Pyridine → HCID 13034993, compound

HRID 2166839Notes

Reaction equation

HRID 2166839 reaction equation
[CH3:1][C:2]1([CH3:12])[CH:4]([CH:5]=[C:6]([Cl:8])[Cl:7])[CH:3]1[C:9](Cl)=[O:10].[Cl:13][C:14]1[CH:30]=[CH:29][C:17]([O:18][C:19]2[CH:20]=[C:21]([CH:26]=[CH:27][CH:28]=2)[CH:22]([OH:25])[C:23]#[CH:24])=[CH:16][CH:15]=1.N1C=CC=CC=1>C1C=CC=CC=1.O>[CH3:1][C:2]1([CH3:12])[CH:4]([CH:5]=[C:6]([Cl:8])[Cl:7])[CH:3]1[C:9]([O:25][CH:22]([C:23]#[CH:24])[C:21]1[CH:26]=[CH:27][CH:28]=[C:19]([O:18][C:17]2[CH:29]=[CH:30][C:14]([Cl:13])=[CH:15][CH:16]=2)[CH:20]=1)=[O:10]

Participants

6

Reactant 3

HCID 1049PyridineHCID 94551Permethric chlorideHCID 54003277HCID 54003277, compound

Product 1

HCID 13034993HCID 13034993, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

In 120 ml of dry benzene was dissolved 11.4 g of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride (cis-/trans-ratio=50:50, approx.) followed by addition of 12.9 g. of 3-(4-chlorophenoxy)-α-ethynylbenzyl alcohol and further by dropwise addition of 7.9 g of pyridine. The mixture was stirred at room temperature overnight. Thereafter, the reaction mixture was diluted with 100 g of water and the benzene layer was separated, washed with dilute hydrochloric acid and water and dried over anhydrous magnesium sulfate. The low-boiling fraction was then distilled off under reduced pressure to recover an oil. This oily product was purified by preparative liquid chromatograpy [column: Water's Associates' Prep LC/System 500, Prep PAK® 500/SILICA; solvent system: diethyl ether:n-hexane=2:98]. The above procedure yielded 20.2 g of 3-(4-chlorophenoxy)-α-ethynylbenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate (yield 90%). The separation of cis- and trans-isomers from each other can be effected by the above-mentioned preparative liquid chromatography. The NMR spectra of such isomers are indicated below.

Workup

  1. additionfollowed by addition of 12.9 g
  2. customthe benzene layer was separated
  3. washwashed with dilute hydrochloric acid and water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. distillationThe low-boiling fraction was then distilled off under reduced pressure
  6. customto recover an oil
  7. customThis oily product was purified by preparative liquid chromatograpy [column: Water's Associates' Prep LC/System 500, Prep PAK® 500/SILICA; solvent system: diethyl ether:n-hexane=2:98]

Sources & evidence

ORD record
ord-721a77e79dd54c59a6863ca441a0cd15
Source dataset
uspto-grants-1983_06
Patent number
US04389412

Reaction notes

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