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Hydrochloric Acid → Methyl alpha-[4-(3-tert.butylphenoxy)-6-dimethylamino-pyrimidin-5-yl]-beta-methoxyacrylate

HRID 1957167
Notes
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Reaction equation

HRID 1957167 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([CH:23]=[CH:24][CH:25]=1)[O:8][C:9]1[C:14]([CH2:15][C:16]([O:18][CH3:19])=[O:17])=[C:13]([N:20]([CH3:22])[CH3:21])[N:12]=[CH:11][N:10]=1)([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].Cl.[C:29](=[O:32])(O)[O-].[Na+].S(OC)(O[CH3:38])(=O)=O>COCCOC.C(OC)=O.[Cl-].[Na+].O.CCCCCC.C(OCC)(=O)C.CCOCC>[C:1]([C:5]1[CH:6]=[C:7]([CH:23]=[CH:24][CH:25]=1)[O:8][C:9]1[C:14]([C:15](=[CH:38][O:32][CH3:29])[C:16]([O:18][CH3:19])=[O:17])=[C:13]([N:20]([CH3:22])[CH3:21])[N:12]=[CH:11][N:10]=1)([CH3:4])([CH3:2])[CH3:3]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

11

Reactant 5

HCID 313Hydrochloric AcidHCID 6497Dimethyl SulfateHCID 24758Sodium hydrideHCID 516892Sodium BicarbonateHCID 19069025Methyl 4-(3-tert.butylphenoxy)-6-dimethylamino-pyrimidin-5-yl-acetate

Product 1

HCID 67742283
Methyl alpha-[4-(3-tert.butylphenoxy)-6-dimethylamino-pyrimidin-5-yl]-beta-methoxyacrylate

Reagents, catalysts & solvents 5

HCID 3283Diethyl EtherSolventHCID 7865Methyl formateSolventHCID 80711,2-DimethoxyethaneSolventHCID 21226206Ethyl acetate hexaneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

Methyl 4-(3-tert.butylphenoxy)-6-dimethylamino-pyrimidin-5-yl-acetate (10.0 g, 29 mmol) is dissolved in a mixture of 1,2-dimethoxyethane (60 ml) and methyl formate (20 ml). Sodium hydride (1.7 g, 80% in oil, 58 mmol) is added in one portion, the temperature being kept at room temperature. After 5 hours the reaction mixture is carefully acidified with hydrochloric acid. After stirring for 1 hour at +5° C. the mixture is neutralized with solid sodium bicarbonat. The intermediate product is extracted with ether and worked up in the usual way. The resulting oil is stirred in dimethylformamide (20 ml) and dimethyl sulfate (4.7 ml, 50 mmol) for 2 hours at room temperature. Dilution with ether washing with brine and chromatography on silicagel (eluant:hexane/ethyl acetate 1:1) gives the methyl α-[4-(3-tert.butylphenoxy)-6-dimethylamino-pyrimidin-5-yl]-β-methoxyacrylate as a single isomer (5.5 g).

Workup

  1. custombeing kept at room temperature
  2. extractionThe intermediate product is extracted with ether
  3. stirringThe resulting oil is stirred in dimethylformamide (20 ml)

Sources & evidence

ORD record
ord-674935cd3e5a408eb6377b792fc1ae70
Source dataset
uspto-grants-1998_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05783580

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes