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 1670656노트

반응식

HRID 1670656 반응식
[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]

참가 물질

6

반응물 4

HCID 638007Pyrido[3,4-b]pyrazine2회HCID 441857941,4-Dimethy-1,2,3,4-tetrahydropyrido[3,4-b]pyrazine4회HCID 577342285,10-Diethyl-5,5a,6,7,8,9,9a,10-octahydropyrido[3,4-b]quinoxaline2회HCID 597630781-(4-Acetyl-3,4-dihydro-2H-pyrido[3,4-b]pyrazin-1-yl)ethanone

생성물 1

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

시약·촉매·용매 1

HCID 22036596Ethyl acetate triethylamine용매

실험 절차

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.

출처 및 근거

ORD 기록
ord-6824f3de134c4d669fbeae58cc32762d
출처 데이터셋
uspto-grants-2011_08
특허 번호
US07994169B2

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