0000000000000729
AUTHOR
Crenguta Dordea
tert-Butyl-calix[4]arenes Substituted at the Narrow Rim with Cobalt Bis(dicarbollide)(1–) and CMPO Groups – New and Efficient Extractants for Lanthanides and Actinides
Calix[4]arene derivatives bearing two residues A(–) derived from cobalt bis(dicarbollide)(1–) (1) and two CMPO groups B at their narrow rim were synthesized from tBu-calix[4]arene in four steps. The first step involved the preparation of tBu-calix[4]arene diether derivatives with appropriate precursors for amino groups (mostly nitriles 3). These were O-alkylated through ring-opening reactions with the zwitterionic dioxane derivative [(8-O(CH2CH2)2O-1,2-C2B9H10)-(1′,2′-C2B9H11)-3,3′-Co]0 (10) to produce ionic nitrile derivatives 4. Reduction of the nitrile groups with BH3·SMe2 (or deprotection in the case of the corresponding phthalimido or Boc derivatives 8) led to a series of diamines 5a–f…
Tetra-CMPO-derivatives of calix[4]arenes fixed in the 1,3-alternate conformation
Calix[4]arene derivatives fixed in the 1,3-alternate conformation and substituted at one side by four carbamoylmethylphosphine oxide (CMPO) residues were synthesised. Two CMPO groups are directly attached to the wide rim, while the second pair is bound to the narrow rim via a tri- or tetramethylene spacer. Similar compounds, in which two CMPO groups at the wide rim are combined with two picolinamide groups or two ionisable carboxylic groups at the narrow rim, were also prepared. Some of these calixarene derivatives were studied as extractants for lanthanides (La3+, Eu3+, Yb3+) and thorium (Th4+) from acidic solution into methylene chloride. For selected samples, stability constants in metha…
26,28-Diallyloxy-5,11,17,23-tetra-tert-butyl-25,27-bis(cyanomethoxy)calix[4]arene in the partial cone conformation
The title compound, C54H66N2O4, crystallizes with two molecules in the asymmetric unit. Both adopt the typical partial cone conformation which was also found for 26,28-diallyloxy-5,17-di-tert-butyl-25,27-bis(cyanomethoxy)-11,23-dinitrocalix[4]arene [Danila, Bohmer & Bolte (2005). Org. Biomol. Chem. 3, 3508–3513]. The crystal structure of the title compound in the 1,2-alternate conformation has been determined recently [Danila, Bohmer & Bolte (2005). Org. Biomol. Chem. 3, 3508–3513].
Anionic tert-butyl-calix[4]arenes substituted at the narrow and wide rim by cobalt bis(dicarbollide)(1−) ions and CMPO-groups. Effect of stereochemistry and ratios of the functional groups on the platform on the extraction efficiency for Ln(III)/An(III)
Abstract Two ionic calix[4]arenes substituted at the narrow rim with an unpaired number ( n ) of cobalt bis(dicarbollide)(1−) anions ( 1 − ) ( n = 1 and 3) and (4 − n ) CMPO groups ( 3c , 4c ) have been synthesized via a three-step procedure based on nitrile substituted calix[4]arene precursors. Conjointly with them, the compound with a paired ratio of the groups, where n = 2 and the same substituents are located in mutually adjacent 1,2-positions, is reported ( 5c ). Another compound with the paired ratio, but from a wide rim series ( 6c ) ( n = 2) was successfully prepared starting from calix[4]arenes substituted with two nitro functions and two –OH sites available for further modific…