4-Toluenesulfonyl chloride → 10-[(4-methylphenyl)sulfonyl]-10H-pyrazolo[1',5':1,2]imidazo[4,5-c]quinolin-6-amine

HRID 415546Notes

Reaction equation

HRID 415546 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]2[N:15]3[C:16]4[C:25]5[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=5)[N:19]=[CH:18][C:17]=4[N:26]=[C:14]3[CH:13]=[CH:12]2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.ClC1C=C(C=CC=1)C(OO)=O.[NH4+:38].[OH-].C1(C)C=CC(S(Cl)(=O)=O)=CC=1>ClCCCl.C(Cl)(Cl)Cl.O>[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([S:8]([N:11]2[N:15]3[C:16]4[C:25]5[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=5)[N:19]=[C:18]([NH2:38])[C:17]=4[N:26]=[C:14]3[CH:13]=[CH:12]2)(=[O:10])=[O:9])=[CH:6][CH:7]=1

Participants

8

Reactant 4

HCID 73974-Toluenesulfonyl chloride2×HCID 14923Ammonium Hydroxide2×HCID 70297m-Chloroperbenzoic acidHCID 6662030510-[(4-methylphenyl)sulfonyl]-10H-pyrazolo[1',5':1,2]imidazo[4,5-c]quinoline

Product 1

HCID 5785376810-[(4-methylphenyl)sulfonyl]-10H-pyrazolo[1',5':1,2]imidazo[4,5-c]quinolin-6-amine

Reagents, catalysts & solvents 3

HCID 111,2-DichloroethaneSolventHCID 962WaterSolventHCID 6212ChloroformSolvent

Conditions

Temperature
70 °C

Procedure

A solution of 10-[(4-methylphenyl)sulfonyl]-10H-pyrazolo[1′,5′:1,2]imidazo[4,5-c]quinoline (0.55 g, 1.5 mmol) in 1,2-dichloroethane (15 mL) was placed in a 48 mL heavy wall glass pressure flask and treated with 3-chloroperoxybenzoic acid (0.56 g, 2.3 mmol). After 1.5 h the reaction was treated with concentrated NH4OH (5 mL, 30%); the flask was sealed and heated to 70° C. Once at temperature, p-toluenesulfonyl chloride (0.31 g, 1.7 mmol) was quickly added, the flask was resealed and heated to 75° C. After 1 h additional NH4OH (1 mL) and p-toluenesulfonyl chloride (50 mg) were added and the flask heated for another hour. After 2 h total, the flask was cooled to ambient temperature, and the reaction mixture was diluted with chloroform (15 mL) and water (10 mL). The phases were separated and the organic portion was washed with 10% Na2CO3 aqueous solution (10 mL) and water (10 mL). The combined aqueous washes were back-extracted with chloroform (20 mL). The combined organic extracts were washed with brine (10 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure to yield an orange solid. The solid was recrystallized twice from acetonitrile to yield 0.14 g of 10-[(4-methylphenyl)sulfonyl]-10H-pyrazolo[1′,5′:1,2]imidazo[4,5-c]quinolin-6-amine as tan crystals, mp 204-206° C.; 1H NMR (500 MHz, DMSO-d6) δ 8.55-8.53 (m, 1H), 8.13 (d, J=2.3 Hz, 1H), 7.68-7.67 (m, 2H), 7.66-7.64 (m, 2H), 7.41-7.389 (m, 1H), 7.35 (d, J=8.2 Hz, 2H), 7.24 (s, 2H), 6.64 (d, J=2.0 Hz, 1H), 3.29 (s, 3H); 13C NMR (125 MHz, DMSO-d6) δ 148.1, 147.6, 147.4, 142.8, 131.7, 131.3, 131.0, 130.9, 128.4, 127.2, 125.9, 125.5, 123.4, 122.7, 111.3, 90.8, 21.5; MS (APCI) m/z 378.06 (M+H)+; Anal. Calcd for C19H15N5O2S: C, 60.47; H, 4.01; N, 18.56. Found: C, 60.21; H, 3.84; N, 18.52.

Workup

  1. customthe flask was sealed
  2. temperatureheated to 75° C
  3. temperaturethe flask heated for another hour
  4. temperaturethe flask was cooled to ambient temperature
  5. customThe phases were separated
  6. washthe organic portion was washed with 10% Na2CO3 aqueous solution (10 mL) and water (10 mL)
  7. extractionThe combined aqueous washes were back-extracted with chloroform (20 mL)
  8. washThe combined organic extracts were washed with brine (10 mL)
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customto yield an orange solid
  13. customThe solid was recrystallized twice from acetonitrile

Sources & evidence

ORD record
ord-fb44c18a291b49cd9782a4d9eea2527a
Source dataset
uspto-grants-2012_01
Patent number
US08088788B2

Reaction notes

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