Hexane → Methyl 3-cyano-4-(n,n-bis(t-butoxycarbonyl)aminomethyl)benzoate

HRID 1839447Notes

Reaction equation

HRID 1839447 reaction equation
CCCCCC.[H-].[Na+].[NH:9]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11].[C:24]([C:26]1[CH:27]=[C:28]([CH:33]=[CH:34][C:35]=1[CH2:36]Br)[C:29]([O:31][CH3:32])=[O:30])#[N:25]>CCOC(C)=O.CN(C=O)C>[C:24]([C:26]1[CH:27]=[C:28]([CH:33]=[CH:34][C:35]=1[CH2:36][N:9]([C:10]([O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[O:11])[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[C:29]([O:31][CH3:32])=[O:30])#[N:25]

Participants

7

Reactant 4

HCID 8058HexaneHCID 24758Sodium hydrideHCID 279800Di-tert-butyl IminodicarboxylateHCID 23450362Methyl 4-bromomethyl-3-cyanobenzoate

Product 1

HCID 23450331Methyl 3-cyano-4-(n,n-bis(t-butoxycarbonyl)aminomethyl)benzoate

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of hexane washed 60% disp. NaH (40 mg, 1 mmol) and DMF (8 mL) was added HN(BOC)2 (203 mg, 0.93 mmol) and stirred for 30 m. The reaction was added methyl 3-cyano-4-(bromomethyl)benzoate (202 mg, 0.80 mmol). After 3.5 h, the reaction was diluted with EtOAc (40 mL) and washed with H2O (6×5 mL). The organic layer was MgSO4 dried and concentrated. The crude material was chromatographed (30 g silica, 10% EtOAc/hexanes) to give the title compound (quant.). IR(CHCl3): 1125, 1370, 1723, 1791, 3020 cm−1; NMR(300 MHz, CDCl3): 1.46 (s, 18H); 3.96 (s, 3H); 5.08 (s, 2H); 7.42 (d, 1H, J=8.4 Hz); 8.23 (d, 1H, J=8.4 Hz); 8.32 (s, 1H); MS(FD): 391.

Workup

  1. washwashed 60%
  2. washwashed with H2O (6×5 mL)
  3. customdried
  4. concentrationconcentrated
  5. customThe crude material was chromatographed (30 g silica, 10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-233b671d4fa347869556c4f3db72a0c3
Source dataset
uspto-grants-2004_01
Patent number
US06677369B2

Reaction notes

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