scholarly journals Photoisomerisierung von trans-1-(3.5-Di-tert-butyl-4-hydroxyplienyl)-2-phenyldiazen / Photoisomerization of trans-1-(3,5-Di-tert-butyl-4-hydroxyphenyl)-2-phenyldiazene

1980 ◽  
Vol 35 (2) ◽  
pp. 233-236 ◽  
Author(s):  
Edgar Hofer
Keyword(s):  
Nmr Spectroscopy ◽  
Title Compound ◽  
Tautomeric Equilibrium ◽  
Tert Butyl ◽  
H Nmr ◽  
Nmr Data ◽  
Trans Isomerization ◽  
Different Temperatures ◽  
Influence Of Solvent

AbstractLight induced isomerizations of the title compound have been studied. The thermal cis-trans isomerization 3→1 occurs via the tautomeric quinonephenylhydrazone (2) as shown by 1H NMR, spectroscopy. The influence of solvent on the thermal cis-trans isomerization is discussed. 1H NMR data of 1, 2 and 3 are given. Values of the tautomeric equilibrium 1⇋2 are determined for various solvents and different temperatures.

Synthesis of metal-free tetraazaisobacteriochlorin and via template condensation of phthalogenes

2020 ◽  
Vol 24 (05n07) ◽  
pp. 878-886
Author(s):  
Semyon V. Dudkin ◽  
Takahiro Kawata ◽  
Svetlana A. Belova ◽  
Yusuke Okada ◽  
Nagao Kobayashi
Keyword(s):  
Mass Spectrometry ◽  
Quantum Chemical ◽  
2D Nmr ◽  
Metal Free ◽  
Tert Butyl ◽  
H Nmr ◽  
Nmr Data ◽  
Template Condensation ◽  
Td Dft ◽  
Low Symmetry

The indium(III) complexes of (4-(tert-butyl)phenyl)-substituted tetraazaisobacteriochlorin (TAiBC) and tetraazachlorin (TAC) were synthesized by direct template condensation of bis(4-(tert-butyl)phenyl)fumaronitrile and tetramethylsuccinonitrile using indium(III) ion as a matrix. The corresponding metal-free tetraazaisobacteriochlorin and tetraazachlorin were obtained by demetallation of their indium(III) complexes. These metal-free complexes were characterized using elemental analysis, mass-spectrometry, 1H and [Formula: see text]C{1H}NMR spectroscopy, UV-vis and MCD spectroscopy as well as DFT and TD-DFT calculations. Due to the low symmetry of the molecules, the NMR data were complex, but could be assigned by collecting 1D- and 2D NMR data and comparing with the results of quantum chemical calculations. From the position of the pyrrole proton signal (6.78 ppm), it was found that the diatropic current of TAiBC is much weaker than that of TAC, and plausibly the weakest among porphyrinoids so far reported. Absorption and MCD spectra were reasonably interpreted using the calculated absorption spectra.

Anwendungen der 2 D-NMR-Spektroskopie in der Organophosphorchemie Beispiel: L-Menthyldichlorphosphan / Applications of the 2D NMR Spectroscopy in the Organophosphorus Chemistry Example: L-Menthyldichlorophosphine

1982 ◽  
Vol 37 (12) ◽  
pp. 1661-1664 ◽  
Author(s):  
Martin Feigel ◽  
Gerhard Hägele ◽  
Axel Hinke ◽  
Gudrun Tossing
Keyword(s):  
Nmr Spectroscopy ◽  
2D Nmr ◽  
2D Nmr Spectroscopy ◽  
H Nmr ◽  
Nmr Parameters ◽  
Nmr Data ◽  
Organophosphorus Chemistry ◽  
C Nmr

2D NMR ist used to determine the 1H NMR parameters of L-Menthyldichlorophosphine. 13C NMR data are given

