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Sodium Hydroxide → (s)-3-[1-(2,4-Dichlorophenyl)-ethylamino]-pyrrolidine-1-carboxylic acid tert-butyl ester

HRID 252098
Notes
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Reaction equation

HRID 252098 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][C@H:10]([NH2:13])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:14][C:15]([C:17]1[CH:22]=[CH:21][C:20]([Cl:23])=[CH:19][C:18]=1[Cl:24])=O.[BH4-].[Na+].[OH-].[Na+]>C1(C)C=CC=CC=1>[CH3:15][CH:17]([CH2:18][CH2:19][CH3:20])[CH3:22].[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][C@H:10]([NH:13][CH:15]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[CH:19][C:18]=2[Cl:24])[CH3:14])[CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 166932',4'-DichloroacetophenoneHCID 854071tert-butyl (3S)-3-aminopyrrolidine-1-carboxylateHCID 4311764Sodium borohydride

Product 2

HCID 78922-MethylpentaneHCID 66853965(s)-3-[1-(2,4-Dichlorophenyl)-ethylamino]-pyrrolidine-1-carboxylic acid tert-butyl ester
Yield 56.7%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Stir a mixture of (S)-3-aminopyrrolidine-1-carboxylic acid tert-butyl ester (10.4 g, 55.7 mmol) and 2,4-dichloroacetophenone (10.5 g, 55 mmol) in dry toluene (400 mL) at 110° C. for 48 h. Concentrate and dissolve the residue in methanol (160 mL), add sodium borohydride (3.37 g, 89 mmol) slowly and stir for 20 min. Add 1 N sodium hydroxide (200 mL) and extract with diethyl ether. Combine the organic layers, wash with water, dry (magnesium sulfate), concentrate and chromatograph on silica gel, eluting with 0:100 to 40:60 ethyl acetate:2-methylpentane to give (S)-3-[1-(2,4-dichlorophenyl)-ethylamino]-pyrrolidine-1-carboxylic acid tert-butyl ester (5.6 g, 28%). 1H NMR (300 MHz, CDCl3) δ 7.41-7.51 (1H, m), 7.34 (1H, s), 7.24 (1H, dd, J=8.38, 1.98 Hz), 4.21-4.36 (1H, m), 3.42-3.57 (2H, m), 3.21-3.33 (1H, m), 3.04-3.15 (1H, m), 2.88-3.03 (1H, m), 1.96-2.05 (1H, m), 1.63-1.72 (1H, m), 1.37-1.47 (9H, m), 1.30 (3H, dd, J=6.59, 1.51 Hz), MS (ES): m/z=359[M+].

Workup

  1. concentrationConcentrate
  2. dissolutiondissolve the residue in methanol (160 mL)
  3. stirringstir for 20 min
  4. extractionextract with diethyl ether
  5. washwash with water
  6. dry with materialdry (magnesium sulfate)
  7. concentrationconcentrate
  8. washchromatograph on silica gel, eluting with 0:100 to 40:60 ethyl acetate

Sources & evidence

ORD record
ord-34b057b6c0c749299f89cfbf2235a42e
Source dataset
uspto-grants-2011_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07868014B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes