Sodium Hydroxide → HCID 54575439, compound

HRID 2405019Notes

Reaction equation

HRID 2405019 reaction equation
[CH3:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([CH3:11])[C:3]=1[N:12]1[CH:17]=[CH:16][CH:15]=[C:14]([CH:18](C(OCC)=O)[C:19]([O:21]CC)=[O:20])[C:13]1=[O:29].O1CCOCC1.[OH-].[Na+]>O>[CH3:11][C:4]1[CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=[C:2]([CH3:1])[C:3]=1[N:12]1[CH:17]=[CH:16][CH:15]=[C:14]([CH2:18][C:19]([OH:21])=[O:20])[C:13]1=[O:29]

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 312751,4-DioxaneHCID 68209677HCID 68209677, compound

Product 1

HCID 54575439HCID 54575439, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
45 °C

Procedure

The crude product solution of diethyl [1-(2,6-dimethyl-4-nitrophenyl)-2-oxo-1,2-dihydropyridin-3-yl]malonate in dioxane (maximum 108 mmol) was introduced as initial charge in 350 ml of water, and 35 ml of concentrated sodium hydroxide solution were slowly added. The reaction mixture was stirred for 90 min at 45° C. After cooling to RT, 100 ml of water were added, followed by washing three times with dichloromethane, and the aqueous phase (pH=14) was admixed with 270 ml of dichloromethane. At 10-15° C., 59.5 ml of concentrated hydrochloric acid were slowly added until the pH=1. Even at a weakly acidic pH, carbon dioxide started to evolve. The reaction mixture was warmed to RT and stirred for 1 h, until the gas stopped evolving. Following phase separation, the organic phase was dried over sodium sulphate, filtered and evaporated to dryness on a rotary evaporator. The residue was stirred with 200 ml of methyl tert-butyl ether for 30 min. The crystalline solid was filtered off with suction, washed with methyl tert-butyl ether and dried in vacuo. 14.8 g (47% over 2 stages) of the desired product were obtained. The mother liquor was largely concentrated, the post-precipitation was filtered off with suction, after-washed and dried in vacuo. A further 5.3 g (17% over 2 stages) of the desired product were obtained.

Workup

  1. temperatureAfter cooling to RT
  2. washby washing three times with dichloromethane
  3. additionAt 10-15° C., 59.5 ml of concentrated hydrochloric acid were slowly added until the pH=1
  4. temperatureThe reaction mixture was warmed to RT
  5. stirringstirred for 1 h, until the gas
  6. customFollowing phase separation
  7. dry with materialthe organic phase was dried over sodium sulphate
  8. filtrationfiltered
  9. customevaporated to dryness on a rotary evaporator
  10. stirringThe residue was stirred with 200 ml of methyl tert-butyl ether for 30 min
  11. filtrationThe crystalline solid was filtered off with suction
  12. washwashed with methyl tert-butyl ether
  13. customdried in vacuo

Sources & evidence

ORD record
ord-2fa300107b9e4a99b52df02b9a93de7d
Source dataset
uspto-grants-2014_08
Patent number
US08802860B2

Reaction notes

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