Diethyl [Chloro(cyano)methyl]phosphonate → 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl (1R,3R)-3-((Z)-2-chloro-2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate

HRID 554028Notes

Reaction equation

HRID 554028 reaction equation
CC(C)([O-])C.[K+].[CH3:7][C:8]1([CH3:30])[C@H:10]([CH:11]=O)[C@H:9]1[C:13]([O:15][CH2:16][C:17]1[C:22]([F:23])=[C:21]([F:24])[C:20]([CH2:25][O:26][CH3:27])=[C:19]([F:28])[C:18]=1[F:29])=[O:14].C(OP([CH:39]([Cl:42])[C:40]#[N:41])(=O)OCC)C>O1CCCC1>[Cl:42]/[C:39](/[C:40]#[N:41])=[CH:11]\[C@H:10]1[C@@H:9]([C:13]([O:15][CH2:16][C:17]2[C:22]([F:23])=[C:21]([F:24])[C:20]([CH2:25][O:26][CH3:27])=[C:19]([F:28])[C:18]=2[F:29])=[O:14])[C:8]1([CH3:7])[CH3:30]

Participants

5

Reactant 3

HCID 10750995Diethyl [Chloro(cyano)methyl]phosphonateHCID 23665647Potassium tert-butoxideHCID 866391442,3,5,6-tetrafluoro-4-methoxymethylbenzyl (1R,3R)-2,2-dimethyl-3-formylcyclopropanecarboxylate

Product 1

HCID 866391432,3,5,6-tetrafluoro-4-methoxymethylbenzyl (1R,3R)-3-((Z)-2-chloro-2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylateYield 3.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 0.27 g of potassium tert-butoxide in 2 ml of tetrahydrofuran was added dropwise to a mixture of 0.70 g of 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl (1R,3R)-2,2-dimethyl-3-formylcyclopropanecarboxylate, 0.42 g of diethyl(chlorocyanomethyl)phosphonate and 5 ml of anhydrous tetrahydrofuran with ice-cooling under a nitrogen atmosphere. After stirring with ice-cooling for 15 minutes, the reaction mixture was poured into a saturated saline solution and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then filtered, and the filtrate was concentrated under reduced pressure. The residue was subject to silica gel column chromatography to obtain 0.03 g of 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl (1R,3R)-3-((Z)-2-chloro-2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate represented by the formula (3):

Workup

  1. temperaturecooling under a nitrogen atmosphere
  2. temperaturecooling for 15 minutes
  3. additionthe reaction mixture was poured into a saturated saline solution
  4. extractionthe mixture was extracted with ethyl acetate
  5. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-226a202433bd4f92aaf6eaaf12503a3a
Source dataset
uspto-grants-2011_11
Patent number
US08048916B2

Reaction notes

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