Triethylamine → Methyl 2-hydroxy-4-[3-hydroxy-3-(4,4-dimethylthiochroman-6-yl)-1-propynyl]benzoate

HRID 840450Notes

Reaction equation

HRID 840450 reaction equation
[C:1]([CH:3]([C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][CH:14]=1)[S:11][CH2:10][CH2:9][C:8]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]=[C:7]3[C:12](=[CH:13][CH:14]=2)[S:11][CH2:10][CH2:9][C:8]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 22619414alpha-Ethynyl-4,4-dimethyl-6-thiochromanmethanol

Product 1

HCID 22619455Methyl 2-hydroxy-4-[3-hydroxy-3-(4,4-dimethylthiochroman-6-yl)-1-propynyl]benzoate

Reagents, catalysts & solvents 4

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

Procedure

2.5 g (10.8 mmol) of α-ethynyl-4,4-dimethyl-6-thiochromanmethanol, 3 g (10.8 mmol) of methyl 2-hydroxy-4-iodobenzoate and 50 ml of triethylamine were introduced into a three-necked flask. The reaction mixture was degassed with nitrogen for 30 min. and then 600 mg (0.86 mmol) of bis(triphenylphosphine)palladium(II) chloride and 240 mg (1.3 mmol) of copper iodide were added successively. Stirring was carried out at room temperature for four hours, the reaction mixture was evaporated to dryness and the residue obtained was taken up in water and ethyl ether. The organic phase was separated by settling, dried over magnesium sulfate and evaporated. The residue obtained was purified by chromatography on a silica column eluted with dichloromethane. 3.2 g (80%) of methyl 2-hydroxy-4-[3-hydroxy-3-(4,4-dimethylthiochroman-6-yl)-1-propynyl]benzoate, with a melting point of 105°-106° C., were recovered.

Workup

  1. customThe reaction mixture was degassed with nitrogen for 30 min.
  2. customthe reaction mixture was evaporated to dryness
  3. customthe residue obtained
  4. customThe organic phase was separated
  5. dry with materialdried over magnesium sulfate
  6. customevaporated
  7. customThe residue obtained
  8. customwas purified by chromatography on a silica column
  9. washeluted with dichloromethane
  10. custom3.2 g (80%) of methyl 2-hydroxy-4-[3-hydroxy-3-(4,4-dimethylthiochroman-6-yl)-1-propynyl]benzoate, with a melting point of 105°-106° C., were recovered

Sources & evidence

ORD record
ord-9fee73dfde774808a7d230800c4bdfc1
Source dataset
uspto-grants-2002_04
Patent number
US06368608B1

Reaction notes

Loading…