynamic Behaviour ◽  
Addition Product ◽  
Donor Ligands ◽  
Chelate Complexes ◽  
H Nmr ◽  
Anionic Complexes ◽  
Derivatives Of ◽  
C Nmr

The reaction of indium(I) halides (InX; X = Cl, Br, I) with tetrahalogeno-ortho-quinones (Y4C6O2; Y = Cl, Br) gives the oxidative addition product Y4C6O2InX, These compounds have been isolated as adducts with neutral bidentate donor ligands (N,N,N′,N′-tetramethylethanediamine (tmen), 1,10-phenanthroline) or as salts of the anionic complexes [Y4C6O2InCl2]− or [Y4C6O2In(Cl)Br]−. The number of coordinated tmen molecules, and hence the structure, depends on the method of preparation. Infrared, 1H NMR, and 13C NMR spectroscopy all confirm that these products are all substituted-catecholato derivatives of indium(III), and the structure of these various neutral or anionic derivatives is discussed. The temperature dependence of the 13C NMR spectra shows that the dynamic behaviour of these compounds (in d6-dmso) is similar to that observed in previous studies of indium(III) chelate complexes.

β-Hydroxydithiozimtsäurederivate als Liganden. Synthese und Charakterisierung neuartiger 1,1-Ethendithiolato- und O,S-Chelatkomplexe / Derivatives of β -Hydroxydithiocinnamic Acids as Ligands. Syntheses and Characterisation of Novel 1,1-Ethenedithiolato and O,S-Chelate Complexes

2007 ◽  
Vol 62 (3) ◽  
pp. 475-482 ◽  
Author(s):  
Karsten Schubert ◽  
Helmar Görls ◽  
Wolfgang Weigand
Keyword(s):  
Bidentate Ligand ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
H Nmr ◽  
Hexyl Ester ◽  
Elemental Analyses ◽  
Derivatives Of ◽  
C Nmr

Starting from 4-bromoacetophenone 1, the 4-bromo-β -hydroxydithiocinnamic acid 2 and the 4-bromo-β -hydroxydithiocinnamic acid hexyl ester 3 were prepared using carbon disulfide and potassium-tert-butylate as a base. Acting as a ligand, the acid gives 1,1-ethenedithiolato complexes with (Ph3P)2Pt(II) (4a), (Et3P)2Pt(II) (4b), dppePt(II) (4c), (Ph3P)2Pd(II) (4d), dppePd(II) (4e), and dppeNi(II) (4f). In contrast to the acid, the deprotonated ester 3 forms a monoanionic bidentate ligand. [O,S] Complexes of Pt(II) (5a), Pd(II) (5b) and Ni(II) (5c) were obtained. All complexes have been fully characterised using 1H NMR, 13C NMR and 31P NMR spectroscopy, mass spectrometry, infrared spectroscopy and elemental analyses. The molecular structures of the complexes 4b and 5a - 5c were determined by X-ray diffraction analyses.

Study of Amino-Imino Tautomerism in Derivatives of 2-, 4- and 6-Aminonicotinic Acid

1994 ◽  
Vol 59 (9) ◽  
pp. 2057-2068 ◽  
Author(s):  
Svatava Smrčková ◽  
Kristina Juricová ◽  
Viktor Prutianov
Keyword(s):  
Ir Spectroscopy ◽  
Hydrogen Bonds ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Amino Derivative ◽  
Ionic Character ◽  
H Nmr ◽  
Amino Derivatives ◽  
Derivatives Of ◽  
C Nmr

13C NMR spectra of p-nitrobenzoyl 2-, 4-, and 6-aminopyridine-3-carboxylates, their hydrochlorides, trifluoroacetates and 1-benzyl derivatives were studied. As found from the chemical shifts of pyridine carbon atoms C-2, C-4 and C-6, the free bases exist in the amino form whereas hydrochlorides and 1-substituted pyridinium derivatives in the imino form. Trifluoroacetates of the 2- and 6-amino derivatives have structure similar to that of amidiniumcarboxylates (parallel hydrogen bonds and partially ionic character) whereas trifluoroacetate of the 4-amino derivative is structurally close to the corresponding hydrochloride. The found structures were confirmed by 1H NMR and IR spectroscopy.

