M. Sajitz, R. Fröhlich, E.-U. Würthwein
FULL PAPER
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0.78 mmol). Rf (TLC) = 0.35 (silica gel; PE/EA, 8:1), m.p. 135– 0.25 (silica gel; PE/EA, 8:1). H NMR (499.83 MHz, [D8]toluene,
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136 °C. H NMR (499.83 MHz, [D8]toluene, 348 K): δ = 1.21 [s, 9
348 K): δ = 1.76 (s, 3 H, CH3), 3.36 (s, 3 H, OCH3), 4.06 (d, 2J
H, C(CH3)3], 4.16 (d, 2J = 15.0 Hz, 1 H, NCHH), 4.92 (d, 2J = = 15.0 Hz, 1 H, NCHH), 4.38 (s, 1 H, NCHH), 5.11 (m, 2 H,
15.0 Hz, 1 H, NCHH), 5.00 (d, 3J = 10.5 Hz, 1 H, CHCH=CHH), CHCH=CH2), 5.57 (s, 1 H, CHCH=CH2), 5.76 (m, 1 H,
5.03 (d, 3J = 17.0 Hz, 1 H, CHCH=CHH), 5.70 (m, 1 H,
CHCH=CH2), 6.23 (m, 1 H, HC=CCH3), 6.93–7.09 (m, 4 H,
CHCH=CH2 ), 6. 27 (s, 1 H, HCCHCH2 ), 6.70 (s, 1 H, CHarom.) ppm. 13C NMR (125.70 MHz, [D8]toluene, 348 K): δ =
HC=CC6H5), 6.98–7.26, 7.42–7.44 (m, 9 H, CHarom.) ppm. 13C 24.8 (CH3), 47.7 (CH2), 52.2 (OCH3), 63.5 (HCCHCH2), 118.3
NMR (125.70 MHz, [D8]toluene, 348 K): δ = 28.9 [C(CH3)3], 39.2 (CHCH=CH2), 126.5, 127.6, 128.3 (CHarom.), 128.7 (CH=CCH3),
[C(CH3)3], 49.2 (CH2), 63.0 (HCCHCH2), 118.4 (CHCH=CHH), 129.3 (CHarom.), 131.6, 135.5, 139.0 (Cipso), 136.7 (CHCH=CH2),
127.2, 127.4, 127.7, 127.8, 127.9, 128.7, 128.9, 129.4, 132.7
156.0 (C=O) ppm. IR (KBr): ν = 3076 (w, CHarom.,olef.), 3058 (m,
˜
(CHarom.), 132.0 (CH=CC6H5), 134.9, 137.1, 139.8, 142.9, 143.6
CHarom.,olef.), 3020 (m, CHarom.,olef.), 2976 (m, CHaliph.), 2954 (s,
CHaliph.), 2920 (m, CHaliph.), 2856 (w, CHaliph.), 1703 [vs, RO(CO)
(Cipso, CHCH=CH ), 176.0 (C=O) ppm. IR (KBr): ν = 3053 (s,
˜
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CHarom.,olef.), 3026 (s, CHarom.,olef.), 2979 (vs, CHaliph.), 2931 (s, NR2], 1637 (m), 1575 (w), 1490 (m), 1461 (s), 1406 (s), 1382 (s),
CHaliph.), 2908 (s, CHaliph.), 2871 (m, CHaliph.), 1625 [vs, (CO)NR2], 1326 (s), 1309 (s), 1276 (s), 1255 (s), 1205 (s), 1159 (w), 1120 (s),
1595 (vs), 1573 (s), 1494 (vs), 1477 (vs), 1442 (vs), 1409 (vs), 1387 1072 (m), 1051 (w), 1014 (m), 993 (s), 962 (m), 950 (m), 933 (m),
(s), 1367 (vs), 1332 (s), 1311 (vs), 1284 (vs), 1199 (vs), 1182 (vs), 894 (m), 871 (vw), 844 (m), 767 (s), 754 (s), 657 (m), 646 (m) cm–1.
1155 (s), 1114 (s), 1078 (s), 1043 (s), 1033 (s), 997 (s), 983 (s), 960
(s), 943 (s), 931 (vs), 908 (m), 883 (m), 856 (w), 835 (w), 786 (s), 184 (71) [M – (CO)OCH3]+, 168 (34), 157 (20), 142 (18), 115 (21).
