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

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.

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

References

1a Singh RP. Subbarao HN. Dev S. Tetrahedron  1980,  37:  843 

1b Siev DV. Semple JE. Org. Lett.  2000,  2:  19 

1c Blanchet C. Joly P. Granier M. Lanneau GF. Cretin M. Persin M. Melnyk O. Durand J.-O. Tetrahedron Lett.  2003,  44:  4191 

1d Podyminogin MA. Lukhtanov EA. Reed MW. Nucleic Acids Res.  2001,  29:  5090 

1e Melnyk O. Duburcq X. Oliver C. Urbès F. Auriault C. Gras-Masse H. Bioconjugate Chem.  2002,  13:  713 

2 Niemeyer MC. Angew. Chem. Int. Ed.  2001,  40:  4128 

3a Guerrero G. Mutin PH. Vioux A. Chem. Mater.  2001,  13:  4367 

3b Gao W. Dickinson L. Grozinger C. Morin F. Reven L. Langmuir  1996,  12:  6428 

3c Frantz R. Durand J.-O. Lanneau GF. Jumas J.-C. Olivier-Fourcade J. Crétin M. Persin M. Eur. J. Inorg. Chem.  2002,  1088 

4a Grison C. Comoy C. Coutrot P. l’Actualité Chimique  2001,  38 

4b Coutrot P. Grison C. Charbonnier-Gérardin C. Tetrahedron  1992,  48:  9841 

5a Bookser BC. Kasibhatla SR. Appleman JR. Erion MD. J. Med. Chem.  2000,  43:  1495 

5b Cushman M. Yang D. Mihalic JT. Chen J. Gerhardt S. Huber R. Fischer M. Kis K. Bacher A. J. Org. Chem.  2002,  67:  6871 

5c Falck JR. Abdali A. Wittenberger SJ. J. Chem. Soc., Chem. Commun.  1990,  953 

5d De Lombaert SD. Stamford LB. Blanchard L. Tan J. Hoyer D. Diefenbacher CG. Wei D. Wallace EM. Moskal MA. Savage P. Jeng AY. Biorg. Med. Chem. Lett.  1997,  7:  1059 

6

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.

7 Carpino LA. Han GY. J. Org. Chem.  1972,  37:  3404 

8a Shioiri T. Ninomiya K. Yamada SI. J. Am. Chem. Soc.  1972,  94:  6203 

8b Ninomiya K. Shioiri T. Yamada S. Tetrahedron  1974,  30:  2151 

9

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.

10 Smaihi M. Gavilan E. Durand JO. Valtchev VP. J. Mater. Chem.  2004,  14:  1347 

11 Pawsey S. Kimberly Y. Reven L. Langmuir  2002,  18:  5205 

12 Lukes I. Borbaruah M. Quin LD. J. Am. Chem. Soc.  1994,  116:  1737 

13 Blanchet C. Joly P. Granier M. Lanneau GF. Cretin M. Persin M. Melnyk O. Durand JO. Tetrahedron Lett.  2003,  44:  4191