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50.5 MHz): d ˆ 170.8, 148.4, 134.3, 130.5, 128.1, 127.0, 126.6, 126.3, 125.1, was treated as described above. DIBAL-H (2.0 mL, 1.5 m solution in
122.4, 119.5, 114.6, 61.1, 54.8, 38.6, 13.7; MS (70 eV, EI): m/z(%): 267 (67) toluene, 3 mmol) was added to a solution of the resultant residue and
2044 ¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0947-6539/02/0809-2044 $ 20.00+.50/0 Chem. Eur. J. 2002, 8, No. 9
Functionalized Heterocycles 2034 ± 2046
1
[NiCl2(dppp)] (0.04 g, 0.08 mmol) in toluene (6 mL) and subsequent 65 8C (hexane); H NMR (CDCl3, 400 MHz): d ˆ 7.4 ± 7.2 (m, 6 H), 7.1 (d,
treatment with NaOH (2 mL, 0.5 m solution in water, 1 mmol), Et2O J ˆ 7.8 Hz, 1 H), 5.1 (s, 2 H), 4.3 (q, J ˆ 7.2 Hz, 2 H), 1.3 (t, J ˆ 7.2 Hz, 3 H);
13
(9 mL), and workup as described above yielded 28 b (0.29 g, 69 %) as a C NMR (CDCl3, 50.5 MHz): d ˆ 169.8, 156.1, 132.3, 130.4, 128.8, 127.8,
1
white solid. M.p. 108 ± 110 8C (hexane); H NMR (CDCl3, 400 MHz): d ˆ 126.2, 124.8, 123.6, 122.5, 120.0, 69.0, 61.5, 14.0; MS (70 eV, EI): m/z(%):
7.98 (d, J ˆ 7.6 Hz, 1 H), 7.35 (dt, J ˆ 7.6, 1.6 Hz, 1 H), 7.25 (dt, J ˆ 7.2, 1.6 Hz, 254 (100) [M]‡; elemental analysis calcd (%) for C16H14O3 (254.3): C 75.57,
1 H), 7.2 (d, J ˆ 7.6 Hz, 1 H), 7.15 (t, J ˆ 7.6 Hz, 1 H), 7.0 (dd, J ˆ 7.6, 1.2 Hz, H 5.55; found: C 75.64, H 5.61.
1 H), 6.7 (dd, J ˆ 7.6, 1.2 Hz, 1 H), 4.9 (s, 2 H), 4.15 (s, 2 H), 3.3 (br s, 2 H);
1-(1-Hydroxy-1-phenylmethyl)-6H-dibenzo[b,d]pyran (29 c): Ether 25 c
13
C NMR (CDCl3, 50.5 MHz): d ˆ 147.4, 137.6, 135.4, 131.3, 127.9, 127.2,
(0.56 g, 2 mmol) was treated with tBuLi (4.4 mL, 1.5 m solution in pentane,
126.7, 125.5, 122.7, 121.5, 115.0, 63.6, 46.5; MS (70 eV, EI): m/z (%): 211 (48)
6.6 mmol). Addition of benzaldehyde (0.26 g, 2.5 mmol) and workup as
[M]‡, 210 (100); elemental analysis calcd (%) for C14H13NO (211.3): C
described above yielded 29 c (0.32 g, 56 %) as a yellow solid. M.p. 47 ± 49 8C
79.59, H 6.20, N 6.63; found: C 79.65, H 6.17, N 6.61. 1
(hexane); H NMR (CDCl3, 400 MHz): d ˆ 7.85 ± 7.75 (m, 1 H), 7.4 ± 7.0 (m,
13
11 H), 6.4 (s, 1 H), 5.0 (s, 2 H), 2.8 (br s, 1 H); C NMR (CDCl3, 50.5 MHz):
1-Bromo-5,6-dihydrophenanthridine (28 c): Amine 25 b (0.64 g, 2 mmol)
was treated with tBuLi (4.7 mL, 1.5 m solution in pentane, 7 mmol). 1,2- d ˆ 155.9, 143.6, 140.5, 134.0, 129.3, 128.9, 128.2, 127.3, 127.2, 127.1, 126.8,
124.9, 123.7, 123.3, 116.4, 72.2, 68.9; MS (70 eV, EI): m/z(%): 288 (100)
Dibromoethane (0.56 g, 3 mmol) was added and the mixture was treated as
[M]‡; elemental analysis calcd (%) for C20H16O2 (288.3): C 83.31, H 5.59;
described above. DIBAL-H (2.0 mL, 1.5 m solution in toluene, 3 mmol) was
found: C 83.18, H 5.64.
added to a solution of the resultant residue and [NiCl2(dppp)] (0.04 g,
0.08 mmol) in toluene (6 mL). Subsequent treatment with NaOH (2 mL,
1-Tributylstannyl-6H-dibenzo[b,d]pyran (29 d): Ether 25 c (0.56 g, 2 mmol)
0.5 m solution in water, 1 mmol) and Et2O (9 mL), and workup as described
was treated with tBuLi (4.4 mL, 1.5 m solution in pentane, 6.6 mmol).
