4-Toluenesulfonyl chloride → HCID 10404184, compound

HRID 1373917Notes

Reaction equation

HRID 1373917 reaction equation
[CH2:1]([O:3][CH2:4][C:5]1[N:6]([NH:18][CH:19]([CH2:22][CH3:23])[CH2:20][CH3:21])[C:7]2[C:16]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[N:10]=[CH:9][C:8]=2[N:17]=1)[CH3:2].C1C=C(Cl)C=C(C(OO)=O)C=1.[NH4+:35].[OH-].C1(C)C=CC(S(Cl)(=O)=O)=CC=1>C(Cl)Cl.O.CO.C(Cl)(Cl)Cl>[CH2:1]([O:3][CH2:4][C:5]1[N:6]([NH:18][CH:19]([CH2:20][CH3:21])[CH2:22][CH3:23])[C:7]2[C:16]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[N:10]=[C:9]([NH2:35])[C:8]=2[N:17]=1)[CH3:2]

Participants

9

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 14923Ammonium HydroxideHCID 70297m-Chloroperbenzoic acidHCID 21075786HCID 21075786, compound

Product 1

HCID 10404184HCID 10404184, compound

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of N-(2-ethoxymethyl-1H-imidazo[4,5-c]quinolin-1-yl)(1-ethylpropyl)amine (1.01 g, 3.23 mmol) in 30 mL of CH2Cl2 was treated with MCPBA (1.04 g, 4.20 mmol, 77% max). After 1.5 h the reaction mixture was treated with 15 mL of concentrated NH4OH solution and p-toluenesulfonyl chloride (0.65 g, 3.39 mmol). After 30 min, the reaction mixture was diluted with CH2Cl2 and water and the phases were separated. The organic portion was washed with 2% Na2CO3 solution and water. The combined aqueous washes were back extracted with CHCl3 (2×). The combined organic portions were washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure to yield a light yellow foam. Chromatography (SiO2, 97:3 CHCl3:MeOH) gave a white foam. The foam was triturated with CH2Cl2/hexanes and filtered to give 2-ethoxymethyl-N1-(1-ethylpropyl)-1H-imidazo[4,5-c]quinoline-1,4-diamine (0.652 g) as a white solid. mp 125–128° C.; 1H NMR (300 MHz, CDCl3) δ 8.66 (dd, J=8.3, 1.1 Hz, 1H), 7.77 (dd, J=7.6, 0.8 Hz, 1H), 7.55–7.48 (m, 1H), 7.33–7.26 (m, 1H), 5.66, (d, J=3.0 Hz, 1H), 5.41 (s, 2H), 4.87 (s, 2H), 3.64 (q, J=7.0 Hz, 2H), 3.32–3.23 (m, 1H), 1.70–1.56 (m, 2H), 1.55–1.41 (m, 2H), 1.27 (t, J=7.1 Hz, 3H), 0.94 (t, J=7.5 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 151.5, 149.1, 145.4, 135.0, 132.4, 128.1, 126.9, 124.1, 122.2, 122.0, 115.9, 67.2, 66.2, 64.0, 24.5, 15.5, 10.2; MS (APCI) m/z 328 (M+H)+; Anal. Calcd for C18H25N5O: C, 66.03; H, 7.70; N, 21.39; Found: C, 65.64; H, 7.89; N, 21.02.

Workup

  1. customthe phases were separated
  2. washThe organic portion was washed with 2% Na2CO3 solution and water
  3. extractionThe combined aqueous washes were back extracted with CHCl3 (2×)
  4. washThe combined organic portions were washed with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto yield a light yellow foam
  9. customThe foam was triturated with CH2Cl2/hexanes
  10. filtrationfiltered

Sources & evidence

ORD record
ord-78310deca949462d8346a144bcb81933
Source dataset
uspto-grants-2007_01
Patent number
US07163947B2

Reaction notes

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