Use of Surfactants to Extract a Platinum Group Metal or Gold from Organic Compositions

Abstract

The present invention is in the field of surfactants to extract a platinum group metal or gold, in particular palladium, from organic compositions. In particular, the invention concerns the use of surfactants to back-extract a platinum group metal or gold, in particular palladium, from organic compositions further comprising an extractant of said platinum group metal or gold, in particular palladium from an aqueous solution.

Claims

1. A process of extraction of at least one metal chosen from the platinum group metals and gold from a first organic liquid composition comprising: at least one metal chosen from the platinum group metals and gold, and an organic solvent, said organic solvent being water immiscible, said process comprising the following steps: a) contacting said first organic liquid composition with a first aqueous solution comprising a surfactant to obtain after phase separation, a second aqueous solution comprising the at least one metal chosen from the platinum group metals and gold and the surfactant, and a second organic liquid composition comprising the organic solvent; b) recovering of said second aqueous solution, said surfactant comprising: an hydrophobic central core of valence m equal to 1, 2 or 3; when m=1, a hydrophilic group G of the following formula, attached to the central core: ##STR00061## wherein: R.sub.7 is selected from H, C|-G, alkyl and CH.sub.2ORi.sub.0; R.sub.10 is H or a monosaccharide selected from glucose, galactose, mannose; w is an integer from 1 to 30; when m=2 or 3, the surfactant being then a dendrimer of generation n, generation chains attached to the central core and branching around the core; and an hydrophilic terminal group at the end of each generation chain; wherein n is an integer from 0 to 12; the hydrophilic terminal group comprises: a mono-, oligo- or polysaccharide residue, a cyclodextrin residue, a polyethylene glycol (PEG) residue, a peptide residue, a tris(hydroxymethyl)aminoethane (Tris), or a 2-amino-2-methylpropane-1,3-diol; the central core being: when m=1, a -L-W group, wherein: W is R.sub.F or a group selected from W.sub.1, W.sub.2 or W.sub.3: ##STR00062## R.sub.F is a C.sub.4-C.sub.10 perfluoroalkyl or a C.sub.1-C.sub.24 alkyl group, R.sub.H is a C.sub.1-C.sub.24 alkyl group, p is 0, 1, 2, 3 or 4; q is 0, 1, 2, 3 or 4; L is a linear or branched C.sub.1-C.sub.12 alkylene group, optionally interrupted by one or more groups Y; Y at each occurrence is chosen from OC(=0)-, C(=0)0-, -0-C(=0)-NH, NHC(=0)-0-, OC(=0)-0-, NHC(=0)-, C(=0)-NH, NHC(=0)NH, NHC(=0)0-, -0-C(=0)-NH, NH, O or S; Y at each occurrence is chosen from S, OC(=0)-, C(=0)0-, -0-C(=0)-NH, NHC(=0)-0-, OC(=0)-0-, NHC(=0)-, C(=0)-NH, NHC(=0)NH, NHC(=0)0-, -0-C(=0)-NH, NH or -0-; when m=2 or 3, a group of formula (Ia) or (Ib): ##STR00063## wherein: W is R.sub.F or a group selected from W.sub.0, W.sub.1, W.sub.2 or W.sub.3: ##STR00064## R.sub.F is a C.sub.4-C.sub.10 perfluoroalkyl or a C.sub.1-C.sub.24 alkyl group, R.sub.H is a C.sub.1-C.sub.24 alkyl group, p is 0, 1, 2, 3 or 4; q is 0, 1, 2, 3 or 4; L is a linear or branched C.sub.1-C.sub.12 alkylene group, optionally interrupted by one or more -0-, S, Z is C(=0)NH or NHC(=0), R is a C.sub.1-C.sub.6 alkyl group, and e is at each occurrence independently selected from 0, 1, 2, 3 or 4.

2. The process according to claim 1, wherein said first organic liquid composition results from the liquid/liquid extraction of an original acidic aqueous phase comprising at least one metal chosen from the platinum group metals and gold, with said organic solvent.

3. The process according to claim 1, wherein the organic solvent comprises or consists of an extractant of the at least one metal chosen from the platinum group metals and gold from an acidic aqueous solution and optionally, an organic diluent and/or a phase modifier.

4. The process according to claim 3, wherein the extractant is chosen from the group comprising malonamides, alkyl sulfides, sulfoxides, hydroxyoximes, amines, ammonium salts, alkyl phosphine oxides, phosphine sulfides, ketones, thio and dithio-diglycolamides.

5. The process according to claim 1, wherein: said second aqueous solution comprises more than 50% of the at least one metal chosen from the platinum group metals and gold comprised in the first organic liquid composition; and/or said second aqueous solution comprises less than 5% of the diluent comprised in the first organic liquid composition; and/or said second aqueous solution comprises less than 2% of the extractant comprised in the first organic liquid composition; and/or said second aqueous solution comprises more than 80% of the surfactant comprised in the first aqueous solution.

6. The process according to claim 1, further comprising, after step b), a step c) of performing a platinum group metal or gold-catalyzed reaction under micellar conditions by contacting said second aqueous solution with the reactants of said platinum group metal or gold-catalyzed reaction to obtain the product of the platinum group metal or gold-catalyzed reaction under micellar conditions.

7. The process according to claim 3, wherein the first organic liquid composition is obtained by extracting an original aqueous phase comprising at least one metal chosen from the platinum group metals and gold, with said extractant in presence of said diluent.

8. The process according to claim 1, wherein said at least one metal chosen from the platinum group metals and gold originates from an aqueous phase comprising nitric acid.

9. The process according to claim 1, wherein the surfactant is selected from: ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## wherein w is as defined in claim 1.

10. The process according to claim 1, wherein the at least one metal chosen from the platinum group metals and gold is palladium.

11. A process of extracting at least one metal chosen from the platinum group metals and gold from a liquid composition to an aqueous solution, said liquid composition comprising: at least one metal chosen from the platinum group metals and gold, an organic solvent, said organic solvent being water immiscible comprising contacting the liquid composition with the surfactant of claim 1.

12. A micelle or an aqueous solution comprising at least one metal chosen from the platinum group metals and gold and a surfactant as defined in claim 1.

13. (canceled)

14. A platinum group metal or gold-catalyzed reaction process under micellar conditions comprising the micelle or aqueous solution according to claim 12.

15. An amphiphilic dendrimer of generation n comprising: an hydrophobic central core of valence m equal to 2 or 3; generation chains attached to the central core and branching around the core; and an hydrophilic terminal group at the end of each generation chain; wherein n is an integer from 0 to 12; the hydrophilic terminal group comprises: a mono-, oligo- or polysaccharide residue, a cyclodextrin residue, a polyethylene glycol (PEG) residue, a peptide residue, a tris(hydroxymethyl)aminoethane (Tris), or a 2-amino-2-methylpropane-1,3-diol; the central core being a group of formula (Ia) or (Ib): ##STR00071## wherein: W is R.sub.F or a group selected from W.sub.0, W.sub.1, W.sub.2 or W.sub.3: ##STR00072## R.sub.F is a C.sub.1-C.sub.24 alkyl group, R.sub.H is a C.sub.1-C.sub.24 alkyl group, p is 0, 1, 2, 3 or 4; q is 0, 1, 2, 3 or 4; L is a linear or branched C.sub.1-C.sub.12 alkylene group, optionally interrupted by one or more -0-, S, Z is C(-0)NH or NHC(O), R is a C.sub.1-C.sub.6 alkyl group, and e is at each occurrence independently selected from 0, 1, 2, 3 or 4.

16. A compound of formula:
W-L-G wherein: G is a hydrophilic group G of the following formula: ##STR00073## wherein: R.sub.7 is selected from H, C.sub.1-C.sub.6 alkyl and CH.sub.2OR.sub.10; R.sub.10 is H or a monosaccharide selected from glucose, galactose, mannose; w is an integer from 1 to 30; W is R.sub.F or a group selected from W.sub.1, W.sub.2 or W.sub.3: ##STR00074## R.sub.F is a C.sub.4-C.sub.10 perfluoroalkyl or a C.sub.1-C.sub.24 alkyl group, R.sub.H is a C.sub.1-C.sub.24 alkyl group, p is 0, 1, 2, 3 or 4; q is 0, 1, 2, 3 or 4; L is a linear or branched C.sub.1-C.sub.12 alkylene group, optionally interrupted by one or more groups Y; Y at each occurrence is chosen from OC(=0)-, C(=0)0-, -0-C(=0)-NH, NHC(=0)-0-, OC(=0)-0-, NHC(=0)-, C(=0)-NH, NHC(=0)NH, NHC(=0)0-, -0-C(=0)-NH, NH, O or S; Y at each occurrence is chosen from S, OC(=0)-, C(=0)0-, -0-C(=0)-NH, NHC(=0)-0-, OC(=0)-0-, NHC(=0)-, C(=0)-NH, NHC(=0)NH, NHC(=0)0-, -0-C(=0)-NH, NH or O; provided that, when G is of formula ##STR00075## then L is interrupted by one more groups Y.

