Propargyl alcohol → 1-Chloro-4-(2-propyn-1-yloxy)phthalazine

HRID 1471335Notes

Reaction equation

HRID 1471335 reaction equation
[CH2:1]([OH:4])[C:2]#[CH:3].[Na].Cl[C:7]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[C:10]([Cl:17])=[N:9][N:8]=1>>[Cl:17][C:10]1[C:11]2[C:16](=[CH:15][CH:14]=[CH:13][CH:12]=2)[C:7]([O:4][CH2:1][C:2]#[CH:3])=[N:8][N:9]=1

Participants

4

Reactant 3

HCID 7859Propargyl alcoholHCID 784901,4-DichlorophthalazineHCID 5360545Sodium

Product 1

HCID 593730081-Chloro-4-(2-propyn-1-yloxy)phthalazineYield 15%

Conditions

Temperature
127 °C

Procedure

To 2-propynol (3 mL) is slowly added sodium (70 mg, 3.04 mmol) followed by 1,4-dichlorophthalazine (400 mg, 2.01 mmol). The brown suspension obtained is stirred under argon for 2 min and then heated at 121-133° C. for 2 h. Excess 2-propynol is removed under vacuum, and the residue is diluted with cold water and then extracted with CHCl3 (120 mL). The extract is washed (brine) and dried. After solvent removal at reduced pressure, the residue is purified on silica gel (25% to 50% ethyl acetate/hexane) to give 66 mg (15%) of 2 as a cream solid, mp 134-136° C. IR 2882, 1404, 1292 cm−1; 1H NMR (CDCl3) δ 2.61 (t, J=2.4 Hz, 1H, C≡CH), 5.33 (d, J=2.4 Hz, 2H, CH2C≡CH), 7.94-8.04 (m, 2H, 6,7-PhthH), 8.24 (m, 5-PhthH), 8.31 ppm (m, 8-PhthH).

Workup

  1. customThe brown suspension obtained
  2. customExcess 2-propynol is removed under vacuum
  3. additionthe residue is diluted with cold water
  4. extractionextracted with CHCl3 (120 mL)
  5. washThe extract is washed (brine)
  6. customdried
  7. customAfter solvent removal at reduced pressure
  8. customthe residue is purified on silica gel (25% to 50% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-48644ac2bb2f47b2b297d5240ca73e69
Source dataset
uspto-grants-2015_04
Patent number
US09012217B2

Reaction notes

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