Acetic Acid → HCID 66809409, compound

HRID 876352Notes

Reaction equation

HRID 876352 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:15][CH:14]([O:16]C(=O)C2C=CC([N+]([O-])=O)=CC=2)[CH2:13][CH:12]1[C:28]([C:30]1[C:38]2[C:33](=[CH:34][C:35]([F:39])=[CH:36][CH:37]=2)[NH:32][CH:31]=1)=[O:29])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.[OH-].[Na+].CC(O)=O>C1COCC1.CO>[CH2:1]([O:8][C:9]([N:11]1[CH2:15][CH:14]([OH:16])[CH2:13][CH:12]1[C:28]([C:30]1[C:38]2[C:33](=[CH:34][C:35]([F:39])=[CH:36][CH:37]=2)[NH:32][CH:31]=1)=[O:29])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 14798Sodium HydroxideHCID 66809662HCID 66809662, compound

Product 1

HCID 66809409HCID 66809409, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of 5 (82.9 g) in THF (600 mL), MeOH (200 mL), and water (100 mL) was added 50% aq. NaOH (16.0 g, 200 mmol) [Note: exothermic; temp. increase: 23.7° C. to 25.9° C.]. After 2 h, glacial HOAc (5.3 g) was added to adjust the pH to 7-8 [Note: the orange-colored solution changed to pale yellow] and the reaction mixture was concentrated in vacuo. Water (500 mL) was added and solvent was removed in vacuo until a thick suspension formed. The solid was collected on a vacuum filter and washed with water (400 mL in portions). The solid was dried in a vacuum oven at 55° C. to afford 42.6 g (83%, 2 steps) of 6 as an off-white solid. 1H NMR (300 MHz, d6-DMSO): δ8.38 (d, J=11.1 Hz, 1H), 8.14 (ddd, J=5.7, 8.7, 14.1 Hz, 1H), 7.35-7.29 (m, 2H), 7.25 (app. dd, J=2.1, 9.9 Hz, 1H), 7.10-6.95 (m, 4H), 5.16-4.98 (m, 2H), 4.90 (app. q, J=13.5, 25.8 Hz, 1H), 4.26 (m, 1H), 3.74 (app. ddd, J=6.3, 11.1, 18.3 Hz, 1H), 3.22 (m, 1H), 2.59 (m, 1H), 1.73 (app. ddd, J=6.6, 12.9, 25.2 Hz, 1H) ppm; 13C NMR (75 MHz, d6-DMSO): 8193.8, 193.3, 160.0 (d, JCF=235.2 Hz), 154.4 (d, JCF=14.5 Hz), 137.5 (d, JCF=26.0 Hz), 137.2 (d, JCF=12.3 Hz), 129.0, 128.5, 128.2 (d, JCF=35.4 Hz), 128.1, 127.4, 123.2, 123.1, 114.4 (d, JCF=11.4 Hz), 110.8 (d, JCF=23.7 Hz), 110.8 (d, JCF=23.7 Hz), 99.0 (d, JCF=25.8 Hz), 69.4, 68.6, 66.5, 66.4, 61.5, 61.2, 54.9, 54.6 ppm. Mass spectrum (ESI), m/z 383.8 [(M+H)+; calcd for C21H20FN2O4: 383.3].

Workup

  1. concentrationwas concentrated in vacuo
  2. additionWater (500 mL) was added
  3. customsolvent was removed in vacuo until a thick suspension
  4. customformed
  5. customThe solid was collected on a vacuum
  6. filtrationfilter
  7. washwashed with water (400 mL in portions)
  8. customThe solid was dried in a vacuum oven at 55° C.

Sources & evidence

ORD record
ord-346b05870bdc41a88261cca80b8d9849
Source dataset
uspto-grants-2015_03
Patent number
US08986993B2

Reaction notes

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