Full Paper
3
H, 18-H), 1.25–1.37 (m, 8 H, 4-H, 5-H, 6-H, 7-H), 1.40 (m, 2 H, 3′- N-Linolenoyl(3-methyl-2-amino-1-butanol) (4i): Yield 62 % of
1
H), 1.50–1.63 (m, 6 H, 3-H, 2′-H, 4′-H), 2.02–2.10 (m, 4 H, 8-H, 17-H), pure compound as a colorless oil. H NMR (500.14 MHz, CDCl ): δ =
3
2
3
5
.14 (t, J = 7.5 Hz, 2 H, 2-H), 2.80 (t, J = 5.5 Hz, 4 H, 11-H, 14-H),
.26 (q, J = 7.0 Hz, 2 H, 1′-H), 3.64 (t, J = 6.4 Hz, 2 H, 2′-H), 5.28–
.42 (m, 6 H, 9-H, 10-H; 12-H, 13-H, 15-H, 16-H), 5.48 (br. s, 1 H,
0.87 (t, J = 6.7 Hz, 2 H, 18-H), 0.91 (d, 3 H, 4′-H), 0.96 (d, 3 H, 5′-H),
1.28 (m, 8 H, 4-H, 5-H, 6-H, 7-H), 1.72 (qn, J = 7.2 Hz, 2 H, 3-H), 1.83
(m, 1 H, 3′-H), 2.03 (m, 4 H, 17-H, 8-H), 2.21 (t, J = 7.4 Hz, 2 H, 2-H),
2.80 (m, 4 H, 11-H, 14-H), 3.63 (dd, J = 6.2, J = 5.0 Hz, 1 H, 1′-H),
13
NH) ppm. C NMR (125.76 MHz, CDCl ): δ = 14.4(C-18), 20.7 (C-17),
3
1
2
2
2
1
5.7–25.8 (C-11, C-14), 25.9 (C-3), 26.0 (C-2′), 27.3 (C-8), 27.4 (C-3′), 3.69 (dd, J = 6.0, J = 9.5 Hz, 2 H, 2′-H), 5.34–5.37 (m, 6 H, 9-H,
1 2
1
3
9.3–29.4 (C-4, C-5, C-6, C-7, C-4′), 37.1 (C-2), 39.4 (C-1′), 62.8 (C-5′),
10-H; 12-H, 13-H, 15-H, 16-H), 5.57 (br. s, 1 H, NH) ppm. C NMR
27.2–132.1 (C-9, C-10, C-12, C-13, C-15, C-16), 173.3 (C-1) ppm. [M
(125.76 MHz, CDCl ): δ = 14.1 (C-18), 18.9 (C-5′), 19.5 (C-4′), 20.7 (C-
3
+
+
Na] Calcd. C H NNaO 386.3035; found C H NNaO 386.3029. 17), 25.7–25.9 (C-3, C-11, C-14), 27.3 (C-8), 29.1 (C-3′), 29.3–29.7 (C-
23
41
2
23 41
2
4
, C-5, C-6, C-7), 36.3 (C-2), 57.2 (C-1′), 64.3 (C-2′), 127.5–130.6 (C-9,
N-Linolenoyl(2-amino-1-propanol) (4e): Yield 86 % of pure com-
+
C-10, C-12, C-13, C-15, C-16), 174.0 (C-1) ppm. [M + Na] Calcd.
C H NNaO 386.3035; found C H NNaO 386.3040.
