ANIONIC DISPLACER MOLECULES FOR HYDROPHOBIC DISPLACEMENT CHROMATOGRAPHY

1 . A process for separating organic compounds from a mixture by reverse-phase displacement chromatography, comprising:

providing a hydrophobic stationary phase;

applying to the hydrophobic stationary phase a mixture comprising organic compounds to be separated;

displacing the organic compounds from the hydrophobic stationary phase by applying thereto an aqueous composition comprising a non-surface active hydrophobic anionic displacer molecule; and

collecting a plurality of fractions eluted from the hydrophobic stationary phase containing the separated organic compounds;

wherein the non-surface active hydrophobic anionic displacer molecule comprises a hydrophobic anion and a counterion, Cl, having the general formula A or B:

wherein in the general formulae A and B, each CM or CM′ is an independent hydrophobic chemical moiety with a negative formal charge selected from: carboxylate (XVI), N-acyl-α-amino acid (XVII), sulfonate (XVIII), sulfate monoester (XIX), phosphate monoester (XX), phosphate diester (XXI), phosphonate monoester (XXII), phosphonate (XXIII), tetraaryl borate (XXIV), boronate (XXV), boronate ester (XXVI); wherein the chemical moieties (I)-(XXVI) have the following chemical structures:

wherein in general formula B, CM and CM′ are independent charged chemical moieties having the same or opposite formal charge and are chemically attached to each other by a doubly connected chemical moiety, R*, which replaces one R 1 , R 2 (if present), R 3 (if present) or R 4 (if present) chemical moiety on CM and replaces one R 1′ , R 2′ (if present), R 3′ (if present) or R 4′ (if present) chemical moiety on CM′;

wherein each of R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 and R 4′ is a linear or branched chemical moiety independently defined by the formula,

—C x X 2x-2r AR 1 —C u X 2u-2s -AR 2 ,

R* is a direct chemical bond or is a doubly connected, linear or branched chemical moiety defined by the formula,

—C x X 2x-2r AR 1 —C u X 2u-2s —,

and R 5 is a linear or branched chemical moiety defined by the formula,

—C x X 2x-2r -AR 2 ;

wherein each AR 1 independently is a doubly connected methylene moiety (—CX 1 X 2 —, from methane), a doubly connected phenylene moiety (—C 6 G 4 -, from benzene), a doubly connected naphthylene moiety (—C 10 G 6 -, from naphthalene) or a doubly connected biphenylene moiety (—C 12 G 8 -, from biphenyl);

wherein AR 2 independently is hydrogen (—H), fluorine (—F), a phenyl group (—C 6 G 5 ), a naphthyl group (—C 10 G 7 ) or a biphenyl group (—C 12 G 9 );

wherein each X, X 1 and X 2 is individually and independently —H, —F, —Cl or —OH;

wherein any methylene moiety (—CX 1 X 2 —) within any —C x X 2x-2r — or within any —C u X 2u-2s — or within any —(CX 1 X 2 ) p — may be individually and independently replaced with an independent ether-oxygen atom, —O—, an independent thioether-sulfur atom, —S—, or an independent ketone-carbonyl group, —C(O)—, in such a manner that each ether-oxygen atom, each thioether-sulfur atom or each ketone-carbonyl group is bonded on each side to an aliphatic carbon atom or an aromatic carbon atom;

wherein not more than two ether-oxygen atoms, not more than two thioether-sulfur atoms and not more than two ketone-carbonyl groups may be replaced into any —C x X 2x-2r — or into any —C u X 2u-2s —;

wherein m x is the total number of methylene groups in each —C x X 2x-2r — that are replaced with ether-oxygen atoms, thioether-sulfur atoms and ketone-carbonyl groups, and m u is the total number of methylene groups in each —C u X 2u-2s — that are replaced with ether-oxygen atoms, thioether-sulfur atoms and ketone-carbonyl groups;

wherein G is individually and independently any combination of —H, —F, —Cl, —CH 3 , —OH, —OCH 3 , —N(CH 3 ) 2 , —CF 3 , —CO 2 Me, —CO 2 NH 2 ; —CO 2 NHMe, —CO 2 NMe 2 ;

wherein G* is individually and independently any combination of —F, —Cl, —R 2 , —OH, —OR 2 , —NR 2 R 3 , —CF 3 , —CO 2 Me, —CO 2 NH 2 ; —CO 2 NHMe, —CO 2 NMe 2 ;

wherein a pair of R 2 , R 2′ , R 3 , R 3′ , R 4 and R 4′ may comprise a single chemical moiety such that R 2 /R 3 , R 2 /R 4 , R 3 /R 4 , R 2′ /R 3′ , R 2′ /R 4′ or R 3′ /R 4′ is individually and independently —(CX 1 X 2 ) p — with p=3, 4, 5 or 6;

