Hydrazine hydrate (1:1) → HCID 178441945, compound

HRID 255014Notes

Reaction equation

HRID 255014 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][N:6]=[CH:7]2.[N:12]([O-])=O.[Na+].O=[C:17]([CH2:21][CH2:22][CH:23]=[CH2:24])[CH2:18][C:19]#[N:20].O.[NH2:26][NH2:27]>S(=O)(=O)(O)O.C(O)(=O)C.O.C(O)C>[CH2:21]([C:17]1[C:18](=[N:12][NH:1][C:2]2[CH:11]=[CH:10][CH:9]=[C:8]3[C:3]=2[CH:4]=[CH:5][N:6]=[CH:7]3)[C:19]([NH2:20])=[N:26][N:27]=1)[CH2:22][CH:23]=[CH2:24]

Participants

9

Reactant 4

HCID 24654Hydrazine hydrate (1:1)HCID 707665-AminoisoquinolineHCID 23668193Sodium NitriteHCID 24975800HCID 24975800, compound

Product 1

HCID 178441945HCID 178441945, compoundYield 26.1%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 962WaterSolventHCID 1118Sulfuric AcidSolvent

Procedure

5-Aminoisoquinoline (175 mg, 1.2 mmole) was mixed in 1.5 mL of 4 M sulfuric acid in an ice bath. To this mixture was slowly added 0.3 mL of an aqueous solution of NaNO2 (80 mg, 1.16 mmole). The resulting diazonium solution was then added to a mixture of 3-oxohept-6-enenitrile (108 mg, 0.88 mmole) obtained as described in Example 22 and NaOAc trihydrate (1.7 g, 12.5 mmole) dissolved in 3 mL of acetic acid and 1.5 mL of water. The mixture was extracted with ethyl acetate. The extracts were dried over Na2SO4, filtered, and evaporated in vacuo to give a sticky residue which was then treated with hydrazine hydrate (36 mg, 0.72 mmole) in 10 mL of ethanol at refluxing temperature for 4 hours. The solvent was removed in vacuo and the brownish oil residue obtained was purified by preparative TLC (CH2Cl2:MeOH=15:1) to yield 55 mg (22%) of the title compound as an orange yellow powder. MS (m/z, ES+): 293 (M+1, 100%), 294 (M+2, 19%); 1H NMR (ppm, 200 MHz, DMSO-d6) δ 9.39 (s, 1H), 8.58 (d, 1H), 8.20 (d, 1H), 8.05 (d, 1H), 7.91 (d, 1H), 7.75 (t, 1H), 6.79 (br s, 2H), 5.90 (m, 1H), 5.20-4.80 (m, 2H), 2.93 (t, 2H), 2.49 (m, 2H).

Workup

  1. customobtained
  2. extractionThe mixture was extracted with ethyl acetate
  3. dry with materialThe extracts were dried over Na2SO4
  4. filtrationfiltered
  5. customevaporated in vacuo
  6. customto give a sticky residue which
  7. temperatureat refluxing temperature for 4 hours
  8. customThe solvent was removed in vacuo
  9. customthe brownish oil residue obtained
  10. customwas purified by preparative TLC (CH2Cl2:MeOH=15:1)

Sources & evidence

ORD record
ord-9ea148bd2df6487eb73ab849aaf4d2a7
Source dataset
uspto-grants-2011_01
Patent number
US07875728B2

Reaction notes

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