1
pound as a colorless oil. H NMR (500.14 MHz, CDCl ): δ = 0.91 (d,
3
23
41
2
23 41
2
J = 6.8 Hz, 3 H, 3′-H), 0.97 (t, J = 7.5 Hz, 3 H, 18-H), 1.25–1.36 (m, 8
H, 4-H, 5-H, 6-H, 7-H), 1.62 (qn, J = 6.8 Hz, 2 H, 3-H), 2.02–2.10 (m,
N-Linolenoyl(2-amino-1-pentanol) (4j): Yield 77 % of pure com-
pound as a colorless oil. H NMR (500.14 MHz, CDCl ): δ = 0.97 (t,
J = 7.5 Hz, 3 H, 18-H), 0.93 (t, J = 7.3 Hz, 3 H, 5′-H), 1.30 (m, 8 H, 4-
H, 5-H, 6-H, 7-H), 1.43 (m, 4 H, 3′-H, 4′-H), 1.62 (qn, J = 7.0 Hz, 2 H,
3-H), 2.04–2.09 (m, 4 H, 17-H, 8-H), 2.19 (t, J = 7.6 Hz, 2 H, 2-H), 2.80
1
4
1
5
H, 8-H, 17-H), 2.18 (t, J = 7.6 Hz, 2 H, 2-H), 2.80 (t, J = 5.2 Hz, 4 H,
3
1-H, 14-H), 3.52 (dd, J = 6.2, J = 11.0 Hz, 1 H, 2′-H), 3.65 (dd, J =
1
2
1
.0, J = 6.2 Hz, 1 H, 2′-H), 4.09 (m, 1 H, 1′-H), 5.28–5.42 (m, 6 H, 9-
2
13
H, 10-H, 12-H, 13-H, 15-H, 16-H), 5.62 (br. s, 1 H, NH) ppm. C NMR
125.76 MHz, CDCl ): δ = 14.4(C-18), 17.2 (C-3′), 20.7 (C-17), 25.7–
(
(
(
m,4 H, 11-H, 14-H), 3.55 (dd, J = 6.2, J = 11.0 Hz, 2 H, 2′-H), 3.69
dd, J = 3.5, J = 11.0 Hz, 1 H, 2′-H), 3.95 (m, 1 H, 1′-H), 5.29–5.42
(
1 2
3
2
7
1
3
5.9 (C-11, C-14), 25.8 (C-3), 27.4 (C-8), 29.3–29.4 (C-4, C-5, C-6, C-
), 36.8 (C-2), 48.0 (C-1′), 67.6 (C-2′), 127.2–132.1 (C-9, C-10, C-12, C-
3, C-15, C-16), 174.2 (C-1) ppm. [M + Na]+ Calcd. C H NNaO
1
2
m, 6 H, 9-H, 10-H; 12-H, 13-H, 15-H, 16-H), 5.57 (br. s, 1 H, NH) ppm.
13
C NMR (125.76 MHz, CDCl ): δ = 14.1 (C-5′), 14.4 (C-18), 19.5 (C-4′
3
2
1
37
2
), 20.7 (C-17), 25.7–25.9 (C-3, C-11, C-14), 27.3 (C-8), 29.3–29.7 (C-4,
58.2722; found C H NNaO 358.2718.
21
37
2
C-5, C-6, C-7), 33.5 (C-3′), 37.0 (C-2), 51.9 (C-1′), 66.3 (C-2′), 127.2–
N-Linolenoyl(1-amino-2-propanol) (4f): Yield 87 % of pure com- 132.1 (C-9, C-10, C-12, C-13, C-15, C-16), 174.4 (C-1) ppm. [M + Na]+
1
pound as a colorless oil. H NMR (500.14 MHz, CDCl ): δ = 0.97 (t,
Calcd. C H NNaO 386.3035; found C H NNaO 386.3038.
3
23 41 2 23 41 2
J = 7.6 Hz, 3 H, 18-H), 1.19 (d, J = 6.3 Hz, 3 H, 3′-H), 1.27–1.37 (m, 8
H, 4-H, 5-H, 6-H, 7-H), 1.63 (qn, J = 7.3 Hz, 2 H, 3-H), 2.02–2.11 (m,
N-Arachidonoylethanolamine (Anandamide, 5a): Yield 81 % of
1
pure compound as a colorless oil. H NMR (500.14 MHz, CDCl ): δ =
3
4
1
1
1
H, 8-H, 17-H), 2.20 (t, J = 7.5 Hz, 2 H, 2-H), 2.80 (t, J = 5.4 Hz, 4 H,
0.83 (t, J = 6.7 Hz, 3 H, 20-H), 1.2–1.3 (m, 6 H, 17-H, 18-H, 19-H),
1.58 (br. s, 1 H, OH), 1.66 (qn, J = 7.5 Hz, 2 H, 3-H), 2.00 (q, J =
7.2 Hz, 2 H, 16-H), 2.06 (c, J = 7.0 Hz, 2 H, 4-H), 2.16 (t, J = 7.4 Hz,