wherein the integer values of each of x, r, u, s, m x , m u are independently selected for each R 1 , R 1′ , R 2 , R 2′ , R 3 , R 3′ , R 4 , R 4′ , R 5 and R*, integer values r and as are the total number of contained, isolated cis/trans olefinic (alkene) groups plus the total number of contained simple monocyclic structures and fall in the ranges 0≦r≦2 and 0≦s≦2, the numeric quantity x+u−m x −m u falls in the range 0≦x+u−m x −m u <11;

wherein at least one aromatic chemical moiety, heterocyclic aromatic chemical moiety, imidazoline chemical moiety, amidine chemical moiety or guanidine chemical moiety is contained within CM or CM′ of A or B;

wherein a group-hydrophobic-index for each R-chemical-moiety (n) is numerically equal to the sum of the number of aliphatic carbon atoms plus the number of olefinic carbon atoms plus the number of thioether-sulfur atoms plus the number of chlorine atoms plus one-fifth the number of fluorine atoms plus one-half the number of ether-oxygen atoms plus one-half the number of ketone-carbon atoms plus one-half the number of aromatic carbon atoms beyond the number six minus the number of hydroxyl-oxygen atoms beyond the number one;

wherein an overall-hydrophobic-index (N) for each [CM] or [CM-R*—CM′] is numerically equal to the sum of the number of aliphatic carbon atoms plus the number of olefinic carbon atoms plus the number of thioether-sulfur atoms plus the number of chlorine atoms plus one-fifth the number of fluorine atoms plus one-half the number of ether-oxygen atoms plus one-half the number of ketone-carbon atoms plus one-half the number of aromatic carbon atoms beyond the number six minus the number of hydroxyl-oxygen atoms beyond the number one;

wherein the group-hydrophobic-indices ( 1 n and 1′ n) for R 1 and R 1′ fall in the range 4.0< 1 n, 1′ n<12.0, the group-hydrophobic-indices ( 2 n, 2′ n, 3 n, 3′ n, 5 n, 5′ n and *n) for R 2 , R 2′ , R 3 , R 3′ , R 5 , R 5′ , R*, when present, fall in the range 0.0≦ 2 n, 2′ n, 3 n, 3′ n, 5 n, 5′ n, *n<12.0 and the group-hydrophobic-indices ( 4 n and 4′ n) for R 4 and R 4′ , when present, fall in the range 0.0≦ 4 n, 4′ n≦5.0;

wherein the overall-hydrophobic-index (N) divided by the value of g falls in the range 10.0≦N/g<24.0;

wherein in A, when the charged moiety, CM, has a formal negative charge, g=1, and in B, when both CM and CM′ have formal negative charges, g=2, and in B when CM and CM′ have opposite formal charges with the overall charge of [CM-R*—CM′] being negative, g=1;

wherein the numeric value of the group-hydrophobic-index calculated for a cyclic chemical moiety is divided equally between the two respective R-chemical-moieties;

wherein R 1 or R 1′ is identified as that R-chemical-moiety when only one such chemical moiety is attached to CM or CM′; wherein R 1 or R 1′ is identified as that R-chemical-moiety having the largest value of the group-hydrophobic-index when there are more than one such R-chemical-moieties attached to CM or CM′; wherein R 4 or R 4′ is identified as that R-chemical-moiety having the smallest value of the group-hydrophobic-index when there are more than three such chemical moieties attached to CM or CM′; and

wherein Cl is a non-interfering, oppositely-charged counter-ion or mixture of such counter-ions, and the value of d is zero, a positive whole number or a positive fraction such that electroneutrality of the overall hydrophobic compound is maintained.

2 . The process of claim 1 wherein the aqueous composition comprising a non-surface active hydrophobic anionic displacer molecule is free of added salt other than a pH buffer.

