Water → 9-bromo-3-(2-bromoacetyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one

HRID 1413013ノート

反応式

HRID 1413013 の反応式
[Br:1][CH:2]1[CH2:23][CH2:22][C:5]2=[CH:6][C:7]3[C:8]4[CH:17]=[CH:16][C:15]([CH:18]([OH:21])[CH2:19][Br:20])=[CH:14][C:9]=4[CH2:10][O:11][C:12]=3[CH:13]=[C:4]2[C:3]1=[O:24].C(=O)(O)[O-].[Na+].[Br-].[Na+].O>C(Cl)Cl.CC1(C)N([O])C(C)(C)CCC1.C(O)(C)C>[Br:1][CH:2]1[CH2:23][CH2:22][C:5]2=[CH:6][C:7]3[C:8]4[CH:17]=[CH:16][C:15]([C:18](=[O:21])[CH2:19][Br:20])=[CH:14][C:9]=4[CH2:10][O:11][C:12]=3[CH:13]=[C:4]2[C:3]1=[O:24]

参加物

8

反応物 4

HCID 962WaterHCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 866883739-Bromo-3-(2-bromo-1-hydroxyethyl)-10,11-dihydro-5H-benzo[d]naphtho[2,3-b]pyran-8(9H)-one

生成物 1

HCID 866883729-bromo-3-(2-bromoacetyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one収率 76%

試薬・触媒・溶媒 3

HCID 2724126Tempo触媒HCID 3776Isopropanol溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
2.5 °C

実験手順

To 9-bromo-3-(2-bromo-1-hydroxyethyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one (approx. 54.4 mmol) in DCM (365 mL) was added sodium bicarbonate (5.45 g), sodium bromide (6.14 g), TEMPO (16.55 mg) and water (60 mL). The solution was cooled between 0-5° C. and 6% bleach (91.5 mL) was added. After 1 h isopropyl alcohol (20 mL) was added and the reaction mixture was warmed to room temperature. Agitation was stopped, the layers separated and the lower organic layer was collected and concentrated removing approximately 345 g of solvent. The slurry was filtered and the cake washed with 50 mL water and then 50 mL DCM (pre-cooled to 5° C.). The solids were collected and dried under vacuum to obtain 9-bromo-3-(2-bromoacetyl)-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one (18.6 g, 76% yield). 400 MHz 1H NMR (CDCl3) δ 8.03-8.01 (m, 1H), 7.85 (d, J=8.2 Hz, 1H), 7.82 (s, 1H), 7.71 (s, 1H), 7.67 (s, 1H), 5.19 (s, 2H), 4.74 (dd, J=4.1, 4.1 Hz, 1H), 4.45 (s, 2H), 3.37-3.29 (m, 1H), 2.99-2.92 (m, 1H), 2.59-2.46 (m, 2H); 100 MHz 13C NMR (CDCl3) δ 190.4, 189.6, 154.2, 136.6, 134.1, 133.9, 132.9, 131.8, 129.3, 127.2, 125.6, 124.2, 123.3, 117.0, 68.1, 49.9, 31.8, 30.4, 25.5.

後処理

  1. addition6% bleach (91.5 mL) was added
  2. temperaturethe reaction mixture was warmed to room temperature
  3. customthe layers separated
  4. customthe lower organic layer was collected
  5. concentrationconcentrated
  6. customremoving approximately 345 g of solvent
  7. filtrationThe slurry was filtered
  8. washthe cake washed with 50 mL water
  9. custom50 mL DCM (pre-cooled to 5° C.)
  10. customThe solids were collected
  11. customdried under vacuum

出典と根拠

ORDレコード
ord-aedaeb99ba8e47d0a7f705b0f4716a1b
出典データセット
uspto-grants-2014_12
特許番号
US08921341B2

反応ノート

読み込み中…