Description

FIGURES

[0293] FIG. 1 shows the results obtained after contacting an equal volume of toluene and aqueous (water+2 wt % surfactant) phases and shaking for 5 min at 20 C., in the conditions described in example 4. The surfactants SDS, TPGS-750-M and DendriTAC H12G.sub.0diTAC (5*2) are respectively used.

EXAMPLES

[0294] General Procedure

[0295] All reagents were from commercial sources and were used as received. All solvents were distilled and dried according to standard procedures. Reactions were checked for completions by TLC (EM Science, silica gel 60 F 254) which were visualized by quenching of u.v. fluorescence (.sub.max=254 nm) or by spraying a 5% sulphuric acid solution in ethanol or a 2% ninhydrin solution in ethanol, and then by heating at 150 C. Flash chromatography were performed using silica gel 60 (40-63 m, 230-400 mesh) or on combiflash Rf 200 apparatus from Teledyne Isco equipped with a UV detector. Size exclusion chromatography was carried out on hydroxypropylated cross-linked dextran (LH 20) from GE Healthcare. Fluorous solid-phase extractions were performed on Fluorochrom columns from SiliCycle. HR-MS spectra were recorded on a mass spectrometer equipped with a TOF analyzer for ESI+experiments at the Laboratoire de Mesures Physiques of University Montpellier 2 (IBMM instrument platform).

[0296] NMR spectra were recorded on BRUCKER Avance 400 spectrometer. Samples were prepared in CDCL.sub.3 (referenced to 7.26 ppm for .sup.1H and 77.16 for .sup.13C), DMSO-d6 (referenced to 2.51 ppm for .sup.1H and 39.52 ppm for .sup.13C), MeOD (referenced to 3.31 ppm for .sup.1H and 49.00 for .sup.13C), D.sub.2O (referenced to 4.79 ppm for .sup.1H). Coupling constant (J) are in Hertz and corrected to the nearest 0.5 Hz. Multiplicities are reported as follows: s, singlet, d, doublet, dd, doublets of doublets, t, triplet, q, quartet, m multiplet, c, complex, and br broad pic. .sup.1H NMR spectral assignments are supported by .sup.1H-.sup.1H COSY and .sup.13C-.sup.1H HSQC. Carbon spectra are supported by .sup.13C-.sup.1H HSQC analysis where necessary.

Example 1: Synthesis of Fluorinated Dendrimeric Surfactants

[0297] 1.1. Synthesis of Oligomeric Hydrosoluble polyTRIS Moieties

##STR00038##

[0298] 1.1.1. Synthesis of Chloro-polyTRIS Oligomer

[0299] Synthesis of Chloro-polyTRIS Oligomer 1a with DPn=9.4

[0300] To a solution of Tris(hydroxymethyl)acrylamidomethane (THAM) (8 g, 45.7 mmol, 12.5 eq) in dry and degassed MeOH under reflux, are added AIBN as radical initiator (60 mg, 0.365 mmol, 0.1 eq) and Chloropropanethiol as transfer reagent (354 l, 3.65 mmol, 1 eq). The mixture is heated at reflux under nitrogen atmosphere until the total disappearance of the starting monomer THAM (monitored by TLC). Then the solution is filtered, concentrated and precipitated twice in Et.sub.2O to give 1a (7.8 g) as a pure white compound (yield=92.8%). The DPn is assessed by 1H-NMR in MeOD, where the integral of the peak at 2.04 ppm is set for 2 protons (middle CH.sub.2 of the CTA (chain transfer agent)), and by dividing the integral of the CH.sub.2 protons of Tris(hydroxymethyl)aminomethane (TRIS) units at 3.80 ppm by six. DPn=(CH2 at 3.80 ppm)/6.

[0301] .sup.1H NMR (MeOD, 400 MHz) , 3.80 (56H, br, CH.sub.2OH), 3.70 (2H, br, CH.sub.2C.sub.1), 2.72-2.50 (4H, c, CH.sub.2CH.sub.2CH.sub.2S, SCH.sub.2), 2.48-2.11 (5H, c, CH.sub.OLIGOMER), 2.00 (2H, m, CH.sub.2CH.sub.2CH.sub.2S), 1.93-1.39 (8H, c, CH.sub.2 OLIGOMER).

[0302] Synthesis of Chloro-polyTRIS Oligomer 1b with DPn=5.2

[0303] To a solution of THAM (5 g, 28.6 mmol, 5 eq) in dry and degassed MeOH under reflux are added AIBN (374 mg, 0.228 mmol, 0.4 eq) and Chloropropanethiol (551 l, 5.7 mmol, 1 eq). The mixture is heated at reflux under a nitrogen atmosphere until total disappearance of the starting monomer THAM (monitored by TLC). Then the solution is filtered, concentrated and precipitated twice in Et.sub.2O to give 1b (5.24 g) as a pure white powder (yield=93.1%). The DPn is assessed by 1H-NMR in MeOD or D.sub.2O, where the integral of the peak at 2.04 ppm is set for 2 Protons (middle CH.sub.2 of the CTA (chain transfer agent)), and by dividing the integral of the CH.sub.2 protons of TRIS at 3.80 ppm by six. DPn=(CH2 at 3.80 ppm)/6.

[0304] .sup.1H NMR (D.sub.2O, 400 MHz) , 4.02-3.71 (31H, br, CH.sub.2OH), 3.68 (2H, m, CH.sub.2C.sub.1), 2.79-2.58 (4H, c, CH.sub.2CH.sub.2CH.sub.2S, SCH.sub.2), 2.56-2.11 (11H, c, CH.sub.OLIGOMER), 2.04 (2H, br, CH.sub.2CH.sub.2CH.sub.2S), 1.93-1.39 (17H, c, CH.sub.2 OLIGOMER).

[0305] 1.1.2. Synthesis of azido-polyTRIS oligomer

Synthesis of Azido-polyTRIS Oligomer 2a

[0306] To a solution of oligomer 1a (4 g, 2.1 mmol, 1 eq) in water (30 ml), is added NaN.sub.3 (419 mg, 6.41 mmol, 3 eq). The reaction mixture is heated at 55 C., after 12H another 3 eq of NaN.sub.3 is added and the solution is heated for another 12H. The solvent is removed under vacuum and the crude is purified over LH20 with pure MeOH. 3.77 g of 2a are recovered as a white powder (yield=94%). (D.sub.2O, 400 MHz) , 3.90-3.59 (CH.sub.2OH), 3.44 (CH.sub.2N.sub.3), 2.71-2.48 (CH.sub.2SCH.sub.2), 2.46-2.00 (CH.sub.OLIGOMER), 1.84-1.25 (25H, c, CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2 OLIGOMER).

[0307] Synthesis of Azido-polyTRIS Oligomer 2b

[0308] To a solution of oligomer 1b (4.23 g, 4 mmol, 1 eq) in water (30 ml), is added NaN.sub.3 (780 mg, 12 mmol, 3 eq). The reaction mixture is heated at 55 C., after 12H another 3 eq of NaN.sub.3 are added and the solution is heated for another 12H. The solvent is removed under vacuum and the crude is purified over LH20 with pure MeOH. 3.4 g of 2b are recovered (yield=80%). (D.sub.2O, 400 MHz) , 3.91-3.74 (CH.sub.2OH), 3.44 (CH.sub.2N.sub.3), 2.77-2.58 (CH.sub.2SCH.sub.2), 2.56-2.11 (CH.sub.OLIGOMER), 1.93-1.44 (CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2 OLIGOMER).

1.2. Amphiphilic Dendrimers Functionalized with polyTris Moieties-Generation 0 (G.sub.0)

[0309] 1.2.1. Synthesis of the Monocatenar Scaffold (Mickal Addition) F6G.sub.0 (AB2)

##STR00039##

Synthesis of compound N-(1,3-dihydroxy-2-methylpropan-2-yl)acrylamide (3)

[0310] This synthesis was already described in Journal of fluorine chemistry by M. Abla, G. Durand, C. Breyton, S. Raynal, C. Ebel, B. Pucci, J. Fluor. Chem. 134, 63 (2012).

Synthesis of compound N-(2-methyl-1,3-bis(prop-2-yn-1-yloxy)propan-2-yl)acrylamide (4)

[0311] ##STR00040##

[0312] To a solution of 3 (1 eq, 2.00 g, 13 mmol) and propargyl bromide (2.3 eq, 3.27 ml, 30 mmol) dissolved in 40 ml of dry DMF and cooled at 0 C., is added finely grinded KOH (2.1 eq, 1.50 g, 26 mmol) in portions over a period of one hour. The reaction mixture is left to warm and stirred overnight at room temperature. The mixture is diluted with 200 ml of EtOAc and washed 4 times with water. All organic phases are pooled, dried over Na.sub.2SO.sub.4 and concentrated in vacuo to dryness. The crude product is purified by silica gel column chromatography (cyclohexane/EtOAc 9:1-7:3 as eluent) to afford 1.48 g of pure 4 as a white powder (yield=50%). TLC Rf=0.3 (Cyclohexane/Ethyl acetate 7/3).

