Water → Methyl 2-chlorodibenzo[b,f]oxepin-11-carboxylate

HRID 2040936Notes

Reaction equation

HRID 2040936 reaction equation
P(OP(O)(O)=O)(O)(O)=O.O.[Cl:11][C:12]1[CH:13]=[CH:14][C:15]([O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[C:16]([C:18](=[CH:23]O)[C:19]([O:21][CH3:22])=[O:20])[CH:17]=1>C(OC)(C)(C)C>[Cl:11][C:12]1[CH:13]=[CH:14][C:15]2[O:25][C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=3[CH:23]=[C:18]([C:19]([O:21][CH3:22])=[O:20])[C:16]=2[CH:17]=1

Participants

5

Reactant 3

HCID 962Water2×HCID 1023Pyrophosphoric acidHCID 66859650Methyl 2-(5-chloro-2-phenoxyphenyl)-3-hydroxyacrylate

Product 1

HCID 58160327Methyl 2-chlorodibenzo[b,f]oxepin-11-carboxylateYield 77.7%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of 415.23 g (2.33 mol) of pyrophosphoric acid and 22.14 g of water at 0° C. was added over methyl 2-(5-chloro-2-phenoxyphenyl)-3-hydroxyacrylate (compound IXa) as obtained in Example 16. The reaction mixture was stirred at 60° C. for 2 hours. After cooling to 20° C., 500 mL of water and 1.4 L of methyl tert-butyl ether were added. The aqueous layer was extracted and washed with 200 mL of methyl tert-butyl ether. The organic phases were combined, washed with 400 mL of an aqueous saturated solution of sodium bicarbonate and 400 mL of saturated sodium chloride, dried over anhydrous sodium sulfate and concentrated to dryness under reduced pressure. The residue was suspended in 400 mL of n-butanol and stirred at room temperature for 1 hour, and at 0° C. for 2 hours. The resulting suspension was filtered, and the solid was dried until constant weight to obtain 161 g of methyl 2-chlorodibenzo[b,f]oxepin-11-carboxylate (compound Xa) as an off-white solid. Yield: 77.7%.

Workup

  1. customas obtained in Example 16
  2. temperatureAfter cooling to 20° C.
  3. extractionThe aqueous layer was extracted
  4. washwashed with 200 mL of methyl tert-butyl ether
  5. washwashed with 400 mL of an aqueous saturated solution of sodium bicarbonate and 400 mL of saturated sodium chloride
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated to dryness under reduced pressure
  8. stirringstirred at room temperature for 1 hour
  9. waitat 0° C. for 2 hours
  10. filtrationThe resulting suspension was filtered
  11. customthe solid was dried until constant weight

Sources & evidence

ORD record
ord-b974036afaf145b0b2e2cc60584522e4
Source dataset
uspto-grants-2013_11
Patent number
US08580972B2

Reaction notes

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