2-Methoxybenzene-1,4-diol → 2,5,8-Trimethoxy-4a,9,9a,10-tetrahydro-9,10-[1,2]benzenoanthracene-1,4-dione

HRID 2306906

反応式

HRID 2306906 の反応式
[CH3:1][O:2][C:3]1[C:16]2[C:7](=[CH:8][C:9]3[C:14]([CH:15]=2)=[CH:13][CH:12]=[CH:11][CH:10]=3)[C:6]([O:17][CH3:18])=[CH:5][CH:4]=1.[CH3:19][O:20][C:21]1[CH:27]=[C:26]([OH:28])[CH:25]=[CH:24][C:22]=1[OH:23]>C1(C)C=CC=CC=1>[CH3:18][O:17][C:6]1[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[C:16]2[C:7]=1[CH:8]1[C:9]3[C:14](=[CH:13][CH:12]=[CH:11][CH:10]=3)[CH:15]2[CH:24]2[C:22]([C:21]([O:20][CH3:19])=[CH:27][C:26](=[O:28])[CH:25]12)=[O:23]

参加物

4

反応物 2

HCID 699882-Methoxybenzene-1,4-diolHCID 831071,4-Dimethoxyanthracene

生成物 1

HCID 226299862,5,8-Trimethoxy-4a,9,9a,10-tetrahydro-9,10-[1,2]benzenoanthracene-1,4-dione収率 48%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
25 °C

実験手順

A solution of 0.70 g (2.90 mmol) of 2 and 1.00 g (7.20 mmol) of 6 in 10 mL of toluene in a sealed tube was heated at 150° C. for 1 day, cooled to 25° C., concentrated to dryness, and column chromatographed on silica gel using a gradient mixture of hexane and ethyl acetate as solvent gave 0.52 g (48% yield) of compounds 5 as a mixture of exo- and endo-(1:1) isomers along with 0.62 g of 6. The exo- and endo-isomers were partially separated by silica gel column and the stereochemistry have not assigned. Compound 5, less polar isomer: MS, m/z 376 (M+), 375. 1H NMR d 7.24-7.18 (m, 2H), 7.08-7.04 (m, 2H), 6.65 (s, 2H, C6,7 Hs), 5.61 (s, 1H), 5.33 (bs, 2H), 3.82 (s, 6H, OMe), 3.48 (s, 3H, OMe), 3.12 (ABd, J=9 Hz, 1H), 3.06 (ABd, J=9 Hz, 1H). More polar isomer: MS, m/z 376 (M+), 375. 1H NMR d 7.40 (m, 2H), 7.16 (m, 2H), 6.60 (ABd, J=8.8 Hz, 1H), 6.56 (Abd, J=8.8 Hz, 1H), 5.65 (s, 1H, ═CH), 5.33 (bs, 2H, C9,10 Hs), 3.76 (s, 3H, OMe), 3.73 (s, 3H, OMe), 3.51 (s, 3H, OMe), 3.13 (Abd, J=9 Hz, 1H), 3.08 (Abd, J=9 Hz, 1H). This mixture of compounds was used in the next step.

後処理

  1. concentrationconcentrated to dryness, and column
  2. customchromatographed on silica gel using
  3. additiona gradient mixture of hexane and ethyl acetate as solvent

出典と根拠

ORDレコード
ord-5e45cc1ea98e4902b7704c132fe8fe70
出典データセット
uspto-grants-2004_12
特許番号
US06828450B2

関連ノート

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