Sodium Carbonate → 3-(9-hydroxynonyl)-2H-1,3-benzoxazine-2,4(3H)-dione

HRID 553262

Reaction equation

HRID 553262 reaction equation
[CH:1]1[CH:2]=[CH:3][C:4]2[O:12][C:10](=[O:11])[NH:9][C:7](=[O:8])[C:5]=2[CH:6]=1.Br[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][OH:23].C(=O)([O-])[O-].[Na+].[Na+].C(OCC)(=O)C.CCCCCCC>CN(C)C(=O)C>[OH:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][N:9]1[C:7](=[O:8])[C:5]2[CH:6]=[CH:1][CH:2]=[CH:3][C:4]=2[O:12][C:10]1=[O:11]

Participants

6

Reactant 4

HCID 10340Sodium CarbonateHCID 162582H-1,3-Benzoxazine-2,4(3H)-dioneHCID 1087001-Nonanol, 9-bromo-HCID 21899848Ethylacetate heptane

Product 1

HCID 219084243-(9-hydroxynonyl)-2H-1,3-benzoxazine-2,4(3H)-dioneYield 80.2%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Conditions

Temperature
77.5 °C

Procedure

A mixture of 6.525 g (40 mmol) of carsalam, 10.26 g (44 mmol) of 9-bromo-1-nonanol, and 5.30 g (50 mmol) of sodium carbonate in 30 mL N,N-dimethylacetamide (DMA) was heated at 75-80° C. for 3 hours. TLC (eluent: ethyl acetate/heptane) indicated the reaction was completed. The reaction was carefully poured into a mixture of ice-water. The resulting white solid was stirred for 1 hour. It was collected on sintered glass funnel, washed with water, hexane and dried in vacuo to yield 9.80 g of 3-(9-hydroxynonyl)-2H-1,3-benzoxazine-2,4(3H)-dione (80%). To a slurry of 6.11 g (20 mmol) of 3-(9-hydroxynonyl)-2H-1,3-benzoxazine-2,4(3H)-dione in 10 mL of N,N-dimethylacetamide at room temperature was added 20.4 mL (20.4 mmol) of potassium t-butoxide in THF solution. The clear brown solution became very thick. More DMA (10 mL) was added, and the mixture was heated at reflux for 5 minutes. 0.664 g (4 mmol) of potassium iodide was added, followed by dropwise addition of 3.34 (20 mmol) of ethyl bromoacetate. The reaction was refluxed for 1 hour, cooled to about 35° C. and poured into ice-water. A gum resulted. The supernatant liquid was decanted and fresh water was added. That procedure was repeated twice. The gum was dissolved in THF. The THF solution was carefully poured into hexane. The resulting solid was collected, washed with hexane and dried in vacuo. The weight of the desired product was 2.36 g (35%). HPLC: 4.39 min.; Mp: 125-128° C. HNMR (M DSO d6): δ 1.25 (12H, m), 1.37 (2H, m), 1.53 (2H, m), 3.28 (2H, m), 3.36 (2H, t), 4.85 (2H, s), 7.07 (2H, m), 7.45 (1H, t), 7.88 (1H, d), 8.70 (1H, t). Anal. Calcd for C18H27NO6: C, 64.07; H, 8.07; N, 4.15. Found: C, 63.71; H, 8.29; N, 4.31.

Workup

  1. customIt was collected on sintered glass funnel
  2. washwashed with water, hexane
  3. customdried in vacuo

Sources & evidence

ORD record
ord-ede4f829176f4391803857c18f6095f1
Source dataset
uspto-grants-2011_05
Patent number
US07951971B1

Linked notes

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