Ethyl oxoacetate → 7-Bromo-3-methylnaphthalen-1-ol

HRID 926149Notes

Reaction equation

HRID 926149 reaction equation
ClC1C=C2C(=CC=1)C(O)=CC(C)=C2.BrC1C=CC(CC(=O)C)=CC=1.[Br:25][C:26]1[CH:35]=[C:34]2[C:29]([CH:30]=[C:31]([CH3:37])[CH:32]=[C:33]2[OH:36])=[CH:28][CH:27]=1.[C:38]([O:42][CH2:43][CH3:44])(=[O:41])[CH:39]=[O:40]>ClCCl.[Ti](Cl)(Cl)(Cl)Cl>[Br:25][C:26]1[CH:35]=[C:34]2[C:29]([CH:30]=[C:31]([CH3:37])[CH:32]=[C:33]2[OH:36])=[CH:28][CH:27]=1.[Br:25][C:26]1[CH:35]=[C:34]2[C:29]([CH:30]=[C:31]([CH3:37])[C:32]([CH:39]([OH:40])[C:38]([O:42][CH2:43][CH3:44])=[O:41])=[C:33]2[OH:36])=[CH:28][CH:27]=1

Participants

8

Reactant 4

HCID 70211Ethyl oxoacetateHCID 7363321-(4-Bromophenyl)propan-2-oneHCID 671262827-Bromo-3-methylnaphthalen-1-olHCID 896768476-Chloro-3-methylnaphthalen-1-ol

Product 2

HCID 671262827-Bromo-3-methylnaphthalen-1-olHCID 89676857Ethyl 2-(7-bromo-1-hydroxy-3-methylnaphthalen-2-yl)-2-hydroxyacetate

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

7-Bromo-3-methylnaphthalen-1-ol was prepared in a similar manner as 6-chloro-3-methylnaphthalen-1-ol in Example 5 except using 1-(4-bromophenyl)propan-2-one instead of 1-(3-chlorophenyl)propan-2-one. To a solution of 7-bromo-3-methylnaphthalen-1-ol (11.5 g, 48.5 mmol) in dichloromethane (145 mL) at 0° C. was added a 1 M titanium(IV) chloride solution in dichloromethane (48.5 mL, 48.5 mmol) and stirred for 20 min. Ethyl glyoxylate (50% solution in PhCH3, 10.6 mL, 53.3 mmol) was added over 15 minutes and stirred for 1 hour at 0° C. The reaction was quenched by the addition of Rochelle's salt solution and stirred at room temperature for 14 hours. The layers were separated, and the aqueous layer was extracted with CH2Cl2. The combined organic layers were dried, filtered, concentrated and purified by flash column chromatography (EtOAc/Hexanes) to provide the desired product. 1H-NMR: 400 MHz, (CDCl3) δ: 8.52 (s, 1H), 8.34 (s, 1H), 7.49 (m, 2H), 7.13 (s, 1H), 5.67 (s, 1H), 4.24 (m, 1H), 4.16 (m, 1H), 2.29 (s, 3H), 1.23 (m, 3H).

Workup

  1. stirringstirred for 1 hour at 0° C
  2. customThe reaction was quenched by the addition of Rochelle's salt solution
  3. stirringstirred at room temperature for 14 hours
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted with CH2Cl2
  6. customThe combined organic layers were dried
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by flash column chromatography (EtOAc/Hexanes)

Sources & evidence

ORD record
ord-58dc057988764d43a99bee0658efa575
Source dataset
uspto-grants-2016_03
Patent number
US09284323B2

Reaction notes

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