Sodium Bicarbonate → (1R)-(+)-cis-Permethric acid

HRID 323923Notes

Reaction equation

HRID 323923 reaction equation
[CH3:1][C:2]1([CH3:13])[C@H:7]2[C@@H:3]1[C@H:4]([C:9](Cl)([Cl:11])[Cl:10])[O:5][C:6]2=[O:8].CC1(C)[C@H]2[C@@H]1[C@@H](C(Cl)(Cl)Cl)OC2=O.C(=O)([O-])O.[Na+].Cl.C(OC)(C)(C)C>CN(C=O)C>[Cl:10][C:9]([Cl:11])=[CH:4][C@H:3]1[C@@H:7]([C:6]([OH:8])=[O:5])[C:2]1([CH3:1])[CH3:13]

Participants

6

Reactant 4

HCID 516892Sodium BicarbonateHCID 10538220(1R,4R,5S)-6,6-dimethyl-2-oxo-4-trichloromethyl-3-oxabicyclo[3.1.0]hexaneHCID 12525223HCID 12525223, compoundHCID 86756611tert-butylmethylether HCl

Product 1

HCID 673647(1R)-(+)-cis-Permethric acid

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of (1R,4R,5S)-6,6-dimethyl-4-(trichloromethyl)-3-oxabicyclo[3.1.0]hexan-2-one (I, R1=X1=X2=Cl) and (1R,4S,5S)-6,6-dimethyl-4-(trichloromethyl)-3-oxabicyclo[3.1.0]hexan-2-one (I, R1=X1=X2=Cl), 0.24 g (0.001 mol), is stirred with sodium hydrogen carbonate, 0.21 g (0.0025 mol), and Pd(C) 5%, 0.01 g, in about 4 ml of DMF at 50° C. under a hydrogen atmosphere of a slight overpressure. After stirring for ½ hour at 50° C. the mixture is stirred at room temperature. Samples taken out for GC analysis are treated with aqueous hydrochloric acid/methyl t-butyl ether and analysed on GC. After 16 hours GC analysis (area-%) shows a content of 39% of II and 32% of unreacted I. The retention time is identical to that of II prepared according to Ref.6, and MS (Mass (intensity in % of base peak): 208 (6) M+, 210 (4) (M+2)+, 175 (25), 173 (78), 165 (27), 163 (39), 111 (22), 109 (28), 91 (100), 77 (46), 39 (64)) is identical to MS of II prepared according to Ref.6.

Workup

  1. stirringis stirred at room temperature
  2. waitAfter 16 hours GC analysis (area-%) shows
  3. customprepared
  4. customprepared

Sources & evidence

ORD record
ord-da76437e83b4464dac9176e69f47776c
Source dataset
uspto-grants-2001_04
Patent number
US06215023B1

Reaction notes

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