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Dimethylformamide → Di-tert-butyl (2-formyl-1,4-phenylene)dicarbamate

HRID 1837291
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HRID 1837291 반응식
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[CH:13][C:12]([NH:15][C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:11][C:10]=1Br)=[O:7])([CH3:4])([CH3:3])[CH3:2].C[Li].C([Li])(C)(C)C.CN(C)[CH:33]=[O:34]>O.CCOCC>[C:1]([O:5][C:6](=[O:7])[NH:8][C:9]1[CH:14]=[CH:13][C:12]([NH:15][C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:11][C:10]=1[CH:33]=[O:34])([CH3:4])([CH3:3])[CH3:2]
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참가 물질

7

반응물 4

HCID 6228DimethylformamideHCID 154289672,5-Bis-tert.-butyloxycarbonylaminobromobenzeneHCID 178418306HCID 178418306, 화합물HCID 178418348HCID 178418348, 화합물

생성물 1

HCID 15539052Di-tert-butyl (2-formyl-1,4-phenylene)dicarbamate

시약·촉매·용매 2

HCID 962Water
용매
2회
HCID 3283Diethyl Ether용매

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온도
-20 °C

실험 절차

3.3 g (0.01 mol) 2,5-bis-tert.-butyloxycarbonylaminobromobenzene from step A are dissolved in 100 ml of water-free tetrahydrofuran under argon. 17 ml of a 1.6 molar etheric methyl lithium solution (0.03 mol) are gradually added. The reaction mixture is cooled to −20° C., 7 ml of a 1.5 molar tert.-butyl lithium solution (0.01 mol) are gradually added. After the addition has ended the solution is stirred for 30 minutes at the given temperature. Subsequently 1.2 g of dimethyl formamide (0.02 mol) are added and the reaction mixture is stirred for one hour at −20° C. After slowly heating to room temperature the reaction mixture is hydrolyzed with water and then poured into ether, the aqueous phase is extracted with ether and then the organic phase is dried over magnesium sulfate. The solvent is distilled away in a rotary evaporator and the residue is purified on silica gel with a petroleum ether/ethyl acetate solvent (9/1).

후처리

  1. additionAfter the addition
  2. stirringthe reaction mixture is stirred for one hour at −20° C
  3. temperatureAfter slowly heating to room temperature the reaction mixture
  4. extractionthe aqueous phase is extracted with ether
  5. dry with materialthe organic phase is dried over magnesium sulfate
  6. distillationThe solvent is distilled away in a rotary evaporator
  7. customthe residue is purified on silica gel with a petroleum ether/ethyl acetate solvent (9/1)

출처 및 근거

ORD 기록
ord-4a2c0866f19048009c8ab72275b25ea7
출처 데이터셋
uspto-grants-2004_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06780998B2

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