Hydrochloric Acid → Momfluorothrin

HRID 1072120Notes

Reaction equation

HRID 1072120 reaction equation
C[Si]([N-:5][Si](C)(C)C)(C)C.[Na+].[CH:11]([CH:13]1[CH:15]([C:16]([O:18][CH2:19][C:20]2[C:25]([F:26])=[C:24]([F:27])[C:23]([CH2:28][O:29][CH3:30])=[C:22]([F:31])[C:21]=2[F:32])=[O:17])[C:14]1([CH3:34])[CH3:33])=O.Cl.O1C[CH2:39][CH2:38][CH2:37]1>>[C:37]([C:38]([CH3:39])=[CH:11][CH:13]1[CH:15]([C:16]([O:18][CH2:19][C:20]2[C:21]([F:32])=[C:22]([F:31])[C:23]([CH2:28][O:29][CH3:30])=[C:24]([F:27])[C:25]=2[F:26])=[O:17])[C:14]1([CH3:34])[CH3:33])#[N:5]

Participants

5

Reactant 4

HCID 313Hydrochloric AcidHCID 8028Tetrahydrofuran3×HCID 2724254Sodium bis(trimethylsilyl)amideHCID 129939974-Methoxymethy-2,3,5,6-tetrafluorobenzyl 3-formyl-2,2-dimethylcyclopropanecarboxylate

Product 1

HCID 59105852Momfluorothrin

Procedure

Under nitrogen atmosphere, 0.54 g of diethyl (1-cyanoethyl) phosphonate was dissolved in 6 ml of tetrahydrofuran and 2.8 ml of a tetrahydrofuran solution of sodium bis(trimethylsilyl)amide (1 mol/l) were added thereto at about 0° C. The mixture was stirred for 30 minutes and 2 ml of a tetrahydrofuran solution containing 1.0 g of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 3-formyl-2,2-dimethylcyclopropanecarboxylate given by formula (7): (prepared by the method described as reference production example 1 below) was added thereto and stirred for 3 hours at room temperature. After that, the reaction mixture was poured into about 20 ml of 1% hydrochloric acid and extracted with 100 ml of ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine, subsequently, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 0.76 g of 4-methoxymethy-2,3,5,6-tetrafluorobenzyl 3-(2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylate given by formula (8): (isomers ratio based on the double bond: Z/E=about 2/1).

Workup

  1. customat about 0° C
  2. custom(prepared by the method
  3. additionwas added
  4. stirringstirred for 3 hours at room temperature
  5. extractionextracted with 100 ml of ethyl acetate
  6. washThe organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine
  7. dry with materialsubsequently, dried over anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-d0fcfb5d15f840969d4e6b153ff6e0f5
Source dataset
uspto-grants-2005_06
Patent number
US06908945B2

Reaction notes

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