Methanesulfonic Acid → HCID 54724215, compound

HRID 1867180Notes

Reaction equation

HRID 1867180 reaction equation
[CH3:1][O:2][C:3]([C:5]1[O:9][C:8]([NH2:10])=[CH:7][CH:6]=1)=[O:4].[OH:11][C:12](=[C:17]1C(=O)OC(C)(C)[O:19][C:18]1=O)[CH2:13][C:14](=O)[CH3:15].CS(O)(=O)=O>O1CCOCC1.C1(C)C=CC=CC=1>[OH:11][C:12]1[CH:13]=[C:14]([CH3:15])[N:10]([C:8]2[O:9][C:5]([C:3]([O:2][CH3:1])=[O:4])=[CH:6][CH:7]=2)[C:18](=[O:19])[CH:17]=1

Participants

6

Reactant 3

HCID 6395Methanesulfonic AcidHCID 5072225Methyl 5-aminofuran-2-carboxylateHCID 547121045-(1-Hydroxy-3-oxobutylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione

Product 1

HCID 54724215HCID 54724215, compoundYield 44.1%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
98 °C

Procedure

To a room temperature solution of methyl-2-amino-5-furoate (4.85 g, 34.4 mmol) in 1,4 dioxane (28.0 mL) was added 5-(1-hydroxy-3-oxobutylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (8.16 g, 44.3 mmol). The reaction was stirred vigorously and heated quickly (within 8 minutes) to an internal temperature of 98° C. Upon reaching temperature, the reaction was maintained for 1.0 hour. At this time, the reaction was cooled to room temperature rapidly using an ice-bath and methane sulfonic acid (3.30 g, 34.4 mmol) was added. The reaction mixture was once again brought to an internal temperature of approximately 100° C. After 1.0 hour the reaction was diluted with 10 mL of toluene and allowed to cool to room temperature on its own accord. A solid formed after 3.0 hours that was collected and subsequently recrystallized from methanol/ethyl acetate (1:1). The developing crystals were allowed to form and stand for 12.0 hours prior to collection to furnish the desired product as a solid (3.78 g, 44%). 1H NMR (400 MHz, d7-DMF) δ 11.34 (s, 1H), 7.43 (app d, J=3.6 Hz, 1H), 6.79 (app d, J=3.6 Hz, 1H), 6.01 (s, 1H), 5.63 (d, J=2.0 Hz, 1H), 3.87 (s, 3H), 2.02 (s, 3H); LC/MS C-18 column, tr=1.47 minutes (5 to 95% acetonitrile/water over 5 minutes at 1 ml/min with detection 254 nm, at 50° C.). ES-MS m/z 250 (M+H). ES-HRMS m/z 250.0696 (M+H calcd for C12H12NO5 requires 250.0710).

Workup

  1. temperaturethe reaction was maintained for 1.0 hour
  2. temperatureAt this time, the reaction was cooled to room temperature
  3. customwas once again brought to an internal temperature of approximately 100° C
  4. temperatureto cool to room temperature on its own accord
  5. customA solid formed after 3.0 hours that
  6. customwas collected
  7. customsubsequently recrystallized from methanol/ethyl acetate (1:1)
  8. customto form
  9. customto collection

Sources & evidence

ORD record
ord-18df55f95eba429c8f442ae8c131b072
Source dataset
uspto-grants-2009_12
Patent number
US07629363B2

Reaction notes

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