Di-tert-butyl dicarbonate → 6-amino-5-methyl-4H-3,1-benzoxazin 2,4-dione

HRID 1603009

Reaktionsgleichung

Reaktionsgleichung von HRID 1603009
[CH3:1][C:2]1[C:7]2[C:8](=[O:13])[O:9][C:10](=[O:12])[NH:11][C:6]=2[CH:5]=[CH:4][C:3]=1[N+:14]([O-])=O.C(OC(OC(OC(C)(C)C)=O)=O)(C)(C)C.[H][H]>CN(C=O)C.[OH-].[OH-].[Pd+2]>[NH2:14][C:3]1[CH:4]=[CH:5][C:6]2[NH:11][C:10](=[O:12])[O:9][C:8](=[O:13])[C:7]=2[C:2]=1[CH3:1]

Komponenten

6

Edukt 3

HCID 90495Di-tert-butyl dicarbonateHCID 219011545-Methyl-6-nitro-1H-benzo[d][1,3]oxazine-2,4-dioneHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 234446576-amino-5-methyl-4H-3,1-benzoxazin 2,4-dioneAusbeute 87,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9942167Palladium hydroxideKatalysatorHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

A mixture of the product of step B (13.5 g, 60.8 mmol), di-tert-butyldicarbonate (6.53 g, 30 mmol) and 20% Pd(OH)2 /C (2.5 g) in 200 mL of DMF was stirred under 5 psi of hydrogen for 20 hours. The catalyst was filtered and the filtrate was evaporated under reduced pressure. The resulting yellow solid was triturated with Et2O, filtered, washed with Et2O and dried affording 10.2 g (87%) of 6-amino-5-methyl-4H-3,1-benzoxazin 2,4-dione. This material (9.0 g, 46.8 mmol) was redissolved in 100 mL of DMF and 15.35 g (70 mmol) of di-tert-butyldicarbonate was added followed by a catalytic amount of DMAP was added. The reaction mixture was stirred at room temperature under nitrogen overnight (ca. 30 hours). The reaction mixture was diluted with 200 mL of 1/2 saturated NaCl, filtered, washed with water then with hexane and dried affording 11.1 g (81%) of 1,1-dimethylethyl (1,4-dihydro-5-methyl-2,4-dioxo-2H-3,1-benzoxazin-6-yl)carbamate: Anal. Calc'd. for C14H16N2O5 : C, 57.53; H, 5.52; N, 9.58. Found: C, 57.47; H, 5.80; N, 9.59.

Aufarbeitung

  1. filtrationThe catalyst was filtered
  2. customthe filtrate was evaporated under reduced pressure
  3. customThe resulting yellow solid was triturated with Et2O
  4. filtrationfiltered
  5. washwashed with Et2O
  6. customdried

Quellen und Nachweise

ORD-Eintrag
ord-bd85add84eb542a98aa34c956c1318bc
Quelldatensatz
uspto-grants-1999_11
Patentnummer
US05985872

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