N,N-bis(trimethylsilyl)Methanesulfonamide → 2-(3,4-dichloro-phenyl)-2-methylthioimino-N-[2-(3-methoxy-4-pent-2-ynyloxy-phenyl)-ethyl]-acetamide

HRID 1017813Notes

Reaction equation

HRID 1017813 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:9](=O)[C:10]([NH:12][CH2:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([O:21][CH2:22][C:23]#[C:24][CH2:25][CH3:26])=[C:17]([O:27][CH3:28])[CH:16]=2)=[O:11])[CH:5]=[CH:6][C:7]=1[Cl:8].C[Si](C)(C)[N:32]([Si](C)(C)C)[S:33]([CH3:36])(=O)=O>C1COCC1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([C:9](=[N:32][S:33][CH3:36])[C:10]([NH:12][CH2:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([O:21][CH2:22][C:23]#[C:24][CH2:25][CH3:26])=[C:17]([O:27][CH3:28])[CH:16]=2)=[O:11])[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

6

Reactant 2

HCID 12503736N,N-bis(trimethylsilyl)MethanesulfonamideHCID 184057762-(3,4-dichloro-phenyl)-N-[2-(3-methoxy-4-pent-2-ynyloxy-phenyl)-ethyl]-2-oxo-acetamide

Product 1

HCID 542459812-(3,4-dichloro-phenyl)-2-methylthioimino-N-[2-(3-methoxy-4-pent-2-ynyloxy-phenyl)-ethyl]-acetamideYield 70.1%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 1.7 g (3.9 mmol) 2-(3,4-dichloro-phenyl)-N-[2-(3-methoxy-4-pent-2-ynyloxy-phenyl)-ethyl]-2-oxo-acetamide in 32 ml THF, 3.0 g (14.0 mmol) N,N-bis(trimethyl-silyl) methanesulfonamide and 0.1 g (0.32 mmol) tetrabutylammonium bromide (TBAF) are added. The mixture is heated at +70° C. for 7 hours. After cooling, the mixture is diluted with ethyl acetate and washed twice with water. After evaporation of the organic phase the residue is purified by flash-chromatography (ethyl acetate 25, hexanes 75) to give 1.31 g (70%) of the 2-(3,4-dichloro-phenyl)-2-methylthioimino-N-[2-(3-methoxy-4-pent-2-ynyloxy-phenyl)-ethyl]-acetamide. 1H-NMR (300 MHz, CDCl3): 1.15 (t, 3 H, CH2CH3), 2.22 (m, 2 H, CH2CH3), 2.73 (s, 3 H, SCH3), 2.83 (t, 2 H, CH2CH2) 3.59 (t, 2 H, CH2CH2) 3.89 (s, 3 H, OCH3) 4.73 (m, 2 H, OCH2) 6.78 (m, 2 H, CH arom.), 7.02 (m, 1 H, CH arom.), 7.12 (t, 1 H, NH), 7.30 and 7.58 (m, 3 H, CH arom.).

Workup

  1. temperatureThe mixture is heated at +70° C. for 7 hours
  2. temperatureAfter cooling
  3. washwashed twice with water
  4. customAfter evaporation of the organic phase the residue
  5. customis purified by flash-chromatography (ethyl acetate 25, hexanes 75)

Sources & evidence

ORD record
ord-532ad6a434ad4721a9989ad7b0e864f7
Source dataset
uspto-grants-2002_11
Patent number
US06479550B1

Reaction notes

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