Meso-rac-Ph(X)P-(CH2)4-P(X)Ph-Liganden in Komplexen des Typs (CO)4M cis(L-L), Untersuchung der Stereoisomerie durch 31 P{ 1 H}-und 13C{1 H}-NMR-Spektroskopie / Meso, rac-Ph(X)P-(CH2)4-P(X)Ph Ligands in Complexes of the Type (CO)4M cis(L-L), Investigation of Stereoisomerism by 31P{1 H} and 13 C{ 1 H} NMR Spectroscopy

1982 ◽  
Vol 37 (7) ◽  
pp. 841-844 ◽  
Author(s):  
Klaus Diemert ◽  
Wilhelm Kuchen ◽  
Jürgen Kutter
Keyword(s):  
Nmr Spectroscopy ◽  
H Nmr ◽  
Nmr Data

Abstract By reaction of M(CO)6 (M = Cr, Mo, W) with the bifunctional aminophosphane Ph(NEt2)P-(CH2)4-P(NEt2)Ph (L-L) octahedral complexes (CO)4M cis(L-L) are obtained. While it is shown by 31P{1H} NMR spectroscopy, that these complexes contain meso-and rac-(L-L) to a different extent, there is evidence from 13C{1H} NMR data obtained for the Mo complex, that the rac-ligand always prevails. As racemisation is observed when the Mo complex reacts with HBr to give (CO)4Mo-cis[Ph(Br)P-(CH2)4-P(Br)Ph] an SN1-mechanism is suggested for this reaction.

In situ preparation of cyclopropanones with the bicyclo[3.1.0]hexan-6-one skeleton (substituted examples of the Loftfield intermediate). Confirmation of a very facile intramolecular alkyl cyclopropanone – dienol rearrangement

1996 ◽  
Vol 74 (1) ◽  
pp. 79-87 ◽  
Author(s):  
T. S. Sorensen ◽  
F. Sun
Keyword(s):  
Nmr Spectroscopy ◽  
Sigmatropic Rearrangement ◽  
Unsaturated Ketone ◽  
Tert Butyl ◽  
H Nmr ◽  
In Situ Preparation ◽  
Rate Determining Step ◽  
Enol Formation ◽  
C Nmr

Four substituted bicyclo[3.1.0]hexan-6-ones (cyclopropanones) were prepared in situ, starting from the corresponding 2,6-dibromocyclohexanone and reductively removing the bromine atoms with the organometallic salt PPN+Cr(CO)4NO− The reaction is essentially instantaneous at −78 or−100 °C, and can be conveniently carried out in an NMR tube for easy characterization of the products by low-temperature 1H and 13C NMR spectroscopy. The1,5-di-tert-butyl and 1-tert-butyl analogs were thermally stable to ca. 0 °C, but the 1-tert-butyl-5-methyl and 1-tert-butyl-5-ethyl derivatives were extremely labile, rearranging at ca. −80 °C into a cross-conjugated enol, where the methyl (or ethyl) substituent was converted into an exomethylene group. These enols were also characterized as in situ species using 1H and 13C NMR spectroscopy, and by allowing the enol → α,β-unsaturated ketone rearrangement to take place at about 25 °C. The mechanism of the enol formation was investigated using a 1 -tert-butyl-5-CD3 analog, and the kH/kD ratio for enol formation was determined to be 6 ± 2. From this, the rate-determining step in the enol formation was postulated as a C-H → H-O transfer of a hydrogen atom in a cyclohexyl oxyallyl intermediate. The 1,5-di-tert-butylbicyclohexanone shows dynamic 1H NMR line broadening, the origin of which is also proposed to involve a cyclohexyl oxyallyl intermediate. Key words: cyclopropanone, oxyallyl, bicyclo[3.1.0]hexan-6-one, dienol, sigmatropic rearrangement.