above yielded 28 c (0.38 g, 73 %) as a yellow solid. M.p. 83 ± 85 8C (hexane);
Addition of tributyltin chloride (0.83 g, 3 mmol) and workup as described
1
H NMR (CDCl3, 400 MHz): d ˆ 8.55 (d, J ˆ 6.8 Hz, 1 H), 7.4 (dt, J ˆ 8.0,
above yielded 29 d (0.565 g, 60 %) as a colorless oil. Rf ˆ 0.15 (hexane/ethyl
1
1.6 Hz, 1 H), 7.3 (dt, J ˆ 7.6, 1.2 Hz, 1 H), 7.2 (d, J ˆ 7.6 Hz, 2 H), 6.9 (t, J ˆ
acetate 60:1); H NMR (CDCl3, 200 MHz): d ˆ 7.7 ± 7.0 (m, 7 H), 5.0 (s,
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13
8.0 Hz, 1 H), 6.65 (d, J ˆ 8.0 Hz, 1 H), 4.1 (s, 3 H); C NMR (CDCl3,
2 H), 1.7 ± 0.9 (m, 27 H); C NMR (CDCl3, 50.5 MHz): d ˆ 155.9, 139.1,
50.5 MHz): d ˆ 149.2, 135.0, 130.8, 128.6, 127.2, 126.7, 126.3, 125.5, 125.3,
133.2, 132.9, 131.8, 130.7, 128.7, 127.8, 127.1, 124.5, 124.1, 117.1, 68.8, 28.9,
122.2, 120.2, 114.5, 46.3; MS (70 eV, EI): m/z(%): 261 (50) [M‡2]‡, 259 (50)
27.2, 13.6, 11.9; MS (70 eV, EI): m/z(%): 415 [M C4H9]‡ (84), 301 (100);
[M]‡, 260 (100), 258 (100); elemental analysis calcd (%) for C13H10BrN
elemental analysis calcd (%) for C25H36OSn (471.3): C 63.72, H 7.70; found:
(260.1): C 60.02, H 3.87, N 5.38; found: C 60.18, H 3.70, N 5.39.
C 63.58, H 7.57.
5,6-Dihydro-1-tributylstannylphenanthridine (28 d): Amine 25 b (0.64 g, [ Pobierz całość w formacie PDF ]
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50.5 MHz): d ˆ 170.8, 148.4, 134.3, 130.5, 128.1, 127.0, 126.6, 126.3, 125.1, was treated as described above. DIBAL-H (2.0 mL, 1.5 m solution in
122.4, 119.5, 114.6, 61.1, 54.8, 38.6, 13.7; MS (70 eV, EI): m/z(%): 267 (67) toluene, 3 mmol) was added to a solution of the resultant residue and
2044 ¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0947-6539/02/0809-2044 $ 20.00+.50/0 Chem. Eur. J. 2002, 8, No. 9
Functionalized Heterocycles 2034 ± 2046
1
[NiCl2(dppp)] (0.04 g, 0.08 mmol) in toluene (6 mL) and subsequent 65 8C (hexane); H NMR (CDCl3, 400 MHz): d ˆ 7.4 ± 7.2 (m, 6 H), 7.1 (d,
treatment with NaOH (2 mL, 0.5 m solution in water, 1 mmol), Et2O J ˆ 7.8 Hz, 1 H), 5.1 (s, 2 H), 4.3 (q, J ˆ 7.2 Hz, 2 H), 1.3 (t, J ˆ 7.2 Hz, 3 H);
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(9 mL), and workup as described above yielded 28 b (0.29 g, 69 %) as a C NMR (CDCl3, 50.5 MHz): d ˆ 169.8, 156.1, 132.3, 130.4, 128.8, 127.8,
1
white solid. M.p. 108 ± 110 8C (hexane); H NMR (CDCl3, 400 MHz): d ˆ 126.2, 124.8, 123.6, 122.5, 120.0, 69.0, 61.5, 14.0; MS (70 eV, EI): m/z(%):
7.98 (d, J ˆ 7.6 Hz, 1 H), 7.35 (dt, J ˆ 7.6, 1.6 Hz, 1 H), 7.25 (dt, J ˆ 7.2, 1.6 Hz, 254 (100) [M]‡; elemental analysis calcd (%) for C16H14O3 (254.3): C 75.57,
