Hydrochloric Acid → 2-Hydrazinyl-5-tosyl-5H-pyrrolo[2,3-b]pyrazine

HRID 1969766Notes

Reaction equation

HRID 1969766 reaction equation
Cl.[S:2]([N:12]1[C:16]2=[N:17][CH:18]=[C:19]([NH:21][NH:22]C(OC(C)(C)C)=O)[N:20]=[C:15]2[CH:14]=[CH:13]1)([C:5]1[CH:11]=[CH:10][C:8]([CH3:9])=[CH:7][CH:6]=1)(=[O:4])=[O:3].S(N1C2=NC=C(N(C(OC(C)(C)C)=O)N)N=C2C=C1)(C1C=CC(C)=CC=1)(=O)=O.C([O-])(O)=O.[Na+]>O1CCOCC1.CCOC(C)=O>[NH:21]([C:19]1[N:20]=[C:15]2[CH:14]=[CH:13][N:12]([S:2]([C:5]3[CH:11]=[CH:10][C:8]([CH3:9])=[CH:7][CH:6]=3)(=[O:3])=[O:4])[C:16]2=[N:17][CH:18]=1)[NH2:22]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 516892Sodium BicarbonateHCID 58009788HCID 58009788, compoundHCID 580099261,1-Dimethylethyl 2-[5-[(4-methylphenyl)sulfonyl]-5H-pyrrolo[2,3-b]pyrazin-2-yl]hydrazinecarboxylate

Product 1

HCID 580098102-Hydrazinyl-5-tosyl-5H-pyrrolo[2,3-b]pyrazineYield 57%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
60 °C

Procedure

HCl (4 M in 1,4-dioxane, 226 mL, 902 mmol) was added to a mixture of tert-butyl 2-(5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)hydrazinecarboxylate and tert-butyl 1-(5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)hydrazinecarboxylate (49.2 g, 122 mmol) in 1,4-dioxane (290 mL). The reaction was heated at about 60° C. for about 2.5 h and then cooled to about 15-20° C. The solid was collected by vacuum filtration, washed with EtOAc (3×50 mL), and then triturated with Et2O (60 mL), collected by vacuum filtration and dried to a constant weight under vacuum to yield 35.6 g of crude solid. The solid was stirred with a mixture of saturated aqueous NaHCO3 and EtOAc (1:1, 400 mL). After about 1 h, the solid was collected by vacuum filtration, washed with ice cold water (3×30 mL) and EtOAc (3×30 mL), and dried in a vacuum oven to a constant weight to afford 2-hydrazinyl-5-tosyl-5H-pyrrolo[2,3-b]pyrazine as a tan solid (21.2 g, 57%): LC/MS (Table 1, Method a) Rt=1.88 min; MS m/z: 304 (M+H)+.

Workup

  1. temperaturecooled to about 15-20° C
  2. filtrationThe solid was collected by vacuum filtration
  3. washwashed with EtOAc (3×50 mL)
  4. customtriturated with Et2O (60 mL)
  5. filtrationcollected by vacuum filtration
  6. customdried to a constant weight under vacuum
  7. customto yield 35.6 g of crude solid
  8. filtrationthe solid was collected by vacuum filtration
  9. washwashed with ice cold water (3×30 mL) and EtOAc (3×30 mL)
  10. customdried in a vacuum oven to a constant weight

Sources & evidence

ORD record
ord-b81fa58635494440b09c125b65d05b42
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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