Reaction of Amphipathic-Type
Thioester and Amine with Hydrophobic Effect in Water

Atsushi Torihata; Chiaki Kuroda

doi:10.1055/s-0030-1261165

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Synlett 2011(14): 2035-2038
DOI: 10.1055/s-0030-1261165

LETTER

Reaction of Amphipathic-Type Thioester and Amine with Hydrophobic Effect in Water

Atsushi Torihata, Chiaki Kuroda*
Department of Chemistry and Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan
Fax: +81(3)39852396; e-Mail: chkkuroda@grp.rikkyo.ne.jp;

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Publication History

Received 18 April 2011
Publication Date:
10 August 2011 (online)

Abstract
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Abstract

The title reaction was studied using sodium 3-(1-oxododec-1-yl)thio- and 3-(1-oxohept-1-yl)thiopropanoate with various chain lengths of amines. The yields of the amides were found to depend on both the chain length of the thioester and that of amine, suggesting the presence of hydrophobic interaction. The amides were obtained in better yields after addition of sodium fluoride. Acylation (dodecanoylation) of some hydrophobic amino acids was also studied to obtain the corresponding amides.

Key words

amines - amides - amino acids - thioesters - hydrophobic effect

References and Notes

1a Organic Reactions in Water Lindström UM. Blackwell Publishing; Oxford: 2007.

Google Scholar
1b Li C.-J. Chem. Rev. 1993, 93: 2023

Google Scholar
1c Li C.-J. Chen L. Chem. Soc. Rev. 2006, 35: 68

Google Scholar
1d Lindström UM. Chem. Rev. 2002, 102: 2751

Google Scholar
2a Kent SBH. Chem. Soc. Rev. 2009, 38: 338

Google Scholar
2b Noren CJ. Wang J. Perler FB. Angew. Chem. Int. Ed. 2000, 39: 450

Google Scholar
2c Weber AL. Orgel LE. J. Mol. Evol. 1979, 13: 193

Google Scholar
3 Nambu H. Hata K. Matsugi M. Kita Y. Chem. Eur. J. 2005, 11: 719

Crossref Google Scholar
4a Kawabata Y. Kinoshita M. Makromol. Chem. 1975, 176: 49

Google Scholar
4b Kawabata Y. Kinoshita M. Makromol. Chem. 1975, 176: 2797

Google Scholar
4c Kawabata Y. Kinoshita M. Makromol. Chem. 1975, 176: 2807

Google Scholar
5 Torihata A. Kuroda C. Bull. Chem. Soc. Jpn. 2010, 83: 1534

Crossref Google Scholar
6 Kurooka S. Hashimoto M. Tomita M. Maki A. Yoshimura Y. J. Biochem. 1976, 79: 533

Google Scholar
8 Dellaria JF. Nordeen C. Swett LR. Synth. Commun. 1986, 16: 1043

Crossref Google Scholar
10a Iimura S. Manabe K. Kobayashi S. Chem. Commun. 2002, 94

Google Scholar
10b Bodanszky M. Int. J. Pept. Protein Res. 1984, 23: 111

Google Scholar

7

Compound 7: IR (KBr): 1684, 1566, 1425 cm^-¹. ^¹H NMR as carboxylic acid (CDCl₃): δ = 0.88 (t, J = 6.4 Hz, 3 H), 1.21-1.37 (m, 6 H), 1.59-1.70 (m, 2 H), 2.55 (t, J = 7.5 Hz, 2 H), 2.69 (t, J = 6.9 Hz, 2 H), 3.11 (t, J = 6.9 Hz, 2 H). ^¹³C NMR as carboxylic acid (CDCl₃): δ = 14.0, 22.4, 23.5, 25.5, 28.6, 31.4, 34.2, 44.0, 177.2, 199.3. MS (FAB): m/z = 263 [M + Na]⁺, 241 [M + H]⁺. HRMS (FAB): m/z [M + H]⁺ calcd for C₁₀H₁₈O₃NaS: 241.0874; found: 241.0865.

