Sodium methanethiolate → Ethyl 2-(methylsulfanyl)-1,3-benzothiazole-6-carboxylate

HRID 1847990Notes

Reaction equation

HRID 1847990 reaction equation
Br[C:2]1[S:3][C:4]2[CH:10]=[C:9]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH:8]=[CH:7][C:5]=2[N:6]=1.[CH3:16][S-:17].[Na+]>C1COCC1>[CH3:16][S:17][C:2]1[S:3][C:4]2[CH:10]=[C:9]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH:8]=[CH:7][C:5]=2[N:6]=1

Participants

4

Reactant 2

HCID 4378561Sodium methanethiolateHCID 12067225Ethyl 2-bromo-6-benzothiazolecarboxylate

Product 1

HCID 86680993Ethyl 2-(methylsulfanyl)-1,3-benzothiazole-6-carboxylateYield 84.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred mixture of 2-bromobenzo[d]thiazole-6-carboxylate (2.3 g, 7.9 mmol) from Step 1 of this Example in THF (15 mL) at 0° C. was added sodium thiomethoxide (607 mg, 8.7 mmol) in one portion. The mixture was allowed to warm to rt and stirred for 20 h. The mixture was partitioned between EtOAc (150 mL) and water (100 mL). The EtOAc layer was separated and washed with water (100 mL) and brine (100 mL), dried over MgSO4, filtered, and concentrated under reduced pressure to afford ethyl 2-(methylthio)benzo[d]thiazole-6-carboxylate (1.7 g, 83%) as a yellow solid which did not require further purification. 1H NMR (300 MHz, DMSO-d6) δ 8.69 (d, J=1.3 Hz, 1H), 8.02 (m, 1H), 7.92 (m, 1H), 4.35 (q, J=7.0 Hz, 2H), 2.83 (s, 3H), 1.35 (t, J=7.1 Hz, 3H). LCMS (ESI) m/z 254 (M+H)+.

Workup

  1. customat 0° C.
  2. customThe mixture was partitioned between EtOAc (150 mL) and water (100 mL)
  3. customThe EtOAc layer was separated
  4. washwashed with water (100 mL) and brine (100 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-aa77e699aa19423986fe23b007f81ee2
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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