756 (vs), 736 (s), 696 (vs), 634 (s), 595 (m), 570 (s), 540 (s), 520 (m)
MS (MicroTOF): calcd. 266.1151 [M + H]+; found 266.1148 [M +
cm–1. GC-MS (EI, 70 eV): m/z = 331.3 [M]+, 316.3 [M – CH3]+, H]+. C15H17NO2 (243.30): calcd. C 74.05, H 7.04, N 5.76; found C
MS (EI, 70 eV): m/z (%) = 243 (100) [M]+, 228 (99) [M – CH3]+,
302.3 [M – C2H5]+, 298.3, 287.3, 274.2 [M – tBu]+, 246.2 [274 –
C2H4]+, 230.2 [M – HN(C=O)C(CH3)3]+, 218.2, 204.2, 191.2,
178.2, 165.2, 152.2, 140.2, 128.2, 115.2, 90.2, 57.2. MS (Micro-
TOF): calcd. 354.1828 [M + Na]+; found 354.1830 [M + Na]+.
C23H25NO (331.45): calcd. C 83.34, H 7.60, N 4.23; found C 83.15,
H 7.42, N 4.12.
73.71, H 6.98, N 5.60.
Methyl 4-Phenyl-3-vinyl-2,3-dihydro-1H-2-benzazepine-2-carboxyl-
ate (5e): This compound was synthesised from 4b[9] (370 mg,
1.50 mmol), LDA (1.65 mmol) and methyl chloroformate
(2.5 equiv., 3.75 mmol, 0.30 mL). The crude product was purified
by column chromatography (silica gel; P/EA, 6:1). The compound
2,2-Dimethyl-1-(4-methyl-3-prop-1-enyl-2,3-dihydro-1H-2-benzaz- was isolated as a colourless oil in a yield of 20 % (89 mg,
epin-2-yl)propan-1-one (5c): This compound was synthesised from
(2-methylallyl){2-[(E/Z)-prop-1-enyl]benzylidene}amine (4c,
299 mg, 1.50 mmol), LDA (1.65 mmol) and pivaloyl chloride
(3.00 mmol, 0.37 mL). The crude product was purified by column
chromatography (silica gel; P/EA, 6:1). The compound was isolated
as a colourless oil in a yield of 64% (272 mg, 0.96 mmol). Rf (TLC)
0.29 mmol). Rf (TLC) = 0.40 (silica gel; PE/EA, 6:1). 1H NMR
(499.83 MHz, [D8]toluene, 348 K): δ = 3.41 (s, 3 H, CH3), 4.26 (d,
2J = 15.5 Hz, 1 H, NCHH), 4.46 (br. s, 1 H, NCHH), 4.97 (d,
3J = 10.0 Hz, 1 H, CHCH=CHH), 5.05 (d, 3J = 17.0 Hz, 1 H,
CHCH=CHH), 5.69 (m, 1 H, CHCH=CH2), 6.36 (s, 1 H,
HCCHCH2), 6.61 (s, 1 H, HC=CC6H5), 6.98–7.14 (m, 7 H,
= 0.60 (silica gel; PE/EA, 7:1). 1H NMR (499.83 MHz, [D8]toluene, CHa r o m . ), 7.41–7.43 (m, 2 H, CHa r o m . ) ppm. 1 3 C NMR
373 K): δ = 1.18 [s, 9 H, C(CH3)3], 1.66 (s, 3 H, CH3C=CH2), 1.88 (125.70 MHz, [D8]toluene, 348 K): δ = 48.1 (CH2), 52.4 (OCH3),
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(s, 3 H, CH3), 4.39 (d, J = 16.0 Hz, 1 H, NCHH), 4.75 (d, J =
61.9 (HCCHCH2), 118.9 (CHCH=CH2), 126.4, 127.1, 127.3, 127.5,
16.0 Hz, 1 H, NCHH), 4.84 [s, 1 H, CHCH=C(CH3)H], 5.07 [s, 1 127.7, 128.3, 128.8 (CHarom.), 131.7 (CH=CC6H5), 136.9, 137.4,
H, CHC(CH3)=CHH], 5.54 (m, 1 H, CHC=CH2), 6.25 (s, 1 H, 139.4, 143.7 (Cipso, CHCH=CH ), 157.8 (C=O) ppm. IR (film): ν
˜
2
HC=CCH3), 6.91–7.09 (m, 4 H, CHarom.) ppm. 13C NMR
(125.70 MHz, [D8]toluene, 373 K): δ = 20.8 (CH3C=CH2), 25.1
= 3055 (s, CHarom.,olef.), 3028 (m, CHarom.,olef.), 2985 (s, CHaliph.),
2956 (m, CHaliph.), 2931 (m, CHaliph.), 2871 (m, CHaliph.), 2856 (m,
(CH3), 29.4 [C(CH3)3], 39.7 [C(CH3)3], 48.4 (CH2), 66.4 CHaliph.), 1697 [vs, (CO)NR2], 1645 (w), 1598 (m), 1573 (w), 1548
