US 12,215,064 B2
Compounds for chromatographic separation of rare earth elements and s-, p-, d-metals, method of separation, and use thereof
Miloslav Polasek, Prague (CZ)
Assigned to USTAV ORGANICKE CHEMIE A BIOCHEMIE AV CR, V.V.I., Prague (CZ)
Appl. No. 17/616,340
Filed by USTAV ORGANICKE CHEMIE A BIOCHEMIE AV CR, V.V.I, Prague (CZ)
PCT Filed May 28, 2020, PCT No. PCT/CZ2020/050035
§ 371(c)(1), (2) Date Dec. 3, 2021,
PCT Pub. No. WO2020/244686, PCT Pub. Date Dec. 10, 2020.
Claims priority of application No. 19178492 (EP), filed on Jun. 5, 2019.
Prior Publication US 2022/0259119 A1, Aug. 18, 2022
Int. Cl. C07D 401/06 (2006.01); B01D 15/42 (2006.01); C07B 59/00 (2006.01); C07D 401/14 (2006.01); C07F 9/6524 (2006.01)
CPC C07B 59/002 (2013.01) [B01D 15/424 (2013.01); C07D 401/06 (2013.01); C07D 401/14 (2013.01); C07F 9/6524 (2013.01); C07B 2200/05 (2013.01)] 18 Claims
 
1. A method of chromatographic separation comprising:
providing a mixture of at least one metal ion selected from Ce, Dy, Er, Eu, Gd, Ho, La, Lu, Nd, Pr, Pm, Sm, Sc, Tb, Tm, Yb, Y, alkaline earth metals, Al, Ga, In, Tl, Sn, Pb, Bi and transitional metals, and at least one further metal ion, wherein said further metal ion is selected from rare earth metal ions, transition metal ions, non-transition metal ions, and actinide ions,
contacting the mixture with at least one compound of general formula (I) to form a chelates;
applying the chelates to a chromatographic column; and
eluting from the chromatographic column a chelate of the at least one metal ion and a chelate of the at least one further metal ion;
wherein:
formula (I) is:

OG Complex Work Unit Chemistry
X is H, C1 to C6 alkyl, F, Cl, Br or I;
Y is N or N-oxide;
Z1, Z2, and Zm, wherein m is 1 or 2, are -CH2-CH2-or -CH2-CH2-CH2-;
A and Am, wherein m is 1 or 2, are independently H, -CH2COOH, -CH2C(O)NH2;
-CH2P(O)(OH)2, or

OG Complex Work Unit Chemistry
n is 1 or 2;
R1, R2, and R3 are independently H, C1 to C6 alkyl, C1 to C6 alkyloxy, C6 to C10 aryloxy, benzyloxy, C1 to C6 alkylthio, C6 to C10 arylthio, F, Cl, Br, I, OH, SH, NH2, C1 to C6 alkylamino, di (C1 to C6 alkyl) amino, C1 to C6 acylamino, di(C1 to C6 acyl) amino, C6 to C10 arylamino, di(C6 to C10 aryl) amino, CN, OH, nitro, COORn, C(O)NHRn, or C(O)N(Rn)2, wherein Rn is independently H, C1 to C10 alkyl, or C6 to C10 aryl;
and/or wherein any neighboring two of R1, R2, and R3 together with any neighboring two carbon atoms of the aromatic cycle form a six-membered ring, optionally substituted with one or more substituents independently selected from the group consisting of OH, SH, CF3, F, Cl, Br, I, C1 to C6 alkyl, C1 to C6 alkyloxy, C1 to C6 alkylthio, NH2, C1 to C6 alkylamino, di(C1 to C6 alkyl) amino, NO2, COOH, COORn, C(O)NHRn, or C(O)N(Rn)2, wherein Rn is independently H, C1 to C10 alkyl, C6 to C10 aryl;
with the proviso that when n is 2 and all of Z1, Z2, Zm are -CH2-CH2-, then A is not -CH2COOH.