E. M. Rustoy, A. Baldessari
FULL PAPER
added to a solution of 5 (480 mg, 3.5 mmol) and ethyl laurate
(1.8 g, 8 mmol) in acetone (10 mL). The suspension was shaken
(200 rpm) at room temperature and the progress of the reaction
monitored by GLC. When 97% of conversion was achieved (24 h),
the enzyme was filtered off and the solvent evaporated. The residue
was washed with hexane and 840 mg (75%) of a solid identified as
183 (14), 138 (28), 119 (55), 98 (19), 84 (21), 79 (100), 57 (33), 52
(91).
Acknowledgments
We thank UBA (project X089), ANPCyT (project PICT 06-08293)
for partial financial support. The authors gratefully acknowledge
M. M Rivero for his assistance in GC analysis.
7 was obtained. M.p. 67–70 °C. FT-IR (KBr): ν
= 2900, 2877,
˜
max
1732, 1625 cm–1. 1H NMR (CDCl3, 200 MHz): δ = 4.19 (t, J =
5.9 Hz, 2 H, CH2–O), 4.07 (s, 2 H, CH2–Cl), 3.59 (t, J = 5.8 Hz, 2
H, CH2–NH), 2.32 (t, J = 7.0 Hz, 2 H, CH2COO), 1.61 (q, J =
7.1 Hz, 2 H, CH2CH2), 1.35–1.21 (m, 16 H, 8×CH2CH2), 0.89 (t,
J = 7.1 Hz, 3 H, CH3) ppm. 13C NMR (CDCl3, 200 MHz): δ =
173.9 (COO), 166.3 (CONH), 62.4 (CH2–O), 42.4 (CH2–Cl), 39.1
(CH2–NH), 34.1 (CH2COO), 33.9, 31.8, 29.5, 29.4, 29.2, 29.0, 24.7,
22.6 (8×CH2), 14.0 (CH3) ppm. EIMS: m/z (%) = 319 [M]+ (4),
200 (2), 183 (23), 119 (98), 84 (54), 55 (51), 43 (100). Tests with
other lipases were performed under the same experimental condi-
tions and are reported in Table 1.
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Lauric Acid as Acylating Agent: As described with ethyl laurate but
using 720 mg (3.5 mmol) of lauric acid. Yield: 1.07 g (95%) of 7.
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One-Pot Procedure: LIP (300 mg) was added to a solution of ethyl
chloroacetate (366 mg, 3 mmol) and ethanolamine (183 mg,
3 mmol) in of acetone (5 mL). The suspension was shaken
(200 rpm) at 55 °C and the progress of the reaction monitored by
GLC. Once 3 was converted into the amide 5 (48 h), lauric acid
(3.5 mmol), LIP (1.2 g), acetone (5 mL) and molecular sieves
(200 mg) were added. After standing for 24 h, the enzyme was fil-
tered off, the solvent was evaporated, and the crude residue purified
1
by flash chromatography on silicia gel and identified by H NMR
spectroscopy as 7. Yield: 695 mg (62%).
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1-[(2-Dodecanoyloxyethylcarbamoyl)methyl]pyridinium Chloride (1):
Pyridine (4 mL) was added dropwise to 7 (440 mg), in an ice-bath,
with vigorous stirring. The reaction mixture was allowed to stand
overnight at room temperature. After addition of hexane (35 mL),
a precipitate identified as 1 (477 mg, 87%) appeared. It was sepa-
rated by filtration and washed twice with hexane to eliminate the
excess of pyridine and lauric acid. M.p. 141–144 °C. FT-IR (KBr):
ν
= 3360, 2988, 2830, 1738, 1622 cm–1. 1H NMR (CDCl3,
˜
max
200 MHz): δ = 9.37 (d, J = 5.5 Hz, 1 H, CH=N), 8.45 (d, J =
7.9 Hz, 2 H, CH=CH), 8.05 (dd, J = 6.6 Hz, 2 H, 2×CH=CH),
5.99 (s, 2 H, CH2–Cl), 4.18 (t, J = 5.8 Hz, 2 H, CH2–O), 3.50 (t, J
= 5.8 Hz, 2 H, CH2–NH), 2.34 (t, J = 7.4 Hz, 2 H, CH2COO),
1.58(c
J = 7.24 Hz, 2 H, CH2CH2), 1.34–1.22(m, 16 H,
8×CH2CH2), 0.88 (t J = 7.04 Hz, 3 H, CH3) ppm. 13C NMR
(CDCl3, 200 MHz): δ = 173.8 (COO), 164.3 (CONH), 146.0
(CH=CH), 145.1 (CH=N), 127.6 (CH=CH), 62.3 (CH2–O), 61.7
(CH2–N), 39.0 (CH2–NH), 34.2 (CH2COO), 31.8, 29.6, 29.3, 29.1,
24.8, 22.6 (CH2), 14.1 (CH3) ppm. EIMS: m/z (%) = 363 [M]+ (4),
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Received: May 31, 2005
Published Online: September 15, 2005
4632
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 4628–4632