[0313] .sup.1H NMR (CDCl.sub.3, 400 MHz) 6.24-6.11 (3H, m, CH.sub.2CH, NH), 5.58 5.58 (1H, dd, J=4.0, 2.0 Hz CH 4.16 (3H, s, CH.sub.2), 4.24-4.27 (1H, t, J=6.2 Hz), 2.53 (2H, t, J=4.0 Hz), 1.43 (3H, s, CH.sub.3); 13C NMR (CDCl.sub.3, 100 MHz) 165.10 (CO), 131.78.67 (CH.sub.2CH), 125.72 (CH.sub.2 CH), 79.44 (CH), 74.76 (CH), 71.70 (CH.sub.2O), 58.38 (CH.sub.2C), 56.28 (C), 18.96 (CH.sub.3) ESI Calcd for C.sub.13H.sub.18NO.sub.3: 236.13 [M+H.sup.+], found m/z 236.13 [M+H.sup.+]. HRMS Calcd for C.sub.13H.sub.18NO.sub.3: 236.1287 [M+H.sup.+], found m/z 236.1293 [M+H.sup.+].

Synthesis of compound N-(2-methyl-1,3-bis(prop-2-yn-1-yloxy)propan-2-yl)-3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)thio)propanamide (5)

[0314] ##STR00041##

[0315] NaBH.sub.4 (396 mg, 10.6 mmol, 2.5 eq) is added by portion to a cold solution of 1H, 1H, 2H, 2H perfluorooctanethiol (1.70 g, 4.46 mmol, 1.05 eq) in dry methanol (10 ml). The reaction mixture is stirred for 30 mn at 0 C. Then this solution is carefully added to a solution of 4 (1 g, 4.25 mmol, 1 eq) in dry methanol (90 ml) and the resulting mixture is stirred for 24 h. After 24 h another 0.5 eq of 1H, 1H, 2H, 2H perfluorooctanethiol and NaBH.sub.4 are added in the same way as previously and the mixture is stirred for another 24 h. The solvent is evaporated in vacuo to dryness, the crude is purified over silica gel (cyclohexane/EtOAc 9:1-7:3 as eluent) to afford compound 5 (1.50 g, yield=57%) as a pure product. TLC Rf=0.42 (Cyclohexane/Ethyl acetate 7/3).

[0316] .sup.1H NMR (CDCl.sub.3, 400 MHz) (5.81 (1H, NH, s), 4.16 (4H, d, J=2.5 Hz CH.sub.2-Alkyne), 3.62 (2H, d, J=9 Hz, CH.sub.2O), 3.50 (2H, d, J=9.0 Hz, CH.sub.2O), 2.82 (2H, t, J=7.0 Hz), 2.74 (2H, t, J=9.0 Hz (CH.sub.2S), 2.38-2.20 (6H, m, CF.sub.2CH.sub.2, CH, CH.sub.2CO), 1.29 (3H, s, CH.sub.3); .sup.13C NMR (CDCl.sub.3, 100 MHz) 170.63 (CO), 79.48 (CH), 74.63 (CH), 71.91 (CH.sub.2O), 58.52 (CH.sub.2C), 56.22 (C), 37.17 (CH.sub.2CO), 31.99 (CH.sub.2CF.sub.2), 27.60 (CH.sub.2S), 22.80 (CF.sub.2CH.sub.2), 19.04 (CH.sub.3); .sup.19F NMR (CDCl.sub.3, 100 MHz) 81.44 (3H, t, J=10.0 Hz), 114.70 (2H, q, J=15.0 Hz), 122.32 (2H, br s, J=12.0 Hz), 123.32 (2H, br s), 123.76 (2H, br s), 126.66 (2H, br s). ESI Calcd for C.sub.21H.sub.23F.sub.13NO.sub.3S: 616.12 [M+H.sup.+], found m/z: 616.12 [M+H.sup.+]. HRMS Calcd for C.sub.21H.sub.23F.sub.13NO.sub.3S: 616.1191 [M+H.sup.+], found m/z 616.1191 [M+H.sup.+].

[0317] 1.2.2. Functionalization with Hydrophilic PolyTris Moieties

##STR00042##

[0318] aSynthesis of F6 G.sub.0diTAC (10*2)

[0319] Sodium ascorbate (169 mg, 0.85 mmol, 1.2 eq), compounds 5 (438 mg, 0.732 mmol, 1 eq) and 2a (3.71 g, 2 mmol, 2.8 eq) (DPn=9.4) are dissolved in DMF (40 ml), the reaction mixture is heated at 50 C., and after 5 minutes copper sulfate pentahydrate (71 mg, 0.28, 0.2 eq) is added. The solution is heated overnight. The solution is filtered and passed through chelex beads, and then the solvent is evaporated under vacuum. The crude is dissolved in a mixture of MeOH/water 9/1, filtered and purified over LH20 MeOH/H.sub.2O 9/1. The purification is followed by TLC (Ethyl Acetate/MeOH 5/5): only fractions with a spot staying at the start were recovered. The solvent is carefully removed in vacuo at a temperature about 0 C. at the beginning and then at room temperature out of the water bath, then diluted with water and freeze dried. The product is further purified by fluorous solid-phase extraction (FSPE). Briefly, the column is equilibrated with 25 ml of a mixture of water and DMF (9/1), then between 100 mg and 400 mg of product are dissolved in 1 ml of this mixture and deposit onto the column, after 25 ml of this eluent is pass through the column to get rid of non-fluorous compounds, then 25 ml of water, followed by 25 ml of a mixture of MeOH and Water (9/1) and finally 25 ml of pure methanol in order to rinse the column. Eluents containing methanol are concentrated in vacuo, dilute with water and freeze dried in order to obtain a fluffy white powder. We obtain 2.25 g of compound F6 G.sub.0diTAC (10*2) with a DPn of 10; yield=72.5%.

[0320] The DPn is assessed by 1H-NMR in DMSO, where integrals of peaks at 4.40 and 4.49 ppm are set for 8 Protons (Two CH.sub.2 in a position of the triazole ring), and by dividing the integral of the CH.sub.2 protons of TRIS at 3.80 ppm by six or dividing the integral of the OH protons, between 5.48 and 4.64 ppm, by three.

[0321] .sup.1H NMR (DMSO-d6, 400 MHz) (8.07 (2H, s, CH triazole), 7.75-6.85 (25H, c, NH), 5.48-4.64 (70H, c, OH), 4.49 (4H, s, C.sub.TRIAZOLECH.sub.2O), 4.40 (4H, s, CH.sub.2CH.sub.2N.sub.TRIAZOLE), 3.94-3.40 (143H, br, CH.sub.2OH, CH.sub.2O), 2.71 (4H, c, CF.sub.2CH.sub.2CH.sub.2S, SCH.sub.2CH.sub.2CO), 2.50 (2H, c, CF.sub.2CH.sub.2), 2.45 (2H, br, CH.sub.2CH.sub.2CH.sub.2S), 2.36 (2H, t, J=7.54 Hz, CH.sub.2CO), 2.29-1.84 (29H, c, CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2S, CH, CH.sub.2CO, CHCO.sub.OLIGOMER), 1.80-1.28 (38H, M, CH.sub.2OLIGOMER), 1.18 (3H, S, CH.sub.3); .sup.13C NMR (DMSO-D6 100 MHZ) 175.68 (CO oligomer), 170.46 (CO), 144.01 (C-triazole), 123.79 (CH-triazole), 71.54 (CH.sub.2O), 64.01 (C.sub.TRIAZOLECH.sub.2O), 62.35 (C), 60.53 (CH.sub.2OH) 56.36 (C), 48.16 (CH.sub.2Ntriazole), 42.16 (C-oligomer), 41.59 (C-oligomer), 36.06 (CH.sub.2CO), 31.13 (CH.sub.2CF.sub.2), 28.27 (CH.sub.2CH.sub.2CH.sub.2S), 26.97 (CF.sub.2CH.sub.2CH.sub.2S), 21.77 (SCH.sub.2CH.sub.2CO), 19.23 (CH.sub.3); .sup.19F NMR (DMSO-d6, 100 MHz) 80.19 (3H, t, J=8.68 Hz), 113.22 (2H, br), 121.73 (2H, br), 122.65 (2H, br), 122.65 (2H, br) 125.74 (2H, br).

