Sodium Hydroxide → 10H-pyrazolo[1',5':1,2]imidazo[4,5-c]quinoline

HRID 415544Notes

Reaction equation

HRID 415544 reaction equation
C(OC(OCC)[CH2:5][C:6]([NH:8][C:9]1[CH:10]=[N:11][C:12]2[C:17]([C:18]=1[NH:19][NH:20][C:21](OC(C)(C)C)=O)=[CH:16][CH:15]=[CH:14][CH:13]=2)=O)C.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.[OH-].[Na+]>C(O)CC.Cl.O>[CH:16]1[CH:15]=[CH:14][CH:13]=[C:12]2[C:17]=1[C:18]1[N:19]3[NH:20][CH:21]=[CH:5][C:6]3=[N:8][C:9]=1[CH:10]=[N:11]2

Participants

7

Reactant 3

HCID 14798Sodium HydroxideHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 66619949tert-butyl N'-[3-(3,3-diethoxypropionylamino)quinolin-4-yl]hydrazinecarboxylate

Product 1

HCID 6661988810H-pyrazolo[1',5':1,2]imidazo[4,5-c]quinolineYield 33.7%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 10311-PropanolSolvent

Conditions

Temperature
125 °C

Procedure

A solution of tert-butyl N′-[3-(3,3-diethoxypropionylamino)quinolin-4-yl]-hydrazinecarboxylate (13.75 g, 32.9 mmol) and pyridinium p-toluenesulfonate (0.206 g, 0.082 mmol) in 1-propanol (250 mL) was placed under a nitrogen atmosphere and heated to 125° C. After 4 h, the reaction was cooled to ambient temperature and concentrated under reduced pressure to yield a dark red oily solid. This material was suspended in HCl (55 mL, 3 M in ethanol) and heated to 100° C. After 1.5 h, the reaction mix was cooled to ambient temperature and concentrated under reduced pressure to give a brown solid. The solid was suspended in water (50 mL), stirred vigorously, and neutralized with drop-wise addition of 10% NaOH aqueous solution until the pH of the liquid was 8. The aqueous mixture was transferred to a separatory funnel and extracted with chloroform (4×25 mL). The combined organic extracts were concentrated under reduced pressure to give a dark red solid. This solid was purified by prep. HPLC (350 g silica gel eluted with 1-20% CMA in chloroform) to give a dark red solid. This material was triturated with ether (75 mL) and filtered to yield 2.31 g of 10H-pyrazolo[1′,5′:1,2]imidazo[4,5-c]quinoline as a red solid.

Workup

  1. temperaturethe reaction was cooled to ambient temperature
  2. concentrationconcentrated under reduced pressure
  3. customto yield a dark red oily solid
  4. temperatureheated to 100° C
  5. waitAfter 1.5 h
  6. additionthe reaction mix
  7. temperaturewas cooled to ambient temperature
  8. concentrationconcentrated under reduced pressure
  9. customto give a brown solid
  10. customThe aqueous mixture was transferred to a separatory funnel
  11. extractionextracted with chloroform (4×25 mL)
  12. concentrationThe combined organic extracts were concentrated under reduced pressure
  13. customto give a dark red solid
  14. customThis solid was purified by prep
  15. washHPLC (350 g silica gel eluted with 1-20% CMA in chloroform)
  16. customto give a dark red solid
  17. customThis material was triturated with ether (75 mL)
  18. filtrationfiltered

Sources & evidence

ORD record
ord-587c3f6dbac941e4822003ea6e89e9df
Source dataset
uspto-grants-2012_01
Patent number
US08088788B2

Reaction notes

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