Ammonium Chloride → (+/-)-2-Methyl-3-((2-amino)benzylamino)-N-(9-chloro-3,4-dihydro-2H-1,5-benzodioxepin-7-ylmethyl)-N-isobutylpropanamide

HRID 1024492Notes

Reaction equation

HRID 1024492 reaction equation
[CH3:1][CH:2]([CH2:23][NH:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[N+:32]([O-])=O)[C:3]([N:5]([CH2:10][C:11]1[CH:21]=[C:20]([Cl:22])[C:14]2[O:15][CH2:16][CH2:17][CH2:18][O:19][C:13]=2[CH:12]=1)[CH2:6][CH:7]([CH3:9])[CH3:8])=[O:4].[Cl-].[NH4+]>C(O)C.O.[Zn]>[CH3:1][CH:2]([CH2:23][NH:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[NH2:32])[C:3]([N:5]([CH2:10][C:11]1[CH:21]=[C:20]([Cl:22])[C:14]2[O:15][CH2:16][CH2:17][CH2:18][O:19][C:13]=2[CH:12]=1)[CH2:6][CH:7]([CH3:8])[CH3:9])=[O:4]

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 58080648(+/-)-2-Methyl-3-((2-nitro)benzylamino)-N-(9-chloro-3,4-dihydro-2H-1,5-benzodioxepin-7-ylmethyl)-N-isobutylpropanamide

Product 1

HCID 46831870(+/-)-2-Methyl-3-((2-amino)benzylamino)-N-(9-chloro-3,4-dihydro-2H-1,5-benzodioxepin-7-ylmethyl)-N-isobutylpropanamide

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 19096565Water ethanolSolvent

Procedure

A mixture of (±)-2-Methyl-3-((2-nitro)benzylamino)-N-(9-chloro-3,4-dihydro-2H-1,5-benzodioxepin-7-ylmethyl)-N-isobutylpropanamide (80 mg), ammonium chloride (53 mg), and zinc powder (106 mg) in 6 ml of EtOH—H2O (9-10) was stirred overnight, and then filtered through a layer of zeolite. The filtercake was rinsed with methanol (5 ml×3), and the combined filtrate was concentrated under reduced pressure. The residue was then partitioned between of dichloromethane and saturated aq. sodium bicarbonate (6 ml each). The aqueous layer was then extracted with dichloromethane (6 ml). The organic layer was washed with brine and then concentrated to yield (±)-2-Methyl-3-((2-amino)benzylamino)-N-(9-chloro-3,4-dihydro-2H-1,5-benzodioxepin-7-ylmethyl)-N-isobutylpropanamide as a resin: MS (m+1)=460.3; 1H NMR (500 MHz, CDCl3) 0.95 (m, 6H), 1.15 (dd, 3H), 2.00 (m, 1H), 2.25 (m, 2H0, 2.60 (q, 1H), 2.70 (q, 1H), 2.90 (m, 1H), 3.05 (m, 1H), 3.10 (m, 1H), 3.20 (q, 1H), 3.35 (q, 1H), 3.45 (q, 1H), 3.70 (m, 2H), 4.25 (m, 2H), 4.35 (m, 2H), 4.55 (m, 2H), 6.6-7.2 (m, 4H), 6.8-7.0 (m, 2H).

Workup

  1. filtrationfiltered through a layer of zeolite
  2. washThe filtercake was rinsed with methanol (5 ml×3)
  3. concentrationthe combined filtrate was concentrated under reduced pressure
  4. customThe residue was then partitioned between of dichloromethane and saturated aq. sodium bicarbonate (6 ml each)
  5. extractionThe aqueous layer was then extracted with dichloromethane (6 ml)
  6. washThe organic layer was washed with brine
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-fc11d2ee389f43f9ae3bf439fb4da0ad
Source dataset
uspto-grants-2014_05
Patent number
US08722896B2

Reaction notes

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