Pyrido[3,4-b]pyrazine → 1-(5-Ethyl-5a,6,7,8,9,9a-hexahydro-5h-pyrido[3,4-b]quinoxalin-10-yl)ethanone

HRID 1670656ノート

反応式

HRID 1670656 の反応式
[CH2:1]([N:3]1[CH:12]2[CH:7]([CH2:8][CH2:9][CH2:10][CH2:11]2)[N:6]([CH2:13][CH3:14])[C:5]2[CH:15]=[N:16][CH:17]=[CH:18][C:4]1=2)[CH3:2].C(N1CCN(C(=O)C)C2C=CN=CC1=2)(=[O:21])C.N1C=CN=C2C=NC=CC=12.CN1CCN(C)C2C=NC=CC1=2>CCOC(C)=O.CCN(CC)CC>[CH2:1]([N:3]1[CH:12]2[CH:7]([CH2:8][CH2:9][CH2:10][CH2:11]2)[N:6]([C:13](=[O:21])[CH3:14])[C:5]2[CH:15]=[N:16][CH:17]=[CH:18][C:4]1=2)[CH3:2]

参加物

6

反応物 4

HCID 638007Pyrido[3,4-b]pyrazine2 回HCID 441857941,4-Dimethy-1,2,3,4-tetrahydropyrido[3,4-b]pyrazine4 回HCID 577342285,10-Diethyl-5,5a,6,7,8,9,9a,10-octahydropyrido[3,4-b]quinoxaline2 回HCID 597630781-(4-Acetyl-3,4-dihydro-2H-pyrido[3,4-b]pyrazin-1-yl)ethanone

生成物 1

HCID 673370301-(5-Ethyl-5a,6,7,8,9,9a-hexahydro-5h-pyrido[3,4-b]quinoxalin-10-yl)ethanone

試薬・触媒・溶媒 1

HCID 22036596Ethyl acetate triethylamine溶媒

実験手順

29 (0.250 g, 1.15 mmol) and 10 ml of THF were placed in a 100 ml Schlenk flask. The solution was cooled to −78° C., 0.51 ml of n-BuLi (1.27 mmol, 1.1 eq; 2.5 M in hexane) were added and the reaction solution was stirred without cooling for 30 minutes. After 30 minutes, the reaction solution was cooled back down to −78° C. and 0.09 ml (0.109 g, 1.4 mmol, ρ=1.1051 g/ml) of acetyl chloride were added, the cooling bath was removed and the mixture was stirred without cooling for 1 hour. The reaction was subsequently stopped by means of 4 ml and extracted three times with 20 ml of DCM. The combined organic phases were dried over Na2SO4 and the solvent was distilled off on a rotary evaporator. The crude product was purified on silica gel (EtOAc/MeOH, 10:2) to give 48 mg (0.18 mmol, 16%) of a colorless solid. Rf=0.16 (EtOAc/NEt3, 10:1). 1H NMR: (300 MHz, CDCl3): δ=1.19 (t, 3J=7.2 Hz, 3H, H3C—CH2—N-5), 1.24 (m, 2H), 1.45 (m, 2H), 1.58 (m, 2H), 1.74 (m, 1H), 2.18 (m, 1H), 3.34 (m, 2J=14.4 Hz, 3J=7.2 Hz, 1H, H3C—CHAB—N-5), 3.53 (m, 1H, C—H), 3.57 (m, 2J=15.2 Hz, 3J=7.2 Hz, 1H, H3C—CHAB—N-5), 4.90 (bs, 1H, C—H), 6.62 (d, 3J=5.6 Hz, 1H, H-4), 8.12 (s, 1H, H-1), 8.08 (d, 3J=5.6 Hz, 1H, H-3). 13C NMR (100 MHz, CDCl3): δ=12.4 (H3C—CH2—N-5), 18.9 (C-7), 22.8 (H3C—CO—N-10), 24.7 (C-8), 25.8 (C-6), 28.5 (C-9), 40.0 (H3C—CH2—N-5), 48.7 (C-9a), 53.7 (C-5a), (C-4), 106.4 (C-4), 120.1 (Cq, C-10a), 145.1, 145.2 (C-1, Cq, C-4a), 147.1 (C-3), 167.1 (C═O) ppm. GC-MS (EI): RT 10.39 min, m/e (%) 260 (11), 259 (M+, 100), 230 (8), 218 (9), 217 (79), 216 (40), 203 (4), 202 (23), 203 (3), 202 (23), 201 (4), 189 (6), 188 (31), 187 (4), 186 (3), 174 (11), 162 (4), 161 (6), 160 (5), 158 (4), 148 (5), 146 (6), 136 (3), 132 (4), 131 (12), 120 (6), 43 (3); IR (neat): ν=3398 (s), 2933 (s), 2863 (m), 1731 (m), 1637 (vs), 1595 (vs), 1512 (s), 1546 (w), 1449 (m), 1397 (s), 1365 (s), 1334 (m), 1285 (s), 1239. (m), 1198 (m), 1168 (vs), 1123 (w), 1067 (w), 1068 (w), 1016 (w), 802 (vs), 718 (w), 668 (m). HRMS (EI): calculated for C15H21N3O 259.1685 [M+], found: 259.1687.

出典と根拠

ORDレコード
ord-6824f3de134c4d669fbeae58cc32762d
出典データセット
uspto-grants-2011_08
特許番号
US07994169B2

反応ノート

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