2 H, 2-H), 2.75–2.78 (m, 6 H, 7-H, 10-H, 13-H); 3.36 (q, J = 5.5 Hz, 2
1-H, 14-H), 3.12 (m, 1 H, 1′-H), 3.44 (ddt, J = 2.3, J = 6.5 Hz, J =
1
2
3
2.1 Hz, 1 H, 1′-H), 3.92 (m, 1 H, 2′-H), 5.29–5.42 (m, 6 H, 9-H, 10-H,
2-H, 13-H, 15-H, 16-H), 5.92 (br. s, 1 H, NH) ppm. 13C NMR
(
125.76 MHz, CDCl ): δ = 14.4 (C-18), 21.1 (C-3′), 20.7 (C-17), 25.6–
3
H, 1′-H); 3.67 (t, J = 5.0 Hz, 2 H, 2′-H), 5.29–5.33 (m, 8 H, 5-H, 6-H,
2
5.7 (C-3, C-11, C-14), 27.3 (C-8), 29.3–29.7 (C-4, C-5, C-6, C-7), 36.9
1
3
8
-H, 9-H, 11-H, 12-H, 14-H, 15-H), 5.81 (br. s, 1 H, NH) ppm. C NMR
(
1
C-2), 47.2 (C-1′), 67.5 (C-2′), 127.3–132.1 (C-9, C-10, C-12, C-13, C-
5, C-16), 174.8 (C-1) ppm. [M + Na] Calcd. C H NNaO 358.2722;
21 37 2
(
(
(
125.76 MHz, CDCl ): δ = 14.1 (C-20), 22.6 (C-19), 25.4 (C-10), 25.6
C-3, C-7, C-13), 26.6 (C-4), 27.2 (C-16); 29.3 (C-17), 31.5 (C-18), 35.9
+
3
found C H NNaO 358.2729.
21
37
2
C-2), 42.4 (C-1′), 62.5 (C-2′), 127.5–129.0 (C-6, C-8, C-9, C-11, C-12,
+
C-14, C-15), 130.5 (C-5), 174.2 (C-1) ppm. HRMS: [M + Na] Calcd.
C H NNaO 370.2722; found C H NNaO 370.2726.
N-Linolenoyl(2-methyl-2-amino-1-propanol) (4g): Yield 63 % of
1
pure compound as a colorless oil. H NMR (500.14 MHz, CDCl ): δ =
22 37
2
22 37
2
3
0
.97 (t, J = 7.5 Hz, 3 H, 18-H), 1.25–1.34 (m, 14 H, 4-H, 5-H, 6-H, 7-
H, 3′-H, 4′-H), 1.60 (qn, J = 7.3 Hz, 2 H, 3-H), 2.03–2.11 (m, 4 H, 8-H,
7-H), 2.16 (t, J = 7.6 Hz, 2 H, 2-H), 2.80 (t, J = 6.5 Hz, 4 H, 11-H, 14-
H), 3.58 (s, 2 H, 2′-H), 5.28–5.42 (m, 6 H, 9-H, 10-H; 12-H, 13-H, 15-
N-Arachidonoylpropanolamine (5b): Yield 73 % of pure com-
1
pound as a colorless oil. H NMR (500.14 MHz, CDCl ): δ = 0.89 (t,
3
1
J = 6.7 Hz, 2 H, 20-H), 1.25–1.35 (m, 6 H, 17-H, 18-H, 19-H), 1.60 (br.
s, 1 H, OH), 1.67 (qn, J = 6.2 Hz, 2 H, 2′-H), 1.73 (qn, J = 7.5 Hz, 2 H,
3-H), 2.05 (q, J = 7.0 Hz, 2 H, 16-H), 2.11 (q, J = 7.0 Hz, 2 H, 4-H),
1
3
H, 16-H), 5.48 (br. s, 1 H, NH) ppm. C NMR (125.76 MHz, CDCl3):
δ = 14.3 (C-18), 20.6, (C-17), 24.9 (C-3′, C-4′), 25.7 (C-11, C-14), 25.8
2
3
5
.20 (t, J = 7.4 Hz, 2 H, 2-H), 2.80–2.84 (m, 6 H, 7-H, 10-H, 13-H);
.42 (q, J = 6.0 Hz, 2 H, 1′-H); 3.62 (t, J = 5.8 Hz, 2 H, 3′-H), 5.34–
(
7
(
C-3), 27.2 (C-8), 29.1–29.6 (C-4, C-5, C-6, C-7), 37.4 (C-2), 56.2 (C-1′),
1.0 (C-2′), 127.0–132.1 (C-9, C-10, C-12, C-13, C-15, C-16), 174.3
C-1) ppm. [M + Na]+ Calcd. C H NNaO 372.2879; found
.41 (m, 8 H, 5-H, 6-H, 8-H, 9-H, 11-H, 12-H, 14-H, 15-H), 5.81 (br. s,
13
2
2
39
2
1 H, NH) ppm. C NMR (125.76 MHz, CDCl ): δ = 14.1 (C-20), 22.6
3
C H NNaO 372.2881.
