Ethenyl Group Research Articles

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Part III:* Vinclozolin

The 60 MHz 1H NMR spectra of racemic vinclozolin, 1, have been studied at 28° in CDCI3 solution with the achiral reagent tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium(III), 2, and the chiral reagents tris[3-(trifluoromethylhydroxymethylene)- d-camphorato] europium(III), 3, and tris[3-(heptafluoropropylhydroxymethylene)- d-camphorato]europium(III), 4. Reagent 3 produced only small lanthanide-induced shifts and no observable enantiomeric shift differences, ΔΔδ, with 3:1 molar ratios as high as 1.40. In contrast, chiral reagent 4 produced substantial ΔΔδ for the proton, Hβ, at C-2 of the ethenyl group syn to the oxazolidinedione ring and smaller ΔΔδ for the anti proton, Hβ, at the above carbon and for the CH3. With a 4:1 molar ratio of 0.581, ΔΔδ of 7.0 Hz was seen for Hβ. A 4:1 ratio of about 0.41 should be optimum for optical purity determinations; as little as 5% of the minor enantiomer should be detectable.

The reactivity of 2-vinylindoles with dimethyl acetylenedicarboxylate

The overall rates of reaction of 1-substltuted-1- (1-methyl-2-indolyl)ethenes with dimethyl acetylenedicarboxylate are considerably lower than those of the corresponding 2-vinyl- pyrroles. Steric interaction between the N-methyl group on the indole ring and the 1-substituent on the ethenyl group prevents the diene system adopting a coplanar cisoid configuration and, thereby, inhibits the π4 + π2 cycloaddition reaction of the system with dimethyl acetylenedicarboxylate. Under such conditions, the indolylethene preferentially undergoes a Michael addition reaction at the 3-position. The π4 + π2 cycloaddition reaction is promoted at elevated temperatures. No evidence was found for a Cope rearrangement of the Michael adducts to give the dihydrocarbazole.

Steroids. Part 20. Rearrangements of 5α,6α-epoxy-10β-ethenyl- and 10β-ethenyl-5α-hydroxy-steroids

Homoallylic participation is not of major importance in the reactions of 5α,6α-epoxy-10β-ethenyl-steroids with boron trifluoride–ether complex, or in the sulphuric acid-catalysed rearrangement of 10β-ethenyl-5α-hydroxy steroids to the 5β-ethenyl-Δ9-compounds. Deuterium substituted in the ethenyl group is not scrambled during the latter rearrangements, and the absence of cationic intermediates other than the C(10) carbocations is indicated.

The application of the Hammett equation to 13C N.M.R. spectroscopy: correlations in the β-nitrostyrenes

A series of 33 β-nitrostyrenes has been prepared and their 13C N.M.R. spectra have been determined in dimethyl sulphoxide and in deuterochloroform (where soluble). Hammett correlations between substituent and the chemical shift of both the para ring carbons and the α-carbon of the ethenyl group have been shown to be only approximate. In contrast, an excellent correlation has been observed between the chemical shift of the β-carbon of the ethenyl group and Hammett σ+ constants in all cases except those involving para substituents capable of exerting a - R effect. Possible reasons for this are considered. The system appears to be the first reported one where 13C measurements for both meta- and para-substituted compounds give rise to correlations in which agreement lies well inside the limits of experimental error, and shows promise as a convenient method for calculating substituent constants and studying their variation with solvent.

Properties of 4-ethenyl and 4-ethynyl analogs of pyridoxal phosphate and their reactions with the apo form of asparatate aminotransferase.

The binding to apoaspartate aminotransferase of analogs of pyridoxal phosphate bearing vinyl, cis- and trans-methylvinyl, and ethynyl groups in place of the fomyl group of the coenzyme has been studied. Details of synthesis of the ethynyl compound are given. The absorption spectra of all of the compounds have been analyzed and pKa values have been determined. The positions of the absorption bands can be related to those of pyridoxine but with bathochromic shifts induced by the ethenyl and ethynyl groups. However, this shift is almost completely lacking for the cis-methylvinyl compound suggesting nonplanarity of the molecule. Binding of the analogs to the apoenzyme is accompanied by a strong bathochromic shift which, from a study of solvent effects on the free analogs, appears to indicate a hydrophobic environment on the enzyme. Nevertheless, the analogs are bound as dipolar ions exclusively. Binding is accompanied by a distinct perturbation of the protein spectrum in the aromatic region. An effect on the spectrum of 1 or more tryptophan residues is indicated. Bands of the bound analogs exhibit positive circular dichroism except for that of the 4-vinyl analog. The 4-ethynyl analog reacts in a more complex way, giving at least two successive products in addition to the initial complex. The final product is reducible by sodium borohydride, is released from the enzyme by boiling, and appears to have the properties of a Schiff base. We postulate that the addition of an amino group of the enzyme to the ethynyl group is followed by tautomeric rearrangement to a Schiff base in which the ring is in a p-quinonoid structure.