348
S. Drescher et al.
3
(d, JC,P = 4.6 Hz, 29 NCH2CH2O–), 58.86 (d, JC,P
2
=
Dotriaconta-15,17-diyn-1,32-diylbis[2-(trimethylammo-
nio)ethylphosphate] (10b, C42H82N2O8P2)
5.4 Hz, 29 NCH2CH2O–), 65.06 (29 –CH2C:C–), 66.07
2
(d, JC,P = 5.4 Hz, 29 –OCH2(CH2)14C:C–), 77.19 (29
Compound 10b was obtained as a white solid in 17% yield
(70 mg) from the phosphorylation reaction of 0.24 g 8b
(0.5 mmol) and subsequent quaternization with an etha-
nolic solution of Me3N following the general procedure
described above. Rf = 0.13 (solvent F); 1H NMR
(400 MHz, CDCl3–CD3OD): d = 1.10–1.14 (m, 48H, 29
–CH2C:C–) ppm; ESI–MS: m/z = 804.1 [M? – H],
806.6 [M? ? H], 828.5 [M? ? Na], 1,631.9 [2M? ? Na].
Hexatriaconta-17,19-diyn-1,36-diylbis[2-(dimethylammo-
nio)ethylphosphate] (9d, C44H86N2O8P2)
Compound 9d was obtained as a white solid in 61% yield
(127 mg) from the phosphorylation reaction of 0.13 g 8d
(0.25 mmol) and subsequent quaternization with an etha-
nolic solution of Me2NH following the general procedure
described above. Rf = 0.55 (solvent E); 1H NMR (400 MHz,
CDCl3–CD3OD): d = 1.14–1.25 (m, 48H, 29 –O(CH2)2
(CH2)12(CH2)2C:C–), 1.36–1.43 (m, 4H, 29 –CH2CH2
C:C–), 1.48–1.55 (m, 4H, 29 –OCH2CH2(CH2)14C:C–),
2.12 (t, 3J = 7.1 Hz, 4H, 29 –CH2C:C–), 2.77 (s, 12H, 49
–CH3), 3.14–3.16 (m, 4H, 29 NCH2CH2O–), 3.77 (q,
J = 6.6 Hz, 4H, 29 –OCH2(CH2)15C:C–), 4.01–4.06 (m,
4H, 29 NCH2CH2O–) ppm; 13C NMR (100 MHz, CDCl3–
CD3OD): d = 19.04 (29 –CH2C:C–), 25.63 (29
–O(CH2)2CH2(CH2)13C:C–), 28.21, 28.69, 28.94, 29.23,
29.32, 29.50, and 29.53 (29 –O(CH2)3(CH2)12CH2C:C–),
3
–OCH2(CH2)12CH2C:C–), 1.95 (t, J = 7.1 Hz, 4H, 29
–CH2C:C–), 2.97 (s, 18H, 69 –CH3), 3.33–3.36 (m, 4H,
29 NCH2CH2O–), 3.62 (q, J = 6.6 Hz, 4H, 29 –OCH2
(CH2)13C:C–), 3.97–4.00 (m, 4H, 29 NCH2CH2O–)
ppm; 13C NMR (100 MHz, CDCl3–CD3OD): d = 19.01
(29 –CH2C:C–), 25.65 (29 –O(CH2)2CH2(CH2)11
C:C–), 28.21, 28.68, 28.93, 29.26, 29.31, and 29.48
3
(29 –O(CH2)3(CH2)10CH2C:C–), 30.65 (d, JC,P
=
6.9 Hz, 29 –OCH2CH2(CH2)12C:C–), 54.12 (t, J =
3.8 Hz, 69 –CH3), 58.60 (d, JC,P = 5.0 Hz, 29 NCH2
2
2
CH2O–), 65.09 (29 –CH2C:C–), 65.74 (d, JC,P
=
6.0 Hz, 29 –OCH2(CH2)13C:C–), 66.48 (b, 29 NCH2
CH2O–), 77.26 (29 –CH2C:C–) ppm; ESI–MS:
m/z = 805.5 [M? ? H], 828.5 [M? ? Na].
