Tributylphosphine → methyl 3-(2-chloro-6-fluorophenyl)-2-hydrazinylidene-3-oxopropanoate

HRID 598153Notes

Reaction equation

HRID 598153 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[C:9](=[O:17])[C:10](=[N+:15]=[N-:16])[C:11]([O:13][CH3:14])=[O:12].C(P(CCCC)CCCC)CCC>C(OC(C)C)(C)C>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[C:9](=[O:17])[C:10](=[N:15][NH2:16])[C:11]([O:13][CH3:14])=[O:12]

Participants

4

Reactant 2

HCID 13831TributylphosphineHCID 86613890Methyl 3-(2-chloro-6-fluorophenyl)-2-diazo-3-oxopropionate

Product 1

HCID 178501731methyl 3-(2-chloro-6-fluorophenyl)-2-hydrazinylidene-3-oxopropanoateYield 63.6%

Reagents, catalysts & solvents 1

HCID 7914Diisopropyl EtherSolvent

Procedure

To 4.90 g (19.1 m=ol) of methyl 3-(2-chloro-6-fluorophenyl)-2-diazo-3-oxopropionate in 100 mL of diisopropyl ether was added 5.2 mL (21 mmol) of tributylphosphine. The bright yellow phosphazine adduct that precipitated from solution after 30 min. was collected, dissolved in dichloromethane and concentrated onto silica gel. The hydrazone product was eluted with a 75% hexanes/ethyl acetate mixture to give 3.14 g of the title compound as an off-white solid. The filtrate from the adduct formation was similarly loaded onto silica gel and eluted to give an additional 1.04 g of the title compound. An overall isolated yield of 4.18 g (85%) of the title compound as a 10:1 mixture of hydrazone isomers was obtained.

Workup

  1. customThe bright yellow phosphazine adduct that precipitated from solution after 30 min.
  2. customwas collected
  3. dissolutiondissolved in dichloromethane
  4. concentrationconcentrated onto silica gel
  5. washThe hydrazone product was eluted with a 75% hexanes/ethyl acetate mixture

Sources & evidence

ORD record
ord-d8e584d5c373422b99ed1d351089a974
Source dataset
uspto-grants-2011_03
Patent number
US07897607B2

Reaction notes

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