Water → HCID 22347447, compound

HRID 1838975Notes

Reaction equation

HRID 1838975 reaction equation
[CH2:1]([O:4][C:5]([CH2:7][C:8]1[CH:9]=[C:10]([S:14]([N:17]=[C:18]=[O:19])(=[O:16])=[O:15])[CH:11]=[CH:12][CH:13]=1)=[O:6])[CH:2]=[CH2:3].[Cl:20][C:21]1[CH:22]=[C:23]([NH2:30])[C:24](=[CH:28][CH:29]=1)[C:25](O)=[O:26].C1N=CN(C(N2C=NC=C2)=O)C=1.O>C1COCC1>[CH2:1]([O:4][C:5]([CH2:7][C:8]1[CH:9]=[C:10]([S:14]([N:17]2[C:25](=[O:26])[C:24]3[C:23](=[CH:22][C:21]([Cl:20])=[CH:29][CH:28]=3)[NH:30][C:18]2=[O:19])(=[O:16])=[O:15])[CH:11]=[CH:12][CH:13]=1)=[O:6])[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 962WaterHCID 666462-Amino-4-chlorobenzoic acidHCID 682631,1'-CarbonyldiimidazoleHCID 22347470HCID 22347470, compound

Product 1

HCID 22347447HCID 22347447, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Following the Synthesis Method (A), 3.27 g (11.6 mmol) of 3-allyloxycarbonylmethylbenzenesulfonyl isocyanate was dissolved in 100 ml of anhydrous THF, then 1.98 g (11.5 mmol) of 4-chloroanthranilic acid was added and the mixture was stirred at room temperature for 2 hours. The reaction solution was cooled with ice water, then 1.87 g (11.5 mmol) of CDI was added and the resultant mixture was stirred under ice cooling for 30 minutes. An excess amount of water was poured into the reaction solution, then the mixture was extracted with ethyl acetate. The organic layer was washed, dried, and concentrated to obtain a crude product. This was crystallized with a small amount of ethyl acetate to obtain 2.0 g (yield 40%) of 3-(3-allyloxycarbonylmethylbenzenesulfonyl)-7-chloro-2,4(1H,3H)-quinazolinedione. The allyl product thus obtained was dissolved in 100 ml of a formic acid-THF (1:9) mixture and 700 mg of triphenylphosphine was added. The reactor was shaded from light and under nitrogen atmosphere, then 700 mg of tetrakis(triphenylphosphine)palladium (0) was added and the resultant mixture was stirred while shaded at room temperature overnight. The reaction solution was concentrated in vacuo and the solid obtained was washed with methylene chloride to obtain 1.47 g (yield 81%) of the above-identified compound. Properties: colorless crystal, Melting point: >200° C. (decomposition), PMR (δ ppm, DMSO-d6): 3.76 (2H, s), 7.13 (1H, s), 7.24 (1H, d), 7.61-7.69 (2H, m), 7.86 (1H, d), 8.05 (2H, s), 12.50 (1H, br).

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe organic layer was washed
  3. customdried
  4. concentrationconcentrated
  5. customto obtain a crude product
  6. customThis was crystallized with a small amount of ethyl acetate

Sources & evidence

ORD record
ord-04397ef4e6f74213bb37f909f480ea98
Source dataset
uspto-grants-2004_01
Patent number
US06677344B2

Reaction notes

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