2-Amino-4-methylphenol → HCID 59297268, compound

HRID 2234742Notes

Reaction equation

HRID 2234742 reaction equation
[CH2:1]([C:4]1([CH2:25][CH2:26][CH3:27])[C:16]2[CH:15]=[C:14]([C:17]([OH:19])=O)[C:13]([O:20][CH3:21])=[CH:12][C:11]=2[C:10]2[C:5]1=[CH:6][C:7]([C:22](O)=[O:23])=[CH:8][CH:9]=2)[CH2:2][CH3:3].S(Cl)(Cl)=O.[NH2:32][C:33]1[CH:38]=[C:37]([CH3:39])[CH:36]=[CH:35][C:34]=1[OH:40].[NH:41]1[CH2:46][CH2:45][CH2:44][CH2:43][CH2:42]1.[Cl-].[NH+]1C=CC=C[CH:49]=1.[O:54]1CCOC[CH2:55]1>O.CN1CCCC1=O>[OH:40][C:34]1[CH:35]=[CH:36][C:37]([CH3:39])=[CH:38][C:33]=1[NH:32][C:17]([C:14]1[C:13]([O:20][CH3:21])=[CH:12][C:11]2[C:10]3[C:5](=[CH:6][C:7]([C:22]([NH:41][C:46]4[CH:45]=[C:44]([CH3:49])[CH:43]=[CH:42][C:55]=4[OH:54])=[O:23])=[CH:8][CH:9]=3)[C:4]([CH2:25][CH2:26][CH3:27])([CH2:1][CH2:2][CH3:3])[C:16]=2[CH:15]=1)=[O:19]

Participants

9

Reactant 6

HCID 72642-Amino-4-methylphenolHCID 8082PiperidineHCID 24386Thionyl ChlorideHCID 312751,4-Dioxane2×HCID 69401Einecs 211-027-4HCID 59297262HCID 59297262, compound

Product 1

HCID 59297268HCID 59297268, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 9,9-dipropyl-3-methoxyfluorene-2,7-dicarboxylic acid (43 g, 0.117 mol), thionyl chloride (30.0 mL, 48.9 g, 0.41 mol), p-dioxane (430 mL) and N-methylpyrrolidinone (2.0 mL), under argon, was stirred and heated under reflux for 3 h. Concentration of the reaction mixture by distillation of p-dioxane (50.0 mL) precipitated the diacid dichloride intermediate. The dark diacid dichloride solution, over a period of 20 min., was added to a cooled (0° C.) stirred solution of 2-amino-4-methylphenol (30.8 g, 0.25 mol), anhydrous piperidine (21.0 mL) and p-dioxane (200 mL) under argon. The resulting mixture was stirred at room temperature for 18 h then treated with water (50.0 mL) to dissolve the pyridinium chloride. The mixture was then added to 1.8 L of water, with stirring, to form the crude product as a granular solid, which was collected, washed with 50% methanol/water (500 mL), and dried to afford N,N′-bis(2-hydroxy-5-methylphenyl)-9,9-dipropyl-3-methoxyfluorene-2,7-dicarboxamide (77.2 g).

Workup

  1. temperatureheated
  2. temperatureunder reflux for 3 h
  3. distillationConcentration of the reaction mixture by distillation of p-dioxane (50.0 mL)
  4. customprecipitated the diacid dichloride intermediate
  5. additionwas added to
  6. stirringwith stirring
  7. customto form the crude product as a granular solid, which
  8. customwas collected
  9. washwashed with 50% methanol/water (500 mL)
  10. customdried

Sources & evidence

ORD record
ord-a17195990fb04666bd86a3e04f6a14b3
Source dataset
uspto-grants-2010_05
Patent number
US07713452B2

Reaction notes

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