Methyl 4-ethynylbenzoate → HCID 9863994, compound

HRID 1018109Notes

Reaction equation

HRID 1018109 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[C:11]([CH2:13][O:14][CH3:15])([CH3:12])[CH2:10][CH2:9][CH2:8][S:7][C:6]=2[CH:16]=1.C[O:18][C:19](=[O:28])[C:20]1[CH:25]=[CH:24][C:23]([C:26]#[CH:27])=[CH:22][CH:21]=1>N1CCCCC1.[Cu]I.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.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:15][O:14][CH2:13][C:11]1([CH3:12])[CH2:10][CH2:9][CH2:8][S:7][C:6]2[CH:16]=[C:2]([C:27]#[C:26][C:23]3[CH:24]=[CH:25][C:20]([C:19]([OH:28])=[O:18])=[CH:21][CH:22]=3)[CH:3]=[CH:4][C:5]1=2

Participants

7

Reactant 2

HCID 640163Methyl 4-ethynylbenzoateHCID 18406081HCID 18406081, compound

Product 1

HCID 9863994HCID 9863994, compoundYield 46.3%

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8082PiperidineSolvent2×

Conditions

Temperature
80 °C

Procedure

To 478 mg (1.59 mmol) of 8-bromo-5-methoxymethyl-5-methyl-2,3,4,5-tetrahydrobenzo[b]thiepine, dissolved in 2.9 ml of piperidine, was added successively 4.8 mg (0.02 eq.) of CuI, 7.0 mg (0.02 eq.) of Ph3P, and 24.1 mg (0.01 eq.) of (Ph3P)4Pd. After heating to 80° C., a solution of 508 mg (2 eq.) of 4-ethynyl-benzoic acid methyl ester in 2.8 ml of piperidine was added within 2 h via dropping funnel and then kept at this temperature for 3 additional h. After cooling, the reaction mixture was poured onto crushed ice/ HCl diluted, extracted with diethylether, the organic phase was washed with water, dried over magnesium sulfate, filtrated and evaporated to dryness. Flash chromatography (SiO2, hexane/ethylacetate 95/5) yielded 270 mg of the title compound as colorless oil.

Workup

  1. temperatureAfter cooling
  2. additionthe reaction mixture was poured
  3. additiondiluted
  4. extractionextracted with diethylether
  5. washthe organic phase was washed with water
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltrated
  8. customevaporated to dryness

Sources & evidence

ORD record
ord-ab8bde07afa641e7973188a8bd98d2e4
Source dataset
uspto-grants-2002_11
Patent number
US06479670B1

Reaction notes

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