Amphiphilic Trithiols RC(CH₂SH)₃

Abstract

We report on the synthesis of the amphiphilic molecules 1,1,1-tris(mercaptomethyl)undecane and 1,1,1-tris(mercaptomethyl)dec-9-ene starting from the corresponding tris(hydroxymethyl) compounds. In addition we describe the synthesis of an amphiphilic phosphite ligand possessing only one alkyl chain. These compounds are potential substrates for the monolayer protection of 2D surfaces and nanoparticles.

thiols - Mitsunobu reaction - ligands - nanostructures - polycycles

References and Notes

1 Pellegrino T. Kudera S. Liedl T. Muñoz Javier A. Manna L. Parak WJ. Small  2005,  1:  48 

2a Ingram RS. Hostetler MJ. Murray RW. J. Am. Chem. Soc.  1997,  119:  9175 

2b Hostetler MJ. Templeton AC. Murray RW. Langmuir  1999,  15:  3782 

2c Song Y. Murray RW. J. Am. Chem. Soc.  2002,  124:  7096 

2d Song Y. Huang T. Murray RW. J. Am. Chem. Soc.  2003,  125:  11694 

2e Guo R. Song Y. Wang GR. Murray W. J. Am. Chem. Soc.  2005,  127:  2752 

2f Woehrle GH. Brown LO. Hutchinson JE. J. Am. Chem. Soc.  2005,  127:  2172 

3 Weibull B. Matell M. Acta Chem. Scand.  1962,  16:  1062 

4 Kolomyjec C. Whelan J. Bosnich B. Inorg. Chem.  1983,  22:  2343 

5 Muth A. Asam A. Huttner G. Barth A. Zsolnai L. Chem. Ber.  1994,  127:  305 

6 Doering WE. Levy LK. J. Am. Chem. Soc.  1955,  77:  509 

7 Feltham RD. Kasenally A. Nyholm RS. J. Organomet. Chem.  1967,  7:  285 

8 Keiter RL. Verkade JG. Inorg. Chem.  1969,  8:  2115 

9

Spectroscopic Data for 2.
¹H NMR (500 MHz, CDCl₃): δ = 0.85 (t, 3 H, CH₃), 1.10-1.40 (m, 18 H, CH₂), 3.94 (d, 6 H, CH₂O, ³ J(P,H) = 1.9 Hz) ppm. ³¹P NMR (202 MHz, CDCl₃): δ = 93.1 (s) ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 14.0, 22.3, 22.6, 29.2, 30.1, 31.8, 34.5, 34.6, 70.7. IR (ATR): 2923, 2854 (CH₂ val.), 1465, 1152, 1037, 954, 855, 730 cm^-1. MS (EI): m/z (%) = 274 (24) [M⁺], 244 (100), 95 (60), 81 (69), 69 (45), 55 (77), 41 (69). Anal. Calcd (%): C, 61.29; H, 9.92. Found: C, 60.81; H, 10.24.

10

CCDC 287796 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

11

Unpublished results.

12 Hughes DL. In Organic Reactions   Vol. 42:  Paquette LA. J. Wiley and Sons, Inc.; New York: 1992.  p.335 

13 Jones PB. Parrish NM. Houston TA. Stapon A. Bansal NP. Dick JD. Townsend CA. J. Med. Chem.  2000,  43:  3304 

14

Spectroscopic Data for 3a,b and 4a,b.
Compound 3a: ¹H NMR (500 MHz, CDCl₃): δ = 0.84 (t, 3 H, CH₃), 1.10-1.40 (m, 18 H, CH₂), 2.30 [s, 9 H, SC(O)CH₃], 2.94 [s, 6 H, CH₂SC(O)CH₃] ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 14.0, 22.6, 23.2, 29.2, 29.5, 29.9, 30.6, 31.8, 35.1, 36.0, 41.0, 194.5 ppm. IR (ATR): 2924, 2853 (CH₂ val.), 1744, 1696 [SC(O)R] cm^-1. MS (EI): m/z (%) = 420 (0.5) [M⁺], 377 (30) [M⁺ - 1 × C(O)CH₃], 335 (57) [M⁺ - 2 × C(O)CH₃], 293 (42) [M⁺ - 3 × C(O)CH₃], 43 (100) [C(O)CH₃].
Compound 3b: ¹H NMR (500 MHz, CDCl₃): δ = 1.10-1.30 (m, 12 H, CH₂), 1.96 (m, 2 H, =CHCH₂), 2.26 [s, 9 H, SC(O)CH₃], 2.91 [s, 6 H, CH₂SC(O)CH₃], 4.86 [dd, 1 H, E, ² J(H,H) = 1.3 Hz, ³ J(H,H) = 10.0 Hz], 4.92 [dd, 1 H, Z, ² J(H,H) = 1.9 Hz, ³ J(H,H) = 17.0 Hz), 5.73 (m, 1 H, =CH) ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 23.2, 28.9, 29.1, 29.9, 30.6, 33.7, 35.1, 36.0, 41.0, 114.1, 139.1, 194.6 ppm. IR (ATR): 2980 (=CH val.), 2854, 2826 (CH val.), 1751, 1692 [SC(O)R] cm^-1. MS (EI): m/z (%) = 404 (0.5) [M⁺] 361 (39) [M⁺ - 1 × C(O)CH₃], 319 (66) [M⁺ - 2 × C(O)CH₃], 277 (40) [M⁺ - 3 × C(O)CH₃], 43 (100) [C(O)CH₃].
Compound 4a: ¹H NMR (500 MHz, CDCl₃): δ = 0.86 (t, 3 H, CH₃), 1.10-1.40 (m, 21 H, CH₂ and SH), 2.55 [d, 6 H, CH₂SH, ³ J(H,H) = 8.8 Hz] ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 14.1, 22.6, 23.2, 29.1, 29.3, 30.1, 31.9, 32.4, 41.4 ppm. IR (ATR): 2922, 2852 (CH val.), 2561 (SH val.) cm^-1. MS (EI): m/z (%) = 294 (100) [M⁺].
Compound 4b: ¹H NMR (500 MHz, CDCl₃): δ = 1.05-1.40 (m, 15 H, CH₂ and SH); 1.98-2.08 (m, 2 H, CH₂CH=CH₂), 2.55 [d, 6 H, CH₂SH, ³ J(H,H) = 8.8 Hz], 4.93 [dd, 1 H, E, ² J(H,H) = 1.3 Hz, ³ J(H,H) = 10.0 Hz], 4.99 [dd, 1 H, Z, ² J(H,H) = 1.3 Hz, ³ J(H,H) = 17.0 Hz], 5.80 (m, 1 H, =CH) ppm. ¹³C NMR (126 MHz, CDCl₃): δ = 23.2, 28.8, 29.0, 29.3, 30.0, 32.4, 33.7, 41.3, 114.2, 139.1. IR (ATR): 2980 (=CH val.), 2925, 2853 (CH val.), 2568 (SH val.) cm^-1. MS (EI): m/z (%) = 278 (53) [M⁺], 41 (100).