Methyl Acrylate → 3-(4-Amino-3,5-dimethylphenyl)propan-1-ol

HRID 2183420Notes

Reaction equation

HRID 2183420 reaction equation
C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.Br[C:24]1[CH:30]=[C:29]([CH3:31])[C:27]([NH2:28])=[C:26]([CH3:32])[CH:25]=1.[C:33](OC)(=[O:36])[CH:34]=[CH2:35].[H-].[Al+3].[Li+].[H-].[H-].[H-]>C1COCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C(N(CC)CC)C>[NH2:28][C:27]1[C:29]([CH3:31])=[CH:30][C:24]([CH2:35][CH2:34][CH2:33][OH:36])=[CH:25][C:26]=1[CH3:32]

Participants

9

Reactant 4

HCID 7294Methyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 905494-Bromo-2,6-xylidineHCID 21226445Aluminium lithium hydride

Product 1

HCID 224724383-(4-Amino-3,5-dimethylphenyl)propan-1-olYield 65.1%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
100 °C

Procedure

Palladium acetate (68 mg) and 720 mg of tris-o-tolylphosphine were mixed in a Schlenk tube under a nitrogen atmosphere. After 15 ml of triethylamine, 6 g of 4-bromo-2,6-dimethylaniline and 3.2 g of methyl acrylate had been added, the tube was heated to 100° C. in an oil bath and kept there for 6 h. The mixture was added to water and extracted 3 times with ethyl ether. After drying in vacuum 6.2 g of a yellow solid was obtained. The solid was dissolved in THF and 3.5 g of lithium aluminum hydride was added. After 6 h the reaction was poured into water and purified by column chromatography (silica, hexane:ethyl acetate 2:1). A mixture of 3-(4-amino-3,5-dimethyl-phenyl-propan-1-ol and 3-(4-amino-3,5-dimethylphenyl)propan-1-ol (3.5 g) was obtained. The mixture was dissolved in ethyl acetate and 50 mg of palladium (10 wt %) on carbon was added. Hydrogen was bubbled through the solution for one h. After removing the palladium catalyst and the solvent, 3.1 g of 3-(4-amino-3,5-dimethyl-phenyl)-prop-2-en-1-ol was obtained. 1H-NMR (200 MHz, CDCl3): 6.77 (s, 2H), 3.64 (t, 2H), 3.47 (b s, 2H) 2.54 (t, 2H), 2.15 (s, 6H), 1.82 ppm (m, 2H).

Workup

  1. extractionextracted 3 times with ethyl ether
  2. dry with materialAfter drying in vacuum 6.2 g of a yellow solid
  3. customwas obtained
  4. custompurified by column chromatography (silica, hexane:ethyl acetate 2:1)
  5. additionA mixture of 3-(4-amino-3,5-dimethyl-phenyl-propan-1-ol

Sources & evidence

ORD record
ord-ded84b1e9ce1401faa3c916fe759f34d
Source dataset
uspto-grants-2005_05
Patent number
US06900153B2

Reaction notes

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