Triethylamine → HCID 86724013, compound

HRID 1475420Notes

Reaction equation

HRID 1475420 reaction equation
[C:1]([O:5][C:6](=[O:20])[N:7]([C:12]1[CH:17]=[C:16]([Cl:18])[N:15]=[N:14][C:13]=1Cl)[CH2:8][C:9]([CH3:11])=[CH2:10])([CH3:4])([CH3:3])[CH3:2].C([O-])=O.[Na+].CCN(CC)CC>[N+](CCCC)(CCCC)(CCCC)CCCC.[Cl-].CS(C)=O.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:1]([O:5][C:6]([N:7]1[C:12]2[CH:17]=[C:16]([Cl:18])[N:15]=[N:14][C:13]=2[C:9]([CH3:11])([CH3:10])[CH2:8]1)=[O:20])([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 2723810Sodium FormateHCID 86724012HCID 86724012, compound

Product 1

HCID 86724013HCID 86724013, compoundYield 55.4%

Reagents, catalysts & solvents 4

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 167845palladium(II) acetateCatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent2×

Conditions

Temperature
100 °C

Procedure

(3,6-Dichloro-pyridazin-4-yl)-(2-methyl-allyl)-carbamic acid tert-butyl ester (239 g), Bu4NCl (251.8 g), sodium formate (64.2 g), Et3N (354 mL) and Pd(OAc)2 (13 g) were dissolved in DMSO (6 L) and water (354 mL). The reaction mixture was heated to 100° C. and held at temperature for 10 minutes, after which time the reaction was complete and the mixture was allowed to cool to room temperature. The mixture was diluted with water (9 L) and extracted with EtOAc (4×3 L). The combined organic extracts were washed with brine (3 L). The emulsion was allowed to separate overnight and the interface back extracted with EtOAc (3 L). The combined organic extracts were dried with magnesium sulfate, filtered and concentrated. Chromatography on silica, eluting with a solvent gradient of 10% EtOAc in heptane to 20% EtOAc in heptane, gave the title compound (118 g) [M+H]+=284.

Workup

  1. temperatureto cool to room temperature
  2. extractionextracted with EtOAc (4×3 L)
  3. washThe combined organic extracts were washed with brine (3 L)
  4. customto separate overnight
  5. extractionthe interface back extracted with EtOAc (3 L)
  6. dry with materialThe combined organic extracts were dried with magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. washChromatography on silica, eluting with a solvent gradient of 10% EtOAc in heptane to 20% EtOAc in heptane

Sources & evidence

ORD record
ord-6be846c96e5849339538a1c9f9fee22a
Source dataset
uspto-grants-2015_04
Patent number
US09018214B2

Reaction notes

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