(9H-Fluoren-9-ylidene)fluoromethyllithium, a Stabilized Fluoroalkenyl Carbanion. Preparation, Reactions, 13C and 19F NMR Spectra

2001 ◽  
Vol 66 (10) ◽  
pp. 1508-1520 ◽  
Author(s):  
Jaroslav Kvíčala ◽  
Andrew Pelter
Keyword(s):  
Nmr Spectroscopy ◽  
Low Temperature ◽  
Methyl Iodide ◽  
Nmr Spectra ◽  
19F Nmr ◽  
19F Nmr Spectra ◽  
13C And 19F Nmr ◽  
C Nmr

(9H-Fluoren-9-ylidene)fluoromethyllithium (1) was prepared by a low-temperature transmetallation of bromo(9H-fluoren-9-ylidene)fluoromethane (2). Whereas the synthesis of unlabeled bromofluoroalkene 2a was based on Wittig-Horner reaction of fluorenone (3) with ethyl (diethoxyphosphoryl)fluoroacetate (4), (1-13C)-labeled compound 2b was obtained via an addition of labeled lithium 1-ethoxy-2-fluoro(2-13C)ethen-1-olate (5) to ketone 3. Fluoroethenyllithium 1 was found by a low-temperature 19F NMR spectroscopy to be stable up to -40 °C; it was reacted with the series of electrophiles, e.g. benzaldehyde (6), methyl iodide (7) or chloro(trimethyl)silane (8). 13C NMR experiments with (1-13C)-labeled 1a proved that fluorocarbenoid 1 is probably monomeric in THF solution in analogy to other halocarbenoids.

13C and 19F NMR Spectra of substituted ethyl α-fluorocinnamates. Application of the DSP-NLR equation

Tetrahedron ◽  
1990 ◽  
Vol 46 (2) ◽  
pp. 335-340 ◽  
Author(s):  
Charles N. Robinson ◽  
Gregory E. Stablein ◽  
Carl D. Slater
Keyword(s):  
Nmr Spectra ◽  
19F Nmr ◽  
19F Nmr Spectra ◽  
13C And 19F Nmr

scholarly journals Selektive Metallierung von BicycIo[3.2.1]octa-2,6-dien, II Distannylierte Derivate und stannylierte tricyclische Sekundärprodukte / Selective Metalation of Bicyclo[3.2.1]octa-2,6-diene, II Distannylated Derivatives and Stannylated Tricyclic Secondary Products

1988 ◽  
Vol 43 (11) ◽  
pp. 1405-1415 ◽  
Author(s):  
N. Hertkorn ◽  
F. H. Köhler
Keyword(s):  
Nmr Spectroscopy ◽  
Low Temperature ◽  
Nmr Spectra ◽  
Considerable Change ◽  
Coupling Constants ◽  
Secondary Products ◽  
Starting Compound ◽  
Derivatives Of ◽  
C Nmr ◽  
Dibromo Derivative

Abstract Distannylated bicyclo[3.2.1]octa-2,6-diene (1) with (CH3)3 Sn groups in positions exo-4 and 7 (7a), endo-4 and 7 (7b), exo-4 and 6 (7c), and probably exo-4 and endo-4 (7d) are obtained when 1 is treated first with an excess of n-BuLi/t-BuOK in alkane and then with (CH3)3 SnCl. Byproducts are monostannylated derivatives of 1 and l,4-bis(trimethylstannyl)but-2-ene (3). The formation of 7a/b/c is best understood when the two possible bicyclo[3.2.1]octa-2,6-dienyl dianions are generated as intermediates. 3,exo-4-Bis(trimethylstannyl)bicyclo[3.2.1]octa-2,6-diene (7e) is ob-tained from the corresponding dibromo derivative of 1 and (CH3)3SnLi with 3-bromo-exo-4-trimethylstannylbicyclo[3.2.1]octa-2,6-diene (9) as an intermediate. The bicyclic stannyl com-pounds are susceptible to a 1,5-homopentadienyl shift of a (CH3)3Sn group at relatively low temperature when the starting compound has the stannyl group in position 4 of 1 and when positions 6 or 7 are unsubstituted. Tricyclo[3.2.1.02.7]oct-3-enes with (CH3)3Sn groups in positions exo-6 (5a), endo-6 (5b), 3 and exo-6 (10a), and 3 and endo-6 (10b) are thus obtained. On further heating, 10b gives l-trimethylstannyl-3-vinylbenzene (11). All compounds have been studied systematically by NMR spectroscopy including δ(119Sn), δ(13C), δ(1H), 4/5J(119/117Sn-119Sn), nJ(119/117Sn-13C) , nJ(119/117Sn-1H), 1J(13C-1H ) , and nJ(1H-1H ). Among all nuclei, 119Sn gives the most simple spectra. From the 13C NMR spectra a series of useful increments of (CH3)3Sn groups emerges. The most interesting coupling constants are 5J(119/117Sn-119Sn), for which a considerable change with the dihedral angle is established, and nJ(119/117Sn-13C). For n = 3 and 4 the latter are especially useful because their angular dependence leads to unambiguous signal assignments.

