Chlorosulfonic acid → Methyl 6-nitro-4-oxo-4H-1-benzopyran-2-carboxylate

HRID 10940Notes

Reaction equation

HRID 10940 reaction equation
ClS(O)(=O)=O.[N+:6]([C:9]1[CH:25]=[CH:24][C:12]([O:13]/[C:14](=[CH:19]\[C:20]([O:22]C)=O)/[C:15]([O:17][CH3:18])=[O:16])=[CH:11][CH:10]=1)([O-:8])=[O:7].[N+](C1C=CC(O/C(=C/C(OC)=O)/C(OC)=O)=CC=1)([O-])=O>>[N+:6]([C:9]1[CH:10]=[CH:11][C:12]2[O:13][C:14]([C:15]([O:17][CH3:18])=[O:16])=[CH:19][C:20](=[O:22])[C:24]=2[CH:25]=1)([O-:8])=[O:7]

Participants

4

Reactant 3

HCID 24638Chlorosulfonic acidHCID 15225348HCID 15225348, compoundHCID 68975323HCID 68975323, compound

Product 1

HCID 14089207Methyl 6-nitro-4-oxo-4H-1-benzopyran-2-carboxylateYield 95%

Conditions

Temperature
60 °C

Procedure

A reaction container equipped with a stirrer, a cooling tube and a thermometer was charged with 79.3 parts by weight of chlorosulfonic acid and warmed to 60° C. Thereto 20.2 parts by weight of a mixture (content: 55.8% by weight, isomer ratio=52/48) containing dimethyl 2-(4-nitrophenoxy)fumarate and dimethyl 2-(4-nitrophenoxy)maleate was added at an inner temperature of 60° C. The inner temperature was raised to 100° C. and the mixture was stirred and kept at the same temperature for 6 hours to obtain a reaction solution containing 6-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran (reaction yield: 95%). The reaction solution was poured gradually into 120 parts by weight of water at 60° C. and the mixture was kept at an inner temperature of 60° C. for 1 hour and then cooled gradually to an inner temperature of 25° C. Precipitated crystals were filtered and dried to obtain 10.8 parts by weight of a crystalline mixture of 6-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran and 6-nitro-2-carboxy-4-oxo-4H-1-benzopyran (the content of 6-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran: 23.0% by weight; the content of 6-nitro-2-carboxy-4-oxo-4H-1-benzopyran: 58.5% by weight). The yield of 6-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran was 24.9% and the yield of 6-nitro-2-carboxy-4-oxo-4H-1-benzopyran was 58.5%.

Workup

  1. customA reaction container equipped with a stirrer, a cooling tube
  2. additionwas added at an inner temperature of 60° C
  3. temperatureThe inner temperature was raised to 100° C.
  4. customto obtain a reaction solution

Sources & evidence

ORD record
ord-daa30c7028e44abdaf2b1a76d660e842
Source dataset
uspto-grants-2006_08
Patent number
US07094914B2

Reaction notes

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