[0322] bSynthesis of F6 G.sub.0diTAC (7*2)

[0323] Sodium ascorbate (285 mg, 1.44 mmol, 1.2 eq), compounds 5 (742 mg, 1.2 mmol, 1 eq) and 2 (3.82 g, 3.62 mmol, 3 eq) (DPn-5) are dissolved in mixture of DMF (100 ml) and water (100 ml), the reaction mixture is heated at 60 C., and after 5 minute copper sulfate pentahydrate (120 mg, 0.48, 0.2 eq) is added. The solution is heated at 60 C. during 3 hours and stirred at room temperature overnight. The solution is filtered and passed through chelex beads, and then the solvent is evaporated under high vacuum. The crude is dissolved in a mixture of MeOH/water 9/1 and filtered and then purified over LH20 MeOH/Water 9/1. The purification is followed by TLC (Ethyl Acetate/MeOH 5/5): only fractions with a spot staying at the start were recovered. The solvent is carefully removed in vacuo at a temperature about 0 C. at the beginning and then at room temperature without the water bath. The mixture is diluted with water, freeze dried and further purified by FSPE as previously described to give 650 mg of compound F6 G.sub.0diTAC (7*2) with a DPn of 7; y=19.8%. The DPn was assessed by 1H-NMR as previously described for F6 G.sub.0diTAC (10*2).

[0324] .sup.1H NMR (DMSO-d6, 400 MHz) (8.06 (2H, s, CH triazole), 7.75-6.81 (20H, c, NH), 5.48-4.62 (58H, c, OH), 4.50 (4H, s, C.sub.TRIAZOLECH.sub.2O), 4.41 (4H, s, CH.sub.2CH.sub.2N.sub.TRIAZOLE), 3.77-3.47 (122H, br, CH.sub.2OH), 2.29-1.84 (28H, c, CH.sub.2S, CF.sub.2CH.sub.2, CH, CH.sub.2CO, CHCO.sub.OLIGOMER), 1.80-1.28 (36H, m, SCH.sub.2OLIGOMER), 1.24 (3H, s, CH.sub.3); .sup.19F NMR (DMSO-d6, 100 MHz) 80.44 (3H, br), 113.34 (2H, q, J=15.0 Hz), 121.92 (2H, br), 122.88 (4H, br), 125.97 (2H, br).

Example 2: Synthesis of Hydrocarbon Dendrimeric Surfactants

[0325] 1.1. Synthesis of the Monocatenar Scaffold (Via Mickal Addition) with Different Hydrocarbon Chain Lengths (AB3 Building Blocks)

##STR00043##

a) Synthesis of Tris(hydroxymethyl)acrylamidomethane (compound 6)

[0326] Synthesis of compound 6 was performed using the procedure described by Pucci et al. (Eur. Polym. J., 1991, 27, 1101). To a stirred solution of tris(hydroxymethyl)aminomethane (3.00 g, 24.8 mmol) in methanolic potassium hydroxide 3N, at 0 C. within a pH range between 8 and 9, acryloyl chloride (3.60 ml, 44.6 mmol) was added dropwise. The reaction mixture was stirred at 0 C. for 1 h and then allowed to warm up to room temperature. After 4 h, the reaction mixture was filtered and the filtrate evaporated in vacuo to dryness. After precipitation and recrystallization from methanol, the desired compound 6 was obtained (3.78 g, 87%) as a white powder. m.p. 136 C.; v.sub.max(NaCl)/cm.sup.1 3420s (br), 1653s, 1560m, 1540m, 1018m; .sub.H (300 MHz; DMSO-d.sub.6) 3.56 (d, 6H, J 5.7, CH.sub.2), 4.76 (t, 3H, J 5.7, OH), 5.54 (dd, 1H, J 2.4, J 9.9, H.sub.a), 6.02 (dd, 1H J 2.4, J 17.1 Hz, H.sub.b), 6.37 (dd, J 9.9, J 17.1, H.sub.c), 7.42 (s, 1H, NH); .sub.c (75.5 MHz; DMSO-d.sub.6) 60.6, 62.6, 125.2, 132.4, 165.5.

b) Synthesis of N-acryloyl-tris[(propargyloxy)methyl]aminomethane (compound 7)

[0327] A solution of tris(hydroxymethyl)acrylamidomethane 6 (500 mg, 2.85 mmol) in anhydrous DMF (10 mL) was stirred at 0 C. with propargyl bromide (80 wt. % in Toluene 1.10 mL, 12.85 mmol). Portions of finely ground KOH (960 mg, 17.14 mmol) were added over a period of 30 min. The reaction mixture was stirred at r.t. and the course of the reaction was monitored by TLC (EtOAc/MeOH 7:3) until complete disappearance of 6. The mixture was concentrated to dryness and the residue partitioned between ethyl acetate (200 mL) and brine (200 mL). The organic layer was washed with water, dried with Na.sub.2SO.sub.4 and the solvent removed at reduce pressure to give the crude product, which was purified by flash chromatography (Hexanes/EtOAc 70:30). After crystallization from ethyl acetate/hexanes, compound 7 was obtained (0.630 g, 76%) as colorless needles. Rf (EtOAc/Hexanes 7:3)=0.65; m.p. 85 C. (from EtOAc/Hexanes). v.sub.max(NaCl)/cm.sup.1 3300s (br), 2124s, 1658s, 1623s, 1555s, 1101s, 799s (br); .sub.H (300 MHz; CDCl.sub.3) 2.44 (t, 3H, J 2.4, CCH), 3.89 (s, 6H, C.sub.qCH.sub.2O), 4.15 (d, 6H, J 2.4, OCH.sub.2CCH), 5.58 (dd, 1H, J 1.8, J 9.9, H.sub.a), 5.86 (s, 1H, NH), 6.06 (dd, 1H, J 9.9, J 17.1, H.sub.c), 6.23 (dd, 1H, J 1.8, J 17.1, H.sub.b); .sub.C (75.5 MHz; CDCl.sub.3) 58.6, 59.3, 68.4, 74.7, 79.5, 126.3, 131.4, 165.3; m/z (TOF.sup.+ HRMS) for C.sub.16H.sub.19NO.sub.4: 290.13868 [M+H].sup.+, found 290.13916; 312.12063 [M+Na].sup.+, found 312.12096.

c) Synthesis of Compound N-(1,3-bis(prop-2-yn-1-yloxy)-2-((prop-2-yn-1-yloxy)methyl)propan-2-yl)-3-(octylthio)propanamide (compound 8 RC.SUB.6.H.SUB.13.)

[0328] ##STR00044##

[0329] NaBH.sub.4 (327 mg, 8.65 mmol, 2.5 eq) is added by portion to a cold solution of octanethiol (0.53 g, 3.63 mmol, 1.05 eq) in dry methanol (10 ml). The reaction mixture is stirred for 30 mn at 0 C. Then this solution is carefully added to a solution of 7 (1 g, 3.46 mmol, 1 eq) in dry methanol (90 ml) and the resulting mixture is stirred for 24 h. After 24 h another 0.5 eq of octanethiol and NaBH.sub.4 are added in the same way as previously and the mixture is stirred for another 24 h. The solvent is evaporated in vacuo to dryness, the crude is purified over silica gel (cyclohexane/EtOAc 9:1-7:3 as eluent) to afford compound 8 (1.2 g, yield=79.6%) as a pure product.

[0330] .sup.1H NMR (CDCL.sub.3, 400 MHz) 5.83 (NH), 4.14 (6H, d, J=2.38 Hz, CH.sub.2CCH), 3.83 (6H, s, CH.sub.2O), 2.75 (2H, t, J=7.35 Hz, SCH.sub.2CH.sub.2CO), 2.50 (2H, t, J=7.45 Hz, SCH.sub.2CH.sub.2), 2.46-2.35 (5H, m SCH.sub.2CH.sub.2CO, CHC), 1.56 (2H, m, CH.sub.2CH.sub.2S), 1.32 (10H, m, CH.sub.25), 0.86 (3H, t, J=6.89 Hz CH.sub.3CH.sub.2); .sup.13C NMR (CDCl.sub.3, 100 MHz) 171.51 (CO), 79.66 (CCH), 74.75 (CCH), 68.66 (CH.sub.2O), 59.46 (C), 58.79 (CH.sub.2CCH), 37.71 (SCH.sub.2CH.sub.2CO), 32.48 (SCH.sub.2CH.sub.2), 31.92 (CH.sub.2), 29.75, 29.31, 29.30, 29.01, (CH.sub.25), 27.77 (SCH.sub.2CH.sub.2CO), 22.75 (CH.sub.2), 14.56 (CH.sub.3).

d) Synthesis of Compound N-(1,3-bis(prop-2-yn-1-yloxy)-2-((prop-2-yn-1-yloxy)methyl)propan-2-yl)-3-(dodecylthio)propanamide (compound 9 RC.SUB.10.H.SUB.21.)

[0331] ##STR00045##

[0332] Same procedure as compound 8 (see table 1).

