Macroheterocycles. 7. Synthesis and extraction capacity of some dibenzo-18-crown-6-derivatives

Derivatives that contain vinyl, formyl, acetyl, carboxy, carbethoxy, -carboxyvinyl, or -carbethoxyvinyl groups in the benzene rings were synthesized from dibenzo-18-crown-6. The ability of the synthesized crown ethers to extract picrates of alkali metals from the aqueous phase to the chloroform phase was investigated.See [1] for Communication 6.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 599–603, May, 1981.     

2,6,8,12-Tetraoxa-4,10(1,4)-dibenzena-1,7(2,7)-difluorenacyclododecaphane-19,79-dione—A new macrocyclic receptor for polar organic molecules

The results of computer-assisted molecular modeling showed that 2,6,8,12-tetraoxa-4,10(1,4)-dibenzena-1,7(2,7)-difluorenacyclododecaphane-1⁹,7⁹-dione is promising as a receptor for polar organic molecules. This compound was synthesized by the reaction of 1,4-bis(bromomethyl)benzene with 2,7-dihydroxyfluoren-9-one in DMF in the presence of anhydrous potassium carbonate under strong dilution. Crystalline complexes of the title compound with DMF and nitrobenzene were isolated and studied by X-ray diffraction. In both complexes the substrate is located in the ligand cavity.     

Study of conformation of cryptahemispherands by two-dimensional NMR spectroscopy

Two-dimensional NMR spectroscopy (NOESY, COSY-DQF) has been used in a study of nitrogen-containing cryptahemispherands and their complexes with alkali metals. On the basis of experimentally established interproton distances, the preferred conformations of these molecules have been established. It has been shown that the important features of structure determining the molecular conformation are (a) the orientation of the N-CH₂(Ar) bond relative to the plane of the crown ether and (b) the length of the methylene bridge (spacer). The spatial and torsional angles have been determined. It has been established that as the length of the bridge is increased, the structure of these molecules approaches a betaine structure, with mutually parallel positions of the phenyl rings. Upon complexation, their orientation changes to mutually perpendicular, and this leads to enlargement of the inner cavity of the molecule and a corresponding rearrangement of its dimensions toward the ionic radius of the alkali metal.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 406–411, March, 1993.     

Macroheterocycles. 51. Synthesis of macrocyclic polyamines in a biphasic system

Macrocyclic polyamines are conveniently synthesized by condensation of bissulfonamides with ditosylates or dibromides of glycols in the biphasic system toluene(xylene)-aqueous sodium hydroxide.For Communication 50, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 401–404, March, 1990.     

Macroheterocycles. 24. Synthesis of new derivatives of diaza-18-crown-6

New derivatives of diaza-18-crown-6 have been prepared by the aminomethylation of N-alkylsulfonamides under the action of N,N-bismethoxymethyldiaza-18-crown-6.For Communication 23, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 413–415, March 1986.     

Bis(fluorenono)phanes: a new class of perspective macrocyclic receptors

Two representatives of a novel class of cyclophanes containing two fragments of 2,7-dioxy-9H-fluoren-9-one bridged by triethylene glycol and p-xylyl linking units have been prepared. X-Ray analysis shows that the former has an anti-conformation and the cavity is self-filling with fluorenone moieties.     

Mannich Reaction as a Key Strategy for the Synthesis of Benzoazacrown Ethers and Benzocryptands

A convenient method for the synthesis of mono- and polycyclic azacrown macrocycles containing aromatic fragments using the Mannich condensation of phenols and secondary diamines has been studied. This new approach allowed the synthesis of bisphenols connected by oligoazaoxaalkane units in good yields without the need to protect the phenolic OH groups. These bisphenols (13-16) were alkylated with ditosylates of polyethylene glycols to give benzoazacrown ethers 25-30. Intermediate bisphenols 13-15 were also treated with three bis(methoxymethyl)-substituted diamines to form benzoazacrowns 10-12 containing internal phenolic functions. Phenol-containing mono- (11) and bicyclic (3, n = 1) compounds, which were synthesized via the Mannich aminomethylation process, were used as building blocks for construction of bi- (32) and tricyclic (33) ligands.     

Bis[(benzo-18-crown-6)-4,5-ylmethyl]-1,3,4,6-diphenylglycoluril: The first representative of a new class of bis(crown ethers) and the synthesis and crystal structure of its complex with sodium picrate

A statistical Monte Carlo computer simulation has shown that the use of a diphenylglycoluril fragment as a rigid linker should give bis(crown ethers) with identically oriented benzocrown rings located closely in space. The syntheses of the first representative of this series, bis[(benzo-18-crown-6)-4,5-ylmethyl]-1,3,4,6-diphenylglycoluril and its complex with sodium picrate have been described. The crystal structure of the complex has been determined by X-ray diffraction: space group $P\bar 1$ , a = 13.976(3) Å, b = 16.723(3) Å, c = 20.578(4) Å, α = 98.74(2)°, β = 106.19(3)°, γ = 114.07(3)°. The complex represents a new type of coordination polymer formed by a combination of coordination and hydrogen bonds and stacking, which are favored by the U-shaped conformation of diphenylglycoluril.     

Macroheterocycles. 27. Amidomethylation of benzo-crown ethers

The synthesis of some novel benzo-crown ethers by -amidomethylation is described.For Communication 26, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1039–1042, August, 1987.