1 H), 7.2 (d, J ˆ 7.6 Hz, 1 H), 7.15 (t, J ˆ 7.6 Hz, 1 H), 7.0 (dd, J ˆ 7.6, 1.2 Hz, H 5.55; found: C 75.64, H 5.61.
1 H), 6.7 (dd, J ˆ 7.6, 1.2 Hz, 1 H), 4.9 (s, 2 H), 4.15 (s, 2 H), 3.3 (br s, 2 H);
1-(1-Hydroxy-1-phenylmethyl)-6H-dibenzo[b,d]pyran (29 c): Ether 25 c
13
C NMR (CDCl3, 50.5 MHz): d ˆ 147.4, 137.6, 135.4, 131.3, 127.9, 127.2,
(0.56 g, 2 mmol) was treated with tBuLi (4.4 mL, 1.5 m solution in pentane,
126.7, 125.5, 122.7, 121.5, 115.0, 63.6, 46.5; MS (70 eV, EI): m/z (%): 211 (48)
6.6 mmol). Addition of benzaldehyde (0.26 g, 2.5 mmol) and workup as
[M]‡, 210 (100); elemental analysis calcd (%) for C14H13NO (211.3): C
described above yielded 29 c (0.32 g, 56 %) as a yellow solid. M.p. 47 ± 49 8C
79.59, H 6.20, N 6.63; found: C 79.65, H 6.17, N 6.61. 1
(hexane); H NMR (CDCl3, 400 MHz): d ˆ 7.85 ± 7.75 (m, 1 H), 7.4 ± 7.0 (m,
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11 H), 6.4 (s, 1 H), 5.0 (s, 2 H), 2.8 (br s, 1 H); C NMR (CDCl3, 50.5 MHz):
1-Bromo-5,6-dihydrophenanthridine (28 c): Amine 25 b (0.64 g, 2 mmol)
was treated with tBuLi (4.7 mL, 1.5 m solution in pentane, 7 mmol). 1,2- d ˆ 155.9, 143.6, 140.5, 134.0, 129.3, 128.9, 128.2, 127.3, 127.2, 127.1, 126.8,
124.9, 123.7, 123.3, 116.4, 72.2, 68.9; MS (70 eV, EI): m/z(%): 288 (100)
Dibromoethane (0.56 g, 3 mmol) was added and the mixture was treated as
[M]‡; elemental analysis calcd (%) for C20H16O2 (288.3): C 83.31, H 5.59;
described above. DIBAL-H (2.0 mL, 1.5 m solution in toluene, 3 mmol) was
found: C 83.18, H 5.64.
added to a solution of the resultant residue and [NiCl2(dppp)] (0.04 g,
0.08 mmol) in toluene (6 mL). Subsequent treatment with NaOH (2 mL,
1-Tributylstannyl-6H-dibenzo[b,d]pyran (29 d): Ether 25 c (0.56 g, 2 mmol)
0.5 m solution in water, 1 mmol) and Et2O (9 mL), and workup as described
was treated with tBuLi (4.4 mL, 1.5 m solution in pentane, 6.6 mmol).
above yielded 28 c (0.38 g, 73 %) as a yellow solid. M.p. 83 ± 85 8C (hexane);
Addition of tributyltin chloride (0.83 g, 3 mmol) and workup as described
1
H NMR (CDCl3, 400 MHz): d ˆ 8.55 (d, J ˆ 6.8 Hz, 1 H), 7.4 (dt, J ˆ 8.0,
above yielded 29 d (0.565 g, 60 %) as a colorless oil. Rf ˆ 0.15 (hexane/ethyl
1
1.6 Hz, 1 H), 7.3 (dt, J ˆ 7.6, 1.2 Hz, 1 H), 7.2 (d, J ˆ 7.6 Hz, 2 H), 6.9 (t, J ˆ
acetate 60:1); H NMR (CDCl3, 200 MHz): d ˆ 7.7 ± 7.0 (m, 7 H), 5.0 (s,
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8.0 Hz, 1 H), 6.65 (d, J ˆ 8.0 Hz, 1 H), 4.1 (s, 3 H); C NMR (CDCl3,
2 H), 1.7 ± 0.9 (m, 27 H); C NMR (CDCl3, 50.5 MHz): d ˆ 155.9, 139.1,
50.5 MHz): d ˆ 149.2, 135.0, 130.8, 128.6, 127.2, 126.7, 126.3, 125.5, 125.3,
133.2, 132.9, 131.8, 130.7, 128.7, 127.8, 127.1, 124.5, 124.1, 117.1, 68.8, 28.9,
122.2, 120.2, 114.5, 46.3; MS (70 eV, EI): m/z(%): 261 (50) [M‡2]‡, 259 (50)
27.2, 13.6, 11.9; MS (70 eV, EI): m/z(%): 415 [M C4H9]‡ (84), 301 (100);
[M]‡, 260 (100), 258 (100); elemental analysis calcd (%) for C13H10BrN
elemental analysis calcd (%) for C25H36OSn (471.3): C 63.72, H 7.70; found:
(260.1): C 60.02, H 3.87, N 5.38; found: C 60.18, H 3.70, N 5.39.
C 63.58, H 7.57.
5,6-Dihydro-1-tributylstannylphenanthridine (28 d): Amine 25 b (0.64 g, [ Pobierz całość w formacie PDF ]