[0333] .sup.1H NMR (CDCL.sub.3, 400 MHz) 5.83 (NH), 4.10 (6H, d, J=2.40 Hz, CH.sub.2CCH), 3.79 (6H, s, CH.sub.2O), 2.71 (2H, t, J=7.45 Hz SCH.sub.2CH.sub.2CO), 2.46 (2H, t, J=7.55 Hz SCH.sub.2CH.sub.2), 2.42-2.33 (5H, m, SCH.sub.2CH.sub.2CO, CHC), 1.52 (2H, m, CH.sub.2CH.sub.2S), 1.38-1.11 (18H, m, CH.sub.29), 0.86 (3H, t, J=6.85 Hz CH.sub.3CH.sub.2); .sup.13C NMR (CDCl.sub.3, 100 MHz) 171.39 (CO), 79.57 (CCH), 74.85 (CCH), 68.54 (CH.sub.2O), 59.51 (C), 58.68 (CH.sub.2CCH), 37.58 (SCH.sub.2CH.sub.2CO), 32.36 (SCH.sub.2CH.sub.2), 31.91 (CH.sub.2), 29.65, 29.62, 29.60, 29.54, 29.45, 29.34, 29.26 29.17, 28.91, (CH.sub.29) 27.66, (SCH.sub.2CH.sub.2CO), 22.68 (CH.sub.2), 14.12 (CH.sub.3). ESI Calcd for C.sub.13H.sub.18NO.sub.3: 492.31 [M+H.sup.+], found m/z 492.31 [M+H.sup.+]. HRMS calculated: C.sub.28H.sub.45NO.sub.4S: 492.3148 [M+H.sup.+], found m/z: 492.3148 [M+H.sup.+].

e) Synthesis of Compound N-(1,3-bis(prop-2-yn-1-yloxy)-2-((prop-2-yn-1-yloxy)methyl)propan-2-yl)-3-(hexadecylthio)propanamide (compound 10 RC.SUB.14.H.SUB.29.)

[0334] ##STR00046##

[0335] Same procedure as compound 8 (see table 1).

[0336] .sup.1H NMR (CDCL.sub.3, 400 MHz) 5.84 (NH), 4.14 (6H, d, J=2.37 Hz, CH.sub.2CCH), 3.84 (6H, s, CH.sub.2O), 2.76 (2H, t, J=7.46 Hz SCH.sub.2CH.sub.2CO), 2.51 (2H, t, J=7.55 Hz, SCH.sub.2CH.sub.2), 2.46-2.39 (5H, m, SCH.sub.2CH.sub.2CO, CHC), 1.56 (2H, m, CH.sub.2CH.sub.2S), 1.39-1.14 (26H, m, CH.sub.213), 0.87 (3H, t, J=6.84 Hz CH.sub.3CH.sub.2); .sup.13C NMR (CDCl.sub.3, 100 MHz) 171.53 (CO), 79.69 (CCH), 74.77 (CCH), 68.70 (CH.sub.2O), 59.49 (C) 58.82 (CH.sub.2CCH), 37.74 (SCH.sub.2CH.sub.2CO), 32.51 (SCH.sub.2CH.sub.2), 32.05 (CH.sub.2), 29.82, 29.79, 29.68, 29.48, 29.40, 29.05, 28.91, (CH.sub.213), 27.66, (SCH.sub.2CH.sub.2CO), 22.81 (CH.sub.2), 14.24 (CH.sub.3). ESI Calcd for C.sub.13H.sub.18NO.sub.3: 548.37 [M+H.sup.+], found m/z 548.38 [M+H.sup.+]. HRMS calculated: C.sub.28H.sub.45NO.sub.4S: 548.3776 [M+H.sup.+], found m/z: 548.3774 [M+H.sup.+].

TABLE-US-00001 TABLE 1 Experimental conditions of Mickal addition (AB3 building blocks). 9 10 RC.sub.2H.sub.4SH Dodecanethiol Hexadecanethiol 0.360 g (1.78.10.sup.3 mol) 0.190 g (7.37 10.sup.4 mol) NaBH.sub.4 0.161 g (4.255.10.sup.3 mol) 0.066 g (1.75 10.sup.3 mol) [00047] 0.4103 g (1.74.10.sup.3 mol) 0.200 g (7.0210.sup.4 mol) Mass of product 0.749 g 0.321 g Yield 88.3% 83.5%
1.2. Synthesis of the monocatenar scaffold (via Mickal addition) with different hydrocarbon chain lengths (AB2 building blocks)

##STR00048##

a) Synthesis of compound N-(2-methyl-1,3-bis(prop-2-yn-1-yloxy)propan-2-yl)-3-(octylthio)propanamide (compound 11)

[0337] ##STR00049##

[0338] Same procedure as compound 8 (experimental conditions given on table 2).

[0339] .sup.1H NMR (CDCL.sub.3, 400 MHz) 5.85 (1H, s, NH), 4.16 (4H, d, J=2.36 Hz CH.sub.2CCH), 3.73 (4H, dd, J=9.04, 51.99 Hz CH.sub.2O), 2.71 (2H, t, J=7.41 Hz SCH.sub.2CH.sub.2CO), 2.52 (2H, t, J=7.41 Hz CH.sub.2S); 2.41 (2H, t, J=2.37 Hz CHC), 2.37 (2H, t, J=7.42 Hz SCH.sub.2CH.sub.2CO), 1.56 (2H, m, CH.sub.2CH.sub.2S), 6=1.42-1.19 (13H, m, CHCH.sub.2, CH.sub.3C), 0.87 ppm (3H, t, J=6.89 Hz CH.sub.3CH.sub.2); 3C NMR (CDCl.sub.3, 100 MHz) 171.35 (CO), 79.72 (CCH), 74.77 (CCH), 72.19 (CH.sub.2O), 58.79 (CH.sub.2CCH), 56.59 (C), 37.87 (SCH.sub.2CH.sub.2CO), 32.57 (SCH.sub.2CH.sub.2), 31.96 (CH.sub.2), 29.80, 29.35, 29.06, 27.87, (CH.sub.26), 22.79 (CH.sub.2), 19.30, 14.24 (CH.sub.3). ESI Calcd for C.sub.13H.sub.18NO.sub.3: 382.13 [M+H], found m/z 382.24 [M+H]. HRMS calculated: C.sub.21H.sub.35NO.sub.3S: 382.2417 [M+H.sup.+], found m/z: 382.2416 [M+H.sup.+].

b) Synthesis of compound N-(2-methyl-1,3-bis(prop-2-yn-1-yloxy)propan-2-yl)-3-(dodecylthio)propanamide (compound 12)

[0340] ##STR00050##

[0341] Same procedure as compound 8 (experimental conditions given on table 2).

[0342] .sup.1H NMR (CDCL.sub.3, 400 MHz) 5.85 (1H, s, NH), 4.09 (4H, d, J=2.39 Hz CH.sub.2CCH), 3.60 (4H, dd, J=9.03, 50.47 Hz CH.sub.2O), 2.70 (2H, t, J=7.40 Hz SCH.sub.2CH.sub.2CO), 2.45 (2H, t, J=7.40 Hz CH.sub.2S), 2.40 (2H, t, J=2.40 Hz SCH.sub.2CH.sub.2CO), 2.34 (2H, t, J=7.40 Hz CHC), 1.51 (2H, m, CH.sub.2CH.sub.2S), 1.36-0.94 (21H, m, CH.sub.3CH.sub.2, CH.sub.3C), 0.81 ppm (3H, t, J=6.87 Hz CH.sub.3CH.sub.2); .sup.13C NMR (CDCl.sub.3, 100 MHz) 171.15 (CO), 79.56 (CCH), 74.68 (CCH), 71.96 (CH.sub.2O), 58.58 (CH.sub.2CCH), 56.40 (C), 37.64 (SCH.sub.2CH.sub.2CO), 32.35 (SCH.sub.2CH.sub.2), 31.87 (CH.sub.2), 29.61, 29.59, 29.57, 29.51, 29.30, 29.22, 28.87, 27.68, (CH.sub.210), 22.64 (CH.sub.2), 19.14, 14.09 (CH.sub.3). ESI Calcd for C.sub.13H.sub.18NO.sub.3: 438.30 [M+H], found m/z 438.30 [M+H.sup.+]. HRMS calculated: C.sub.25H.sub.43NO.sub.3S: 438.3039 [M+H.sup.+], found m/z: 438.3042 [M+H.sup.+].

c) Synthesis of compound N-(2-methyl-1,3-bis(prop-2-yn-1-yloxy)propan-2-yl)-3-(hexadecylthio)propanamide (compound 13)

[0343] ##STR00051##

[0344] Same procedure as compound 8 (experimental conditions given on table 2).

[0345] .sup.1H NMR (CDCL.sub.3, 400 MHz) 5.85 (1H, s, NH), 4.10 (4H, d, J=2.37 Hz CH.sub.2CCH); 3.61 (4H, dd, J=9.03, 50.74 Hz CH.sub.2O), 2.71 (2H, t, J=7.40 Hz SCH.sub.2CH.sub.2CO), 2.46 (2H, t, J=7.40 Hz CH.sub.2S), 2.40 (2H, t, J=2.37 Hz SCH.sub.2CH.sub.2CO), 2.35 (2H, t, J=7.40 Hz CHC), 1.52 (2H, m, CH.sub.2CH.sub.2S), 1.38-1.11 (29H, m, CH.sub.3CH.sub.2, CH.sub.3C), 0.82 (3H, t, J=6.85 Hz CH.sub.3CH.sub.2); .sup.13C NMR (CDCl.sub.3, 100 MHz) 171.17 (CO), 79.59 (CCH), 74.69 (CCH), 72.01 (CH.sub.2O), 58.62 (CH2-CCH), 56.44 (C), 37.69 (SCH.sub.2CH.sub.2CO), 32.39 (SCH.sub.2CH.sub.2), 31.92 (CH.sub.2), 29.69, 29.66, 29.61, 29.55, 29.36, 29.26, 28.91, 27.72, (CH.sub.210), 22.69, (CH.sub.2), 19.17, 14.12 (CH.sub.3). ESI Calcd for C.sub.13H.sub.18NO.sub.3: 494.36 [M+H], found m/z 494.37 [M+H.sup.+]. HRMS calculated: C.sub.29H.sub.51NO.sub.3S: 494.3666 [M+H.sup.+], found m/z: 494.3668 [M+H.sup.+].

TABLE-US-00002 TABLE 2 Experimental conditions of Mickal addition (AB2 building blocks). 11 12 13 RC.sub.2H.sub.4SH Octanethiol Dodecanethiol Hexadecanethiol 0.269 g (1.84.10.sup.3 0.269 g (1.84.10.sup.3 0.231 g (8.9.10.sup.-4 mol) mol) mol) NaBH.sub.4 0.165 g (4.37.10.sup.3 0.1598 g (4.22.10.sup.3 0.0804 g (2.13.10.sup.3 mol) mol) mo1) [00052] 0.412 g (1.75.10.sup.3 mol) 0.412 g (1.75.10.sup.3 mol) 0.200 g (8.5.10.sup.4 mol) Mass of Product 0.450 g 0.237 g 0.280 g Yield 67.44% 45.20% 66.71%
1.3. Functionalization with hydrophilic PolyTris moieties

[0346] a) Synthesis of Hydrocarbon dendriTAC H8G.sub.0triTAC (5*3) (Compound 14)

##STR00053##

[0347] Sodium ascorbate (57 mg, 0.286 mmol, 1.1 eq), compound 11 (112 mg, 0.26 mmol, 1 eq) and azido-polyTRIS oligomer 2b (DPn5) (1.006 g, 1.01 mmol, 3.9 eq) are dissolved in mixture of DMF (7 ml) and water (4 ml), the reaction mixture is heated to 55 C., and after 5 minutes copper sulfate pentahydrate (17 mg, 0.068 mmol, 0.26 eq) is added. The solution is stirred at 60 C. during 3 hours and then at room temperature overnight. The solution is filtered and passed through chelex beads, and then the solvent is carefully removed under high vacuum. The crude is dissolved in a mixture of MeOH/water 9/1 and filtered and then purified over LH20 MeOH/Water 9/1. The purification is followed by TLC (Ethyl Acetate/MeOH 5/5) only fraction where only compounds staying at the start were recovered. The solvent is carefully removed in vacuo at a temperature around 0 C. at the beginning and then at room temperature without the water bath, diluted with water and freeze dried to obtain 377 mg of compound 14 as a white powder (yield=43.03%).

[0348] .sup.1H NMR (DMSO-d6, 400 MHz) 8.05 (3H, s, CH triazole), 7.71-6.79 (16H, c, NH), 5.39-4.56 (48H, c, OH), 4.47 (6H, s, C.sub.TRIAZOLECH.sub.2O), 4.40 (6H, s, CH.sub.2CH.sub.2N.sub.TRIAZOLE), 3.86-3.42 (133H, br, CH.sub.2OH, CH.sub.2O), 2.68 (4H, c, CH.sub.2CH.sub.2S, SCH.sub.2CH.sub.2CO), 2.37-1.86 (27H, c, CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2S, CH, CH.sub.2CO, 1Ha CH.sub.2CH.sub.2CO CHCOLIGOMER), 1.82-1.09 (42H, c, CH.sub.2alkyl chain CH.sub.2 OLIGOMER), 0.85 (3H, t, J=6.95 Hz CH.sub.3).

[0349] b) Synthesis of Hydrocarbon dendriTAC H12G.sub.0triTAC (5*3) (Compound 15)

##STR00054##

[0350] Same procedure as compound 14 (see experimental conditions on table 3).

[0351] .sup.1H NMR (DMSO-d6, 400 MHz) 8.04 (3H, s, CH triazole), 7.78-6.69 (25H, c, NH), 5.43-4.57 (75H, c, OH), 4.48 (6H, d, J=7.31 Hz C.sub.TRIAZOLECH.sub.2O), 4.40 (6H, s, CH.sub.2CH.sub.2N.sub.TRIAZOLE), 3.86-3.37 (150H, br, CH.sub.2OH, CH.sub.2O), 2.72 (4H, c, CH.sub.2CH.sub.2S, SCH.sub.2CH.sub.2CO), 2.29-1.84 (40H, c, CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2S, CH, CH.sub.2CO, 1Ha CH.sub.2CH.sub.2CO CHCO.sub.OLIGOMER), 1.79-1.13 (75H, c, CH.sub.2akyl chain CH.sub.2 OLIGOMER), 0.85 (3H, t, J=6.63 Hz CH.sub.3).

[0352] c) Synthesis of Hydrocarbon dendriTAC H16G.sub.0triTAC (5*3) (Compound 16)

##STR00055##

[0353] Same procedure as compound 14 (see experimental conditions on table 3).

[0354] .sup.1H NMR (DMSO-d6, 400 MHz) 8.03 (3H, s, CH triazole), 7.74-6.75 (19H, c, NH), 5.50-4.56 (50H, c, OH), 4.47 (6H, d, J=7.64 Hz O.sub.TRIAZOLECH.sub.2O), 4.39 (6H, s, CH.sub.2CH.sub.2N.sub.TRIAZOLE), 3.91-3.41 (96H, br, CH.sub.2OH, CH.sub.2O), 2.68 (4H, c, CH.sub.2CH.sub.2S, SCH.sub.2CH.sub.2CO), 2.32-1.83 (24H, c, CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2S, CH, CH.sub.2CO, 1Ha CH.sub.2CH.sub.2CO CHCO.sub.OLIGOMER), 1.80-1.01 (50H, c, CH.sub.2alkyl chain CH.sub.2 OLIGOMER), 0.85 (3H, t, J=6.73 Hz CH.sub.3).

[0355] d) Synthesis of Hydrocarbon dendriTAC H8G.sub.odiTAC(5*2) (Compound 17)

##STR00056##

[0356] Same procedure as compound 14 (see experimental conditions on table 3); equivalents number of oligomer 2b is 2.6 instead of 3.9.

[0357] .sup.1H NMR (DMSO-d6, 400 MHz) 8.04 (2H, s, CH triazole), 7.74-6.75 (19H, c, NH), 5.57-4.58 (54H, c, OH), 4.49 (4H, C.sub.TRIAZOLECH.sub.2O), 4.40 (4H, s, CH.sub.2CH.sub.2N.sub.TRIAZOLE), 3.97-3.43 (110H, br, CH.sub.2OH, CH.sub.2O), 2.57 (3H, m, Ha CH.sub.2CH.sub.2S oligomer SCH.sub.2CH.sub.2CO), 2.45 (3H, m, Hb CH.sub.2CH.sub.2S oligomer CH.sub.2CH.sub.2S), 2.29 (2H, m, SCH.sub.2CH.sub.2CO), 2.27-1.85 (27H, c, CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2S, CH, CH.sub.2CO, 1Ha CH.sub.2CH.sub.2CO CHCO.sub.OLIGOMER), 1.76-1.09 (50H, c, CH.sub.2alkyl chain CH.sub.2 OLIGOMER), 0.85 (3H, t, J=6.80 Hz CH.sub.3).

[0358] e) Synthesis of Hydrocarbon dendriTAC H12G.sub.odiTAC(5*2) (Compound 18)

##STR00057##

[0359] Same procedure as compound 14 (see experimental conditions on table 3); equivalents number of oligomer 2b is 2.6 instead of 3.9.