Conformational structure of ethylene glycol dibenzoate. Vibrational and NMR spectra

1981 ◽  
Vol 46 (8) ◽  
pp. 1913-1929 ◽  
Author(s):  
Bohdan Schneider ◽  
Pavel Sedláček ◽  
Jan Štokr ◽  
Danica Doskočilová ◽  
Jan Lövy
Keyword(s):  
Ethylene Glycol ◽  
Vibrational Spectra ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
Conformational Structure ◽  
Infrared And Raman Spectra ◽  
H Nmr ◽  
Liquid States ◽  
Crystalline Forms ◽  
C Nmr

It was found that three crystalline forms of ethylene glycol dibenzoate can be prepared. Infrared and Raman spectra of these three forms, as well as of the glassy and liquid states, were measured. From 3JHH coupling constants obtained by analysis of the 13C satellite band of the -CH2- group in 1H NMR spectra, and from the 3JCH coupling constants of the -CO.O.CH2- fragment obtained by analysis of the carbonyl band in 13C NMR spectra it was found that in the liquid state the -CH2-CH2- group exists predominantly in the gauche conformational structure, and the bonds C-O-C-C assume predominantly a trans orientation. The results of the analysis of NMR and vibrational spectra were used for the structural interpretation of conformationally sensitive bands in vibrational spectra of ethylene glycol dibenzoate.

E-Homolupane Derivatives Substituted in Position 17 and 22a. 1H NMR, 13C NMR and IR Spectra

1995 ◽  
Vol 60 (4) ◽  
pp. 619-635 ◽  
Author(s):  
Václav Křeček ◽  
Stanislav Hilgard ◽  
Miloš Buděšínský ◽  
Alois Vystrčil
Keyword(s):  
Nmr Spectra ◽  
2D Nmr ◽  
Coupling Constants ◽  
Side Chain ◽  
Oxidation Reactions ◽  
H Nmr ◽  
Complete Assignment ◽  
Nmr Techniques ◽  
Intramolecular Association ◽  
C Nmr

A series of derivatives with various oxygen functionalities in positions 17,22a or 19,20 was prepared from diene I and olefin XVI by addition and oxidation reactions. The structure of the obtained compounds was confirmed by 1H NMR, 13C NMR and IR spectroscopy. The kind of intramolecular association of the 17α-hydroxy group was studied in connection with modification of the side chain and substitution in position 22a. Complete assignment of the hydrogen signals and most of the coupling constants was accomplished using a combination of 1D and 2D NMR techniques. The 1H and 13C NMR spectra are discussed.

Preparation of 2,3-Dideoxy-2,3-epimino and 3,4-Dideoxy-3,4-epimino Derivatives of 1,6-Anhydro-β-D-hexopyranoses by Mitsunobu Reaction

1998 ◽  
Vol 63 (6) ◽  
pp. 813-825 ◽  
Author(s):  
Jiří Kroutil ◽  
Tomáš Trnka ◽  
Miloš Buděšínský ◽  
Miloslav Černý
Keyword(s):  
Nmr Spectra ◽  
Mitsunobu Reaction ◽  
Derivatives Of ◽  
C Nmr

A series of new 2-, 3- and 4-benzylamino-2-, 3- and 4-deoxy derivatives of 1,6-anhydro-β-D-hexopyranoses were prepared from 1,6:2,3- and 1,6:3,4-dianhydro-β-D-hexopyranoses by treatment with benzylamine and converted into 2,3-(N-benzylepimino)-2,3-dideoxy- and 3,4-(N-benzylepimino)-3,4-dideoxy-β-D-hexopyranoses of the D-allo, D-galacto and D-talo configuration by Mitsunobu reaction. The structures of benzylamino and benzylimino derivatives were confirmed by 1H and 13C NMR spectra.