22
39
2
(C-19), 25.6 (C-10), 25.7 (C-3, C-7, C-13), 26.6 (C-4), 27.2 (C-16); 29.3
(
C-17), 31.5 (C-18), 32.4 (C-2′), 36.0 (C-2), 36.2 (C-1′), 59.2 (C-3′),
7
. N-Linolenoyl(2-amino-1-butanol) (4h): Yield 78 % of pure com-
1
127.5–129.0 (C-6, C-8, C-9, C-11, C-12, C-14, C-15), 130.5 (C-5), 174.2
pound as a colorless oil. H NMR (500.14 MHz, CDCl ): δ = 0.92 (t,
J = 5.0 Hz, 3 H, 4′-H), 0.97 (t, J = 7.4 Hz, 3 H, 18-H), 1.30 (m, 8 H, 4-
H, 5-H, 6-H, 7-H), 1.48 (m, 2 H, 3′-H), 1.62 (m, 2 H, 3-H), 2.04–2.09
3
+
(C-1) ppm. HRMS: [M + Na] Calcd. C H NNaO 384.2879; found
23 39 2
C H NNaO 384.2883.
23
39
2
(
1
m, 4 H, 17-H, 8-H), 2.19 (t, J = 7.5 Hz, 2 H, 2-H), 2.80 (m, 4 H, 11-H,
N-Arachidonoylbutanolamine (5c): Yield 69 % of pure compound
1
4-H), 3.55 (dd, J = 5.6, J = 10.9 Hz, 1 H, 2′-H), 3.67 (dd, J = 3.3,
as a colorless oil. H NMR (500.14 MHz, CDCl ): δ = 0.88 (t, J = 6.6 Hz,
1
2
1
3
J = 10.8 Hz, 2 H, 2′-H), 3.95 (m, 1 H, 2′-H),5.32–5.38 (m, 6 H, 9-H,
1
2 H, 20-H), 1.25–1.35 (m, 6 H, 17-H, 18-H, 19-H), 1.59 (m, 4 H, 2′-H,
3′-H), 1.71 (qn, J = 7.5 Hz, 2 H, 3-H), 2.04 (q, J = 6.9 Hz, 2 H, 16-H),
2
0-H; 12-H, 13-H, 15-H, 16-H), 5.57 (br. s, 1 H, NH) ppm. 13C NMR
(
125.76 MHz, CDCl ): δ = 14.1 (C-4′), 14.4 (C-18), 19.5 (C-3′), 20.7 (C- 2.10 (q, J = 6.9 Hz, 2 H, 4-H), 2.16 (t, J = 7.3 Hz, 2 H, 2-H), 2.80–2.84
3
1
5
1
7), 25.5, 25.6 (C-11, C-14), 25.8 (C-3), 27.3 (C-8), 29.2–29.7 (C-4, C- (m, 6 H, 7-H, 10-H, 13-H); 3.28 (q, J = 6.7 Hz, 2 H, 1′-H); 3.67 (t, J =
, C-6, C-7), 37.0 (C-2), 51.8 (C-2′), 66.3 (C-1′), 127.2–132.1 (C-9, C-
6.0 Hz, 2 H, 4′-H), 5.34–5.38 (m, 8 H, 5-H, 6-H, 8-H, 9-H, 11-H, 12-H,
14-H, 15-H), 5.68 (br. s, 1 H, NH) ppm. C NMR (125.76 MHz, CDCl3):
+
13
0, C-12, C-13, C-15, C-16), 174.3 (C-1) ppm. [M + Na] Calcd.
C H NNaO 372.2879; found C H NNaO 372.2874.
δ = 14.1 (C-20), 22.6 (C-19), 25.6 (C-10), 25.7 (C-3, C-7, C-13), 26.3
22
39
2
22 39
2
Eur. J. Org. Chem. 2016, 518–528
www.eurjoc.org
525
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim