Diethyl Malonate → HCID 18349838, compound

HRID 2268221Notes

Reaction equation

HRID 2268221 reaction equation
[H-].[Na+].C1COCC1.C(OCC)(=O)CC(OCC)=O.[CH3:19][C:20]1[C:21](/[CH:34]=[CH:35]/[C:36]([O:38][C:39]2[CH:50]=[CH:49][CH:48]=[CH:47][C:40]=2[C:41]([O:43]CC=C)=[O:42])=[O:37])=[CH:22][C:23]2[C:24]([CH3:33])([CH3:32])[CH2:25][CH2:26][C:27]([CH3:31])([CH3:30])[C:28]=2[CH:29]=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[CH3:19][C:20]1[C:21](/[CH:34]=[CH:35]/[C:36]([O:38][C:39]2[CH:50]=[CH:49][CH:48]=[CH:47][C:40]=2[C:41]([OH:43])=[O:42])=[O:37])=[CH:22][C:23]2[C:24]([CH3:33])([CH3:32])[CH2:25][CH2:26][C:27]([CH3:30])([CH3:31])[C:28]=2[CH:29]=1

Participants

7

Reactant 4

HCID 7761Diethyl MalonateHCID 8028Tetrahydrofuran2×HCID 24758Sodium hydrideHCID 86757637HCID 86757637, compound

Product 1

HCID 18349838HCID 18349838, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Procedure

117 mg (4.9 mmol) of sodium hydride (80% in oil) and 15 ml of THF are introduced into a round-bottomed flask under a stream of nitrogen. 540 μl (3.6 mmol) of diethyl malonate are then added dropwise and the mixture is stirred until the evolution of gas has ceased. This solution is introduced dropwise into a mixture of 1.4 g (3.24 mmol) of allyl (E)-2-[3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)acryloyloxy]benzoate, 20 ml of THF and 187 mg of tetrakis(triphenylphosphine)palladium(0) and stirred at room temperature for three hours. The reaction medium is poured into water and extracted with ethyl ether, and the organic phase is separated out after settling has taken place, dried over magnesium sulphate and evaporated. The residue obtained is purified by chromatography on a column of silica eluted with a mixture of heptane and ethyl acetate (95/5). After evaporating the solvents, 800 mg (63%) of (E)-2-[3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)acryloyloxy]benzoic acid, with a melting point of 137-8° C., are collected.

Workup

  1. stirringstirred at room temperature for three hours
  2. extractionextracted with ethyl ether
  3. customthe organic phase is separated out after settling
  4. dry with materialdried over magnesium sulphate
  5. customevaporated
  6. customThe residue obtained
  7. customis purified by chromatography on a column of silica
  8. washeluted with a mixture of heptane and ethyl acetate (95/5)
  9. customAfter evaporating the solvents, 800 mg (63%) of (E)-2-[3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)acryloyloxy]benzoic acid
  10. customwith a melting point of 137-8° C., are collected

Sources & evidence

ORD record
ord-7f3ad30656064f54ab3f876343e682c0
Source dataset
uspto-grants-2001_12
Patent number
US06326510B1

Reaction notes

Loading…