11412
V. Bertini et al. / Tetrahedron 60 (2004) 11407–11414
3
1
9.14, 113.42, 123.22, 126.40, 129.01, 132.06, 133.90,
36.01, 136.54, 137.63, 168.14. GC-MS (CI, m/z, %): 278
4.6.1. 4-Aminomethylstyrene hydrochloride (1a). Yield
89%. Mp 180 8C (dec.; 2-propanol); [lit. : 160–170 8C
2
7
C
K1
(dec.)]. IR (KBr, n, cm ) 989 and 901 (CH ]CH). H
1
(
M C1, 100). Anal. Calcd. for C H NO : C, 77.96; H,
1
8
15
2
2
5
.45; N, 5.05. Found: C, 77.86; H, 5.47; N, 5.04.
NMR (CD OD, ppm) 4.11 (s, 2H); 5.29 (dd, 1H, JgemZ
3
0
.90 Hz; J Z10.9 Hz); 5.83 (dd, 1H, JgemZ0.90 Hz;
cis
JtransZ17.6 Hz); 6.76 (dd, 1H, J Z10.9 Hz; JtransZ
1
4.4.3. N-[4-(4-Vinylphenyl)butyl]phthalimide (4c).
Reagent 3c. Yield 63%. White grains. Mp 117–119 8C.
cis
1
7.6 Hz); 7.42–7.52 (m, 4H). C NMR 44.09, 115.36,
3
K1
Purity 98% by HPLC. IR (KBr, n, cm ) 1703 (C]O), 992,
127.91, 130.35, 133.80, 137.37, 139.93. Anal. Calcd. for
C H ClN: C, 63.72; H, 7.13; N, 8.26; Cl, 20.90. Found: C,
1
13 (CH ]CH). H NMR (CDCl ppm) 1.69 (m, 4H); 2.64
9
9 12
2
3
6
3.75; H, 7.12; N, 8.22; Cl, 20.88.
(
t, 2H, JZ7.0 Hz); 3.71 (t, 2H, JZ7.0 Hz); 5.18 (dd, 1H,
JgemZ1.0 Hz; J Z10.9 Hz); 5.69 (dd, 1H, JgemZ1.0 Hz;
cis
4
.6.2. 4-Aminoethylstyrene hydrochloride (1b). Yield
7%. Mp 210 8C (ethanol); [lit. : 210 8C]. IR (KBr, n,
JtransZ17.6 Hz); 6.68 (dd, 1H, J Z10.9 Hz; J
Z
C
cis
trans
1
1
6
3
7
cm ) 994 and 912 (CH ]CH). H NMR (CD OD, ppm)
1
7.6 Hz); 7.13–7.36 (m, 4H); 7.67–7.85 (m, 4H).
K1
1
NMR 28.14, 28.53, 35.07, 37.76, 112.94, 123.18, 126.20,
28.59, 132.14, 133.87, 135.27, 136.66, 141.73, 168.43.
GC-MS (EI, m/z, %): 305 (M , 100). Anal. Calcd. for
2
3
2
1
1
7
1
.92–3.03 (m, 2H); 3.12–3.23 (m, 2H); 5.21 (dd, 1H, Jgem
Z
1
C
.0 Hz; J Z10.9 Hz); 5.76 (dd, 1H, JgemZ1.0 Hz; JtransZ
cis
7.6 Hz); 6.72 (dd, 1H, J Z10.9 Hz; JtransZ17.6 Hz);
cis
C H NO : C, 78.66; H, 6.27; N, 4.59. Found: C, 78.62; H,
2
0
19
2
1
.24–7.44 (m, 4H). C NMR 34.22, 41.89, 114.08,
3
6
.26; N, 4.58.
27.75, 130.03, 137.52, 137.70, 138.04. Anal. Calcd. for
C H ClN: C, 65.39; H, 7.68; N, 7.63; Cl, 19.30. Found: C,
1
0 14
4.4.4. N-[6-(4-Vinylphenyl)hexyl]phthalimide (4d).
Reagent 3d. Yield 59%. White needles. Mp 75–77 8C.
6
5.42; H, 7.69; N, 7.65; Cl, 19.30.
