Methyl p-toluenesulfonate → 2-(5-acetyl-2-ethylamino-phenylimino)-3-benzyl-5-[(N-methyl-phenylamino)-methylene]-thiazolidin-4-one

HRID 600824Notes

Reaction equation

HRID 600824 reaction equation
[CH2:1]([N:8]1[C:12](=[O:13])[C:11](=[CH:14][N:15]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH3:16])[S:10][C:9]1=S)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C)C=CC(S(OC)(=O)=O)=CC=1.[NH2:36][C:37]1[CH:38]=[C:39]([C:46](=[O:48])[CH3:47])[CH:40]=[CH:41][C:42]=1[NH:43][CH2:44][CH3:45]>CN(C=O)C.CC#N>[C:46]([C:39]1[CH:40]=[CH:41][C:42]([NH:43][CH2:44][CH3:45])=[C:37]([N:36]=[C:9]2[N:8]([CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[C:12](=[O:13])[C:11](=[CH:14][N:15]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[CH3:16])[S:10]2)[CH:38]=1)(=[O:48])[CH3:47]

Participants

6

Reactant 3

HCID 6645Methyl p-toluenesulfonateHCID 219373693'-Amino-4'-(ethylamino)acetophenoneHCID 723711903-benzyl-5-[(N-methyl-phenylamino)-methylene]-2-thioxo-thiazolidin-4-one

Product 1

HCID 730702912-(5-acetyl-2-ethylamino-phenylimino)-3-benzyl-5-[(N-methyl-phenylamino)-methylene]-thiazolidin-4-oneYield 9.6%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
125 °C

Procedure

A mixture of 3-benzyl-5-[(N-methyl-phenylamino)-methylene]-2-thioxo-thiazolidin-4-one (0.40 g, 1.2 mmol) and methyl p-toluenesulfonate (0.26 g, 1.4 mmol) in DMF (2 mL, anhyd) was heated at 125° C. After 2 h, the reaction mixture was cooled and an aliquot (0.4 mL) of the intermediate was transferred to an oven-dried vial. The intermediate was diluted with MeCN (2 mL, anhyd) and charged with 3′-amino-4′-ethylamino-acetophenone (53 mg, 0.30 mmol). The reaction mixture was warmed to 50° C., charged with TEA (100 μL), sealed and heated at 65° C. After 16 h, the reaction mixture was cooled, concentrated and chromatographed (silica gel, 0:100 to 50:50 EtOAc-Hex) to give the title product (14 mg) as a yellow solid. 1H-NMR (CDCl3): δ 7.92 (1H, s), 7.65 (1H, dd), 7.50 (1H, d), 7.27-7.42 (7H, m), 7.14-7.23 (3H, m), 6.48 (1H, d), 5.12 (2H, s), 4.27 (1H, br s), 3.51 (3H, s), 3.02 (2H, q), 2.45 (3H, s), 1.01 (3H, t); MS (ESI): 485 (MH+).

Workup

  1. temperaturethe reaction mixture was cooled
  2. temperatureThe reaction mixture was warmed to 50° C.
  3. customsealed
  4. temperatureheated at 65° C
  5. waitAfter 16 h
  6. temperaturethe reaction mixture was cooled
  7. concentrationconcentrated
  8. customchromatographed (silica gel, 0:100 to 50:50 EtOAc-Hex)

Sources & evidence

ORD record
ord-c8c71d8c899a4c4cb657da5ee32e9e32
Source dataset
uspto-grants-2011_03
Patent number
US07902237B2

Reaction notes

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