Acetyl chloride → (RS)alpha-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-(3-oxo-3-methoxymethoxy-1propynyl)-cyclopropane-carboxylate

HRID 569519Notes

Reaction equation

HRID 569519 reaction equation
[CH3:1][C:2]1([CH3:29])[C@@H:4]([C:5]#[C:6][C:7]([OH:9])=[O:8])[C@H:3]1[C:10]([O:12][CH:13]([C:27]#[N:28])[C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([O:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:15]=1)=[O:11].[H-].[Na+].Cl[CH2:33][O:34][CH2:35]Cl.COCOC.C(Cl)(=O)C.P(O)(O)([O-])=O.[Na+]>CN(C)C=O.CO>[CH3:1][C:2]1([CH3:29])[C@@H:4]([C:5]#[C:6][C:7](=[O:9])[O:8][CH2:33][O:34][CH3:35])[C@H:3]1[C:10]([O:12][CH:13]([C:27]#[N:28])[C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([O:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:15]=1)=[O:11]

Participants

9

Reactant 6

HCID 6367Acetyl chlorideHCID 8020DimethoxymethaneHCID 10967Bis(Chloromethyl) EtherHCID 24758Sodium hydrideHCID 23672064Monosodium phosphateHCID 53972231(RS)alpha-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-(3-hydroxy-3-oxo-1-propynyl)-cyclopropane-carboxylate

Product 1

HCID 54503448(RS)alpha-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-(3-oxo-3-methoxymethoxy-1propynyl)-cyclopropane-carboxylate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Procedure

A solution of 3 g of (RS)α-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-(3-hydroxy-3-oxo-1-propynyl)-cyclopropane-carboxylate in 30 ml of anhydrous dimethylformamide was cooled to +10° C. and 300 mg of 61% sodium hydride in oil were added in portions thereto. Then, over 15 minutes, 2.5 ml of chloromethyl ether solution prepared by mixing 4.5 ml of methylal and 0.52 ml of methanol and slowly adding 3.53 ml of acetyl chloride after which the mixture was stirred for 36 hours at room temperature. The mixture was stirred for 2 hours and was then poured into an aqueous solution of monosodium phosphate. The mixture was extracted with ethyl acetate and the organic phase was washed with water, dried and evaporated to dryness. The residue was chromatographed over silica gel and eluted with a 75-25 mixture of cyclohexane-ethyl acetate to obtain 2 g of (RS)α-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-(3-oxo-3-methoxymethoxy-1propynyl)-cyclopropane-carboxylate.

Workup

  1. stirringThe mixture was stirred for 2 hours
  2. extractionThe mixture was extracted with ethyl acetate
  3. washthe organic phase was washed with water
  4. customdried
  5. customevaporated to dryness
  6. customThe residue was chromatographed over silica gel
  7. washeluted with a 75-25 mixture of cyclohexane-ethyl acetate

Sources & evidence

ORD record
ord-6993c52a9709414f9a845b75bea54f55
Source dataset
uspto-grants-1988_03
Patent number
US04732903

Reaction notes

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