Carbon Disulfide → Methyl 5-(benzylsulfanyl)-1,3-thiazole-4-carboxylate

HRID 2165996Notes

Reaction equation

HRID 2165996 reaction equation
CC(C)([O-])C.[K+].[N+:7]([CH2:9][C:10]([O:12][CH3:13])=[O:11])#[C-:8].[C:14](=[S:16])=[S:15].[CH2:17](Br)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>O1CCCC1>[C:18]1([CH2:17][S:15][C:14]2[S:16][CH:8]=[N:7][C:9]=2[C:10]([O:12][CH3:13])=[O:11])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

6

Reactant 4

HCID 6348Carbon DisulfideHCID 7498Benzyl BromideHCID 547815Methyl isocyanoacetateHCID 23665647Potassium tert-butoxide

Product 1

HCID 15077124Methyl 5-(benzylsulfanyl)-1,3-thiazole-4-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Procedure

A solution of 31.3 g of potassium t-butoxide in 280 ml of tetrahydrofuran was cooled to -50° and a solution of 27.7 g of methyl isocyanoacetate in 230 ml of tetrahydrofuran was added dropwise at -50° to -40°. The resulting brown suspension was stirred 15 minutes then cooled to -78°, then a solution of 16.8 ml of carbon disulfide in 225 ml tetrahydrofuran was added dropwise while maintaining the temperature below -50°. The pinkish-brown thick suspension was allowed to warm to -15° to 10° over 15 to 20 minutes. To the reaction mixture, a solution of 33.3 ml of benzyl bromide in 140 ml tetrahydrofuran was added dropwise at -15° to -5°. The reaction mixture was stirred at ambient temperature for 30 minutes, refluxed for 20 minutes, then cooled and the bulk of the solvent evaporated. To the oily residue, 1000 ml ice-water was added. After several minutes, the product soldified. The tan solid was collected, washed twice with water, follewed by hexane and dried giving 68.8 g of methyl 5-(phenylmethylthio)-4-thiazolecarboxylate, m.p. 90°-92°.

Workup

  1. temperaturethen cooled to -78°
  2. temperaturewhile maintaining the temperature below -50°
  3. temperatureto warm to -15° to 10° over 15 to 20 minutes
  4. stirringThe reaction mixture was stirred at ambient temperature for 30 minutes
  5. temperaturerefluxed for 20 minutes
  6. temperaturecooled
  7. customthe bulk of the solvent evaporated
  8. additionTo the oily residue, 1000 ml ice-water was added
  9. waitAfter several minutes
  10. customThe tan solid was collected
  11. washwashed twice with water
  12. customdried

Sources & evidence

ORD record
ord-9f7160494ffe41369d94ff1178459068
Source dataset
uspto-grants-1990_07
Patent number
US04943312

Reaction notes

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