(HCC=CH2), 118.3 [CHC(CH3)=CHH], 126.6, 127.1, 128.9 (w), 1494 (m), 1450 (s), 1421 (s), 1411 (s), 1379 (s), 1340 (m), 1326
(CHarom.), 129.9 (CH=C–CH3), 132.5 (CHarom.), 135.2, 139.2, (m), 1311 (m), 1265 (vs), 1213 (m), 1193 (m), 1159 (m), 1124 (m),
139.5 (Cipso, CH=CCH3), 144.0 (CH3C=CH2), 176.0 (C=O) ppm. 1093 (m), 1078 (m), 1047 (m), 1033 (m), 1008 (m), 997 (m), 966
IR (film): ν = 3055 (s, CHarom.,olef.), 3020 (m, CHarom.,olef.), 2977
(m), 935 (m), 896 (m), 871 (w), 842 (w), 740 (vs), 703 (vs), 659 (w),
˜
(s, CHaliph.), 2937 (m, CHaliph.), 2975 (m, CHaliph.), 1622 [vs, (CO)- 597 (vw), 588 (w), 472 (vs) cm–1. GC-MS (EI, 70 eV): m/z = 305.2
NR2], 1575 (vw), 1492 (m), 1477 (s), 1438 (s), 1406 (s), 1379 (m),
[M]+, 290.2 [M – CH3]+, 278.2, 272.2, 258.2, 246.2 [M – (CO)-
1365 (m), 1305 (m), 1265 (vs), 1199 (m), 1174 (s), 1139 (w), 1110 OCH3]+, 230.2 [M – H2N(CO)OCH3]+, 215.2, 204.2, 191.2, 176.2,
(w), 1053 (vw), 1033 (vw), 1010 (w), 974 (w), 954 (vw), 918 (m), 165.2, 152.2, 128.2, 115.2, 101.2, 91.2, 77.2, 59.1. MS (MicroTOF):
896 (m), 875 (vw), 846 (vw), 738 (vs), 704 (vs) cm–1. MS (EI,
calcd. 328.1308 [M + Na]+; found 328.1308 [M + Na]+. C20H19NO2
(305.37): calcd. C 78.66, H 6.27, N 4.59; found C 78.42, H 6.65, N
70 eV): m/z (%) = 283 (52) [M]+, 268 (28) [M – CH3]+, 255 (8), 226
[(CH3)3C=O]+ (76), [M – C(CH3)3]+ 198 [M – C]+ (21), 183 [M – 4.34.
HN(C=O)C(CH3)3]+ (31), 167 (22), 142 (20), 129 (11), 102 (2), 83
Methyl 4-Methyl-3-(prop-1-en-1-yl)-2,3-dihydro-1H-2-benzazepine-
(37), 57 (100) [C(CH3)3]+. MS (MicroTOF): calcd. 306.1828 [M +
H]+; found 306.1827 [M + H]+. C19H25NO (283.41): calcd. C 80.52,
H 8.89, N 4.94; found C 80.09, H 9.01, N 4.69.
2-carboxylate (5f): This compound was synthesised from 4c
(299 mg, 1.50 mmol), LDA (1.65 mmol) and methyl chloroformate
(2.5 equiv., 3.75 mmol, 0.30 mL). The crude product was purified
by column chromatography (silica gel; P/EA, 7:1). The compound
was isolated as a colourless solid in a yield of 68 % (263 mg,
Methyl 4-Methyl-3-vinyl-2,3-dihydro-1H-2-benzazepine-2-carboxyl-
ate (5d): This compound was synthesised from (allyl){2-[(E/Z)-
prop-1-enyl]benzylidene}amine (4a,[9] 278 mg, 1.50 mmol), LDA 1.02 mmol). Rf (TLC) = 0.48 (silica gel; PE/EA 7:1), m.p. 74 °C.
(1.65 mmol) and methyl chloroformate (2.5 equiv., 3.75 mmol,
0.30 mL). The crude product was purified by column chromatog-
raphy (silica gel; P/EA, 8:1, 6:1). The compound was isolated as a
colourless oil in a yield of 47% (174 mg, 0.72 mmol). Rf (TLC) =
1H NMR (499.83 MHz, [D8]toluene, 348 K): δ = 1.71 (s, 3 H,
2
CH3CCH2), 1.81 (s, 3 H, CH3), 3.36 (s, 3 H, OCH3), 4.19 (d, J =
15.5 Hz, 1 H, NCHH), 4.40 (s, 1 H, NCHH), 4.83 [s, 1 H,
CHC(CH3)=CHH], 5.05 [s, 1 H, CHC(CH3)=CHH], 5.40 [s, 1 H,
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Eur. J. Org. Chem. 2009, 2342–2353