Pyridine → HCID 50031, compound

HRID 2052375Notes

Reaction equation

HRID 2052375 reaction equation
Cl[C:2]([C@H:4]1[C@H:6]([CH:7]=[C:8]([Cl:13])[C:9]([F:12])([F:11])[F:10])[C:5]1([CH3:15])[CH3:14])=[O:3].N1C=CC=CC=1.[C:22]([CH:24]([OH:38])[C:25]1[CH:30]=[CH:29][CH:28]=[C:27]([O:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[CH:26]=1)#[N:23]>O>[Cl:13][C:8]([C:9]([F:12])([F:11])[F:10])=[CH:7][C@@H:6]1[C@H:4]([C:2]([O:38][CH:24]([C:22]#[N:23])[C:25]2[CH:30]=[CH:29][CH:28]=[C:27]([O:31][C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)[CH:26]=2)=[O:3])[C:5]1([CH3:15])[CH3:14]

Participants

5

Reactant 3

HCID 1049PyridineHCID 93218Benzeneacetonitrile, alpha-hydroxy-3-phenoxy-, (alphaS)-HCID 86736786trans-3-[2-Chloro-3,3,3-trifluoropropenyl]-2,2-dimethylcyclopropanecarbonyl chloride

Product 1

HCID 50031HCID 50031, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To the residue of (+)-cis/trans-1-chlorocarbonyl-3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane (obtained in Example 18) was added a mixture of pyridine (0.12 g) and (+)-α-cyano-3-phenoxybenzyl alcohol (0.33 g) and the mixture thus obtained was stirred for a period of 16 hours at the ambient temperature. Water (20 ml) was added and the mixture extracted with diethyl ether (3×10 ml). The combined extracts were washed with water, saturated sodium bicarbonate solution, and water and dried over anhydrous sodium sulphate. After removal of the ether by evaporation under reduced pressure the residual oil was subjected to preparative thick-layer chromatography, using 2 mm thick silica on glass with chloroform as eluent, to yield (+)-α-cyano-3-phenoxybenzyl (+)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate (Rf 0.52), and the corresponding trans isomers (Rf 0.42), each containing about 90-95% of the Z-isomer. Spectral data: infra red (CHCl3) 1740, 1660, 1590, 1480, 1460 cm-1 ; n.m.r. (CCl4): 6.90-7.50τ, 1.60-2.70τ, 1.50-1.00τ, and specific peaks at 6.3τ (benzylic H), 6.85, 6.50, 6.11 and 5.84τ (vinylic H) tentatively assigned to the Z-cis, E-cis, Z-trans and E-trans isomers respectively.

Workup

  1. customthe mixture thus obtained
  2. extractionthe mixture extracted with diethyl ether (3×10 ml)
  3. washThe combined extracts were washed with water, saturated sodium bicarbonate solution, and water
  4. dry with materialdried over anhydrous sodium sulphate
  5. customAfter removal of the ether
  6. customby evaporation under reduced pressure the residual oil

Sources & evidence

ORD record
ord-08a65bc10b4c4e9f93b6c5eda6687830
Source dataset
uspto-grants-1980_01
Patent number
US04183948

Reaction notes

Loading…