Tetrahydrofuran → trans t-Butyl 2-(4-bromophenyl)cyclopropane carboxylate

HRID 561070Notes

Reaction equation

HRID 561070 reaction equation
[H-].[Na+].C(OP([CH2:11][C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])(OCC)=O)C.[Br:19][C:20]1[CH:27]=[CH:26][C:23]([CH:24]=O)=[CH:22][CH:21]=1.[NH4+].[Cl-].[CH2:30]1COCC1>CC(OC)(C)C>[Br:19][C:20]1[CH:27]=[CH:26][C:23](/[CH:24]=[CH:11]/[C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])=[CH:22][CH:21]=1.[Br:19][C:20]1[CH:27]=[CH:26][C:23]([C@@H:24]2[CH2:30][C@H:11]2[C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])=[CH:22][CH:21]=1

Participants

8

Reactant 5

HCID 8028Tetrahydrofuran3×HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 707414-BromobenzaldehydeHCID 2773685tert-Butyl diethylphosphonoacetate

Product 2

HCID 11482956tert-Butyl (2E)-3-(4-bromophenyl)prop-2-enoateHCID 53247776trans t-Butyl 2-(4-bromophenyl)cyclopropane carboxylateYield 97.5%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Procedure

The trans t-butyl 3-(4-bromophenyl)acrylate was prepared as follows: A flame dried three-neck flask equipped with a thermometer, an addition funnel and a N2 inlet was charged with NaH (3.96 g, 99.1 mmol, 1.1 eq.) and anhydrous THF (120 mL). With moderate stirring under N2, a solution of t-butyl diethylphosphonoacetate (23.2 mL, 99.1 mmol, 1.1 eq.) dissolved in anhydrous THF (20 mL) was charged dropwise via addition funnel over a period of 30 min. The resulting mixture changed from a slurry to a clear, light yellow colored solution. An exotherm from 25° C. to 35° C. was observed during the addition. After completing the addition, the solution was stirred at RT for 30 min. A solution of 4-bromobenzaldehyde (15.9 g, 86.1 mmol, 1.0 eq) dissolved in anhydrous THF (20 mL) was charged to the above solution dropwise via the addition funnel over a period of 30 min. An exotherm from 25° C. to 35° C. was observed. The reaction mixture was stirred at RT for 1 h. The reaction mixture was analyzed for completion using 1H NMR. The reaction mixture was diluted by the sequential addition of MTBE (200 mL) and sat. NH4Cl (150 mL). The organic layer was separated and washed with H2O (25 mL), and sat. NH4Cl (25 mL). After drying over MgSO4, the organic layer was evaporated to dryness to give 23.7 g desired product as a white solid (97.5% yield). 1H NMR (400 MHz, CDCl3-d) δ ppm 1.55 (s, 9H) 6.38 (d, 1H) 7.39 (d, 2H) 7.45-7.59 (m, 3H).

Workup

  1. customA flame dried three-neck flask
  2. customequipped with a thermometer, an addition funnel and a N2 inlet
  3. additionwas charged dropwise via addition funnel over a period of 30 min
  4. additionAn exotherm from 25° C. to 35° C. was observed during the addition
  5. additionthe addition
  6. stirringthe solution was stirred at RT for 30 min
  7. additionwas charged to the above solution dropwise via the addition funnel over a period of 30 min
  8. customfrom 25° C. to 35° C.
  9. stirringThe reaction mixture was stirred at RT for 1 h
  10. customThe organic layer was separated
  11. washwashed with H2O (25 mL), and sat. NH4Cl (25 mL)
  12. dry with materialAfter drying over MgSO4
  13. customthe organic layer was evaporated to dryness

Sources & evidence

ORD record
ord-9d175c9299f0408ca0be18b0c84f4b51
Source dataset
uspto-grants-2011_11
Patent number
US08063215B2

Reaction notes

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