PAPER
Hetero- and Carbocycles from 2-Azahepta-2,4-dien-6-ynyllithium Compounds
2143
IR (film): 3078 (w), 3062 (m), 3030 (w), 3020 (w), 2981 (w), 2956
N-[(Trimethylsilyl)methyl]-2-(phenylethynyl)phenylmethan-
(
1
w), 2875 (m), 2216 (w), 1697 (m), 1637 (s), 1371 (m), 1274 (m),
070 (m), 1026 (m), 993 (m), 918 (s), 756 (s), 690 (s), 543 cm (s).
imine (31)
–
1
Treatment of aldehyde 30 (1.03 g, 5.00 mmol) with (trimethylsi-
lyl)methanamine (0.52 g, 5 mmol) according to the general proce-
dure for 9 gave 31 as a yellowish oil; yield: 1.15 g (79%).
1
H NMR (300 MHz, CDCl , 25 °C): d = 4.31–4.34 (m, 2 H,
3
3
CH CH=CH ), 5.78 (dm, J = 10.2 Hz, 1 H, CH=CH ), 5.27 (dm,
2
2
2
3
J = 17.0 Hz, 1 H, CH=CH ), 6.03–6.16 (m, 1 H, CH=CH ), 7.35–
IR (film): 3080 (w), 3060 (w), 3031 (w), 2954 (m), 2896 (m), 2873
(m), 2788 (w), 2216 (w), 1627 (m), 1417 (m), 1247 (s), 879 (m), 854
(s), 756 (s), 736 (w), 690 (s), 595 (s), 476 cm (s).
2
2
4
7
1
.57 (m, 8 H), 8.08–8.13 (m, 1 H), 8.91 (t, J = 1.3 Hz, 1 H, CH=N).
–
1
3
C NMR (75 MHz, CDCl , 25 °C): d = 63.8 (CH CH=CH ), 86.6
3
2
2
1
(
1
C≡C), 95.1 (C≡C), 116.4, 123.1, 126.5, 127.5, 128.6, 128.8, 129.2,
30.4, 131.7, 132.6, 136.0, 136.9, 160.7.
H NMR (300 MHz, CDCl , 25 °C): d = 0.10 (s, 9 H, SiCH ), 3.50
3
3
(s, 2 H, NCH ), 7.34–7.40 (m, 5 H), 7.53–7.57 (m, 3 H), 7.96–8.00
2
+
(m, 1 H), 8.74 (s, 1 H, N=CH).
MS (EI): m/z (%) = 245 [M] (100.00), 204 (27.42), 176 (8.25), 168
(
1
3
62.59), 127 (56.76), 115 (5.12), 98 (5.21), 57 (19.11).
C NMR (75 MHz, CDCl , 25 °C): d = –2.4 (SiCH ), 55.2 (NCH ),
3 3 2
8
1
6.9 (C≡C), 94.7 (C≡C), 123.3, 126.0, 128.6, 128.7, 128.8, 129.5,
31.7, 132.6, 137.7, 157.0, 179.9 (N=CH).
Anal. Calcd for C H N: C, 88.13; H, 6.16; N, 5.71. Found: C,
1
8
15
8
8.13; H, 6.08; N, 5.63.
HRMS: m/z [M + H]+ calcd for C H NSi: 292.1521; found:
1
9
22
3
-Butyl-2-vinylnaphthalen-1-amine (28)
292.1516.
Treatment of 26 (0.23 g, 1.00 mmol) according to the general pro-
cedure for 19 using aq NH Cl soln (5 mL) as electrophile and sub-
sequent chromatographic purification (EtOAc–pentane, 1:10) gave
3-Phenylnaphthalen-1-amine (33)
Imine 31 (2.91 g, 1.00 mmol) was treated as was described for
4
2
8 as a yellowish oil; yield: 0.10 g (44%).
amine 19 using aq NH Cl soln (5 mL) as electrophile. The crude
slurry (ca. 200 mg) was mixed in THF (15 mL) with 1 M TBAF in
THF (1 mL, 1 mmol) and the resulting soln was stirred at r.t. for 30
4
IR (film): 3462 (w), 3379 (w), 3057 (w), 2956 (s), 2929 (s), 2862
(
m), 1672 (w), 1616 (s), 1566 (w), 1498 (w), 1458 (w), 1396 (m),
–
1
min. H O (10 mL) was added and the mixture was extracted with
2
1
384 (w), 1346 (w), 1288 (w), 1249 (w), 1105 (w), 997 cm (m).
Et O (3 × 20 mL). The combined organic extracts were dried
2
1
3
H NMR (400 MHz, CDCl , 25 °C): d = 0.97 (t, J = 7.3 Hz, 3 H,
3
(MgSO ) and the residue was purified by flash chromatography
4
CH CH CH CH ), 1.38–1.48 (m, 2 H, CH CH CH CH ), 1.60–
2
2
2
3
2
2
2
3
(Et O–pentane, 1:1) to give 33 as a colorless solid; yield: 0.14 g
2
1
.67 (m,
2 H, CH CH CH CH ), 2.71–2.74 (m, 2 H,
2 2 2 3
(62%); mp 98–100 °C.
3
CH CH CH CH ), 4.47 (br s, 2 H, NH ), 5.57 (dd, J = 18.0,
2
2
2
3
2
2
3
2
IR (KBr): 3427 (s), 3354 (s), 3215 (m), 3053 (w), 3033 (w), 2923
J = 2.1 Hz, 1 H, CH=CH ), 5.76 (dd, J = 11.4, J = 2.1 Hz, 1 H,
2
3
2
(w), 1624 (s), 1591 (s), 1568 (m), 1512 (s), 1496 (s), 1454 (m), 1423
CH=CH ), 6.86 (dd, J = 18.0 Hz, J = 11.4 Hz, 1 H, CH=CH ),
7
1
2
2
–1
(
(
m), 1404 (s), 1076 (m), 856 (s), 842 (s), 777 (s), 761 (s), 690 cm
s).
.15 (s, 1 H), 7.38–7.45 (m, 2 H), 7.70–7.73 (m, 1 H), 7.78–7.80 (m,
H).
1H NMR (300 MHz, CDCl
d, J = 1.6 Hz, 1 H), 7.33–7.52 (m, 6 H), 7.67–7.70 (m, 2 H), 7.79–
.86 (m, 2 H).
, 25 °C): d = 4.20 (br s, 2 H, NH ), 7.03
2
1
3
3
C NMR (100 MHz, CDCl , 25 °C): d = 14.1 (CH CH CH CH ),
3
2
2
2
3
(
2
2.9
(CH CH CH CH ),
32.8 (CH CH CH CH ), 34.2
2
2
2
3
2 2 2 3
7
(
CH CH CH CH ), 117.8, 119.3, 120.8, 121.2, 122.4, 124.4, 125.9,
2 2 2 3
1
3
1
28.0, 133.5, 134.2, 138.9, 139.6.
C NMR (75 MHz, CDCl , 25 °C): d = 109.4, 117.3, 120.8, 123.0,
3
HRMS: m/z [M + H]+ calcd for C H N: 226.1596; found:
2
125.1, 126.4, 127.4, 127.5, 128.8, 129.0, 134.8, 139.3, 141.5, 142.6.
1
6
20
26.1590.
MS (EI, 70 eV): m/z (%) = 219 [M]+ (100.00), 202 (3.28), 191
(
(
7.09), 165 (3.58), 152 (1.35), 140 (2.64), 115 (2.98), 109 (6.95), 97
2.8).
Anal. Calcd for C H N: C, 85.29; H, 8.50; N, 6.22. Found: C,
1
6
19
8
5.23; H, 8.59; N, 6.19.
HRMS: m/z [M + H]+ calcd for C H N: 220.1126; found:
1
6
14
3
-Phenyl-2-vinylnaphthalen-1-amine (29)
220.1121.