scholarly journals A Natural Triglyceride from the Methanol Root Extract of Cyphostemma Adenocaule (Steud. Ex A. Rich.) Wild & R.B.Drumm

2020 ◽  
Author(s):  
Abdulbasit Haliru Yakubu ◽  
Iliya Ibrahim ◽  
Abdulqadir bukar bababe ◽  
Hassan Yesufu ◽  
mohammed Garba Tom
Keyword(s):  
Mobile Phase ◽  
Nmr Spectra ◽  
Radical Scavenging Activity ◽  
Radical Scavenging ◽  
Solvent System ◽  
Root Extract ◽  
H Nmr ◽  
Signal Peak ◽  
Methylene Group ◽  
C Nmr

<p><i>Cyphostemma adenocaule </i>(Steud. ex A. Rich.) is one of the specie plant that belongs to the family vitacea. In this study, Trilinolein was isolated and characterized from the methanol root extract of the plant. Column chromatography over silica gel granules as the stationary phase and eluted with a mobile phase mixture of n-Hex-EtA; EtA-CHCL3 and CHCL<sub>3</sub>-MeOH with gradient increasing polarity, followed by a second column using saphadex-LH20 and 100% MeOH as stationary and mobile phase vehicle respectively. TLC was developed with EtA 15: CHCL3<sub> </sub>8: MeOH 4: H<sub>2</sub>O 1 as solvent system; sprayed with 10% H<sub>2</sub>SO<sub>4 </sub>,Vanillin-sulphuric acid, and/ or Polyethylene glycol PEG and heat for spot detection and confirmation of bioactive principles. Compound CA1 was obtained and purified with CHCL3 to give a yellow semi-solid compound (0.23g). The <sup>1</sup>H-NMR spectra showed 9 different signals; a signal peak of a glycerol (-C<b>H<sub>2</sub></b>OCOR-) moiety on the first α-C chain and on the third αʹ-C at 4.143-4.187ppm and 4.296-4.325ppm respectively, while that of a β glycerol (-C<b>H</b>COR-) at 5.286ppm. Signals of an allylic methylene group at 2.023-2.035ppm, Olefenic hydrogen group at signal peak of 5.362ppm and a diallylic methylene group at signal 2.790ppm were also observed. In the <sup>13</sup>C NMR spectra of compound CA1, 57 carbon atoms where observed, multiple signals overlapping at a range of 14.13-34.21ppm corresponding to the aliphatic CH3 (<b>C18</b>), CH2 (<b>C2, C3, C4, C5, C6, C7, C15, C16, and C17</b>) and allylic (<b>C8, C14</b>) carbon atoms. Signals at 127.90-130.24ppm were assigned to the olefienic C atoms (<b>C9, C10, C12</b>, and <b>C13</b>) while signal of 172.87ppm and 173.32ppm were assigned to the carbonyl (<b>C</b>=O) carbon atoms (<b>C1 </b>and<b> C2</b>) respectively (Table 2). </p> <p>Analysis with DEPT-135, H-H COSY, HMBC and HSQC assignments of CA1 augments assignment of signals made for CA1 from <sup>1</sup>H-NMR and <sup>13</sup>C-NMR and corresponded to that of Trilinolein <u>(<a href="https://pubchem.ncbi.nlm.nih.gov/#query=C57H98O6">C<sub>57</sub>H<sub>98</sub>O<sub>6</sub></a>, </u>MW 879.4 g/mol). The isolated compound was positive for the acrolein test for triglycerides; fat & oil and had an IC<sub>50</sub> of 46.08µg/ml radical scavenging activity.</p>

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.

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.

