Diisopropylamine → HCID 68953726, compound

HRID 2384911Notes

Reaction equation

HRID 2384911 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)=[CH:8][C:9]=1Br)=[O:4].[CH3:18][Si:19]([C:22]#[CH:23])([CH3:21])[CH3:20].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(NC(C)C)(C)C>CN(C=O)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.CCOCC>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)=[CH:8][C:9]=1[C:23]#[C:22][Si:19]([CH3:21])([CH3:20])[CH3:18])=[O:4]

Participants

9

Reactant 4

HCID 7912DiisopropylamineHCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 689498673-Bromo-5-(4-chloro-phenyl)-thiophene-2-carboxylic acid methyl ester

Product 1

HCID 68953726HCID 68953726, compoundYield 57.3%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

React 3-bromo-5-(4-chloro-phenyl)-thiophene-2-carboxylic acid methyl ester (0.66 g, 2.0 mmol) with (trimethylsilyl)acetylene (216 mg, 2.2 mmol), Pd(PPh3)2Cl2 (140 mg, 0.20 mmol), CuI (38.2 mg, 0.20 mmol), PPh3 (210 mg, 0.80 mmol) and diisopropyl amine (3.3 mL, 30 mmol) in DMF (1.0 mL) at 120° C. for 30 min in a microwave reactor. Treat the mixture with Et2O (15 mL), filter, pour into 0.1 M HCl (15 mL), and extract with Et2O (3×10 mL). Wash the combined organic layers with saturated NaHCO3 (20 mL) and water (20 mL). Purify the crude material by chromatography, eluting with 30% CH2Cl2/hexane to give 400 mg (57%) of the title compound. LC-MS/ES m/z (35Cl) 349.0 [M+H]+.

Workup

  1. filtrationfilter
  2. additionpour into 0.1 M HCl (15 mL)
  3. extractionextract with Et2O (3×10 mL)
  4. washWash the combined organic layers with saturated NaHCO3 (20 mL) and water (20 mL)
  5. customPurify the crude material by chromatography
  6. washeluting with 30% CH2Cl2/hexane

Sources & evidence

ORD record
ord-aa1d3fe9f1ff464fa6a3eb25bd687d8a
Source dataset
uspto-grants-2012_09
Patent number
US08263772B2

Reaction notes

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