18-Crown-6 → [1-(2-Bromoethyl)-2-(phenylmethylene)hydrazino]oxoacetic acid, ethyl ester

HRID 1449138Notes

Reaction equation

HRID 1449138 reaction equation
CS(O[CH2:6][CH2:7][N:8]([C:17](=[O:23])[C:18]([O:20][CH2:21][CH3:22])=[O:19])[N:9]=[CH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)(=O)=O.[Br-:24].[Li+].C1OCCOCCOCCOCCOCCOC1>CC(C)=O>[Br:24][CH2:6][CH2:7][N:8]([C:17](=[O:23])[C:18]([O:20][CH2:21][CH3:22])=[O:19])[N:9]=[CH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 2855718-Crown-6HCID 82050Lithium BromideHCID 86736835[1-[2-[(Methylsulfonyl)oxy]ethyl]-2-(phenylmethylene)hydrazino]oxoacetic acid, ethyl ester

Product 1

HCID 86736837[1-(2-Bromoethyl)-2-(phenylmethylene)hydrazino]oxoacetic acid, ethyl ester

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

3.4 g. of the ethyl ester product from part (b) are dissolved in 100 ml. of acetone. 1.3 g. (50% excess) of lithium bromide and 0.1 g. of 18-Crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) are added and the mixture is stirred for three hours at 50°. After the reaction has been completed as determined by TLC, the solvent is distilled off and the reaction mixture is taken up in 50 ml. of methylene chloride and shaken with 50 ml. of water. The organic phase is dried and concentrated to yield the crude product as an oil which, after scratching, crystallizes in several hours. Recrystallization from isopropanol yields purified [1-(2-bromoethyl)-2-(phenylmethylene)hydrazino]oxoacetic acid, ethyl ester; m.p. 56°-57°.

Workup

  1. distillationthe solvent is distilled off
  2. stirringof methylene chloride and shaken with 50 ml
  3. customThe organic phase is dried
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-466452f8402449648ab2e784f0f00b82
Source dataset
uspto-grants-1980_02
Patent number
US04189482

Reaction notes

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