Treatment of 27 (0.25 g, 1.00 mmol) according to the general pro-
cedure for 19 using aq NH Cl soln (5 mL) as electrophile and sub-
sequent chromatographic purification (EtOAc–pentane, 1:10) gave
Anal. Calcd for C H N: C, 87.64; H, 5.98; N, 6.39. Found: C,
1
6
13
4
8
7.31; H, 5.79; N, 6.30.
2
9 as a yellowish oil; yield: 0.11 g (46%).
N-Benzyl-2-[(trimethylsilyl)ethynyl]phenylmethanimine (34)
1
7
IR (film): 3448 (m), 3365 (m), 3078 (m), 3055 (m), 3030 (w), 3001
Treatment of 2-[(trimethylsilyl)ethynyl]benzaldehyde (1.01 g,
5.00 mmol) according to the general procedure for 9 gave 34 as a
yellowish solid; yield: 0.84 g (58%); mp 46–48 °C; purity (GC):
95%.
(w), 1614 (s), 1564 (m), 1492 (s), 1440 (m), 1396 (s), 1373 (m),
–
1
1
001 (m), 925 (m), 869 (m), 788 (m), 767 (s), 744 (s), 702 cm (s).
1
H NMR (300 MHz, CDCl , 25 °C): d = 4.65 (br s, 2 H, NH ), 5.48–
3
2
3
3
5
.58 (m, 2 H, CH=CH ), 6.57 (dd, J
= 18.4, J = 11.7 Hz, 1 H,
IR (KBr): 3063 (w), 3032 (w), 2961 (m), 2932 (w), 2882 (w), 2818
(m), 2156 (s), 1638 (s), 1593 (m), 1497 (w), 1472 (m), 1439 (m),
1371 (m), 1250 (s), 1229 (m), 1192 (m), 1028 (m), 845 (s), 764 (s),
2
trans
cis
CH=CH ), 7.23 (s, 1 H), 7.32–7.48 (m, 7 H), 7.72–7.78 (m, 1 H),
7
2
.81–7.86 (m, 1 H).
–
1
1
3
700 (s), 484 cm (m).
C NMR (75 MHz, CDCl , 25 °C): d = 117.6, 119.5, 119.7, 121.4,
3
1
1
1
23.0, 125.3, 126.4, 126.9, 127.9, 128.6, 130.1, 133.1, 135.4, 139.5,
H NMR (300 MHz, CDCl , 25 °C): d = 0.27 (s, 9 H, SiCH ), 4.86
3
3
4
40.2, 142.1.
(d, J = 1.5 Hz, 2 H, NCH Ph), 7.24–7.29 (m, 1 H), 7.31–7.35 (m, 6
H), 7.46–7.50 (m, 1 H), 8.07–8.11 (m, 1 H), 8.91 (t, J = 1.5 Hz, 1
2
4
+
MS (EI): m/z (%) = 245 [M] (100.00), 228 (29.94), 215 (9.69), 189
H, CH=N).
(
(
1.27), 166 (3.35), 141 (2.04), 127 (12.88), 98 (1.44), 84 (1.69), 57
6.22).
1
3
C NMR (75 MHz, CDCl , 25 °C): d = 0.1 (SiCH ), 65.4
3
3
(
1
NCH Ph), 100.6 (C≡C), 102.1 (C≡C), 124.2, 126.4, 127.2, 128.2,
28.7, 128.9, 130.3, 132.9, 137.3, 139.4, 160.8 (N=CH).
2
Anal. Calcd for C H N: C, 88.13; H, 6.16; N, 5.71. Found: C,
8
1
8
15
8.12; H, 6.02; N, 5.60.
HRMS: m/z [M + H]+ calcd for C H NSi: 292.1521; found:
1
9
22
2
92.1516.
Synthesis 2007, No. 14, 2135–2144 © Thieme Stuttgart · New York