Potassium Carbonate → 7-benzyloxy-N4-[(2,2-dimethyl[1,3]dioxolan-4-yl)methyl]quinoline-3,4-diamine

HRID 598387

Reaction equation

HRID 598387 reaction equation
S(S([O-])=O)([O-])=O.[Na+].[Na+].C(=O)([O-])[O-].[K+].[K+].[CH2:15]([O:22][C:23]1[CH:32]=[C:31]2[C:26]([C:27]([NH:36][CH2:37][CH:38]3[CH2:42][O:41][C:40]([CH3:44])([CH3:43])[O:39]3)=[C:28]([N+:33]([O-])=O)[CH:29]=[N:30]2)=[CH:25][CH:24]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>O.ClCCl.CC[N+]1C=CC(C2C=C[N+](CC)=CC=2)=CC=1.[Br-].[Br-]>[CH2:15]([O:22][C:23]1[CH:32]=[C:31]2[C:26]([C:27]([NH:36][CH2:37][CH:38]3[CH2:42][O:41][C:40]([CH3:44])([CH3:43])[O:39]3)=[C:28]([NH2:33])[CH:29]=[N:30]2)=[CH:25][CH:24]=1)[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 24489Sodium DithioniteHCID 67051130(7-Benzyloxy-3-nitro-quinolin-4-yl)[(2,2-dimethyl[1,3]dioxolan-4-yl)methyl]amine

Product 1

HCID 670510967-benzyloxy-N4-[(2,2-dimethyl[1,3]dioxolan-4-yl)methyl]quinoline-3,4-diamineYield 100%

Reagents, catalysts & solvents 3

HCID 114742621,1'-Diethyl-4,4'-bipyridinium dibromideCatalystHCID 962WaterSolvent3×HCID 6344DichloromethaneSolvent

Procedure

A solution of sodium dithionite (85% pure, 135.07 g, 659.42 mmol) and potassium carbonate (101.27 g, 732.73 mmol) in water (450 mL) was added dropwise to a mechanically stirred mixture of ethyl viologen dibromide (1.1 g, 2.93 mmol) and (7-benzyloxy-3-nitro-quinolin-4-yl)[(2,2-dimethyl[1,3]dioxolan-4-yl)methyl]amine (60.0 g, 146.54 mmol) in dichloromethane (500 mL) and water (50 mL). The reaction mixture was stirred at ambient temperature overnight and then diluted with water (600 mL) and stirred for an additional 10 minutes. The organic phase was separated and the aqueous layer was reextracted with dichloromethane (400 mL). The combined organic layers were washed with water (800 mL) and brine (800 mL), dried over sodium sulfate, and concentrated under reduced pressure to afford 55.60 g of 7-benzyloxy-N4-[(2,2-dimethyl[1,3]dioxolan-4-yl)methyl]quinoline-3,4-diamine as a brown foam. 1H-NMR (300 MHz, CDCl3) δ 8.38 (s, 1H), 7.83 (d, J=9.3 Hz, 1H), 7.51-7.28 (m, 6H), 7.18 (dd, J=9.2, 2.5 Hz, 1H), 5.16 (s, 2H), 4.35 (br s, 1H), 4.30-4.18 (m, 1H), 4.02 (dd, J=8.3, 6.5 Hz, 1H), 3.81 (br s, 2H), 3.68 (dd, J=8.3, 6.1 Hz, 1H), 3.60-3.46 (m, 1H), 3.40-3.25 (m, 1H), 1.52 (s, 3H), 1.37 (s, 3H); MS (APCI) m/z 380.0 (M+H)+.

Workup

  1. stirringstirred for an additional 10 minutes
  2. customThe organic phase was separated
  3. washThe combined organic layers were washed with water (800 mL) and brine (800 mL)
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b5ae80c3c6144dd9ba51534717919eef
Source dataset
uspto-grants-2011_03
Patent number
US07897597B2

Linked notes

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