Triethylamine → Ethyl 2-hydroxy-5-[[4-(4-methylphenoxysulfonyl)phenyl]ethynyl]benzoate

HRID 1653917

Reaction equation

HRID 1653917 reaction equation
[OH:1][C:2]1[CH:12]=[CH:11][C:10](I)=[CH:9][C:3]=1[C:4]([O:6][CH2:7][CH3:8])=[O:5].[C:14]([C:16]1[CH:21]=[CH:20][C:19]([S:22]([O:25][C:26]2[CH:31]=[CH:30][C:29]([CH3:32])=[CH:28][CH:27]=2)(=[O:24])=[O:23])=[CH:18][CH:17]=1)#[CH:15].C(N(CC)CC)C.I.C(N(CC)CC)C>O1CCCC1.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>[OH:1][C:2]1[CH:12]=[CH:11][C:10]([C:15]#[C:14][C:16]2[CH:17]=[CH:18][C:19]([S:22]([O:25][C:26]3[CH:31]=[CH:30][C:29]([CH3:32])=[CH:28][CH:27]=3)(=[O:23])=[O:24])=[CH:20][CH:21]=2)=[CH:9][C:3]=1[C:4]([O:6][CH2:7][CH3:8])=[O:5]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 10889681Triethylamine hydroiodideHCID 13013012Ethyl 2-hydroxy-5-iodobenzoateHCID 194234104-Methylphenyl 4-ethynylbenzenesulfonate

Product 1

HCID 19423388Ethyl 2-hydroxy-5-[[4-(4-methylphenoxysulfonyl)phenyl]ethynyl]benzoate

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

Ethyl 2-hydroxy-5-iodobenzoate (58.5 g, 0.2 mol), 4-methylphenyl 4-ethynylbenzenesulfonate (54.4 g, 0.2 mol) and triethylamine (40 g, 0.4 mol) were dissolved in tetrahydrofuran (100 g). The solution was heated to 50° C. and dichlorobis(triphenylphosphine)palladium (0.5 g, 0.72 mmol) and copper(I)iodide (1 g, 5.2 mmol) were) added simultaneously with stirring. The reaction mixture turned dark and triethylamine hydroiodide started to precipitate after about 10 min. After keeping at 45° C. for 45 min, the suspension was poured into dilute hydrochloric acid and the mixture was extracted with toluene. The toluene solution was evaporated to dryness. The residue was triturated with acetonitrile, filtered off and dried. Yield 73 g, (84%). The pooled material from several batches (270 g) was recrystallized from acetonitrile (1.2 l). Yield 250 g.

Workup

  1. additionadded simultaneously
  2. customto precipitate after about 10 min
  3. additionthe suspension was poured into dilute hydrochloric acid
  4. extractionthe mixture was extracted with toluene
  5. customThe toluene solution was evaporated to dryness
  6. customThe residue was triturated with acetonitrile
  7. filtrationfiltered off
  8. customdried
  9. customThe pooled material from several batches (270 g) was recrystallized from acetonitrile (1.2 l)

Sources & evidence

ORD record
ord-27359a37178a4bbab4b2cf9f9c3d5332
Source dataset
uspto-grants-1995_04
Patent number
US05403930

Linked notes

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