Methyl p-toluenesulfonate → 3-(3'-benzyl-3,5-dimethyl-4'-oxo-4-phenyl-3',4'-dihydro-3H-[2,5']-bithiazolyliden-2'-ylideneamino)-4-(ethylamino)benzonitrile

HRID 1241956Notes

Reaction equation

HRID 1241956 reaction equation
[CH3:1][N:2]1[C:6]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)=[C:5]([CH3:13])[S:4][C:3]1=S.C1(C)C=CC(S(OC)(=O)=O)=CC=1.C1(OC)C=CC=CC=1.[CH2:35]([N:42]1[C:46](=[O:47])[CH2:45][S:44][C:43]1=[N:48][C:49]1[CH:50]=[C:51]([CH:54]=[CH:55][C:56]=1[NH:57][CH2:58][CH3:59])[C:52]#[N:53])[C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1>CC#N>[CH2:35]([N:42]1[C:46](=[O:47])[C:45](=[C:3]2[N:2]([CH3:1])[C:6]([C:7]3[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=3)=[C:5]([CH3:13])[S:4]2)[S:44][C:43]1=[N:48][C:49]1[CH:50]=[C:51]([CH:54]=[CH:55][C:56]=1[NH:57][CH2:58][CH3:59])[C:52]#[N:53])[C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1

Participants

6

Reactant 4

HCID 6645Methyl p-toluenesulfonateHCID 7519AnisoleHCID 126587363,5-dimethyl-4-phenyl-3H-thiazole-2-thioneHCID 219373763-(3-Benzyl-4-oxothiazolidin-2-ylideneamino)-4-ethylaminobenzonitrile

Product 1

HCID 865901983-(3'-benzyl-3,5-dimethyl-4'-oxo-4-phenyl-3',4'-dihydro-3H-[2,5']-bithiazolyliden-2'-ylideneamino)-4-(ethylamino)benzonitrileYield 64.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
120 °C

Procedure

To an 8 mL vial was added 3,5-dimethyl-4-phenyl-3H-thiazole-2-thione (100 mg, 0.45 mmol), methyl p-toluenesulfonate (126 mg, 0.68 mmol) and anhydrous anisole (0.5 mL). The reaction was heated to 120° C. and stirred for 3 h. The cooled reaction mixture was diluted with anhydrous MeCN (3 mL) and then treated with 3-(3-benzyl-4-oxothiazolidin-2-ylideneamino)-4-(ethylamino)benzonitrile (50 mg, 0.14 mmol) and TEA (70 μL, 0.50 mmol). The reaction mixture was warmed to 80° C. and the resulting solution was allowed to stir for 16 h. The product mixture was concentrated under reduced pressure and chromatographed (silica gel, 1:1 EtOAc/Hex) to yield the title product (48.3 mg, 64%) as a yellow solid. 1H-NMR (CDCl3): δ 7.40 (5H, m), 7.33 (2H, m), 7.25 (3H, m), 7.23 (2H, m), 6.46 (1H, d), 5.18 (2H, s), 4.28 (1H, m), 3.46 (3H, s), 2.99 (2H, m), 2.28 (3H, s), 1.01 (3H, t); MS(ESI): 538 (MH+).

Workup

  1. customThe cooled reaction mixture
  2. temperatureThe reaction mixture was warmed to 80° C.
  3. stirringto stir for 16 h
  4. concentrationThe product mixture was concentrated under reduced pressure
  5. customchromatographed (silica gel, 1:1 EtOAc/Hex)

Sources & evidence

ORD record
ord-4eab5e773b374ef397fabd84ecfedcfa
Source dataset
uspto-grants-2006_10
Patent number
US07115640B2

Reaction notes

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