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Hydrazine → [[(Propane-1,3-diyl)dioxy]bis[(2-amino-5-methoxy-1,4-phenylene)carbonyl]]bis[2-(hydroxymethyl)-4-methylpyrrolidine]

HRID 915710
Notes
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Reaction equation

HRID 915710 reaction equation
NN.[CH2:3]([O:28][C:29]1[CH:34]=[C:33]([O:35][CH3:36])[C:32]([C:37]([N:39]2[CH2:43][C:42](=[CH2:44])[CH2:41][CH:40]2[CH2:45][OH:46])=[O:38])=[CH:31][C:30]=1[N+:47]([O-])=O)[CH2:4][CH2:5][O:6][C:7]1[CH:12]=[C:11]([O:13][CH3:14])[C:10]([C:15]([N:17]2[CH2:21][C:20](=[CH2:22])[CH2:19][CH:18]2[CH2:23][OH:24])=[O:16])=[CH:9][C:8]=1[N+:25]([O-])=O.C(Cl)(Cl)Cl.CO>CO.[Ni]>[CH2:5]([O:6][C:7]1[CH:12]=[C:11]([O:13][CH3:14])[C:10]([C:15]([N:17]2[CH2:21][CH:20]([CH3:22])[CH2:19][CH:18]2[CH2:23][OH:24])=[O:16])=[CH:9][C:8]=1[NH2:25])[CH2:4][CH2:3][O:28][C:29]1[CH:34]=[C:33]([O:35][CH3:36])[C:32]([C:37]([N:39]2[CH2:43][CH:42]([CH3:44])[CH2:41][CH:40]2[CH2:45][OH:46])=[O:38])=[CH:31][C:30]=1[NH2:47]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 9321Hydrazine3×HCID 21584188Chloroform methanolHCID 86606191[[(Propane-1,3-diyl)dioxy]bis[(2-nitro-5-methoxy-1,4-phenylene)carbonyl]]bis[2-(hydroxymethyl)-4-methylidenepyrrolidine]

Product 1

HCID 86606192[[(Propane-1,3-diyl)dioxy]bis[(2-amino-5-methoxy-1,4-phenylene)carbonyl]]bis[2-(hydroxymethyl)-4-methylpyrrolidine]Yield 63%

Reagents, catalysts & solvents 2

HCID 935NickelCatalyst3×HCID 887MethanolSolvent3×

Procedure

A solution of hydrazine (23 mg, 23 μL, 0.72 mmol) in MeOH (5 mL) was added dropwise to a solution of the diol 35 (95 mg, 0.145 mmol) and Raney Ni (20 mg) in MeOH (15 mL) heated at reflux. After 1 hour at reflux TLC (90% CHCl3/MeOH) revealed some amine formation. The reaction mixture was treated with further Raney Ni (20 mg) and hydrazine (23 mg, 23 μL, 0.72 mmol) in MeOH (5 mL) and was heated at reflux for an additional 30 minutes at which point TLC revealed complete reaction. The reaction mixture was then treated with enough Raney Ni to decompose any remaining hydrazine and heated at reflux for a further 1.5 hours. Following cooling to room temperature the mixture was filtered through a sinter and the resulting filtrate evaporated in vacuo. The resulting residue was then treated with CH2Cl2 (30 mL), dried (MgSO4), filtered and evaporated in vacuo to provide the bis-amine (36) as a yellow oil (54 mg, 63%): 1H NMR (270 MHz, CDCl3) (diastereoisomers) δ 6.73 (s, 2Harom), 6.32 (s, 2Harom), 4.60-4.30 (m, 2H, NCHCH2OH), 4.19 (t, 4H, J=5.87 Hz, OCH2CH2CH2O), 3.78-3.50 (m, 14H, NCHCH2OH, NCH2CHCH3 and OCH3), 2.40-1.55 (m, 8H, NCH2CHCH3, OCH2CH2CH2O and NCH2CHCH3CH2), 1.00-0.95 (m, 6H, NCH2CHCH3); MS (EI), m/z (relative intensity) 600 (M+, 16), 459 (46), 345 (16), 206 (13), 186 (17), 180 (31), 166 (37), 149 (6), 142 (76), 100 (6), 98 (13), 97 (29), 84 (81), 69 (7), 55 (100).

Workup

  1. temperatureheated
  2. temperatureat reflux
  3. temperaturewas heated
  4. temperatureat reflux for an additional 30 minutes at which point TLC
  5. customreaction
  6. temperatureheated
  7. temperatureat reflux for a further 1.5 hours
  8. filtrationwas filtered through a sinter
  9. customthe resulting filtrate evaporated in vacuo
  10. additionThe resulting residue was then treated with CH2Cl2 (30 mL)
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. customevaporated in vacuo

Sources & evidence

ORD record
ord-bb2d3cd74e4141b4a7b1a3d719250394
Source dataset
uspto-grants-2007_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07265105B2

Reaction notes

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