Trichlorsilylierung sperriger Dialkylchlorphosphane und Tetraalkyldiphosphane mit Hexachlordisilan / Trichlorosilylation of Bulky Dialkylchlorophosphanes and Tetraalkyldiphosphanes with Hexachlorodisilane

1991 ◽  
Vol 46 (12) ◽  
pp. 1609-1612 ◽  
Author(s):  
Reiner Martens ◽  
Wolf-Walther du Mont ◽  
Lutz Lange
Keyword(s):  
Silver Bromide ◽  
Tert Butyl ◽  
Nmr Data

Chlorodiisopropylphosphane reacts with hexachlorodisilane to give diisopropyl(trichlorosilyl)phosphane which reacts with the educt chlorophosphane to produce tetraisopropyldiphosphane. Tetraisopropyldiphosphane reacts with hexachlorodisilane to provide diisopropyl(trichlorosilyl)phosphane. With di-tert-butylchlorophosphane and tetra-tert-butyldiphosphane, the corresponding reactions leading to di-tert-butyl(trichlorosilyl)phosphane are much slower; while the product does not react further with di-tert-butylchlorophosphane, it does with chlorodiisopropylphosphane. A stable 1:1 complex is formed from di-tert-butyl(trichlorosilylphosphane) with silver bromide. Products are characterized on the basis of analytical and 1H, 13C, 29Si and 31P NMR data.

Tri(Terf-Butyl)plumbyl-phosphanes, Synthesis and Multinuclear Magnetic Resonance

2000 ◽  
Vol 55 (10) ◽  
pp. 939-945 ◽  
Author(s):  
Max Herberhold ◽  
Christian Köhler ◽  
Volker Tröbs ◽  
Bernd Wrackmeyer
Keyword(s):  
Magnetic Resonance ◽  
Phosphorus Atom ◽  
Coupling Constants ◽  
Tert Butyl ◽  
Nmr Data ◽  
Butyl Group ◽  
Tert Butyl Group ◽  
Multinuclear Magnetic Resonance

AbstractThe reaction of tri(tert-butyl)plumbyl-lithium (1) with various phosphorus chlorides was studied. With diphenyl- and amino(phenyl)phosphorus chlorides the formation of hexa(tertbutyl) diplumbane (2) and tetraphenyldiphosphane (3) or the respective 1,2-bis(am ino)-1,2-diphenyl- diphosphanes [e. g. 5: amino = PhCH2(tBu)N] was dominant. The presence of at least one tert-butyl group at the phosphorus atom gave access to tri(tert-butyl)plumbyl-di(tert-butyl) phosphane (4) and to tri(tert-butyl)plumbyl-amino(tert-butyl)phosphanes [amino = tBu(H)N (6), Me(Ph)N (7), PhCH2(Me)N (8), PhCH2(tBu)N (9)] via the reaction of 1 with the corresponding phosphorus chlorides. Side products were again 2 and the corresponding diphosphanes, unidentified compounds, and in two cases, bis(phosphanyl)-di(tert-butyl)plumbanes [phosphanyl = tBu(H)N(tBu)P (10), Me(Ph)N(tBu)P (11)]. Trimethylplumbyl-benzyl(methyl)- amino(tert-butyl)phosphane (12) was prepared for comparison. All compounds were characterized by their 1H , 13C, 15N (9 ),31P and 207Pb NMR data. The coupling constants 1J(207Pb,31P) are large and negative, whereas the coupling constants 1J(207Pb, 13C) are small and can be of either sign. The coupling constants 2J(31P-N-13C) of 6 - 12 indicate a preferred conformation of the substituents at phosphorus and nitrogen

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.

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.

Azaborolyl-Komplexe, 27 / Azaborolyl Complexes, 27

1992 ◽  
Vol 47 (5) ◽  
pp. 635-639 ◽  
Author(s):  
Günter Schmid ◽  
Wolfgang Meyer-Zaika
Keyword(s):  
Mass Spectrometry ◽  
Benzene Solution ◽  
Stable Complex ◽  
Intramolecular Rearrangement ◽  
The Novel ◽  
Intramolecular Coordination ◽  
Tert Butyl ◽  
Nmr Data ◽  
Stereoselective Reactions ◽  
Ab Ring

Alkenyl substituted 1H-1,2-azaborolyl (Ab) complexes are promising candidates for stereoselective reactions, due to the chirality of the AbM moiety and the intramolecular coordination of the alkenyl group to the metal atom. The synthesis of [1-tert-butyl-2-methy1-3-(4-penten- l -y1)-η5-1H-1,2-azaborolyl]-bis(triphenylphosphine)rhodium (3) is achieved by the reaction of AbLi (2) [from AbH (1)] with (Ph3P)3RhCl. In benzene solution one PPh3 ligand of 3 is substituted by the C=C group of the pentenyl substituent. Simultaneously the η5-coordination of the Ab ring changes to an allylic η3-coordination forming 4. Steric reasons seem to be responsible for this intramolecular rearrangement. The shorter 2-propen-1-yl substituent is unable to act in the same way and therefore only forms the stable complex [1-tert-butyl-2-methyl-3-(2-propen- l -yl)-η5-1H-1,2-azaborolyl]-bis(triphenylphosphine)rhodium (7). Mass spectrometry, 1H, 11B and 31P NMR data were used to characterize the novel complexes.