Direct observation of low spin – high spin electronic ground states and cross-over exchange in manganocene derivatives, (η5-C5H4R)2Mn, R = H, CH3, C2H5 by paramagnetic nuclear magnetic resonance

1986 ◽  
Vol 64 (1) ◽  
pp. 71-75 ◽  
Author(s):  
Daniel Cozak ◽  
François Gauvin ◽  
Jacques Demers
Keyword(s):  
Nmr Spectra ◽  
Spin Exchange ◽  
Exchange Process ◽  
Paramagnetic Species ◽  
Temperature Range ◽  
H Nmr ◽  
Low Field ◽  
Spin Electronic ◽  
Electronic Ground ◽  
C Nmr

The paramagnetic 1H nmr spectra for manganocene (1) and 1.1′-dimethylmanganocene (2), and the 13C nmr spectra for 1,1′-diethylmanganocene (3) have been recorded in toluene solvent over a −90 to 90 °C temperature range. 1 shows a low field and a high field ring proton resonance in its spectrum near −59 °C. At higher temperatures the low field resonance is prevalent and becomes gradually averaged due to a fast spin exchange process that dominates the spectrum at 90 °C. For the ring substituted derivatives 2 and 3, resonances due to only one paramagnetic species were detected in the low temperature range. Above ambient temperature a new spectrum due to rapid spin exchange averaging is observed for these complexes. Results are readily interpreted in terms of ground state molecular cross-over exchanges between the 2E2g, 6A1g, and 2A1g spin states of the complexes.

Photoreaktionen von Dekacarbonyldirhenium mit Allen und unverzweigten Allenderivaten / Photoreactions of Decacarbonyldirhenium with Allene and Unbranched Derivatives of Allene

1995 ◽  
Vol 50 (4) ◽  
pp. 649-660 ◽  
Author(s):  
Cornelius G. Kreiter ◽  
Wolfgang Michels ◽  
Gerhard Heeb
Keyword(s):  
Nmr Spectra ◽  
Crystal And Molecular Structure ◽  
Reaction Products ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Oxidative Rearrangement ◽  
Dirhenium Complexes ◽  
Derivatives Of ◽  
By Products

Decacarbonyldirhenium (1) reacts upon UV irradiation with allene (2), 1,2-butadiene (3) and 2,3-pentadiene (4) preferentially by CO substitution and oxidative rearrangement to the corresponding enneacarbonyl-μ-η1:3-endiyl-dirhenium complexes 5, 9, and 15 and to the octacarbonyl-μ-η2:2-allene-dirhenium complexes 6, the stereoisomers 10, 11, and 16. At elevated temperature 5, 9, and 15 loose CO and yield by a reductive rearrangement also the complexes 6, 10, 11, and 16. In addition to these main products, depending upon the allene derivative used, various by-products are obtained.By-products of the reaction o f 1 with 2 are octacarbonyl-μ-η3:3-(2,3-dimethylene-buta-1,4- diyl)dirhenium (7) and μ-η2:2-allene-hexacarbonyl-μ-η1:3-1-propene-1,3-diyl-dirheniurn (8). The photo reaction of 1 with 3 yields, in addition to 9-11, tetracarbonyl-η3-(E-5-ethylidene- 4-methyl-2-cyclopenten-1-yl)rhenium (12) and tetracarbonyl-η3-(Z-5-ethyliden-4- methyl-2-cyclopenten-1-yl)rhenium (13) as a mixture of isomers. 1 and 4 form the by-products tetracarbonyl-η3-(EZ-3-penten-2-yl)rhenium (17), tetracarbonyl-η3-(EE-3-penten-2-yl)rhenium (18) and heptacarbonyl-μ-η1:2:1:2-(4,5-dimethyl-2,6-octadiene-3,6-diyl)dirhenium (19) with an unusually bridging and chelating ligand. The constitutions of the reaction products have been concluded from the IR and 1H NMR spectra. For 19 the crystal and molecular structure has been determined by X-ray diffraction analysis.

Sign in / Sign up

Export Citation Format

Share Document