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

HRID 2190960Notes

Reaction equation

HRID 2190960 reaction equation
Br[CH2:2][CH:3]1[CH2:5][CH2:4]1.[C:6]([CH:11]1[S:16][CH2:15][CH2:14][CH2:13][S:12]1)([O:8][CH2:9][CH3:10])=[O:7].[H-].[Na+]>CN(C)C=O>[CH:5]1([CH2:4][C:11]2([C:6]([O:8][CH2:9][CH3:10])=[O:7])[S:12][CH2:13][CH2:14][CH2:15][S:16]2)[CH2:3][CH2:2]1

Participants

5

Reactant 3

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

Product 1

HCID 22285400Ethyl 2-(cyclopropylmethyl)-1,3-dithiane-2-carboxylateYield 97.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of bromomethylcyclopropane (19.5 g, 0.144 mol) and 2-carboethoxy 1,3-dithiane (25.0 g, 0.130 mol) in dry N,N-dimethylformamide (55 mL) was added drop wise over 20 minutes to an ice cooled suspension of sodium hydride (60% oil dispersion, 6.24 g, 0.156 mol, 1.2 eq; pre-washed twice with n-pentane) in benzene (165 mL). The suspension was stirred at room temperature for 18 hours and then poured into 15% aqueous ammonium chloride. The mixture was extracted with methyl tert-butyl ether and the organic phase was separated, washed with water and then brine, dried over magnesium sulfate and filtered. The solvent was evaporated from the filtrate to give ethyl 2-(cyclopropylmethyl)-1,3-dithiane-2-carboxylate (31.2 g, 97.4%) as a light brown oil. 1H-NMR (400 MHz, CDCl3): δ=0.07-0.15 (m, 2H), 0.37-0.47 (m, 2H), 0.76-0.89 (s, 1H), 1.25 (t, J=8 Hz, 3H), 1.70-1.85 (m, 1H), 1.88 (d, J=8 Hz, 2H), 2.01-2.13 (m, 1H), 2.54-2.65 (m, 2H), 3.13-3.26 (m, 2H), 4.19 (q, J=8 Hz, 2H).

Workup

  1. temperaturecooled
  2. washpre-washed twice with n-pentane) in benzene (165 mL)
  3. additionpoured into 15% aqueous ammonium chloride
  4. extractionThe mixture was extracted with methyl tert-butyl ether
  5. customthe organic phase was separated
  6. washwashed with water
  7. dry with materialbrine, dried over magnesium sulfate
  8. filtrationfiltered
  9. customThe solvent was evaporated from the filtrate

Sources & evidence

ORD record
ord-5983842d7b864169bf30aa40b6bb5137
Source dataset
uspto-grants-2012_12
Patent number
US08324417B2

Reaction notes

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