3
30.57 (d, JC,P = 7.7 Hz, 29 –OCH2CH2(CH2)14C:C–),
43.25 (49 –CH3), 58.83 (d, JC,P = 6.1 Hz, 29 NCH2
Tetratriaconta-16,18-diyn-1,34-diylbis[2-(trimethylammo-
nio)ethylphosphate] (10c, C44H86N2O8P2)
3
2
CH2O–), 59.01 (d, JC,P = 3.8 Hz, 29 NCH2CH2O–),
Compound 10c was obtained as a white solid in 50% yield
(105 mg) from the phosphorylation reaction of 0.13 g 8c
(0.25 mmol) and subsequent quaternization with an etha-
nolic solution of Me3N following the general procedure
described above. Rf = 0.19 (solvent F); 1H NMR
(400 MHz, CDCl3–CD3OD): d = 0.98–1.10 (m, 44H, 29
–O(CH2)2(CH2)11(CH2)2C:C–), 1.20–1.27 (m, 4H, 29
–CH2CH2C:C–), 1.31–1.38 (m, 4H, 29 –OCH2CH2
2
65.09 (29 –CH2C:C–), 66.19 (d, JC,P = 5.4 Hz, 29
–OCH2(CH2)15C:C–), 77.22 (29 –CH2C:C–) ppm; ESI–
MS: m/z = 832.0 [M? – H], 835.1 [M? ? H], 856.1
[M? ? Na]
Triaconta-14,16-diyn-1,30-diylbis[2-(trimethylammo-
nio)ethylphosphate] (10a, C40H78N2O8P2)
Compound 10a was obtained as a white solid in 20% yield
(78 mg) from the phosphorylation reaction of 0.22 g 8a
(0.5 mmol) and subsequent quaternization with an etha-
nolic solution of Me3N following the general procedure
described above. Rf = 0.12 (solvent F); 1H NMR
(400 MHz, CDCl3–CD3OD): d = 1.17–1.55 (m, 44H, 29
3
(CH2)13C:C–), 1.96 (t, J = 7.1 Hz, 4H, 29 –CH2C:
C–), 2.93 (s, 18H, 69 –CH3), 3.32–3.34 (m, 4H, 29
NCH2CH2O–), 3.59 (q, J = 6.6 Hz, 4H, 29 –OCH2
(CH2)14C:C–), 3.94–3.99 (m, 4H, 29 NCH2CH2O–)
ppm; 13C NMR (100 MHz, CDCl3–CD3OD): d = 18.57
(29 –CH2C:C–), 25.26 (29 –O(CH2)2CH2(CH2)12C:
C–), 27.87, 28.31, 28.58, 28.91, 28.97, and 29.16 (29
3
–OCH2(CH2)11CH2C:C–), 2.16 (t, J = 7.1 Hz, 4H, 29
–CH2C:C–), 3.13 (s, 18H, 69 –CH3), 3.50–3.55 (m, 4H,
29 NCH2CH2O–), 3.77 (q, J = 6.6 Hz, 4H, 29 –OCH2
(CH2)12C:C–), 4.11–4.17 (m, 4H, 29 NCH2CH2O–)
ppm; 13C NMR (100 MHz, CDCl3–CD3OD): d = 19.03
(29 –CH2C:C–), 25.68 (29 –O(CH2)2CH2(CH2)10
3
–O(CH2)3(CH2)11CH2C:C–), 30.24 (d, JC,P = 7.4 Hz,
29 –OCH2CH2(CH2)13C:C–), 53.61 (t, J = 3.7 Hz, 69
–CH3), 58.60 (d, 2JC,P = 5.9 Hz, 29 NCH2CH2O–), 65.77
2
(d, JC,P = 5.2 Hz, 29 –OCH2(CH2)14C:C–), 77.19 (29
–CH2C:C–) ppm; ESI–MS: m/z = 868.0 [M? ? Cl],
834.0 [M? ? H], 867.7 [M? ? Na].
C:C–), 28.22, 28.69, 28.95, 29.27, 29.34, 29.46, and
3
29.49 (29 –O(CH2)3(CH2)9CH2C:C–), 30.68 (d, JC,P
=
6.9 Hz, 29 –OCH2CH2(CH2)11C:C–), 54.14 (t, J =
3.7 Hz, 69 –CH3), 58.66 (d, JC,P = 5.2 Hz, 29
Hexatriaconta-17,19-diyn-1,36-diylbis[2-(trimethylammo-
nio)ethylphosphate] (10d, C46H90N2O8P2)
2
NCH2CH2O–), 65.12 (29 –CH2C:C–), 65.77 (d,
2JC,P = 6.1 Hz, 29 –OCH2(CH2)12C:C–), 66.43 (b,
29 NCH2CH2O–), 77.20 (29 –CH2C:C–) ppm; ESI–
MS: m/z = 777.6 [M? ? H], 799.5 [M? ? Na].
Compound 10d was obtained as a white solid in 56%
yield (120 mg) from the phosphorylation reaction of
0.13 g 8d (0.25 mmol) and subsequent quaternization with
an ethanolic solution of Me3N following the general
123