Solubilization of alkali metals in tetrahydrofuran and diethyl ether by use of a cyclic polyether

Chapter 7 – ELECTRODES SELECTIVE TO CATIONS

(cis-syn-cis) [15128-65-1] C20H36O6 (MW 372.50)

InChI = 1S/C20H36O6/c1-2-6-18-17(5-1)23-13-9-21-11-15-25-19-7-3-4-8-20(19)26-16-12-22-10-14-24-18/h17-20H,1-16H2/t17-,18+,19+,20-

InChIKey = BBGKDYHZQOSNMU-JVSBHGNQSA-N


(cis-anti-cis) [56468-35-0]

InChI = 1S/C20H36O6/c1-2-6-18-17(5-1)23-13-9-21-11-15-25-19-7-3-4-8-20(19)26-16-12-22-10-14-24-18/h17-20H,1-16H2/t17-,18+,19-,20+

InChIKey = BBGKDYHZQOSNMU-FGYAAKKASA-N







(complexation agent; promoter of halide reactions, carbon, oxygen, and sulfur anion reactions, eliminations, oxidations, and reductions)



Physical Data: mp 38–54 °C (mixture of isomers); cis-syn-cis isomer mp 61–62 °C; cis-anti-cis isomer (two forms) mp 69–70 °C and 83–84 °C. 1H NMR: (mixture of isomers, C6D6) 3.3–4.0 ppm (20H multiplet) and 0.9–2.2 ppm (16H multiplet).



Form Supplied in: all isomers are colorless crystals.



Preparative Methods: a mixture of diastereomers is prepared in 58–69% yield by the hydrogenation of Dibenzo-18-crown-6 in n-butanol over 5% ruthenium on alumina at 1000 psi.1 This mixture has been separated into the cis-syn-cis and cis-anti-cis isomers.2 Direct synthesis of the trans-syn-trans (mp 120–121 °C) and trans-anti-trans (mp 77–80 °C) isomers from trans-1,2-cyclohexanediol has been reported.3, 4



Handling, Storage, and Precautions: toxic orally; eye and skin irritant, with possible permanent injury; absorbed by skin. Use in a fume hood.

Dicyclohexano‐18‐crown‐6

1.

Four complexes of potassium bis-(N-3(or 5)-substituted salicylidene-S-valinato)cobaltate (III) were synthesized, where the salicylaldehyde residue was substituted in the 5-position with Br, CH3, and NO2 groups and in the 3-position with the CH3 group. The diastereomers Λ (SS) and Δ (SS) of the complexes were separated, the structure and configuration demonstrated by elementary analysis and physical methods. The kinetics of the base-catalyzed epimerization of the complexes in aqueous solutions was studied. The rate constants and activation parameters of the epimerization were found.




2.

The electronic influence of the substituents in the 5-position on the rate of exchange of a proton of the neighboring ligand is transmitted according to resonance and inductive mechanisms through the phenolic oxygen atom and increases the stereoselectivity with increasing electron acceptor properties of the substituents.




3.

An increase in steric hindrances close to the reaction reaction center the stereoselectivity in the series studied.

Solubilization of alkali metals in tetrahydrofuran and diethyl ether by use of a cyclic polyether

Citations

Chapter 7 – ELECTRODES SELECTIVE TO CATIONS

Dicyclohexano‐18‐crown‐6

Amino acids as C-H acids

III – Complexes of Ia and IIa Cations in Organic and Biological Chemistry

Reactions to Form Alkalides

Related Papers (5)

Crystalline Salt Complexes of Macrocyclic Polyethers

Alkali anions. Preparation and crystal structure of a compound which contains the cryptated sodium cation and the sodium anion

Stability constants of cyclic polyether complexes with univalent cations

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New Macrocyclic Polyethers