Sodium Carbonate → 1,1-Dimethylethyl cyclopropyl[(2,3-dichloro-5-ethenylphenyl)methyl]carbamate

HRID 337551

Reaktionsgleichung

Reaktionsgleichung von HRID 337551
CC([C:5]1([N:8]([CH2:12][C:13]2[CH:18]=[C:17](Br)[CH:16]=[C:15]([Cl:20])[C:14]=2[Cl:21])[C:9](=[O:11])[O-:10])[CH2:7][CH2:6]1)(C)C.C(B1O[C:27](C)(C)[C:26]([CH3:32])([CH3:31])O1)=C.[C:33]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:34]=1.C([O-])([O-])=O.[Na+].[Na+]>O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(O)CC.CN(C=O)C>[CH:5]1([N:8]([CH2:12][C:13]2[CH:18]=[C:17]([CH:33]=[CH2:34])[CH:16]=[C:15]([Cl:20])[C:14]=2[Cl:21])[C:9](=[O:11])[O:10][C:26]([CH3:32])([CH3:31])[CH3:27])[CH2:6][CH2:7]1

Komponenten

9

Edukt 4

HCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 52330122-Ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 866516601,1-Dimethylethyl[(5-bromo-2,3-dichlorophenyl)methyl]cyclopropylcarbamate

Produkt 1

HCID 668954141,1-Dimethylethyl cyclopropyl[(2,3-dichloro-5-ethenylphenyl)methyl]carbamate

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 167845palladium(II) acetateKatalysatorHCID 962WaterLösungsmittelHCID 10311-PropanolLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

1,1-Dimethylethyl[(5-bromo-2,3-dichlorophenyl)methyl]cyclopropylcarbamate (1 eq.) from the previous step and 2-ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1 eq.) were combined in a 2:1 (v/v) mixture of DMF:n-PrOH (0.1 M). To this solution was then added palladium(II) acetate (0.05 eq.) and triphenylphosphine (0.15 eq.) before the vessel was repeatedly evacuated and back-filled with nitrogen. Finally, 2 N aq. Na2CO3 (2 eq.) was added and the resulting biphasic suspension was heated at 90° C. for 18 h. The now black suspension was cooled to RT, diluted with water and extracted with 1:1 (v/v) hexanes:ether. The combined organic extracts were then washed further with 1 N aq. NaOH, water and brine. This was then dried over Na2SO4, filtered and the filtrate concentrated in vacuo to afford a pale yellow oil. Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→9:1 (v/v) Hex:EtOAc) afforded the title compound as a colorless oil.

Aufarbeitung

  1. additionback-filled with nitrogen
  2. temperatureThe now black suspension was cooled to RT
  3. extractionextracted with 1:1 (v/v) hexanes
  4. washThe combined organic extracts were then washed further with 1 N aq. NaOH, water and brine
  5. dry with materialThis was then dried over Na2SO4
  6. filtrationfiltered
  7. concentrationthe filtrate concentrated in vacuo
  8. customto afford a pale yellow oil
  9. customPurification of the crude product
  10. customthus obtained by way of flash chromatography (SiO2, Hex→9:1 (v/v) Hex:EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-af88e6ed50ec483dbfe8b8c842d3812f
Quelldatensatz
uspto-grants-2014_11
Patentnummer
US08889714B2

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