Sulfuric Acid → 4-(chloromethyl)-6-methyl-2H-chromen-2-one

HRID 402909Notes

Reaction equation

HRID 402909 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.C([O:11][C:12](=O)[CH2:13][C:14](=O)[CH2:15][Cl:16])C.S(=O)(=O)(O)O>O>[Cl:16][CH2:15][C:14]1[C:6]2[C:5](=[CH:4][CH:3]=[C:2]([CH3:1])[CH:7]=2)[O:8][C:12](=[O:11])[CH:13]=1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 2879P-CresolHCID 69484Ethyl 4-chloroacetoacetate

Product 1

HCID 9074424-(chloromethyl)-6-methyl-2H-chromen-2-oneYield 86%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a mixture of 4-methylphenol (21.6 g, 200 mmol) and 4-chloro-3-oxo-butyric acid ethyl ester (32.9 g, 200 mmol) is added dropwise during 30 min. at 0° C. a mixture of concentrated sulfuric acid (180 mL) and water (60 mL). The resulting clear solution is stirred for 18 h at room temperature, during which time a white precipitate is formed. The reaction mixture is poured over crushed ice (1 kg) and the formed precipitate is collected, washed with water and dried in vacuo at 50° C. to yield the title compound as a white powder (35.8 g, 172 mmol, 86%). 1H NMR (400 MHz, CDCl3, 298 K): δ=7.45 (s, 1H), 7.40 (d, J=8.6 Hz, 1H), 7.29 (d, J=8.6 Hz, 1H), 6.58 (s, 1H), 4.69 (s, 1H), 2.46 (s, 3H).

Workup

  1. additionis added dropwise during 30 min. at 0° C.
  2. customis formed
  3. additionThe reaction mixture is poured
  4. customthe formed precipitate is collected
  5. washwashed with water
  6. customdried in vacuo at 50° C.

Sources & evidence

ORD record
ord-4d9e68f5928448c9bea0089e30f41320
Source dataset
uspto-grants-2014_06
Patent number
US08742132B2

Reaction notes

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