Diethyl Carbonate → alpha-Methyl-alpha-(3-phenoxyphenyl)-malonic acid diethyl ester

HRID 1074579Notes

Reaction equation

HRID 1074579 reaction equation
[OH-].[Na+].O(C1C=C(C(=O)C)C=CC=1)[C:4]1C=CC=C[CH:5]=1.[CH3:19][CH:20](O)C1C=CC=C(OC2C=CC=CC=2)C=1.[BH4-].[Na+].CC(Br)C1C=CC=C(OC2C=CC=CC=2)C=1.P(Br)(Br)Br.[C-]#N.[Na+].[CH3:60][C:61]([C:68]1[CH:73]=[CH:72][CH:71]=[C:70]([O:74][C:75]2[CH:80]=[CH:79][CH:78]=[CH:77][CH:76]=2)[CH:69]=1)([C:65]([OH:67])=[O:66])[C:62]([OH:64])=[O:63].C(=O)(OCC)OCC>C(O)C.CS(C)=O>[CH2:4]([O:66][C:65](=[O:67])[C:61]([CH3:60])([C:68]1[CH:73]=[CH:72][CH:71]=[C:70]([O:74][C:75]2[CH:80]=[CH:79][CH:78]=[CH:77][CH:76]=2)[CH:69]=1)[C:62]([O:64][CH2:19][CH3:20])=[O:63])[CH3:5]

Participants

12

Reactant 9

HCID 7766Diethyl CarbonateHCID 8929Sodium CyanideHCID 14798Sodium HydroxideHCID 24614Phosphorus tribromideHCID 36249Ethanone, 1-(3-phenoxyphenyl)-HCID 4311764Sodium borohydrideHCID 128824191-(3-Phenoxyphenyl)ethanolHCID 14670609alpha-Methyl-alpha-(3-phenoxy-phenyl)-malonic acidHCID 19915504alpha-(3-Phenoxyphenyl)ethyl bromide

Product 1

HCID 19915501alpha-Methyl-alpha-(3-phenoxyphenyl)-malonic acid diethyl ester

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 702EthanolSolvent

Procedure

Several methods are disclosed for the preparation of the compound. The compound has been prepared for example by hydrolysis of 2-(phenoxy-phenyl)-3-propionitrile with sodium hydroxide in 50% aqueous ethanol for 72 hours (Swiss patent specification No. 527 155). The starting nitrile was prepared by methylation of m-phenoxy-acetophenone followed by reduction to α-methyl-3-phenoxy-benzyl alcohol with sodium borohydride and followed by halogenation of the obtained product to α-methyl-3-phenoxy-benzyl bromide with phosphorus tribromide and reaction with sodium cyanide in anhydrous dimethyl sulfoxide (Swiss patent specification No. 527 155). According to another process α-methyl-α-(3-phenoxy-phenyl)-malonic acid is decarboxylated in a melt at 130°-160° C. The starting material was prepared by reacting α-(3-phenoxy-phenyl)-acetic acid diethyl ester with diethyl carbonate to obtain α-methyl-α-(3-phenoxyphenyl)-malonic acid diethyl ester which was hydrolyzed in aqueous alcohol by boiling it together with sodium hydroxide. The reaction mixture of the last step was purified by washing with ether in order to remove the starting ester as the hydrolysis was only partial (Swiss patent specification No. 527 155).

Workup

  1. customSeveral methods are disclosed for the preparation of the compound
  2. customis decarboxylated in a melt at 130°-160° C
  3. customThe starting material was prepared

Sources & evidence

ORD record
ord-946bebcceb6a477881b7ea65ba8cf303
Source dataset
uspto-grants-1983_07
Patent number
US04393008

Reaction notes

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