[0360] .sup.1H NMR (DMSO-d6, 400 MHz) 8.05 (2H, s, CH triazole), 7.77-6.72 (21H, c, NH), 5.30-4.56 (53H, c, OH), 4.49 (4H, C.sub.TRIAZOLECH.sub.2O), 4.40 (4H, s, CH.sub.2CH.sub.2N.sub.TRIAZOLE), 3.95-3.41 (104H, br, CH.sub.2OH, CH.sub.2O), 2.57 (3H, m, Hb CH.sub.2CH.sub.2S oligomer SCH.sub.2CH.sub.2CO), 2.45 (3H, m, Hb CH.sub.2CH.sub.2S oligomer CH.sub.2CH.sub.2S), 2.31 (2H, m, SCH.sub.2CH.sub.2CO), 2.26-1.82 (27H, c, CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2S, CH, CH.sub.2CO, 1Ha CH.sub.2CH.sub.2CO CHCO.sub.OLIGOMER), 1.77-1.11 (50H, c, CH.sub.2alkyl chain CH.sub.2 OLIGOMER), 0.85 (3H, t, J=6.75 Hz CH.sub.3).

[0361] f) Synthesis of Hydrocarbon dendriTAC H16G.sub.0diTAC(5*2) (Compound 19)

##STR00058##

[0362] Same procedure as compound 14 (see experimental conditions on table 3); equivalents number of oligomer 2b is 2.6 instead of 3.9.

[0363] .sup.1H NMR (DMSO-d6, 400 MHz) 8.04 (2H, s, CH triazole), 7.79-6.56 (18H, c, NH), 5.45-4.57 (50H, c, OH), 4.48 (4H, d, J=7.52 Hz C.sub.TRIAZOLECH.sub.2O), 4.40 (4H, s, CH.sub.2CH.sub.2N.sub.TRIAZOLE), 3.93-3.41 (100H, br, CH.sub.2OH, CH.sub.2O), 2.29-1.84 (25H, c, CH.sub.2CH.sub.2CH.sub.2S, CH.sub.2S, CH, CH.sub.2CO, 1Ha CH.sub.2CH.sub.2CO CHCO.sub.OLIGOMER), 1.79-1.03 (50H, c, CH.sub.2alkyl chain CH.sub.2 OLIGOMER), 0.85 (3H, t, J=6.70 Hz CH.sub.3).

TABLE-US-00003 TABLE 3 Experimental conditions for the cycloaddition step. Final surfactant 14 15 16 17 18 19 Propargyl compound 11 12 13 8 9 10 mass 0.112 g 0.075 g 0.054 g 0.150 g 0.146 g 0.150 g mol 2.57 .Math. 10.sup.4 1.5 .Math. 10.sup.4 9.87 .Math. 10.sup.5 3.39 .Math. 10.sup.4 3.34 .Math. 10.sup.4 3.04 .Math. 10.sup.4 Oligomer 2b 1.006 g 0.775 g 0.518 g 1.059 g 0.929 g 1.631 g (1.01 .Math. 10.sup.3 (7.07 .Math. 10.sup.4 (3.85 .Math. 10.sup.4 (10.21 .Math. 10.sup.4 (8.85 .Math. 10.sup.4 (7.9 .Math. 10.sup.4 mol) mol) mol) mol) mol mol) Copper (II) sulfate 17 mg 17 mg 6 mg 32 mg 23 mg 20 mg (0.07 .Math. 10.sup.4 (6.81 .Math. 10.sup.5 (2.57 .Math. 10.sup.5 (1.02 .Math. 10.sup.4 (8.82 .Math. 10.sup.5 (7.9 .Math. 10.sup.5 mol) mol) mol) mol) mol) mol) Sodium ascorbate 57 mg 49 mg 215 mg 85 mg 71 mg 66 mg (2.86 .Math. 10.sup.4 (2.47 .Math. 10.sup.4 (1.08 .Math. 10.sup.4 (4.32 .Math. 10.sup.4 (3.7 .Math. 10.sup.4 (7.9 .Math. 10.sup.5 mol) mol) mol) mol) mol mol) Mass of product 0.377 g 0.212 g 0.130 g 0.236 g 0.499 g 0.162 g Yield 43.03% 40.69% 28.80% 29.99% 62.87% 21.74%

Example 3: Synthesis of the F- or H-TAC Telomers

[0364] The synthesis of F- and H-TAC telomers (Scheme 3) was already reported by Pucci et al. (European Polymer Journal. 1991, 27, 1101-1106; Curr. Med. Chem. Anticancer Agents. 2 (2002) 645-665).

##STR00059##

[0365] F- or H-TAC telomers are obtained by free radical telomerization of an acryloyl monomer derived from Tris, the tris(hydroxymethyl)acrylamidomethane (THAM), or from its peracetylated analogue (tris(acetoxymethyl)acrylamidomethane), in the presence of an alkane (for H-TAC) or a fluoroalkanethiol (for F-TAC) as a transfer reagent called telogen. The synthesis of the two polymerizable monomers THAM or peracetylated THAM analogue is performed as previously reported (Jasseron et al. European Journal of Medicinal Chemistry 2003, 38, 825-836; Astafyeva et al. J. Mater. Chem. B 2015, 3, 2892-2907). The physico-chemical parameters of the resulting telomers (molecular weight, Hydrophilic Lipophilic Balance, electric charge) can be adjusted through both the starting material and the experimental conditions (Pucci et al., ibid.). Telomerization experiments are respectively performed in methanol (MeOH), when the monomer THAM is used as starting material, and in tetrahydrofuran (THF) for peracetylated THAM. The use of this later monomer is necessary for the synthesis of telomers with a degree of polymerization (DPn; average number of repeating units on the polymeric backbone+1 (telogen moiety)) higher than 15 due to the limited solubility of polyTris oligomers in pure methanol for such DPn values (Giusti et al., New J. Chem. 2002, 26, 1724-1732). Alternatively, it is also possible to synthetise telomers with a DPn higher than 15 starting from THAM using a mixture of MeOH/H2O (90/10 to 80/20, v/v) as solvent.

##STR00060##

[0366] Synthesis of F- and H-TAC Surfactants.

[0367] Reagents and conditions: (a) AIBN/THF, reflux (62-66%); (b) i: AIBN/CH.sub.3OH, reflux or ii: AIBN/[CH.sub.3OH/H2O, 90/10, v/v], reflux (62-73%); (c) MeONa cat./MeOH, room temperature (100%).

[0368] Telomerization experiments are carried out by refluxing monomer THAM or peracetylated THAM in dry and degassed appropriate solvent, under a nitrogen atmosphere, in the presence of alkane- or fluoroalkanethiol as transfer reagent and AIBN (a,a-azobisisobutyronitrile) as radical initiator. The AIBN concentration in the reaction mixture is ten times lower than the telogen one (C. M. Starks, Free radical telomerization, Academic Press, New York, 1974). The starting proportions of monomer THAM or peracetylated THAM and telogen used are reported in table 4. These proportions are chosen taking into account previous results obtained with THAM telomerization. The reaction is monitored by thin layer chromatography and pursued until complete disappearance of each monomer (4 to 12 h). For telomers prepared starting from THAM, the solution is then concentrated and subsequently precipitated in diethyloxyde. The precipitate is dissolved in water and freeze dried to give final surfactants as white powders. As regards peracetylated telomers, after total disappearance of monomer peracetylated THAM, a final treatment under Zempln conditions (Astafyeva et al., ibid.) provides the desired water soluble telomers in satisfactory yields and NMR analysis confirms the total disappearance of acetyl groups. Telomers with DPn>15 are all purified by precipitation in diethyloxyde. The resulting precipitate is dissolved in water and a dialysis (cut off of 1000) is performed overnight, the solution is freeze dried to obtain final surfactants as white powders.

[0369] For all the series of telomers, the degree of polymerization depends on the telogen/monomer ratio adjusted through both starting materials and experimental conditions (Pucci et al. European Polymer Journal 1988, 24, 1077-1086). For a given transfer reagent, it may vary from one (monoadduct) to several tens. DPn are determined in 1H-NMR or 19F-NMR by comparing the area of typical signals ascribed to each monomer and telogen.

[0370] For example, in the case of hydrocarbon telomers (H-TAC) DPn values are determined by comparing peaks area assigned to the terminal methyl signal in the hydrocarbon tail (d 0.9 ppm, integral 3H) respectively to hydroxyl groups of THAM (d 4.5-5.3 ppm, integral 3 nH) or to methylene protons of peracetylated THAM (d 4.32 ppm, integral 6nH). Concerning fluorocarbon telomers (F-TAC) the DPn is assessed by quantification of fluorine using 19F-NMR as described by Astafyeva et al. (ibid.).