Preparation and electron transfer-induced cis-trans isomerization reactions of 1-(5-nitro-2-furyl)-, 1-(5-nitro-2-thienyl)-, and 1-(4-nitrophenyl)-2-R ethylenes

1989 ◽  
Vol 54 (6) ◽  
pp. 1675-1682 ◽  
Author(s):  
Josef Prousek ◽  
Viktor Hayden
Keyword(s):  
Electron Transfer ◽  
Nmr Spectroscopy ◽  
Electron Donor ◽  
Radical Anion ◽  
Wittig Reaction ◽  
H Nmr ◽  
Trans Isomerization ◽  
Ct Complex

Mixtures of E- and Z-isomers of 1,2-bis(5-nitro-2-furyl)ethylene (I), 1-(5-nitro-2-furyl)-2-(4-nitrophenyl)ethylene (II), 1,2-bis(4-nitrophenyl)ethylene (III), 1-(5-methoxycarbonyl-2-furyl)-2-(4-nitrophenyl)ethylene (IV), 1-(5-methoxycarbonyl-2-furyl)-2-(5-nitro-2-furyl)ethylene (V) and 1-(5-methoxycarbonyl-2-furyl)-2-(5-nitro-2-thienyl)ethylene (VI) were prepared by the Wittig reaction. These derivatives were isomerized by electron transfer-induced reactions via the radical anion in the CT-complex using aniline as electron donor at 25 °C in the light or at 80 °C in the dark. The starting as well as the final E:Z ratio was determined by 1H NMR spectroscopy. In all cases only the cis → trans isomerization was observed.

Application of NMR Spectroscopy to the Study of Piperidine Derivatives. Part III: Molecular Dynamics Study of N-Benzyl-4-[N-Benzyloxyacetyl)-(2-Fluorophenyl)]Amino-3-Methyl Piperidine

1993 ◽  
Vol 47 (3) ◽  
pp. 357-359 ◽  
Author(s):  
A. L. Cholli ◽  
M. L. Lau
Keyword(s):  
Molecular Dynamics ◽  
Nmr Spectroscopy ◽  
High Resolution ◽  
Detailed Analysis ◽  
Room Temperature ◽  
Variable Temperature ◽  
Proton Nmr ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Nmr Data

High-resolution 1H NMR has been used to study the molecular dynamics of the piperidine derivative. Detailed analysis of variable temperature NMR data allowed the identification of the origin of two sets of methyl resonance peaks with unequal intensities in the room-temperature proton NMR spectrum of the compound.

Unsymmetrisch substituierte Phosphinoschwefeldiimide – NMR-Untersuchungen über die Konfiguration in Lösung/ Unsymmetrically Substituted Phosphino Sulfur Diimides – NMR Studies on the Configuration in Solution

1988 ◽  
Vol 43 (8) ◽  
pp. 985-992 ◽  
Author(s):  
Max Herberhold ◽  
Stefan M. Frank ◽  
Bernd Wrackmeyer
Keyword(s):  
Nmr Spectroscopy ◽  
Low Temperatures ◽  
Room Temperature ◽  
Coupling Constants ◽  
Nmr Studies ◽  
Tert Butyl ◽  
Nmr Data

AbstractThe phosphino-substituted sulfur diimides S(N-PtBu2)2 (1), tBu;P(NSN)PRR′ (R = R′ - phenyl (2a), cyclohexyl (2b), isopropyl (2c), ethyl (2d); R = phenyl, R′ = tert-butyl (2e)) and tBu2P(NSN)tBu (3) were studied in solution by 1H, 13C and 31P NMR spectroscopy**. The coupling constants 4J(31P31P) of the compounds containing different phosphino groups, 2a-e, depend both on the nature of the solvent and the temperature. The NMR results are interpreted in accord with a rapid Z/E⇄ E/Z interconversion at room temperature and the predominance of a single configurational isomer at low temperatures. There is no indication for the presence of the “symmetrical” configurations, Z/Z or E/E respectively, in solution in appreciable amounts. 15N NMR data are also reported for a series of sulfur diimides.

Optimized synthesis of a tert-butyl-phenyl-substituted tetrapyridophenazine ligand and its Ru(ii) complexes and determination of dimerization behaviour of the complexes through supramolecular “Fingerhakel”

2015 ◽  
Vol 44 (19) ◽  
pp. 8889-8905 ◽  
Author(s):  
K. Ritter ◽  
C. Pehlken ◽  
D. Sorsche ◽  
S. Rau
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Nmr Spectroscopy ◽  
Ruthenium Complex ◽  
Dimerization Constant ◽  
Π Interactions ◽  
Tert Butyl ◽  
H Nmr

A high dimerization constant of a ruthenium complex is observed with the aid of 1H-NMR spectroscopy. The solid state molecular structure indicates that multiple π-interactions are the reason for strong dimerization.

