Sulfuric Acid → 1-(2-nitrobenzyl)pyrrolidine

HRID 239199Notes

Reaction equation

HRID 239199 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][CH:9]=[CH:8][C:5]=1[CH2:6]Br)([O-:3])=[O:2].[N+:12]([C:15]1C=C[CH:18]=[CH:17][C:16]=1C)([O-])=O.[N+](C1C=CC=CC=1C(Br)Br)([O-])=O.N1CCCC1.OS(O)(=O)=O.[O-]S([O-])(=O)=O.[Mg+2]>ClC1C=CC=CC=1.C(Cl)Cl>[N+:1]([C:4]1[CH:11]=[CH:10][CH:9]=[CH:8][C:5]=1[CH2:6][N:12]1[CH2:15][CH2:16][CH2:17][CH2:18]1)([O-:3])=[O:2]

Participants

9

Reactant 6

HCID 1118Sulfuric AcidHCID 69442-NitrotolueneHCID 24083Sulfuric acid magnesium salt (1:1)HCID 31268PyrrolidineHCID 77569alpha-Bromo-2-nitrotoluene2×HCID 110663413-Nitro-o-dibromomethyl benzene

Product 1

HCID 2643101-(2-nitrobenzyl)pyrrolidineYield 89%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 7964ChlorobenzeneSolvent

Procedure

To a solution of the crude 2-nitrobenzyl bromide (185 g, containing approximately 21% by weight of the 2-nitrobenzyl bromide (approximately 39 g, 180 mmol) besides the starting material 2-nitrotoluene and by-products of its bromination such as 2-nitrobenzal bromide) in chlorobenzene were added methylene chloride (500 ml) and pyrrolidine (28.1 g, 395 mmol). The solution was stirred at room temperature overnight. Then, the solution was cooled to 0° C. and aqueous solution of H2SO4 (200 g, 10% per weight) were added. The aqueous phase was extracted four times with methylene chloride (30 ml each). The aqueous phase was then treated with saturated aqueous solution of K2CO3 until the gas evolution had ceased. Then, it was extracted four times with methylene chloride (30 ml each). The combined organic phases were washed with water and brine and dried over MgSO4 affording a yellow liquid (yield: 89%). The product obtained was sufficient pure (>95%) for subsequent steps without further purification.

Workup

  1. temperatureThen, the solution was cooled to 0° C.
  2. extractionThe aqueous phase was extracted four times with methylene chloride (30 ml each)
  3. additionThe aqueous phase was then treated with saturated aqueous solution of K2CO3 until the gas evolution
  4. extractionThen, it was extracted four times with methylene chloride (30 ml each)
  5. washThe combined organic phases were washed with water and brine

Sources & evidence

ORD record
ord-29c76f272c35415dbbaa9fd0a954608d
Source dataset
uspto-grants-2014_02
Patent number
US08642780B2

Reaction notes

Loading…