3 . The process of claim 1 wherein CM has a general formula XXIV or XXV:

wherein in the general formula XXIV, R 1 is phenyl, 4-EtC 6 H 4 —, 4- n PrC 6 H 4 —, 4- n BuC 6 H 4 —, 4-MeOC 6 H 4 —, 4-FC 6 H 4 —, 4-MeC 6 H 4 —, 4-MeOC 6 H 4 —, 4-EtC 6 H 4 —, 4-ClC 6 H 4 —, or C 6 F 5 —; and each of R 2 , R 3 and R 4 independently are phenyl, 4-FC 6 H 4 —, 4-MeC 6 H 4 —, 4-MeOC 6 H 4 —, 4-EtC 6 H 4 —, 4-ClC 6 H 4 — or C 6 F 5 —; and

wherein in the general formula XXV, R 1 is 4-(4- n BuC 6 H 4 )C 6 H 4 — or 4-(4- n BuC 6 H 4 )-3-ClC 6 H 3 —

4 . The process of claim 1 wherein CM has a general formula selected from 4-R 1 C 6 H 4 SO 3 H, 5-R 1 -2-HO—C 6 H 3 SO 3 H, 4-R 1 —C 6 H 4 —C 6 H 3 X-4′-SO 3 H, and 4-R 1 —C 6 H 4 —C 6 H 3 X-3′-SO 3 H, wherein R 1 is CH 3 (CH 2 ) n , wherein n=4-10 and X is H or OH.

5 . The process of claim 1 wherein CM has a general formula XVIII or XXIII:

wherein in the general formula XVIII and in the general formula XXIII, R 1 is C 6 H 5 (CH 2 ) n —, wherein n=5-11.

6 . The process of claim 1 wherein CM has a general formula selected from 5-R 1 -2-HO—C 6 H 3 CO 2 H and R 1 C(O)NHCH(C 6 H 5 )CO 2 H, wherein R 1 is CH 3 (CH 2 ) n —, wherein n=4-10.

7 . The process of claim 1 wherein CM has a general formula 4-R 1 C 6 H 4 PO 3 H 2 wherein R 1 is CH 3 (CH 2 ) n —, wherein n=4-10.

8 . The process according to claim 1 wherein Cl is a non-interfering inorganic cation or mixture of such non-interfering cations selected from the groups: alkali metal ions (Li + , Na + , K + , Rb + , Cs + ), alkaline earth metal ions (Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ), divalent transition metal ions (Mn 2+ , Zn 2+ ) and NH 4 + ; wherein Cl is a non-interfering organic cation or mixture of such non-interfering cations selected from the groups: protonated primary amines (1+), protonated secondary amines (1+), protonated tertiary amines (1+), protonated diamines (2+), quaternary ammonium ions (1+), sulfonium ions (1+), sulfoxonium ions (1+), phosphonium ions (1+), bis-quaternary ammonium ions (2+) that may contain C 1 -C 6 alkyl groups and/or C 2 -C 4 hydroxyalky groups.

9 . The process according to claim 1 wherein the aqueous composition comprising a non-surface active hydrophobic anionic displacer molecule comprises up to about 25 volume % of an organic solvent.

10 . The process of claim 2 wherein CM has a general formula XXIV or XXV:

wherein in the general formula XXIV, R 1 is phenyl, 4-EtC 6 H 4 —, 4- n PrC 6 H 4 —, 4- n BuC 6 H 4 —, 4-MeOC 6 H 4 —, 4-FC 6 H 4 —, 4-MeC 6 H 4 —, 4-MeOC 6 H 4 —, 4-EtC 6 H 4 —, 4-ClC 6 H 4 —, or C 6 F 5 —; and each of R 2 , R 3 and R 4 independently are phenyl, 4-FC 6 H 4 —, 4-MeC 6 H 4 —, 4-MeOC 6 H 4 —, 4-EtC 6 H 4 —, 4-ClC 6 H 4 — or C 6 F 5 —; and

wherein in the general formula XXV, R 1 is 4-(4- n BuC 6 H 4 )C 6 H 4 — or 4-(4- n BuC 6 H 4 )-3-ClC 6 H 3 —

11 . The process of claim 2 wherein CM has a general formula selected from 4-R 1 C 6 H 4 SO 3 H, 5-R 1 -2-HO—C 6 H 3 SO 3 H, 4-R 1 —C 6 H 4 —C 6 H 3 X-4′-SO 3 H, and 4-R 1 —C 6 H 4 —C 6 H 3 X-3′-SO 3 H, wherein R 1 is CH 3 (CH 2 ) n , wherein n=4-10 and X is H or OH.

12 . The process of claim 2 wherein CM has a general formula XVIII or XXIII:

wherein in the general formula XVIII and in the general formula XXIII, R 1 is C 6 H 5 (CH 2 ) n —, wherein n=5-11.

13 . The process of claim 2 wherein CM has a general formula selected from 5-R 1 -2-HO—C 6 H 3 CO 2 H and R 1 C(O)NHCH(C 6 H 5 )CO 2 H, wherein R 1 is CH 3 (CH 2 ) n —, wherein n=4-10.

14 . The process of claim 2 wherein CM has a general formula 4-R 1 C 6 H 4 PO 3 H 2 wherein R 1 is CH 3 (CH 2 ) n —, wherein n=4-10.