Dichloromethane → HCID 118452647, compound

HRID 1773241

Reaction equation

HRID 1773241 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[O:11][C:12]([F:15])([F:14])[F:13].[CH3:16][C:17]1(C)[C:21](C)(C)OB(C(C)=C)O1.C(Cl)Cl.C([O-])([O-])=O.[Na+].[Na+]>CCOC(C)=O.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].COCCOC>[N+:8]([C:6]1[CH:5]=[CH:4][C:3]([O:11][C:12]([F:15])([F:14])[F:13])=[C:2]([C:17]([CH3:21])=[CH2:16])[CH:7]=1)([O-:10])=[O:9]

Participants

9

Reactant 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolaneHCID 247216412-Bromo-4-nitro(trifluoromethoxy)benzene

Product 1

HCID 118452647HCID 118452647, compoundYield 93.6%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolvent2×HCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

2-bromo-4-nitro-1-(trifluoromethoxy)benzene (0.56 g, 1.97 mmol), 4,4,5,5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane (0.50 g, 2.96 mmol), PdCl2(dppf).CH2Cl2 adduct (0.16 g, 0.20 mmol), and Na2CO3 (0.63 g, 5.92 mmol) were combined in a 20 mL microwave vial and DME (15.78 mL) and Water (3.94 mL) were added. The mixture was stirred at RT for 6 s and then heated to 120° C. in the microwave for 30 min. The crude mixture was diluted with EtOAc and Water. The organic layer was washed with water and brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The crude was diluted with DCM and silica gel was added. The mixture was concentrated under reduced pressure to dry-load material for purification. The crude was purified via silica gel FCC, 100% Heptane-100% EtOAc to give 4-nitro-2-(prop-1-en-2-yl)-1-(trifluoromethoxy)benzene (456 mg). 1H NMR (400 MHz, DMSO-d6) δ 2.08-2.13 (m, 3H), 5.21 (p, J=1.0 Hz, 1H), 5.43 (p, J=1.5 Hz, 1H), 7.68 (dq, J=9.0, 1.6 Hz, 1H), 8.21 (d, J=2.9 Hz, 1H), 8.28 (dd, J=9.0, 2.9 Hz, 1H).

Workup

  1. temperatureheated to 120° C. in the microwave for 30 min
  2. washThe organic layer was washed with water and brine
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. additionThe crude was diluted with DCM and silica gel
  7. additionwas added
  8. concentrationThe mixture was concentrated under reduced pressure
  9. customto dry-load material
  10. customfor purification
  11. customThe crude was purified via silica gel FCC, 100% Heptane-100% EtOAc

Sources & evidence

ORD record
ord-51b6b1bb5fa94c2ca2e94bc982a643d7
Source dataset
uspto-grants-2016_02
Patent number
US09255093B2

Linked notes

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