1,10-Phenanthroline → Methyl 2-(p-chlorophenoxy)-2-[p-(p-chlorophenoxy)phenyl]propionate

HRID 1863309Notes

Reaction equation

HRID 1863309 reaction equation
[CH:1](NC(C)C)(C)C.N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.C([Li])CCC.[CH3:27][O:28][C:29](=[O:53])[CH:30]([O:45][C:46]1[CH:51]=[CH:50][C:49]([Cl:52])=[CH:48][CH:47]=1)[C:31]1[CH:36]=[CH:35][C:34]([O:37][C:38]2[CH:43]=[CH:42][C:41]([Cl:44])=[CH:40][CH:39]=2)=[CH:33][CH:32]=1.CI>O1CCCC1.CCCCCC.O.CN(C)P(N(C)C)(N(C)C)=O>[Cl:52][C:49]1[CH:50]=[CH:51][C:46]([O:45][C:30]([C:31]2[CH:32]=[CH:33][C:34]([O:37][C:38]3[CH:43]=[CH:42][C:41]([Cl:44])=[CH:40][CH:39]=3)=[CH:35][CH:36]=2)([CH3:1])[C:29]([O:28][CH3:27])=[O:53])=[CH:47][CH:48]=1

Participants

10

Reactant 5

HCID 13181,10-PhenanthrolineHCID 6328Methyl iodideHCID 7912DiisopropylamineHCID 12531843Methyl(p-chlorophenoxy)[p-(p-chlorophenoxy)phenyl]acetateHCID 178418339Butyllithium

Product 1

HCID 12531902Methyl 2-(p-chlorophenoxy)-2-[p-(p-chlorophenoxy)phenyl]propionate

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-70 °C

Procedure

A solution of 2.02 g of N,N-diisopropylamine and 5 mg of 1,10-phenanthroline in 15 ml of dry tetrahydrofuran is cooled to 0° C. under argon and a solution of 0.017 mole of n-butyllithium in hexane is added dropwise while keeping the temperature of 0°-5° C. After 15 minutes, the solution is cooled to -70° C. and a solution of 6.05 g of methyl(p-chlorophenoxy)[p-(p-chlorophenoxy)phenyl]acetate in 10 ml of tetrahydrofuran is added over 15 minutes while keeping the temperature at -70° C. to -65° C. After 15 minutes 3.58 g of hexamethylphosphoramide is added. After 1/2 hour, 4.26 g of methyl iodide is added in one portion. The color lightens slowly over one hour. The mixture is allowed to warm to room temperature and the reaction mixture is stirred overnight. The mixture is poured into 100 ml of water and extracted with two 75 ml portions of ether. The extracts are washed with four 50 ml portions of 10% HCl, water, saturated NaHCO3, saturated brine and dried (MgSO4). Evaporation of the solvent yields a brown oil, which is filtered through 30 g of silica gel (benzene eluent) to yield the product as a light yellow oil, which solidifies on standing.

Workup

  1. customthe temperature of 0°-5° C
  2. customat -70° C. to -65° C
  3. waitAfter 1/2 hour
  4. waitThe color lightens slowly over one hour
  5. temperatureto warm to room temperature
  6. extractionextracted with two 75 ml portions of ether
  7. washThe extracts are washed with four 50 ml portions of 10% HCl, water, saturated NaHCO3, saturated brine
  8. dry with materialdried (MgSO4)
  9. customEvaporation of the solvent
  10. customyields a brown oil, which
  11. filtrationis filtered through 30 g of silica gel (benzene eluent)

Sources & evidence

ORD record
ord-bb09760689474cf5a71c33de8628e7b5
Source dataset
uspto-grants-1979_09
Patent number
US04168385

Reaction notes

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