195Pt- und 19F-NMR-Spektren der Fluoro-Chloro-Platinate(IV), [PtFnCl6-n]2-, n = 0-6 / 195Pt and 19F NMR Spectra of the Fluoro-Chloro-Platinates(IV), [PtFnCl6-n]2-, n = 0-6

1993 ◽  
Vol 48 (9) ◽  
pp. 1169-1174 ◽  
Author(s):  
E. Parzich ◽  
G. Peters ◽  
W. Preetz
Keyword(s):  
Nmr Spectroscopy ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
19F Nmr ◽  
Complex Ions ◽  
19F Nmr Spectra ◽  
Trans Influence ◽  
Wide Range ◽  
A Minor ◽  
Cl Atom

The 10 complex ions of the system [PtFnCl6-n]2-, n = 0—6, including the three pairs of stereoisomers for n = 2, 3, 4 have been characterized by 195Pt and 19F NMR spectroscopy in CD2Cl2 solution. A wide range from 4731 ([PtCl6]2-) to 11816 ppm ([PtF6]2-) is covered by the clearly separated 195Pt resonances. The chemical shift δ(195Pt) depends nearly linearly on the sum of the electronegativities of the ligands. In accordance with increasing deshielding of the 195Pt nucleus by increasing coordination with F ligands an averaged major downfield shift of 1181 ppm per substitution of Cl by F is observed, while a minor averaged value of 354 ppm downfield is found for the trans/mer isomers in comparison to the related cis/fac isomers. Coupling with 19F results in characteristic 195Pt multiplets, with 1J(PtF) coupling constants for symmetric F—Pt—F axes of averaged 1890 Hz about 31% larger than 1J(PtF•) for asymmetric F•—Pt—Cl′ axes with averaged 1296 Hz. The data reflect the trans influence of the ligands. Highly resolved and expanded 195Pt spectra reveal clearly separated isotopomer signals with intensities according to the expected statistical ratios given by the natural abundance of 35Cl and 37Cl. For [Pt35Cln37Cl6-n]2- five distinct signals related to n = 6-2 with 0,18 ppm highfield shift per 37Cl atom have been reliably assigned. Resolved isotopomer peaks have also been observed for mer-[PtF335Cl3]2-/mer-[PtF335Cl237Cl]2- with 0,21 ppm and for [PtF535Cl]2/[PtF537Cl]2- with 0,32 ppm highfield shift per 37Cl atom, respectively. The 19F resonances of symmetric axes appear at higher field, in the range from —357 to —382 ppm, than those of asymmetric axes, from —266 to —287 ppm. Under high resolution compounds with inequivalent F nuclei show multiplets originating from homonuclear 2J(FF•) couplings of about 40 Hz.

19F NMR spectra of 1,2-dihaloperfluoropropanes

1972 ◽  
Vol 6 (2) ◽  
pp. 200-208 ◽  
Author(s):  
A De Marco ◽  
G Gatti
Keyword(s):  
Nmr Spectra ◽  
19F Nmr ◽  
19F Nmr Spectra

Automated analysis and simulation of 19F-NMR-spectra

1985 ◽  
Vol 29 (1-2) ◽  
pp. 191
Author(s):  
Gerhard Hägele ◽  
Winfried Boenigk ◽  
Michael Engelhardt
Keyword(s):  
Nmr Spectra ◽  
Automated Analysis ◽  
19F Nmr ◽  
19F Nmr Spectra

Méthylhalogénocyclopropanation des éthoxy-alcènes diversement alkylés. Identification stéréochimique des adduits et étude de la stéréosélectivité

1982 ◽  
Vol 60 (15) ◽  
pp. 1933-1941 ◽  
Author(s):  
Roger Barlet ◽  
Raymond Le Goaller ◽  
Claude Gey
Keyword(s):  
Nmr Spectroscopy ◽  
Methyl Iodide ◽  
Intermediate Stage ◽  
Complex Salt ◽  
Carbene Complex ◽  
Iodide Ion ◽  
Halogen Exchange ◽  
C Nmr

Ethoxy-alkenes act as excellent carbene acceptors in the methylmonohalogenocyclopropanation reaction mediated by 1,1-dichloroethane and iodide-ion free methyl iodide. As well as chlorinated adducts, a large proportion of brominated products are obtained by means of halogen exchange at the carbene complex – salt intermediate stage. Adduct stereochemistry is determined by 1H and 13C nmr spectroscopy. The syn-stereoselectivity of the reaction is discussed in electronic and steric terms. [Journal Translation]

Structural studies of digitoxin and related cardenolides by two-dimensional NMR

1990 ◽  
Vol 68 (2) ◽  
pp. 272-277 ◽  
Author(s):  
Torbjörn Drakenberg ◽  
Peter Brodelius ◽  
Deane D. McIntyre ◽  
Hans J Vogel
Keyword(s):  
Nmr Spectroscopy ◽  
Nmr Spectra ◽  
Chair Conformation ◽  
Coupling Constants ◽  
Two Dimensional ◽  
Structural Studies ◽  
Solution Conformation ◽  
Phase Sensitive ◽  
Multiple Relay ◽  
C Nmr

The 1H and 13C NMR spectra of the cardenolides digitoxigenin, digoxigenin, digitoxin, and mono- and bis-digitoxigenin digitoxosides have been completely assigned by two-dimensional NMR spectroscopy. The techniques used include phase-sensitive COSY, multiple relay COSY, and carbon–proton correlation (HETCOR and HMQC) spectra. Various aspects of the solution conformation of the steroid moiety of digitoxin and digoxigenin could be determined from coupling constants and NOE difference experiments and they are indicative of an all-chair conformation. The carbohydrate rings in digitoxin and the mono- and bis-digitoxigenin digitoxosides are also in the chair conformation. Keywords: cardenolides, digitoxigenin, digitoxin, 2-dimensional NMR, conformational analysis.

Acidity measurements in THF. III. Aldimines and ketimines

1983 ◽  
Vol 61 (12) ◽  
pp. 2729-2734 ◽  
Author(s):  
Robert R. Fraser ◽  
Monique Bresse ◽  
Noemi Chuaqui-Offermanns ◽  
K. N. Houk ◽  
N. G. Rondan
Keyword(s):  
Nmr Spectroscopy ◽  
Methyl Iodide ◽  
Quantitative Estimation ◽  
Steric Effects ◽  
Alkyl Substitution ◽  
C Nmr ◽  
Abinitio Calculations

The relative acidities of fiteen aldimines and ketimines have been measured in THF using either 13C nmr spectroscopy or trapping experiments with methyl iodide. The pKA's are found to vary over a range of more than four pK units. The effects of structure on acidity indicate the acid-weakening effect of alkyl substitution in ketimines to be due to steric effects. This interpretation is supported by the results of abinitio calculations. The data also permit a quantitative estimation of the preference for the syn configuration of lithiated imines to be at least four kcal/mol. The anti selectivity previously reported for the lithiation of endocyclic imines can be accounted for by angular constraints, as indicated by both abinitio calculations and pKa data on this class of imine.

Sign in / Sign up

Export Citation Format

Share Document