Ethanol → HCID 19710573, compound

HRID 2260384Notes

Reaction equation

HRID 2260384 reaction equation
[CH2:1]([CH:3]1[CH:12]=C[CH2:10][C:9]2[C:8](=[O:13])[C:7]([O:14][CH3:15])=[CH:6][C:5](=[O:16])[C:4]1=2)[CH3:2].[Cl:17]Cl.CCO.[K+].[Br-].[CH:24]([Cl:27])(Cl)Cl>C(Cl)(Cl)(Cl)Cl.CCOC(C)=O>[Cl:17][CH:12]1[CH:24]([Cl:27])[CH2:10][C:9]2[C:8](=[O:13])[C:7]([O:14][CH3:15])=[CH:6][C:5](=[O:16])[C:4]=2[CH:3]1[CH2:1][CH3:2]

Participants

8

Reactant 5

HCID 702EthanolHCID 6212ChloroformHCID 24526ChlorineHCID 253877Potassium BromideHCID 10822679HCID 10822679, compound

Product 1

HCID 19710573HCID 19710573, compound

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
25 °C

Procedure

To a stirred solution of 5,8-dihydro-5-ethyl-2-methoxynaphthalene1,4-dione (2.00 g, 9.16 mmol) in CHCl3 (100 mL, passed through silica gel prior to use), a solution of Cl2 in CCl4 (8.3 mL, ~1.1M) was added dropwise over a 5 min period. After addition, the reaction was allowed to stir an additional 30 min at 25° C. Analysis (NMR) indicated partial consumption of the starting material. An additional portion of the Cl2 solution (4 mL) was added. The reaction was allowed to stir at 25° C. for 1 hr. The analysis now indicated the absence of starting material. The solvent was removed in vacuo to give an orange syrup. The addition of 95% EtOH (10 mL) and steam bath warming prompted solidification. The solvent was removed in vacuo to given an orange solid. Crystallization from 95% EtOH (dissolved in boiling solvent (10 mL), hot filtered, allowed to cool to rt) yielded a yellow granular solid (1.37 g, 52%, pure by TLC (5% EtOAc/95% CHCl3), approximately a 2:1 mixture of diastereomers by NMR); mp 115°-118° C.; 1H NMR (CDCl3) δ1.03 (overlapping t, 3H), 1.90 (m, 2H), 2.93 (m, 1H), 3.27 (m, 2H), 3.82 (s, 3H), 4.40 (m, 2H), 5.90 and 5.92 (overlapping s, 1H); IR (KBr) 2970, 2938, 1675, 1652, 1633, 1609, 1226, 855 cm-1.

Workup

  1. additionwas added dropwise over a 5 min period
  2. additionAfter addition
  3. customconsumption of the starting material
  4. additionAn additional portion of the Cl2 solution (4 mL) was added
  5. stirringto stir at 25° C. for 1 hr
  6. customThe solvent was removed in vacuo
  7. customto give an orange syrup
  8. temperaturewarming
  9. customThe solvent was removed in vacuo
  10. customCrystallization from 95% EtOH (dissolved in boiling solvent (10 mL), hot filtered, allowed to cool to rt)
  11. customyielded a yellow granular solid (1.37 g, 52%

Sources & evidence

ORD record
ord-e4993c8c52c04fe5a0aeeef0b1bed054
Source dataset
uspto-grants-1995_12
Patent number
US05476933

Reaction notes

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