Sulfuric Acid → 4-(4-Pyridylmethyl)-1(2H)-phtalazinone

HRID 2181383Notes

Reaction equation

HRID 2181383 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([CH:7]=O)=[CH:3][CH:2]=1.C([N:11]([CH2:14][CH3:15])CC)C.O.[NH2:17]N.C(O[C:23](=[O:25])[CH3:24])(=O)C.OS(O)(=O)=O.[CH2:31]1[CH2:35]O[CH2:33][CH2:32]1>O>[N:1]1[CH:2]=[CH:3][C:4]([CH2:7][C:14]2[C:15]3[C:24](=[CH:33][CH:32]=[CH:31][CH:35]=3)[C:23](=[O:25])[NH:17][N:11]=2)=[CH:5][CH:6]=1

Participants

8

Reactant 6

HCID 1118Sulfuric AcidHCID 7918Acetic AnhydrideHCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 133894-PyridinecarboxaldehydeHCID 24654Hydrazine hydrate (1:1)

Product 1

HCID 7899544-(4-Pyridylmethyl)-1(2H)-phtalazinone

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
40 °C

Procedure

500 g of phthalidyl-3-triphenylphosphonium chloride (1.160 mol) is suspended in 2250 ml of tetrahydrofaran (THF). At 5° C., 110.7 ml of pyridine-4-aldehyde (124.2 g, 1.160 mol) is added, and then 161.7 ml of triethylamine (117.4 g, 1.160 mol) is metered into the white suspension. After the addition is completed, the reaction mixture is stirred for 1 hour at 40° C., then mixed with 62.0 ml of hydrazine hydrate (63.9 g, 1.276 mol) and stirred for 8 hours at 70° C. Then, 32.7 ml of acetic acid anhydride (35.5 g, 0.348 mol) is added, and the stirring is continued for 2.5 hours at 20° C. Then, the reaction mixture is mixed first with 1500 ml of water, then with 367 ml of 4 M H2SO4 solution. About 2500 ml of THF/water is distilled off from this reaction solution in a vacuum. The suspension that is obtained is filtered via a glass frit. The filtrate is mixed with 50% sodium hydroxide solution up to a pH of 8.0 (about 185 ml). The precipitated product is filtered off, washed with 450 ml of water and dried at 60° C. 264.2 g (96% of theory) of a slightly yellowish solid is obtained.

Workup

  1. additionAfter the addition
  2. stirringstirred for 8 hours at 70° C
  3. waitthe stirring is continued for 2.5 hours at 20° C
  4. distillationAbout 2500 ml of THF/water is distilled off from this reaction solution in a vacuum
  5. customThe suspension that is obtained
  6. filtrationis filtered via a glass frit
  7. additionThe filtrate is mixed with 50% sodium hydroxide solution up to a pH of 8.0 (about 185 ml)
  8. filtrationThe precipitated product is filtered off
  9. washwashed with 450 ml of water
  10. customdried at 60° C
  11. custom264.2 g (96% of theory) of a slightly yellowish solid is obtained

Sources & evidence

ORD record
ord-2574804bf243425785814ef179cde6c1
Source dataset
uspto-grants-2005_05
Patent number
US06891041B2

Reaction notes

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