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

HRID 843706노트

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HRID 843706 반응식
[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]

참가 물질

6

반응물 3

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

생성물 1

HCID 234446576-amino-5-methyl-4H-3,1-benzoxazin 2,4-dione수율 87.3%

시약·촉매·용매 2

HCID 9942167Palladium hydroxide촉매HCID 6228Dimethylformamide용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-a16e6e034f2e4f49a4d8aca9763b45af
출처 데이터셋
uspto-grants-2002_04
특허 번호
US06380189B1

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