Tetra-CMPO-derivatives of calix[4]arenes fixed in the 1,3-alternate conformation

Abstract

Calix[4]arene derivatives fixed in the 1,3-alternate conformation and substituted at one side by four carbamoylmethylphosphine oxide residues (=CMPO) were synthesized. 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 20 as extractants for lanthanides (La 3+ , Eu 3+ , Yb 3+) and thorium (Th 4+) from acidic solution to methylenechloride. For selected samples stability constants in methanol were determined by spectrophotometric titrations. Three compounds (1b', 13, 17) in the 1,3-alternate conformation and one intermediate in the cone conformation (18) were confirmed by a crystal structure.

Synthesis of new p-tert-butylcalix[4]arene-based polyammonium triazolyl amphiphiles and their binding with nucleoside phosphates

“…Then the di- and tetraalkylated products were nitrated according to literature procedures [ 33 – 34 ] affording the di or tetranitro derivatives 2a , b and 6a , b in good yields. The reduction of the nitro groups to the corresponding amines was successfully performed by hydrazine hydrate [ 35 – 36 ]. In this case, Ni on silica/alumina was used as the catalyst instead of pyrophoric Raney nickel.…”

“…Solvents were purified according to standard methods [ 53 ]. 3-Bis[2-( tert -butoxycarbonylamino)ethyl]propargylamine [ 54 ], 1a (5,11,17,23-tetra- tert- butyl-25,27-dibutoxy-26,28-dihydroxycalix[4]arene) [ 32 ]; 2a (5,17-di- tert -butyl-11,23-dinitro-25,27-dibutoxy-26,28-dihydroxycalix[4]arene) [ 33 ], 3a (5,17-di- tert -butyl-11,23-diamino-25,27-dibutoxy-26,28-dihydroxycalix[4]arene) [ 33 ], 1b (5,11,17,23-tetra- tert -butyl-25,27-dioctyloxy-26,28-dihydroxycalix[4]arene) [ 34 ], 2b (5,17-di- tert -butyl-11,23-dinitro-25,27-dioctyloxy-26,28-dihydroxycalix[4]arene) [ 34 ], as well as 5a (5,11,17,23-tetra- tert- butyl-25,26,27,28-tetrabutoxycalix[4]arene) [ 36 ], 6a (5,11,17,23-tetranitro-25,26,27,28-tetrabutoxycalix[4]arene) [ 36 ], 7a (5,11,17,23-tetraamino-25,26,27,28-tetrabutoxycalix[4]arene) [ 35 ] and 5b (5,11,17,23-tetra -tert -butyl-25,26,27,28-tetraoctyloxycalix[4]arene) [ 35 ], 6b (5,11,17,23-tetranitro-25,26,27,28-tetraoctyloxycalix[4]arene) [ 35 ], 7b (5,11,17,23-tetraamino-25,26,27,28-tetraoctyloxycalix[4]arene) [ 36 ] and N -(2-aminoethyl)pentacosa-10,12-diynamide [ 50 ] were prepared following literature procedures. TLC was performed on Merck UV 254 plates with Vilber Lourmat VL-6.LC UV lamp (254 nm) control.…”

Interaction of hydrated protons with octyl‐phenyl‐N,N‐diisobutylcarbamoylmethyl phosphine oxide (CMPO): NMR and theoretical study

“…In spite of the relatively high stability of the complexes of TOPO with most cations including H 3 O + , bidentate ligands with another donor, additional to the phosphine oxide group were construed. Prominent among them is the ‘classical’ extraction agent octyl‐phenyl‐ N , N ‐diisobutylcarbamoylmethylphosphine oxide (CMPO) which is still under lively interest38–43 (for the structure of CMPO, see Scheme ). Considering the interesting behavior37 of TOPO with HP, we decided to put CMPO under analogous scrutiny.…”