TABLE-US-00004 TABLE 4 Conditions of F- or H-TAC synthesis Initial Condition [monomer]/ Yield Compound R Monomer [telogen] solvent DPn (%) F.sub.6TAC.sub.7 C.sub.6F.sub.13 THAM 3 MeOH 7 62.2 F.sub.6TAC.sub.13 C.sub.6F.sub.13 THAM 5 MeOH 13 58.2 F.sub.6TAC.sub.18 C.sub.6F.sub.13 THAM(OAc) 15 THF 18 46.6 F.sub.6TAC.sub.22 C.sub.6F.sub.13 THAM(OAc) 20 THF 22 55.7 H.sub.8TAC.sub.6 C.sub.6H.sub.13 THAM(OAc) 5 THF 6 56.4 H.sub.8TAC.sub.8 C.sub.6H.sub.13 THAM 5 MeOH 8 50.5 H.sub.8TAC.sub.9 C.sub.6H.sub.13 THAM 6 MeOH 9 49 H.sub.12TAC.sub.6 C.sub.10F.sub.21 THAM 6 MeOH 6 38.8 H.sub.12TAC.sub.9 C.sub.10F.sub.21 THAM 8 MeOH 9 44.8

Example 4: Study of the Phases Separation

[0371] An equal volume of organic solvent and aqueous (water+amhiphile) phases were contacted and shaken for 5 min at 20 C. The mixture was let to separate for 5 mins, and phase separation was visually characterized. In the case of the presence of an emulsion, the mixture was centrifuged at 5000 rpm for 3 min, then visually observed again. When persisting in this case, the emulsion was qualified as stable.

TABLE-US-00005 Solvent toluene toluene toluene toluene toluene toluene Amphiphile Sodium TPGS- H8-TAC6 F6-TAC6 Zonyl UR Brij 35 (amount) dodecyl 750M (2% wt) (2% wt) (2% wt) (2% wt) sulfate (SDS) (2% wt) (2% wt) Result Stable Stable Clean Clean Stable Stable Emulsion Emulsion phase phase Emulsion Emulsion separation separation Zonyl UR is a fluorinated phosphate (mixture of mono & di esters, DuPont product), Brij 35 is a non-ionic surfactant (C12-(EO)23).

[0372] The surfactants of the invention enable clean phase separation, whereas the surfactants SDS, TPGS-750M, Zonyl UR and Brij 35 lead to a stable emulsion.

Example 5: Study of the Phases Separation in Presence of an Extractant

[0373] An equal volume of organic (extractant+diluent) and aqueous (water+amhiphile) phases were contacted and shaken for 5 min at 20 C. The mixture was let to separate for 5 mins, and phase separation was visually characterized. In the case of the presence of an emulsion, the mixture was centrifuged at 5000 rpm for 3 min, then visually observed again. When persisting in this case, the emulsion was qualified as stable.

TABLE-US-00006 Diluent toluene toluene toluene toluene toluene toluene none Extractant DMDBTD- DMDBTD- DMDBTD- DMDBTD- DMDBTD- BESO TBP (amount) MA MA MA MA MA (0.3 (pure) (0.5 (0.5 (0.5 (0.5 (0.5 mol/L) mol/L) mol/L) mol/L) mol/L) mol/L) Amphiphile H8TAC6 F6TAC6 H16G.sub.0triTAC H12G.sub.0diTAC F6TAC17 F6TAC17 F6TAC17 (amount) (2% wt) (2% wt) (5 * 3) (5 * 2) (2% wt) (2% wt) (2% wt) (2% wt) (1% wt) Result Clean Clean Clean Clean Clean Clean Clean phase phase phase phase phase phase phase separation separation separation separation separation separation separation DMDBTDMA = dimethyldibutyltetradecylmalonamide, BESO = Bis-ethylhexyl sulfoxide, TBP = tributylphosphate.

[0374] The surfactants of the invention enable clean phase separation.

Example 6: Extraction of an Organic Phase Comprising Pd Using the Surfactants of the Invention

[0375] An organic phase loaded with Pd was prepared by contacting a solvent (see table below) with an aqueous solution of nitric acid containing Pd(II) nitrate, followed by shaking for 1 h, and phase separation. The so obtained organic phase (800 L) was contacted with an aqueous phase (400 L, see table below), and the system was shaken in a closed cap vial for 30 min at 20 C. The phases were allowed to separate for 5 min, then 200 L of each phase were taken for quantitative Pd analysis (performed with a SpectroArcos ICP-AES spectrometer). The back extraction yield was determined as follows: yield=amount of Pd in final aqueous phase/amount of Pd in initial organic phase. Quantitative recovery of Pd (within the analytical limits) was checked in all cases (amount of Pd in initial organic phase=amount of Pd in final aqueous phase+amount of Pd in final organic phase).

TABLE-US-00007 Diluent toluene toluene none Extractant DMDBTDMA BESO TBP (amount) (0.5 mol/L) (0.3 mol/L) (pure) Pd-back extraction yield 50% 2.50% 13% with water alone Pd-back extraction yield 72% 31% 78% with F6-TAC17 (2% wt)

Example 7: Buchwald-Hartwig Cross-Coupling Reaction Using Commercial Palladium Source in Presence of the Surfactants of the Invention, Compared to TPGS-750M

General Procedure (Wagner et al., Green Chemistry 16:4170-4178)

[0376] Amine (1.2 equiv.) and aryl halide (1 equiv.) were added to an aqueous solution of surfactant (2 wt %, 1 mL/mmol). The mixture was degassed by bubbling Argon, and NaOt-Bu (1.5 equiv.), [(cinnamyl)PdCl].sub.2 (1.1 mol %) and t-BuXPhos (4.4 mol %) were added. The mixture was stirred (at 1200 rpm) at 50 C. (2-24 h). Volatiles were evaporated and the crude residue was purified by chromatography on silica gel.

N-(3-Methylphenyl)-4-methoxybenzamide

[0377] Following the general procedure of the Buchwald-Hartwig cross-coupling reaction, we used [(cinnamyl)PdCl].sub.2 (5.7 mg, 0.011 mmol), t-BuXPhos (18.7 mg, 0.044 mmol), 3-bromotoluene (121 L, 1.0 mmol), p-methoxybenzamide (181 mg, 1.2 mmol) and NaOt-Bu (144 mg, 1.5 mmol) in presence of various surfactants (20 mg in 1 mL of water). Purification was performed by column chromatography on silica gel with the following eluent:n-heptane/ethyl acetate (7/3 to 5/5). After evaporation, N-(3-Methylphenyl)-4-methoxybenzamide was recovered as white solid. 1H NMR (400 MHz, CDCl3) 2.34 (s, 3H), 3.87 (s, 3H), 6.95-6.97 (m, 3H), 7.25 (t, J=7.7 Hz, 1H), 7.41 (d, J=7.7 Hz, 1H), 7.51 (s, 1H), 7.80 (d, J=8.9 Hz, 2H), 7.87 (br s, 1H); 13C NMR (101 MHz, CDCl3) 21.5, 55.4, 113.9, 117.2, 120.8, 125.1, 127.2, 128.8, 128.9, 138.0, 138.9, 162.4, 165.2.

[0378] Results are shown in the table below:

TABLE-US-00008 Yield Surfactant (2%) (%) Surfactant (2%) Yield (%) TPGS-750-M 93 F6TAC7 81 F6 G.sub.0diTAC (10*2) 79 F6TAC13 82 H8G.sub.0triTAC (5*3) 88 F6TAC17 78 H8G.sub.0diTAC (5*2) 88 H8TAC6 89 H12G.sub.0diTAC (5*2) 86 H8TAC8 84 H12G.sub.0triTAC (5*3) 85 H8TAC9 86 H16G.sub.0triTAC (5*3) 86 H12TAC6 84 H16G.sub.0diTAC (5*2) 89 H12TAC9 84

Example 8: Suzuki-Miyaura Cross-Coupling Reaction Using Back-Extracted Palladium in Micellar Medium

[0379] To a solution of back-extracted palladium in water (80 L) containing the surfactant H12G.sub.0diTAC (5*2) (2% w:w) were added 3-bromoanisole (1 eq., 12.5 mg, 0.00848 mL, 0.0667 mmol), phenylboronic acid (1.2 eq., 9.75 mg, 0.08 mmol), Bippyphos (4.4%, 3.83 mg, 0.00733 mmol) and triethylamine (1.86 eq., 12.5 mg, 0.0172 mL, 0.124 mmol). The reaction mixture was stirred at room temperature for 16 h in a Bioshake IQ at 1 800 rpm. The aqueous phase was extracted with ethyl acetate. This organic phase was evaporated and the crude residue was purified by chromatography on silica gel using ethyl acetate and n-heptane as eluent to provide 1-methoxy-3-phenylbenzene (10.4 mg, 0.057 mmol, 34% yield). 1H NMR (400 MHz, CDCl3): 7.58 (d, J=5.2 Hz, 2H), 7.44 (t, J=5.1 Hz, 2H), 7.37-7.34 (m, 2H), 7.18 (d, J=5.1 Hz, 1H), 7.13 (s, 1H), 6.91-6.89 (m, 1H), 3.87 (s, 3H).