Sodium hydride → 3,4-Dihydro-7-(2-hydroxy-3-phenoxypropoxy)-4-iminocoumarin

HRID 1706455Notes

Reaction equation

HRID 1706455 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6](=[NH:13])[CH2:7][C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1.[H-].[Na+].[Na].Cl[CH2:18][CH:19]([OH:28])[CH2:20][O:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>CN(C=O)C>[OH:28][CH:19]([CH2:20][O:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[CH2:18][O:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6](=[NH:13])[CH2:7][C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 943001-Chloro-3-phenoxy-2-propanolHCID 5360545SodiumHCID 1357023124-Amino-2H-1-benzopyran-2,7(3H)-dione

Product 1

HCID 203314213,4-Dihydro-7-(2-hydroxy-3-phenoxypropoxy)-4-iminocoumarinYield 92%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a warm stirred suspension of 3,4-dihydro-7-hydroxy-4-iminocoumarin (17.7 g; 0.1 mole) in dry DMF (75 ml) was added sodium hydride (2.4; 0.1 mole) portionwise and the mixture refluxed for 1.5 hours to complete formation of the sodium salt. A solution of 1-chloro-3-phenoxy-2-propanol (18.7 g; 0.1 mole) in dry DMF (10 mol) was added dropwise at reflux and the mixture stirred at reflux for an additional 4 hours. The solvent was removed in vacuo and water (200 ml) added to the residue. The yellow solid was filtered off, washed well with water and dried in vacuo over P2O5 to give 30.0 g (92%) of crude product which was suitable for most purposes. Recrystallisation from ethyl acetate gave material of m.p. 213°-214°; νmax (mull) 3320, 3200, complex carbonyl region 1690-1590 cm-1,. τ(DSMO); 5.82(5H, m); 5.35(2H, broad exchangeable s); 4.85(1H, s); 3.2-2.52(8H, m with 1 proton removed after D2O exchange); 2.02(1H, d,) (Found: C, 64.52; H, 5.26; N, 3.78; C18H17NO5 0.5 H2O requires; C, 64.28; H, 5.39; N, 4.16%). By the same procedure the compounds in Table III were prepared.

Workup

  1. temperaturethe mixture refluxed for 1.5 hours
  2. temperatureat reflux
  3. stirringthe mixture stirred
  4. temperatureat reflux for an additional 4 hours
  5. customThe solvent was removed in vacuo and water (200 ml)
  6. additionadded to the residue
  7. filtrationThe yellow solid was filtered off
  8. washwashed well with water
  9. dry with materialdried in vacuo over P2O5

Sources & evidence

ORD record
ord-c33aa664010549c8b0ead56128b5a4cf
Source dataset
uspto-grants-1980_06
Patent number
US04207335

Reaction notes

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