Triethylamine → Methyl 2-hydroxy-4-[3-hydroxy-3-(4,4-dimethylchroman-8-yl)prop-1-ynyl]benzoate

HRID 22990Notes

Reaction equation

HRID 22990 reaction equation
[C:1]([CH:3]([C:5]1[CH:6]=[CH:7][CH:8]=[C:9]2[C:14]=1[O:13][CH2:12][CH2:11][C:10]2([CH3:16])[CH3:15])[OH:4])#[CH:2].[OH:17][C:18]1[CH:27]=[C:26](I)[CH:25]=[CH:24][C:19]=1[C:20]([O:22][CH3:23])=[O:21].C(N(CC)CC)C>O.C(OCC)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I>[OH:17][C:18]1[CH:27]=[C:26]([C:2]#[C:1][CH:3]([OH:4])[C:5]2[CH:6]=[CH:7][CH:8]=[C:9]3[C:14]=2[O:13][CH2:12][CH2:11][C:10]3([CH3:16])[CH3:15])[CH:25]=[CH:24][C:19]=1[C:20]([O:22][CH3:23])=[O:21]

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 11380407Methyl 4-iodosalicylateHCID 22592658alpha-Ethynyl-4,4-dimethylchroman-8-methanol

Product 1

HCID 22592586Methyl 2-hydroxy-4-[3-hydroxy-3-(4,4-dimethylchroman-8-yl)prop-1-ynyl]benzoate

Reagents, catalysts & solvents 4

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

3.00 g (13.9 mmol) of α-ethynyl-4,4-dimethylchroman-8-methanol, 3.90 g (13.9 mmol) of methyl 2-hydroxy-4-iodobenzoate and 100 ml of triethylamine are introduced into a three-necked flask. The reaction mixture is degassed with nitrogen for 30 minutes and then 780 mg (1.1 mmol) of bis(triphenylphosphine)-palladium(II) chloride and 320 mg (1.7 mmol) of copper iodide are successively added. The reaction mixture is stirred at room temperature for 4 hours and is evaporated to dryness and the residue obtained is taken up in water and ethyl ether. The organic phase is separated by settling, dried over magnesium sulphate and evaporated. The residue obtained is purified by chromatography on a silica column eluted with a mixture composed of 50% ethyl acetate and 50% heptane. 2.85 g (56%) of methyl 2-hydroxy-4-[3-hydroxy-3-(4,4-dimethylchroman-8-yl)prop-1-ynyl]benzoate are collected in the form of a white solid with a melting point of 122-123° C.

Workup

  1. customThe reaction mixture is degassed with nitrogen for 30 minutes
  2. customis evaporated to dryness
  3. customthe residue obtained
  4. customThe organic phase is separated
  5. dry with materialdried over magnesium sulphate
  6. customevaporated
  7. customThe residue obtained
  8. customis purified by chromatography on a silica column
  9. washeluted with a mixture
  10. custom2.85 g (56%) of methyl 2-hydroxy-4-[3-hydroxy-3-(4,4-dimethylchroman-8-yl)prop-1-ynyl]benzoate are collected in the form of a white solid with a melting point of 122-123° C.

Sources & evidence

ORD record
ord-43c799283167438b9340da17161c31a5
Source dataset
uspto-grants-2005_02
Patent number
US06849658B2

Reaction notes

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