Tributylvinyltin → HCID 59164494, compound

HRID 1894017Notes

Reaction equation

HRID 1894017 reaction equation
[CH3:1][O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8](I)[C:7]([C:11]([F:14])([F:13])[F:12])=[CH:6][C:5]=1[NH:15][C:16](=[O:18])[CH3:17].[CH2:20]([Sn](CCCC)(CCCC)C=C)[CH2:21]CC.O.O.[F-].[K+]>C1(C)C=CC=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8]([CH:20]=[CH2:21])[C:7]([C:11]([F:14])([F:13])[F:12])=[CH:6][C:5]=1[NH:15][C:16](=[O:18])[CH3:17]

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 23708904Potassium fluoride dihydrateHCID 591644332-Acetylamino-5-iodo-4-trifluoromethyl-benzoic acid methyl ester

Product 1

HCID 59164494HCID 59164494, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Procedure

A solution of 2-acetylamino-5-iodo-4-trifluoromethyl-benzoic acid methyl ester (18.0 g, 46.5 mmol) in dry toluene (72 mL) was degassed for 5 min at the ultrasound bath. The solution was then treated with tributyl(vinyl)tin (28 mL, 93 mmol) and tetrakis-(triphenylphosphine)-palladium (2.77 g, 2.33 mmol), and heated to reflux for 2 h. The mixture was allowed to cool to r.t. and potassium fluoride dihydrate (22 g) was then added. This suspension was stirred for 30 min at r.t. and was then filtered on a short pad of silica gel. The filter was washed with diethyl ether and the filtrate was concentrated in vacuo. The crude product was taken up in hexanes and the suspension was filtered. The filtrate was concentrated in vacuo again and allowed to stand at r.t. for 7 d. The solid formed was filtered, washed with hexanes and combined with the product previously isolated to give 2-acetylamino-4-trifluoromethyl-5-vinyl-benzoic acid methyl ester (10.0 g, 34.8 mmol, 75%) as a beige solid, m.p. 79-81° C., ESI-MS: m/z 288 [M+H]+.

Workup

  1. temperatureheated
  2. temperatureto reflux for 2 h
  3. filtrationwas then filtered on a short pad of silica gel
  4. washThe filter was washed with diethyl ether
  5. concentrationthe filtrate was concentrated in vacuo
  6. filtrationthe suspension was filtered
  7. concentrationThe filtrate was concentrated in vacuo again
  8. waitto stand at r.t. for 7 d
  9. customThe solid formed
  10. filtrationwas filtered
  11. washwashed with hexanes
  12. custompreviously isolated

Sources & evidence

ORD record
ord-de7a59ce701c4e508b0e1c9d0543e06a
Source dataset
uspto-grants-2013_08
Patent number
US08513268B2

Reaction notes

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