Organoborierung von Alkinylstannanen, VIII [1] Zur Reaktion von Alkinyltrimethylstannanen mit 1-Boracyclopentanen und Methylbis(tert-butyl)boran / Organoboration of Alkynylstannanes, VIII [1] The Reaction of Alkynyltrimethylstannanes with 1-Boracyclopentanes and Methy Ibis (tert-butyl) borane

1978 ◽  
Vol 33 (8) ◽  
pp. 855-861 ◽  
Author(s):  
Axel Schmidt ◽  
Bernd Wrackmeyer
Keyword(s):  
Analogous Reaction ◽  
Tert Butyl ◽  
Nmr Data ◽  
New Compounds ◽  
C Nmr

Abstract 1-Organyl-1-boracyclopentanes react with alkynyltrimethylstannanes to give 1-bora-cyclohexylid(2)enes as the only products. The analogous reaction with methylbis (tert-butyl)borane leads to a nonstatistical distribution of organoboration products. Structure and stereochemistry of the new compounds are discussed on the basis of methanolysis reactions and 1H, 11B and 13C NMR data.

Vom "criss-cross"-Schema abweichende Cycloadditionsreaktionen an das Azin-System [1] Zum Cycloadditionsverhalten von Hexafluoracetonazin gegenüber N.N-Dialkyl-cyanamiden [2] / Cycloaddition Reactions of Azines Violating the "criss-cross" Cycloaddition Scheme [1] Cycloaddition Behaviour of Hexafluoroacetone Azine towards N,N-Dialkyl-cyanamides [2]

1982 ◽  
Vol 37 (3) ◽  
pp. 361-367 ◽  
Author(s):  
Klaus Burger ◽  
Friedrich Hein ◽  
Joachim Firl
Keyword(s):  
Molar Ratio ◽  
Addition Reactions ◽  
Cycloaddition Reactions ◽  
Reaction Conditions ◽  
Tert Butyl ◽  
Nmr Data ◽  
System 1 ◽  
New Compounds ◽  
C Nmr

Abstract Depending upon the molar ratio of the educts and the reaction conditions used, hexa-fluoroacetone azine (1) reacts with N,N-dialkyl-cyanamides (2) to give 3,4,6-triazaocta-2,4,6-trienes (6) and/or 4,4-bis(trifluoromethyl)-1,4-dihydro-1,3,5-triazines (7). Cyclo-addition reactions of 6 with tert-butyl isocyanide and 1-diethylamino(propine) are de-scribed. IR, 1H, 19F, and 13C NMR data of the new compounds are discussed.

Reactivity and NMR Spectroscopic Properties of Tri(tert-butyl)plumbyl-amine

1997 ◽  
Vol 52 (10) ◽  
pp. 1181-1184 ◽  
Author(s):  
Max Herberhold ◽  
Volker Tröbs ◽  
Hong Zhou ◽  
Bernd Wrackmeyer
Keyword(s):  
Magnetic Resonance ◽  
Spectroscopic Properties ◽  
Two Dimensional ◽  
Pyrazole Derivatives ◽  
Coupling Constant ◽  
Tert Butyl ◽  
Magnetic Resonance Data ◽  
Nmr Data ◽  
Resonance Data

Tri(tert-butyl)plumbyl-amine 1 was prepared and studied by one- (1D) and two-dimensional (2D) 1H, 13C, 15N and 207Pb NMR which allowed determination of the coupling signs 1J(207Pb,13C) (> 0), 2J(207Pb,13C) (> 0), 1J(207Pb,15N) (> 0; reduced coupling constant 1K(207Pb,I5N) < 0) and 2J(207Pb-N-1H) (< 0). Transamination of 1 with aniline and pyrazole afforded the corresponding aniline (2) and pyrazole derivatives (3), respectively. N-Lithiation of 1, followed by treatment with Me3SiCl gave the tri(tert-butyl)plumbyl-trimethylsilyl-amine 5. The multinuclear magnetic resonance data of 2, 3 and 5 are presented. Trimethylplumbylphenyl- amine and trimethylplumbyl-tert-butyl(dimethyl)silyl-amine were prepared and their NMR data were measured for comparison.

Trimethylene sulfite conformations: Effects of sterically demanding substituants at C-4,6 on ring geometry as assessed by 1H and 13C nuclear magnetic resonance

1978 ◽  
Vol 56 (15) ◽  
pp. 2019-2024 ◽  
Author(s):  
Gerald W. Buchanan ◽  
Catherine M. E. Cousineau ◽  
Thomas C. Mundell
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Computer Analysis ◽  
Chemical Shifts ◽  
Tert Butyl ◽  
Nmr Data ◽  
Ring Geometry ◽  
13C Nuclear Magnetic Resonance ◽  
Sterically Demanding ◽  
C Nmr

1H and 13C nmr data for eight phenyl, diphenyl- and di-tert-butyl-2-oxo-1,3,2-dioxathianes, substituted at C-4 and/or C-6 are presented. Vicinal couplings obtained from 1H spectra by iterative computer analysis indicate chair geometries for all materials except trans-4,6-disubstituted compounds. 13C chemical shifts are corroborative.

Neue Phosphorchalkogenahalogenide / New Phosphorus Chalcogena Halides

1991 ◽  
Vol 46 (9) ◽  
pp. 1165-1168 ◽  
Author(s):  
Roger Blachnik ◽  
Kerstin Hackmann ◽  
Hans-Peter Baldus
Keyword(s):  
Silver Chloride ◽  
Silver Bromide ◽  
Nmr Data ◽  
Mercury Halides

α-P4Se3Br2 and α-P4Se3CL2 were prepared from α-P4Se3I2 by reaction with silver bromide resp. silver chloride in CS2-solution. Using bismuth or mercury halides it was also possible to obtain β-P4X3Br2 and β-P4X3Cl2 from β-P4X3I2 (X = S, Se). The 31P NMR data of these compounds are given.

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.

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