Carbamic acid, methylenebis-, diethyl ester (9CI) → HCID 19910062, compound

HRID 1534654Notes

Reaction equation

HRID 1534654 reaction equation
[Br:1][CH2:2][C:3]([C:5]([CH2:7][Br:8])=[CH2:6])=[CH2:4].[CH2:9](NC(OCC)=O)[NH:10][C:11]([O:13][CH2:14][CH3:15])=[O:12]>ClC(Cl)C.B(F)(F)F.CCOCC>[C:11]([N:10]1[CH2:4][C:3]([CH2:2][Br:1])=[C:5]([CH2:7][Br:8])[CH2:6][CH2:9]1)([O:13][CH2:14][CH3:15])=[O:12]

Participants

5

Reactant 2

HCID 19407Carbamic acid, methylenebis-, diethyl ester (9CI)HCID 111181502,3-bis(bromomethyl)-1,3-butadiene

Product 1

HCID 19910062HCID 19910062, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 63651,1-DichloroethaneSolventHCID 8000Boron trifluoride etherateSolvent

Procedure

To a solution of 2,3-bis (bromomethyl)-1,3-butadiene (4.8 g) and methylenediurethane (3.9 g) in dichloroethane (40 ml), borontrifluoride etherate (0.3 ml) was added. The reaction mixture was refluxed for 10 hours and washed with 10% sodium bicarbonate solution (30 ml×3). The organic phase was filtered though silicagel and evaporation of the solvent to give 1-carboethoxy-4,5-bis(bromomethyl)-1,2,3,6-tetrahydropyridine (6.14 g, yield 90%) which was cyclized with 40% methylamine (1.8 ml) and potassium carbonate (15 g) in acetonitrile (50 ml) for 2 hours at room temperature. The solid was filtered off and the filtrate was purified by silicagel column chromatography to give 3-carboethoxy-8-methyl-3,8-diazabicyclo[4.3.0]non-1(6)-ene (2.57 g, yield 68%). This amine was refluxed in 20% hydrochloric acid (50 ml) and evaporation gave the title compound (1.35 g, yield 80%).

Workup

  1. temperatureThe reaction mixture was refluxed for 10 hours
  2. washwashed with 10% sodium bicarbonate solution (30 ml×3)
  3. filtrationThe organic phase was filtered though silicagel and evaporation of the solvent

Sources & evidence

ORD record
ord-5a311eebe4ed4541bfb51bbfe0585e86
Source dataset
uspto-grants-1992_02
Patent number
US05089621

Reaction notes

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