9

Typical Procedure for the Amidation Reaction: Thioester 6 (0.065 mmol) was added to a stirred mixture of amine 3 (0.13 mmol) in H₂O (5 mL), and the mixture was stirred at r.t. for 24 h. The mixture was extracted with Et₂O, and the ethereal layer was washed with aq NaHCO₃ solution, and dried over Na₂SO₄. After evaporation of the solvent, the product was purified by silica gel column chromatography using hexane-EtOAc as eluent.

11

An aqueous solution of NaOH (0.5 M, 0.26 mL) was added in the reaction of 8 triflate (0.13 mmol) with 6 (0.065 mmol).

12

Compound 9a: mp 60-61 ˚C. IR (KBr): 3315, 1739, 1647, 1552, 1213 cm^-¹. ^¹H NMR (CDCl₃): δ = 0.88 (t, J = 7.0 Hz, 3 H), 0.89 (t, J = 7.0 Hz, 3 H), 1.23-1.39 (m, 22 H), 1.55-1.69 (m, 4 H), 2.24 (t, J = 7.4 Hz, 2 H), 4.04 (d, J = 5.0 Hz, 2 H), 4.15 (t, J = 6.7 Hz, 2 H), 5.94 (br, 1 H). ^¹³C NMR (CDCl₃): δ = 14.0, 14.1, 22.5, 22.7, 25.4, 25.6, 28.4, 29.2, 29.3 (2 × C), 29.4, 29.6 (2 × C), 31.3, 31.9, 36.4, 41.3, 65.7, 170.3, 173.2. EIMS: m/z = 341 [M⁺], 201, 118. HRMS: m/z [M + H]⁺ calcd for C₂₀H₄₀NO₃: 342.3008; found: 342.3002.

13

Compound 9b: mp 45-46 ˚C. IR (KBr): 3296, 1732, 1639, 1552, 1186 cm^-¹. ^¹H NMR (CDCl₃): δ = 0.88 (t, J = 6.7 Hz, 3 H), 0.89 (t, J = 6.2 Hz, 3 H), 1.22-1.37 (m, 22 H), 1.55-1.69 (m, 4 H), 2.15 (t, J = 7.5 Hz, 2 H), 2.53 (t, J = 5.9 Hz, 2 H), 3.52 (q, J = 5.9 Hz, 2 H), 4.09 (t, J = 6.8 Hz, 2 H), 6.07 (br, 1 H). ^¹³C NMR (CDCl₃): δ = 14.0, 14.1, 22.5, 22.7, 25.6, 25.7, 28.5, 29.3 (3 × C), 29.5, 29.6 (2 × C), 31.4, 31.9, 34.0, 34.7, 36.8, 173.0, 173.2. EIMS: m/z = 355 [M⁺], 215, 132. HRMS: m/z [M + H]⁺ calcd for C₂₁H₄₂NO₃: 356.3165; found: 356.3134.

14

Compound 11a: oil. IR (NaCl): 3307, 1736, 1651, 1539, 1198 cm^-¹. ^¹H NMR (CDCl₃): δ = 0.88 (t, J = 6.8 Hz, 3 H), 0.89 (t, J = 6.8 Hz, 3 H), 0.90 (d, J = 7.0 Hz, 3 H), 0.94 (d,
J = 7.0 Hz, 3 H), 1.22-1.39 (m, 22 H), 1.59-1.69 (m, 4 H), 2.10-2.21 (m, 1 H), 2.23 (t, J = 7.7 Hz, 2 H), 4.07-4.18 (m, 2 H), 4.58 (dd, J = 4.6, 8.8 Hz, 1 H), 5.94 (br d, J = 9.0 Hz, 1 H). ^¹³C NMR (CDCl₃): δ = 14.0, 14.1, 17.7, 18.9, 22.5, 22.7, 25.6, 25.7, 28.5, 29.2, 29.3 (2 × C), 29.5, 29.6 (2 × C), 31.3, 31.4, 31.9, 36.8, 56.8, 65.4, 172.4, 173.0. EIMS: m/z = 383 [M⁺], 254. HRMS: m/z [M + H]⁺ calcd for C₂₃H₄₆NO₃: 384.3478; found: 384.3478.

