Formamide → Methyl 4,5,6,7-tetrahydrobenzo[d]thiazole-7-carboxylate

HRID 1051954Notes

Reaction equation

HRID 1051954 reaction equation
P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:2].[CH:15]([NH2:17])=O.Br[CH:19]1[C:24](=O)[CH2:23][CH2:22][CH2:21][CH:20]1[C:26]([O:28][CH3:29])=[O:27]>O1CCOCC1>[S:2]1[C:19]2[CH:20]([C:26]([O:28][CH3:29])=[O:27])[CH2:21][CH2:22][CH2:23][C:24]=2[N:17]=[CH:15]1

Participants

5

Reactant 3

HCID 713FormamideHCID 14817Phosphorus sulfide (P2S5)HCID 83646766HCID 83646766, compound

Product 1

HCID 90303216Methyl 4,5,6,7-tetrahydrobenzo[d]thiazole-7-carboxylate

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
100 °C

Procedure

At 0° C., finely crushed P4S10 (9.35 g, 21.0 mmol) was added to a mixture of formamide (4.73 g, 105.0 mmol) in dioxane (28.5 mL). Subsequently, the mixture was stirred in a sealed vial at 100° C. for 1.5 h, cooled to RT and filtrated. The filtrate was added to a mixture of methyl 2-bromo-3-oxocyclohexanecarboxylate (2.06 g, 8.76 mmol) in dioxane (16.5 mL) and stirred in a sealed vial at 80° C. overnight. The mixture was quenched by the addition of aq. sat. NaHCO3 and extracted with EtOAc. The comb. org. layers were washed with brine, dried over MgSO4, and conc. in vacuo. Purification by means of CC (10-40% EtOAc/Hept) provided a yellow oil.

Workup

  1. temperaturecooled to RT
  2. filtrationfiltrated
  3. stirringstirred in a sealed vial at 80° C. overnight
  4. customThe mixture was quenched by the addition of aq. sat. NaHCO3
  5. extractionextracted with EtOAc
  6. washlayers were washed with brine
  7. dry with materialdried over MgSO4
  8. customPurification by means of CC (10-40% EtOAc/Hept)
  9. customprovided a yellow oil

Sources & evidence

ORD record
ord-263acd6711eb446e9db5559b644bf796
Source dataset
uspto-grants-2016_07
Patent number
US09388198B2

Reaction notes

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