Synthesis of Phosphonic Acids with the Semicarbazide Group for the Functionalization of Metal Oxide and Zeolite Nanoparticles

Tristan Doussineau; Jean-Olivier Durand; Michel Granier; Monique Smaïhi; Valentin Valtchev

doi:10.1055/s-2004-829565

LETTER

Synthesis of Phosphonic Acids with the Semicarbazide Group for the Functionalization of Metal Oxide and Zeolite Nanoparticles

Tristan Doussineau*^a, Jean-Olivier Durand^a, Michel Granier^a, Monique Smaïhi^b, Valentin Valtchev^c
^a Chimie Moleculaire et Organisation du Solide, UMR 5637 cc 007 Université Montpellier, 2, Place Eugène Bataillon, 34095 Montpellier Cedex 05, France
Fax: +33(4)67143852; e-Mail: doussine@iemm.univ-montp2.fr;
^b Institut Européen des Membranes, UMR 5635 cc 047 Université Montpellier, 2, Place Eugène Bataillon, 34095 Montpellier Cedex 05, France
^c Laboratoire des Matériaux Minéraux, (LMM) UMR 7016, ENSCMu, 3 rue Alfred Werner, 68093 Mulhouse, France

Abstract

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Abstract

The syntheses of two phosphonic acids possessing the Fmoc-protected semicarbazide group are described. The key step was the Curtius rearrangement, performed in the presence of dibenzyl phosphonate esters. Preliminary experiments showed that the phosphonic acid can be grafted at the surface of oxide nanoparticles and colloidal zeolite nanocrystals, without deprotection of the Fmoc group.

Key words

nanoparticle - zeolite - Curtius’ rearrangement - phosphonic acid - grafting

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References

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Experimental Procedure for 2b: KH 30% in mineral oil (4.0 g, 30.0 mmol) was suspended in dry DMF (150 mL) at 0 °C. Dibenzylphosphite (8.0 g, 30.0 mmol) was added dropwise. Methyl 11-bromo undecanoate (7.3 g, 26.1 mmol) was then rapidly added. The reaction was allowed to warm to r.t. after 15 min. After 6 h, the reaction was quenched at at 0 °C by careful addition of H₂O (100 mL). The mixture was extracted with EtOAc (3 × 100 mL) and the organic phase washed with a minimum amount of H₂O, dried over MgSO₄, the solvents were then evaporated. Flash chromatography (Et₂O) afforded 2b (8.94 g, 74%). ¹H NMR (CDCl₃): δ = 1.26-1.85 (m, 18 H, CH₂), 2.34 (t, 2 H, ³ J _H-H = 7.65 Hz), 3.70 (s, 3 H), 5.00 (m, 4 H), 7.38 (s, 10 H) ppm. ¹³C NMR (CDCl₃): δ = 22.68 (td, 1 C, ² J _C-P = 5.28 Hz), 25.35 (t, 1 C), 26.42 (td, 1 C, ¹ J _C-P = 139.77 Hz), 29.39-29.74 (m, 5 C), 30.89 (td, 1 C, ³ J _C-P = 17.06 Hz), 34.51 (t, 1 C), 51.85 (q, 1 C), 67.41 (td, 2 C, ³ J _C-P = 6.46 Hz), 128.28 (d, 4 C), 128.73 (d, 2 C), 128.97 (d, 4 C), 136.97 (sd, 2 C, ³ J _C-P = 5.94 Hz), 174.73 (s, 1 C, C=O) ppm. IR (NaCl pellets): ν (CH_arom.) = 3090, 3064, 3033; ν (CH_2aliph) = 2928, 2854; ν (C=O_ester) = 1736 cm^-1. MS (FAB⁺, NBA): m/z [MH⁺] = 461.

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Data for 5b: IR (KBr): ν (NH) = 3306; ν (CH _arom) = 3063, 3038; ν (CH₂) = 2922, 2850; ν (POH) = 3500-2500, 2347; ν (C=O) = 1731; ν (C=O) = 1661; δ (NH) = 1556; ν (P=O) 1264 and 1217, 1157, 1098, 898, 759, 738 cm^-1. ¹H NMR (CDCl₃, 1 drop of TFA: δ = 1.30-1.60 (m, 16 H), 1.88-2.04 (m, 2 H), 3.22 (t, ³ J = 6.90 Hz, 2 H), 4.26 (t, ³ J = 5.80 Hz, 1 H), 4.70 (d, ³ J = 5.80 Hz, 2 H), 7,35-7.48 (m, 4 H), 7,55 (d, ³ J = 7.40 Hz, 2 H), 7.81 (d, ³ J = 7.33 Hz, 2 H) ppm. ¹³C NMR (DMSO): δ = 23.62 (td, 1 C, ² J _C-P = 4.19 Hz), 28.82 (td,1 C, ¹ J _C-P = 178.63 Hz), 29.58-29,90 (m, 7 C, CH₂), 30.98 (td, 1 C, ³ J _C-P = 16.17 Hz), 47.42 (t, 1 C), 67.00 (d, 1 C), 120.97 (d, 2 C), 126.23 (d, 2 C), 127.98 (d, 2 C), 128.56 (d, 2 C), 141.57 (s, 2 C), 144.53 (s, 2 C), 157.71 (s, 1 C, C=O), 159.10 (s, 1 C, C=O) ppm. ³¹P NMR (DMSO): δ = 24.97 ppm. MS (ES⁺, Q-TOF): m/z [(M - H + Na) + H⁺] = 540.3.

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