Ammonium Chloride → N-butyl-2,2'-imino-bis(8-nitroquinoline)

HRID 2188610Notes

Reaction equation

HRID 2188610 reaction equation
Cl[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[C:5]([N+:12]([O-:14])=[O:13])[CH:6]=[CH:7][CH:8]=2)[N:3]=1.CC([O-])(C)C.[Na+].[CH2:21]([NH:25][C:26]1[CH:35]=[CH:34][C:33]2[C:28](=[C:29]([N+:36]([O-:38])=[O:37])[CH:30]=[CH:31][CH:32]=2)[N:27]=1)[CH2:22][CH2:23][CH3:24].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl-].[NH4+]>C1(C)C=CC=CC=1>[CH2:21]([N:25]([C:26]1[CH:35]=[CH:34][C:33]2[C:28](=[C:29]([N+:36]([O-:38])=[O:37])[CH:30]=[CH:31][CH:32]=2)[N:27]=1)[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[C:5]([N+:12]([O-:14])=[O:13])[CH:6]=[CH:7][CH:8]=2)[N:3]=1)[CH2:22][CH2:23][CH3:24]

Participants

7

Reactant 5

HCID 25517Ammonium ChlorideHCID 3194532-Chloro-8-nitroquinoline2×HCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 67057974N-butyl-8-nitro-2-quinoline amine

Product 1

HCID 86257935N-butyl-2,2'-imino-bis(8-nitroquinoline)Yield 38%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

2-chloro-8-nitroquinoline (122 mg; 0.59 mmol) and NaOtBu (77.5 mg; 0.81 mmol) are added to a violet suspension of N-butyl-8-nitro-2-quinoline amine (0.17 g; 0.69 mmol), tris(dibenzylidene-acetone)-dipalladium(0) (13 mg; 0.014 mmol) and rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (17 mg; 0.027 mmol) in 5 ml of toluene under argon. The medium is heated under reflux for 3 hours, then 2-chloro-8-nitroquinoline (22 mg; 0.11 mmol) is again added. Heating is continued for 2 hours 30 minutes then 10 ml of a saturated ammonium chloride solution are added. The product is extracted with 3×30 ml of CH2Cl2 and the solvent is evaporated under reduced pressure. The product is purified by silica gel chromatography, eluted with CH2Cl2/hexane (80/20, v/v) to yield N-butyl-2,2′-imino-bis(8-nitroquinoline) in the form of a yellow powder (0.11 g; 0.26 mmol, yield=38%). NMR-1H (250 MHz, CDCl3) δ, ppm: 8.14 (d, 3J (H, H)=9.0 Hz, 2H); 7.99 (dd, 3J (H, H)=7.5 Hz, 4J (H, H)=1.5 Hz, 2H); 7.93 (dd, 3J (H, H)=8.0 Hz, 4J (H, H)=1.5 Hz, 2H); 7.73 (d, 3J (H, H)=9.0 Hz, 2H); 7.43 (m, 2H); 4.45 (t, 3J (H, H)=7.5 Hz, 2H); 1.83 (m, 2H); 1.47 (m, 2H); 0.98 (t, 3J (H, H)=7.5 Hz, 3H). NMR-13C (63 MHz, CDCl3) δ, ppm: 156.2 (Cq); 146.4 (Cq); 138.7 (Cq); 137.0 (CH); 131.5 (CH); 126.2 (Cq); 124.2 (CH); 122.8 (CH); 117.3 (CH); 48.9 (CH2); 30.4 (CH2); 20.3 (CH2); 13.9 (CH3). MS (CID, NH3): m/z=418 (MH+). Analysis (%) for C22H19N5O4: calculated C, 63.30; H, 4.59; N, 16.78. found C, 63.18; H, 4.49; N, 16.39. UV/vis [CH3OH/20 mM Tris-HCl pH=7.4 containing 150 mM NaCl (1/1, v/v)]: λ nm (ε M−1 cm−1)=210 (91,400), 226 (53,500, shoulder), 270 (42,100), 294 (26,700, shoulder), 383 (28,400).

Workup

  1. temperatureThe medium is heated
  2. temperatureunder reflux for 3 hours
  3. temperatureHeating
  4. extractionThe product is extracted with 3×30 ml of CH2Cl2
  5. customthe solvent is evaporated under reduced pressure
  6. customThe product is purified by silica gel chromatography
  7. washeluted with CH2Cl2/hexane (80/20

Sources & evidence

ORD record
ord-4771c4f25aea411cbb5feb414e5e0d8c
Source dataset
uspto-grants-2012_12
Patent number
US08324196B2

Reaction notes

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