Dimethylformamide → HCID 16041932, compound

HRID 545174Notes

Reaction equation

HRID 545174 reaction equation
[CH3:1][N:2](C=O)C.Br[C:7]1[CH:8]=[C:9]2[C:35](=[CH:36][CH:37]=1)[O:34][C:12]1([CH2:17][CH2:16][N:15]([C:18]([C:20]3[CH:29]=[C:28]([O:30][CH3:31])[C:27]4[C:22](=[C:23]([O:32][CH3:33])[CH:24]=[CH:25][CH:26]=4)[N:21]=3)=[O:19])[CH2:14][CH2:13]1)[CH2:11][C:10]2=[O:38]>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:31][O:30][C:28]1[C:27]2[C:22](=[C:23]([O:32][CH3:33])[CH:24]=[CH:25][CH:26]=2)[N:21]=[C:20]([C:18]([N:15]2[CH2:14][CH2:13][C:12]3([CH2:11][C:10](=[O:38])[C:9]4[C:35](=[CH:36][CH:37]=[C:7]([C:1]#[N:2])[CH:8]=4)[O:34]3)[CH2:17][CH2:16]2)=[O:19])[CH:29]=1

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 16041747HCID 16041747, compound

Product 1

HCID 16041932HCID 16041932, compound

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

118 mg of zinc cyanide, 69.3 mg of Pd(PPh3)4 and 3 mL of DMF were added to 511 mg of the bromo compound obtained in Example 9, and heated under a nitrogen atmosphere at 80° C., and the reaction mixture was stirred for 39 hours. After cooled, the reaction mixture was diluted with 30 mL of ethyl acetate, washed successively with diluted aqueous ammonia, water and saturated brine, then dried over sodium sulfate, and concentrated. Ethyl ether was added to the resulting residue, and the insoluble solid thus formed was taken out through filtration. This was washed with ethyl ether and dried under reduced pressure to obtain the intended compound as a pale yellow-brown solid. 1H-NMR (300 MHz, CDCl3) δ: 8.20 (1H, d, J=2.0 Hz), 7.71 (1H, d, J=8.2 Hz), 7.74 (1H, dd, J=8.6, 2.0 Hz), 7.42 (1H, t, J=8.2 Hz), 7.19 (1H, s), 7.13 (1H, d, J=8.6 Hz), 7.08 (1H, d, J=8.2 Hz), 4.63-4.54 (1H, m), 4.26-4.17 (1H, m), 4.08 (3H, s), 4.03 (3H, s), 3.64-3.52 (1H, m), 3.42-3.29 (1H, m), 2.88 (1H, d, J=16.8 Hz), 2.81 (1H, d, J=16.8 Hz), 2.23-2.13 (1H, m), 2.09-1.85 (3H, m). MS [M+H]+=458.

Workup

  1. temperatureAfter cooled
  2. washwashed successively with diluted aqueous ammonia, water and saturated brine
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated
  5. additionEthyl ether was added to the resulting residue
  6. customthe insoluble solid thus formed
  7. filtrationwas taken out through filtration
  8. washThis was washed with ethyl ether
  9. customdried under reduced pressure

Sources & evidence

ORD record
ord-0f2c7caec5cf48bf9c67b9cd37d2845e
Source dataset
uspto-grants-2011_05
Patent number
US07935712B2

Reaction notes

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