15

Compound 11b: oil. IR (NaCl): 3288, 1741, 1651, 1543, 1192 cm^-¹. ^¹H NMR (CDCl₃): δ = 0.88 (t, J = 6.8 Hz, 3 H), 0.89 (t, J = 6.8 Hz, 3 H), 0.94 (d, J = 6.3 Hz, 3 H), 0.95 (d, J = 6.0 Hz, 3 H), 1.23-1.39 (m, 23 H), 1.46-1.72 (m, 6 H), 2.21 (t, J = 7.5 Hz, 2 H), 4.12 (t, J = 5.8 Hz, 2 H), 4.65 (dt, J = 5.0, 8.7 Hz, 1 H), 5.84 (br d, J = 8.0 Hz, 1 H). ^¹³C NMR (CDCl₃): δ = 14.0, 14.1, 22.1, 22.5, 22.7, 22.8, 24.9, 25.5, 25.6, 28.4, 29.2, 29.3 (2 × C), 29.5, 29.6 (2 × C), 31.3, 31.9, 36.6, 41.9, 50.6, 65.5, 172.8, 173.4. EIMS: m/z = 397 [M⁺], 268, 86. HRMS: m/z [M + H]⁺ calcd for C₂₄H₄₈NO₃: 398.3634; found: 398.3616.

16

Compound 11c: oil. IR (NaCl): 3300, 1738, 1653, 1537, 1192 cm^-¹. ^¹H NMR (CDCl₃): δ = 0.88 (t, J = 6.9 Hz, 3 H), 0.89 (t, J = 6.8 Hz, 3 H), 0.90 (d, J = 6.8 Hz, 3 H), 0.93 (t,
J = 7.2 Hz, 3 H), 1.22-1.40 (m, 24 H), 1.58-1.72 (m, 4 H), 1.83-1.94 (m, 1 H), 2.22 (t, J = 7.6 Hz, 2 H), 4.11 (dt, J = 10.7, 6.7 Hz, 1 H), 4.14 (dt, J = 10.7, 6.7 Hz, 1 H), 4.62 (dd, J = 4.6, 8.5 Hz, 1 H), 5.97 (br d, J = 8.5 Hz, 1 H). ^¹³C NMR (CDCl₃): δ = 11.6, 14.0, 14.1, 15.4, 22.5, 22.7, 25.2, 25.5, 25.7, 28.5, 29.2, 29.3 (2 × C), 29.5, 29.6 (2 × C), 31.3, 31.9, 36.8, 38.1, 56.1, 65.4, 172.3, 172.8. EIMS: m/z = 397 [M⁺], 268, 86. HRMS: m/z [M + H]⁺ calcd for C₂₄H₄₈NO₃: 398.3634; found: 398.3647.

17

Compound 11d: mp 45-46 ˚C. IR (KBr): 3326, 1732, 1645, 1523, 1209 cm^-¹. ^¹H NMR (CDCl₃): δ = 0.88 (t, J = 6.6 Hz, 3 H), 0.90 (t, J = 6.0 Hz, 3 H), 1.23-1.38 (m, 22 H), 1.52-1.68 (m, 4 H), 2.17 (t, J = 7.6 Hz, 2 H), 3.11 (dd, J = 5.8, 14.0 Hz, 1 H), 3.14 (dd, J = 6.0, 14.0 Hz, 1 H), 4.04-4.15 (m, 2 H), 4.90 (dt, J = 7.7, 6.0 Hz, 1 H), 5.90 (br d, J = 8.0 Hz, 1 H), 7.08-7.34 (m, 5 H). ^¹³C NMR (CDCl₃): δ = 14.0, 14.1, 22.5, 22.7, 25.5, 25.6, 28.4, 29.2, 29.3 (2 × C), 29.4, 29.6 (2 × C), 31.3, 31.9, 36.6, 38.0, 52.9, 65.7, 127.0, 128.5 (2 × C), 129.3 (2 × C), 136.0, 171.8, 172.6. EIMS: m/z = 431 [M⁺], 232, 120. HRMS: m/z [M + H]⁺ calcd for C₂₇H₄₆NO₃: 432.3478; found: 432.3491.