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DOI: 10.1055/s-0030-1261165
Reaction of Amphipathic-Type Thioester and Amine with Hydrophobic Effect in Water
Publication History
Publication Date:
10 August 2011 (online)
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
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References and Notes
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.
9Typical 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.
11An 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).
12Compound 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.
13Compound 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.
14Compound 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.
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.
16Compound 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.
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.