1-Bromo-2-Chloroethane → 1-(Carboethoxy)-1-(4-methoxybenzylthio)cyclopropane

HRID 260691Notes

Reaction equation

HRID 260691 reaction equation
C[Si](C)(C)N[Si](C)(C)C.[Li].[C:11]([CH2:16][S:17][CH2:18][C:19]1[CH:24]=[CH:23][C:22]([O:25][CH3:26])=[CH:21][CH:20]=1)([O:13][CH2:14][CH3:15])=[O:12].CN1C[CH2:32][CH2:31]N(C)C1=O.BrCCCl>O1CCCC1>[C:11]([C:16]1([S:17][CH2:18][C:19]2[CH:20]=[CH:21][C:22]([O:25][CH3:26])=[CH:23][CH:24]=2)[CH2:32][CH2:31]1)([O:13][CH2:14][CH3:15])=[O:12]

Participants

6

Reactant 4

HCID 78491-Bromo-2-ChloroethaneHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 108476441-(Carboethoxy)-1-(4-methoxybenzylthio)methaneHCID 57426343Lithium bis(trimethylsilyl)amide2×

Product 1

HCID 224002171-(Carboethoxy)-1-(4-methoxybenzylthio)cyclopropaneYield 21%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Cool lithium hexamethyldisilazane (6 mL of a 1.0M solution in tetrahydrofuran, 6.0 mmol) to -78° C. Add, by cannula transfer, a solution of 1-(carboethoxy)-1-(4-methoxybenzylthio)methane (1.36 g, 5.66 mmol) in tetrahydrofuran (10 mL). Stir for 45 minutes, add 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) (0.73 mL, 6.0 mmol) followed by 1-bromo-2-chloroethane (050 mL, 6.0 mmol) and stir to room temperature overnight. Cool to -78° C., add lithium hexamethyldisilazane (6.0 mL, 6.0 mmol) and stir at room temperature for 24 hours. Quench with saturated ammonium chloride (5 mL) and partition between ethyl acetate (30 mL) and water (30 mL). Separate the organic phase, dry (Na2SO4) and evaporate the solvent in vacuo. Purify by chromatography (5:1 hexane/ethyl acetate to 2.5:1 hexane/ethyl acetate) to give 1-(carboethoxy)-1-(4-methoxybenzylthio)cyclopropane (317 mg, 21%).

Workup

  1. additionAdd, by cannula transfer
  2. stirringstir to room temperature overnight
  3. stirringstir at room temperature for 24 hours
  4. customQuench with saturated ammonium chloride (5 mL)
  5. custompartition between ethyl acetate (30 mL) and water (30 mL)
  6. customSeparate the organic phase
  7. dry with materialdry (Na2SO4)
  8. customevaporate the solvent in vacuo
  9. customPurify by chromatography (5:1 hexane/ethyl acetate to 2.5:1 hexane/ethyl acetate)

Sources & evidence

ORD record
ord-d167598279a6418ab3eea9df7c49b1b9
Source dataset
uspto-grants-1996_06
Patent number
US05529996

Reaction notes

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