Sulfuric Acid → HCID 10881454, compound

HRID 1953190Notes

Reaction equation

HRID 1953190 reaction equation
[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([CH:15]=[CH:16][CH:17]=1)[C:8]([CH2:10][C:11]([O:13][CH3:14])=[O:12])=O)[CH2:2][CH3:3].[CH3:18][O:19][C:20]1[CH:21]=C(O)[CH:23]=[CH:24][CH:25]=1.OS(O)(=O)=O.C(OCC)(=O)C>ClCCCl.O>[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([C:8]2[C:23]3[C:14](=[CH:21][C:20]([O:19][CH3:18])=[CH:25][CH:24]=3)[O:13][C:11](=[O:12])[CH:10]=2)[CH:15]=[CH:16][CH:17]=1)[CH2:2][CH3:3]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 8857Ethyl AcetateHCID 90073-MethoxyphenolHCID 10014332HCID 10014332, compound

Product 1

HCID 10881454HCID 10881454, compoundYield 86%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolvent2×HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

A solution of methyl 3-(prop-1-yloxy)benzoylacetate (745 g) (a compound of Formula (a)) in 1,2-dichloroethane was combined under nitrogen with a solution of 3-methoxyphenol (488 g) in 1,2-dichloroethane (2.5 L) and cooled to 0° C. Concentrated H2SO4 (626 mL) was added dropwise and the mixture was stirred vigorously at RT for 90 minutes. Ethyl acetate (3 L) and H2O (3 L) were added and the layers were equilibrated and separated. The aqueous layer was extracted again with ethyl acetate and the combined organic layers were washed with H2O, 5% aqueous NA2CO2CO3, 5% aqueous NaOH, H2O, and brine (2 L each). The organic phase was dried with MgSO4 and concentrated to dryness to yield 841 g (86%) of 4-[3-(prop-1-yloxy)phenyl]-7-methoxycoumarin. The product was recrystallized from ethanol/isopropanol followed by ethyl acetate/isopropanol to give 533 g (63% recovery) of 4-[3'-(prop-1-yloxy)phenyl]-7-methoxycoumarin. 300 MHz 1H NMR (CDCl3) δ 1.05 (t, J=7 Hz, 3 H), 1.83 (m, J=7 Hz, 2 H), 3.88 (s, 3 H), 3.96 (t, J=7 Hz, 2 H), 6.21 (s, 1 H), 6.79 (dd, J1 =2 Hz, J2 =9 Hz, 1 H), 6.88 (d, J=2 Hz, 1 H), 6.94 (m, 3 H), 7.40 (t, J 8 Hz, 1 H), 7.42 (d, J=9 H).

Workup

  1. customseparated
  2. extractionThe aqueous layer was extracted again with ethyl acetate
  3. washthe combined organic layers were washed with H2O, 5% aqueous NA2CO2CO3, 5% aqueous NaOH, H2O, and brine (2 L each)
  4. dry with materialThe organic phase was dried with MgSO4
  5. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-8a37ecdd055542018a6ea06a080339a1
Source dataset
uspto-grants-2000_09
Patent number
US06114549

Reaction notes

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