K1
Purity 99% by HPLC. IR (KBr, n, cm ) 1707 (C]O), 988,
1
66 (CH ]CH). H NMR (CDCl , ppm) 1.30–1.72 (m,
4.6.3. 4-Aminobutylstyrene hydrochloride (1c). Yield
8
and 905 (CH ]CH). H NMR (CD OD, ppm) 1.63–1.75
9
K1
0%. Mp 207–210 8C (acetonitrile); IR (KBr, n, cm ) 985
2
3
8
H); 2.58 (t, 2H, JZ7.5 Hz); 3.67 (t, 2H, JZ7.5 Hz); 5.18
1
2
3
(
dd, 1H, JgemZ1.0 Hz; J Z10.9 Hz); 5.69 (dd, 1H, JgemZ
cis
(
1
m, 4H); 2.57–2.69 (m, 2H); 2.90–2.95 (m, 2H); 5.16 (dd,
H, JgemZ1.1 Hz; J Z10.9 Hz); 5.71 (dd, 1H, JgemZ
1
.0 Hz; JtransZ17.6 Hz); 6.68 (dd, 1H, J Z10.9 Hz;
cis
cis
JtransZ17.6 Hz); 7.11 (m, 2H); 7.31 (m, 2H); 7.71 (m,
1
3
1.1 Hz; JtransZ17.6 Hz); 6.69 (dd, 1H, JcisZ10.9 Hz;
2
3
1
H); 7.83 (m, 2H). C NMR 26.72, 28.53, 28.79, 31.18,
5.54, 38.02, 112.81, 123.17, 126.13, 128.55, 132.19,
33.85, 135.10, 136.73, 142.43, 168.47. Anal. Calcd. for
13
JtransZ17.6 Hz); 7.10–7.36 (m, 4H). C NMR 28.08,
2
9.16, 35.89, 40.70, 113.26, 117.32, 129.70, 136.97,
37.99, 142.63. Anal. Calcd. for C H ClN: C, 68.07;
1
H, 8.57; N, 6.62; Cl, 16.74. Found: C, 68.05; H, 8.58; N,
1
2 18
C H NO : C, 79.25; H, 6.95; N, 4.20. Found: C, 79.20; H,
2
2
23
2
6
.93; N, 4.18.
6
.64; Cl, 16.78.
4
.5. Hydrazinolysis of Phthalimides 4a–d
4
8
9
1
2
1
.6.4. 4-Aminohexylstyrene hydrochloride (1d). Yield
K1
0%. Mp 150–153 8C (acetonitrile); IR (KBr, n, cm
90 and 900 (CH ]CH). H NMR (CD OD, ppm) 1.30–
)
1
Phthalimide 4a–d (38.3 mmol) was dissolved in 95%
ethanol (50 mL) and treated under nitrogen and stirring at
reflux with a solution of hydrazine hydrate (2.74 g,
2
3
.50 (m, 4H); 1.55–1.75 (m, 4H); 2.61 (t, 2H, JZ7.4 Hz);
.90 (t, 2H, JZ7.4 Hz); 5.15 (dd, 1H, JgemZ1.1 Hz; J Z
cis
5
4.7 mmol) in 95% ethanol (5 mL) for 2.5 h up to the
0.9 Hz); 5.70 (dd, 1H, JgemZ1.1 Hz; JtransZ17.6 Hz); 6.69
disappearance of 4a–d (TLC, eluent benzene). After
removal of the solvent at reduced pressure the solid residue
was taken with chloroform (50 mL) and treated with 20%
aqueous NaOH (50 mL). The aqueous phase was separated,
extracted with chloroform (3!50 mL) and the extracts
combined and dried over Na SO . The removal of chloro-
(
dd, 1H, J Z10.9 Hz; JtransZ17.6 Hz); 7.12–7.33 (m, 4H).
cis
3
1
C NMR 27.31, 28.53, 29.69, 32.27, 36.42, 40.79, 113.05,
17.20, 129.63, 136.69, 138.08, 143.53. Anal. Calcd. for
C H ClN: C, 70.13; H, 9.25; N, 5.84; Cl, 14.78. Found: C,
1
1
4 22
7
0.09; H, 9.26; N, 5.82; Cl, 14.81.
2
4
form afforded the free bases 5a (90%), 5b (92%), 5c (80%)
and 5d (75%) as oils which were transformed into their
hydrochlorides without distillation. The free base 5a was
vacuum distilled and characterized. Bp 58–60 8C/1 torr,
4
(
.7. 2-Methoxy-6-hydroxybenzylamine hydrochloride
10)
A solution of 2-methoxy-6-methoxymethoxybenzaldehyde
(7) (1.1425 g; 5.8 mmol) in 95% ethanol (12 mL) was
2
6
1
[
(
lit. : 58–60 8C/0.7 torr]. H NMR (CDCl , ppm) 1.76
3
19
bs, 2H); 3.84 (s, 2H); 5.22 (dd, 1H, JgemZ0.9 Hz; J Z
cis
treated with a solution of hydroxylamine hydrochloride
(0.4864 g, 7.0 mmol) in dry pyridine (2.3 mL) under stirring
at room temperature for 90 min and at 0 8C for 30 min
to facilitate the oxime precipitation. The white solid was
filtered, dried, weighed (0.7210 g) and used without further
purification. The mother liquors were concentrated to afford
additional 0.2208 g of 2-methoxy-6-methoxymethoxy-
benzaldoxime (8) for an overall yield of 77%. Mp 131–
1
6
0.9 Hz); 5.72 (dd, 1H, JgemZ0.9 Hz; JtransZ17.6 Hz);
.70 (dd, 1H, J Z10.9 Hz; JtransZ17.6 Hz); 7.24–7.39
cis
(
m, 4H).
4
.6. Hydrochlorides 1a–d
A solution of the amine 5a–d (25 mmol) in dry diethyl ether
500 ml) was cooled to 0 8C and treated under stirring up to
K1
(
135 8C; IR (n, cm ) 3178, 1626, 1596, 1582, 1478, 1071.
saturation with dry gaseous hydrochloric acid. The white
precipitate was filtered, washed with fresh ether, dried and
crystallized to afford the hydrochloride derivative 1a–d.
A solution of 8 (3.13 g; 14.8 mmol) in 95% ethanol (43 mL)
was treated with an equal volume of 2 M NaOH followed by