Thionyl Chloride → (S)alpha-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[(Z)3-oxo-3-(1-methoxy-1-trifluoromethylethoxy)-1-propenyl]-cyclopropane-carboxylate

HRID 569535

Reaction equation

HRID 569535 reaction equation
[CH3:1]C1(C)[C@@H](/C=C\C(Cl)=O)[C@H]1C(O[C@H](C#N)C1C=CC=C(OC2C=CC=CC=2)C=1)=O.S(Cl)(Cl)=O.[CH3:34][C:35]1([CH3:62])[C@@H:37](/[CH:38]=[CH:39]\[C:40]([OH:42])=[O:41])[C@H:36]1[C:43]([O:45][C@H:46]([C:60]#[N:61])[C:47]1[CH:52]=[CH:51][CH:50]=[C:49]([O:53][C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)[CH:48]=1)=[O:44].[CH3:63][C:64]([C:67]([F:70])([F:69])[F:68])([OH:66])C>C(Cl)Cl>[CH3:34][C:35]1([CH3:62])[C@@H:37](/[CH:38]=[CH:39]\[C:40](=[O:42])[O:41][C:64]([O:66][CH3:1])([C:67]([F:70])([F:69])[F:68])[CH3:63])[C@H:36]1[C:43]([O:45][C@H:46]([C:60]#[N:61])[C:47]1[CH:52]=[CH:51][CH:50]=[C:49]([O:53][C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)[CH:48]=1)=[O:44]

Participants

6

Reactant 4

HCID 24386Thionyl ChlorideHCID 681821,1,1-Trifluoro-2-methylpropan-2-olHCID 13093798(S)alpha-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[Z-2-carboxy-ethenyl]-cyclopropanecarboxylateHCID 13335684(S)alpha-cyano-3-phenoxy-benzyl (IR,cis) 2,2-dimethyl-3-[(Z) 3-chloro-3-oxo-1-propenyl]-cyclopropane carboxylate

Product 1

HCID 70489227(S)alpha-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[(Z)3-oxo-3-(1-methoxy-1-trifluoromethylethoxy)-1-propenyl]-cyclopropane-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Under inert atmosphere, a mixture of 1.02 g of (S)α-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[(Z)3-chloro-3-oxo-1-propenyl)-cyclopropane-carboxylate prepared by reaction of thionyl chloride and (S)α-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[(Z)3-hydroxy-3-oxo-1-propenyl]-cyclopropane-carboxylate and 9 ml of methylene chloride were stirred and 1.12 g of 1-methyl-1-trifluoromethyl-ethanol were added thereto. The mixture was stirred for 48 hours at room temperature and was then evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and eluted with a 8--2 mixture of hexane-ethyl ether to obtain 250 mg of (S)α-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[(Z)3-oxo-3-(1-methoxy-1-trifluoromethylethoxy)-1-propenyl]-cyclopropane-carboxylate with a melting point of 59° C. and a specific rotation of [α]D20 =+57°±2° (c=0.4% in benzene).

Workup

  1. stirringThe mixture was stirred for 48 hours at room temperature
  2. customwas then evaporated to dryness under reduced pressure
  3. customThe residue was chromatographed over silica gel
  4. washeluted with a 8--2 mixture of hexane-ethyl ether

Sources & evidence

ORD record
ord-64778fa4d1a34e928d762c2bd9e088d9
Source dataset
uspto-grants-1988_03
Patent number
US04732903

Linked notes

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