Ammonium Chloride → N-Ethoxycarbonyl-2-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-4-piperidinone

HRID 371150Notes

Reaction equation

HRID 371150 reaction equation
[Mg].[CH2:2]([O:9][C:10]1[CH:15]=[C:14]([C:16]([CH3:24])([CH3:23])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH:13]=[CH:12][C:11]=1Br)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[CH2:26]([O:28][C:29]([N:31]1[CH:36]=[CH:35][C:34](=[O:37])[CH2:33][CH2:32]1)=[O:30])[CH3:27].[Cl-].[NH4+]>O1CCCC1.CCOCC>[CH2:26]([O:28][C:29]([N:31]1[CH2:32][CH2:33][C:34](=[O:37])[CH2:35][CH:36]1[C:11]1[CH:12]=[CH:13][C:14]([C:16]([CH3:24])([CH3:23])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])=[CH:15][C:10]=1[O:9][CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1)=[O:30])[CH3:27]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 53141691(2H)-Pyridinecarboxylic acid, 3,4-dihydro-4-oxo-, ethyl esterHCID 5462224MagnesiumHCID 128821642-(Benzyloxy)-1-bromo-4-(2-methyloctan-2-YL)benzene

Product 1

HCID 13519476N-Ethoxycarbonyl-2-[2-benzyloxy-4-(1,1-dimethylheptyl)phenyl]-4-piperidinoneYield 71%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent3×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

To 3.45 (0.142 mole) of magnesium is added a solution of 27.6 g (0.071 mole) of 2-benzyloxy-1-bromo-4-(1,1-dimethylheptyl)benzene in 71 ml of tetrahydrofuran, at such a rate that gentle reflux occurs. The Grignard solution is allowed to cool to 25° C. over 30 minutes, diluted with 71 ml of ether, the mixture cooled to -12° C. and 2.13 g (0.0112 mole) cuprous iodide is added followed by addition of 8.00 g (0.0473 mole) of N-ethoxycarbonyl-2,3-dihydro-4(1H)-pyridinone in 47 ml of ether over 20 minutes. The reaction is stirred 30 minutes longer at -12° C. and then added to 2 liters ether and 600 ml saturated ammonium chloride. The organic extract is washed with three 600 ml portions of saturated ammonium chloride, dried over magnesium sulfate and evaporated to an oil. This crude product is purified via column chromatography on 2 kg of silica gel eluting in 500 ml fractions with 50% ether-hexane to yield (fractions 17-24) 16.0 g (71%) of the title compound as an oil.

Workup

  1. temperatureat such a rate that gentle reflux
  2. temperaturethe mixture cooled to -12° C.
  3. extractionThe organic extract
  4. washis washed with three 600 ml portions of saturated ammonium chloride
  5. dry with materialdried over magnesium sulfate
  6. customevaporated to an oil
  7. customThis crude product is purified via column chromatography on 2 kg of silica gel eluting in 500 ml fractions with 50% ether-hexane

Sources & evidence

ORD record
ord-a3f5c26fcc564ff5aead469c059649b5
Source dataset
uspto-grants-1985_07
Patent number
US04529732

Reaction notes

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