Aniline → HCID 54724207, compound

HRID 1867064Notes

Reaction equation

HRID 1867064 reaction equation
[OH:1][C:2]1[CH:7]=[C:6]([CH3:8])O[C:4](=[O:9])[CH:3]=1.[NH2:10][C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][C:18]=1[CH3:19])[CH2:14][OH:15].O1C=CC=CC1=O.NC1C=CC=CC=1>ClC1C=CC=CC=1Cl.C(#N)C.O>[OH:1][C:2]1[CH:7]=[C:6]([CH3:8])[N:10]([C:11]2[CH:12]=[C:13]([CH2:14][OH:15])[CH:16]=[CH:17][C:18]=2[CH3:19])[C:4](=[O:9])[CH:3]=1

Participants

7

Reactant 4

HCID 6115AnilineHCID 681542H-Pyran-2-oneHCID 586243(3-Amino-4-methylphenyl)methanolHCID 546757574-Hydroxy-6-methyl-2-pyrone2×

Product 1

HCID 54724207HCID 54724207, compound

Reagents, catalysts & solvents 2

HCID 72391,2-DichlorobenzeneSolvent2×HCID 18373917Acetonitrile--water (1/1)Solvent

Conditions

Temperature
165 °C

Procedure

4-Hydroxy-6-methyl-2-pyrone (23.0 g, 182.2 mmol) and 3-Amino 4-methylbenzyl alcohol (25.0 g, 182.2 mmol) were taken up in 25 ml of 1,2-dichlorobenzene. The solution was heated to 165° C. in a 250 ml round bottom flask equipped with a J-Kem temperature controller probe, and a heating mantle. In a separate 250 ml round bottom flask 4-Hydroxy-6-methyl-2-pyrone (23.0 g, 182.2 mmol) was suspended in 25 ml of 1,2-dichlorobenzene and also heated to 165° C. The pyrone solution was poured into the flask containing the aniline and the reaction stirred at 165° C. for 20 minutes. The reaction was allowed to cool to room temperature. Reaction contents were washed with saturated NaHCO3 (aq.). Separated the organic and aqueous layers. Aqueous layer was made acidic with dropwise addition of concentrated HCl. The product was extracted from the acidic aqueous layer with n-BuOH. N-BuOH removed in vacuo to produce a reddish brown oil. (8.5 g, 19%). Contents carried forward to next reaction with no further purification. 1H NMR (300 MHz, CD3OD) δ 7.35 (m, 2H), 7.08 (s, 1H), 6.08 (br s, 1H), 5.81 (br s, 1H), 4.60 (s, 2H), 2.01 (s, 3H), 1.87 (s, 3H). LC/MS, tr=1.42 minutes (5 to 95% acetonitrile/water over 5 minutes at 1 ml/min with detection 254 nm, at 50° C.). ES-MS m/z 246.1131 (M+H). ES-HRMS m/z 246.1107 (M+H calcd for C14H16NO3 requires 246.1125).

Workup

  1. customequipped with a J-Kem temperature controller probe
  2. temperaturealso heated to 165° C
  3. temperatureto cool to room temperature
  4. customReaction contents
  5. washwere washed with saturated NaHCO3 (aq.)
  6. customSeparated the organic and aqueous layers
  7. additionAqueous layer was made acidic with dropwise addition of concentrated HCl
  8. extractionThe product was extracted from the acidic aqueous layer with n-BuOH
  9. customN-BuOH removed in vacuo
  10. customto produce a reddish brown oil
  11. customContents carried forward to next reaction with no further purification

Sources & evidence

ORD record
ord-c6937c97444446bda0d0490d24263ba9
Source dataset
uspto-grants-2009_12
Patent number
US07629363B2

Reaction notes

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