Preparation and properties of rhodium(I) and iridium(I) diolefin complexes of heterodifunctional phosphorus–imine chelating ligands and a related iminophosphine. 103Rh NMR parameters of the rhodium complexes obtained via indirect two-dimensional 31P, 103Rh{1H} NMR spectroscopy

1995 ◽  
Vol 73 (5) ◽  
pp. 635-642 ◽  
Author(s):  
David J. Law ◽  
Glen Bigam ◽  
Ronald G. Cavell
Keyword(s):  
Nmr Spectroscopy ◽  
Chemical Shift ◽  
1H Nmr Spectroscopy ◽  
Rhodium Complexes ◽  
Chelating Ligands ◽  
Two Dimensional ◽  
H Nmr ◽  
Nmr Parameters ◽  
Nmr Data

Treatment of [M(cod)Cl]2 (M = Rh, Ir) with iminophosphoranophosphine ligands of the type Ph2PQP(Ph2)=NSiMe3 (Q = CH2, CH2CH2, 1,2-C6H4) afforded the new metallacycles [Formula: see text] through elimination of Me3SiCl, ultimately "anchoring" the ligand to the metal through a metal–nitrogen σ bond. The phosphine functionality completes the chelate. Cationic complexes of the type [M(cod)L2]+PF6− (M = Rh or Ir; L2 = Ph2PQPPh2NR where Q = CH2, CH(CH3), 1,2-C6H4, and R = p-C6F4CN, C6H2F(NO2)2, and C6H3(NO2)2 or L = Ph2PN=C(H)Ph) were readily prepared by treating [M(cod)Cl]2 with L2 and KPF6. The detection and chemical shift determination of the insensitive 103Rh nucleus was easily accomplished via 31P detected indirect two-dimensional 31P, 103Rh{1H} NMR spectroscopy. The 103Rh, 1H, and 31P NMR data are discussed. Keywords: rhodium, iridium, phosphoranimine, iminophosphine, Rh NMR.

Das JerJ-Butyl-Kation in Lösungen von Aluminiumbromid in Mono-, Di- und Tribrommethan / The terf-Butyl-Cation in Solutions of Aluminium Bromide in Mono-, Di- and Tribromomethane

1979 ◽  
Vol 34 (7) ◽  
pp. 891-895 ◽  
Author(s):  
Peter Brüggeller ◽  
Erwin Mayer
Keyword(s):  
Nmr Spectroscopy ◽  
Chemical Shift ◽  
Dilute Solutions ◽  
Concentrated Solutions ◽  
Nmr Chemical Shift ◽  
Tert Butyl ◽  
H Nmr ◽  
Saturated Solutions

Abstract The tert-butyl cation is formed from tert-BuBr in concentrated solutions of AlBr3 in CH3Br, CH2Br2 and CHBr3 and was characterized by 1H NMR spectroscopy. Stabilization of the cation depends strongly on the AlBr3 concentration: in CH3Br saturated with AlBr3, C(CH3)3+ is formed in 80% yield; in dilute solutions of AlBr3 in CH3Br the usual de-composition occurs. In saturated solutions of AlBr3 in CH2Br2 and CHBr3 the C(CH3)3+ yield is 60 and 40%, resp. The concentration of the cation decreases in all three solvents by 20 to 30% within 10 days at room temp. In concentrated solutions of AlBr3 in CH3Br the formation of the methyl-tert-butylbromonium ion as a rapidly equilibrating species is suggested. The 1H NMR chemical shift of C(CHs)3+ in the presence of AlBr3 (δ = 5.19 in CHsBr, δ = 5.23 in CH2Br2, δ = 5.35 in CHBr3) indicates strong deshielding in comparison with shifts in SbF5 and SbF5/SO2

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