Methyl phenylacetate → HCID 68870927, compound

HRID 494602Notes

Reaction equation

HRID 494602 reaction equation
C(NC(C)C)(C)C.[Li].[C:9]1([CH2:15][C:16]([O:18][CH3:19])=[O:17])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.Br[CH2:21][CH:22]1[CH2:25][CH2:24][CH2:23]1.[Li+].[I-]>O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C>[CH:22]1([CH2:21][CH:15]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[C:16]([O:18][CH3:19])=[O:17])[CH2:25][CH2:24][CH2:23]1

Participants

7

Reactant 4

HCID 7559Methyl phenylacetateHCID 66321Lithium iodideHCID 2734658(Bromomethyl)cyclobutaneHCID 45051747Lithium diisopropylamine

Product 1

HCID 68870927HCID 68870927, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
0 °C

Procedure

To a stirring solution of freshly prepared lithium diisopropylamine (76.5 mmol) in 500 mL of tetrahydrofuran at 0° C. was added methyl phenylacetate (10.44 g, 69.50 mmol) in 125 mL tetrahydrofuran dropwise over 30 minutes. After stirring at 0° C. for 1 hour the reaction mixture was cooled to −78° C. and treated with 50 mL of hexamethylphosphoric triamide followed by the dropwise addition of bromomethyl cyclobutane (9.37 mL, 83.4 mmol) and LiI (200 mg). The reaction mixture was stirred for 18 hours warming to 25° C. The reaction was quenched over 1 L of water containing 250 mL of sat. NH4Cl and extracted 3× with ethyl acetate. The combined organic layers were washed sequentially with saturated sodium bicarbonate, brine, and dried over MgSO4 yielding the crude product as an oil that was used without further purification. 1H NMR (300 MHz, CDCl3): δ ppm 1.59 (m, 2H) 1.89 (m, 5H) 2.17 (m, 2H) 3.47 (t, J=7.54 Hz, 1H) 3.64 (s, 3H) 7.31 (m, 5H). MS (ESI+) m/z=236 (M+NH4)+.

Workup

  1. temperaturewas cooled to −78° C.
  2. stirringThe reaction mixture was stirred for 18 hours
  3. temperaturewarming to 25° C
  4. customThe reaction was quenched over 1 L of water containing 250 mL of sat. NH4Cl
  5. extractionextracted 3× with ethyl acetate
  6. washThe combined organic layers were washed sequentially with saturated sodium bicarbonate, brine
  7. dry with materialdried over MgSO4 yielding the crude product as an oil that
  8. customwas used without further purification

Sources & evidence

ORD record
ord-a4ebd198853c4b17b5bc3939c557d90a
Source dataset
uspto-grants-2009_05
Patent number
US07538105B2

Reaction notes

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