Sodium hydride → Ethyl 2-(cyclopropylmethyl)-1,3-dithiane-2-carboxylate

HRID 1062457Notes

Reaction equation

HRID 1062457 reaction equation
[H-].[Na+].Br[CH2:4][CH:5]1[CH2:7][CH2:6]1.[S:8]1[CH2:13][CH2:12][CH2:11][S:10][CH:9]1[C:14]([O:16][CH2:17][CH3:18])=[O:15]>C1(C)C=CC=CC=1.CN(C=O)C>[CH:7]1([CH2:6][C:9]2([C:14]([O:16][CH2:17][CH3:18])=[O:15])[S:8][CH2:13][CH2:12][CH2:11][S:10]2)[CH2:5][CH2:4]1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 81503BromomethylcyclopropaneHCID 88552Ethyl 1,3-dithiane-2-carboxylate

Product 1

HCID 22285400Ethyl 2-(cyclopropylmethyl)-1,3-dithiane-2-carboxylateYield 85.9%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of NaH (95%, 2.8 g, 111 mmol) in dry toluene (120 mL) stirring at 0° C. was dropwise added, over 10 minutes, a solution of bromomethylcyclopropane (15 g, 111 mmol), and ethyl 1,3-dithiane-2-carboxylate (17.77 g, 92.58 mmol) in dry DMF (40 mL). The ice bath was removed and the solution was stirred overnight at rt. Water was added to the solution and the phases were separated. The organic phase was dried over MgSO4, then evaporated to give 19.6 g (50%) of ethyl 2-(cyclopropylmethyl)-1,3-dithiane-2-carboxylate, which was used in the next step without purification. 1H NMR (CDCl3): δ 4.26 (2H, q, J=7.2 Hz), 3.30-3.23 (2H, m), 2.69-2.64 (2H, m), 2.16-2.11 (1H, m), 1.96 (2H, d, J=6.8 Hz), 1.91-1.81 (1H, m), 1.34 (3H, t, J=7.2 Hz), 0.93-0.86 (1H, m), 0.52-0.47 (2H, m), 0.20-0.16 (2H, m).

Workup

  1. additionwas dropwise added, over 10 minutes
  2. customThe ice bath was removed
  3. stirringthe solution was stirred overnight at rt
  4. additionWater was added to the solution
  5. customthe phases were separated
  6. dry with materialThe organic phase was dried over MgSO4
  7. customevaporated

Sources & evidence

ORD record
ord-1cc0038cd33940ad9679aa17d7e8acb5
Source dataset
uspto-grants-2005_11
Patent number
US06960601B2

Reaction notes

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