Hydrochloric Acid → 1,3-Propanediol, 2-methyl-2-((2-triphenylenylmethyl)amino)-, hydrochloride, hydrate (2:2:1)

HRID 1583280Notes

Reaction equation

HRID 1583280 reaction equation
[CH:1]1[C:18]2[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][C:2]=1[CH:19]=O.[CH3:21][C:22]([NH2:27])([CH2:25][OH:26])[CH2:23][OH:24].C1(C)C=CC(S(O)(=O)=O)=CC=1.[BH3-]C#N.[Na+].CC1C(Br)=C(O)C(Br)=CC=1C1(C2C=C(Br)C(O)=C(Br)C=2C)OS(=O)(=O)C2C=CC=CC1=2.[ClH:74]>CCO.CCOCC.O.C1(C)C=CC=CC=1>[ClH:74].[CH3:21][C:22]([NH:27][CH2:19][C:2]1[CH:3]=[CH:4][C:5]2[C:6]3[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=3)[C:12]3[C:17](=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:18]=2[CH:1]=1)([CH2:25][OH:26])[CH2:23][OH:24]

Participants

11

Reactant 6

HCID 313Hydrochloric Acid2×HCID 15312-Amino-2-methyl-1,3-propanediolHCID 6101p-Toluenesulfonic acidHCID 6451Bromocresol GreenHCID 5003444Sodium cyanoborohydride2×HCID 13375435Triphenylene-2-carbaldehyde

Product 1

HCID 1756811,3-Propanediol, 2-methyl-2-((2-triphenylenylmethyl)amino)-, hydrochloride, hydrate (2:2:1)

Reagents, catalysts & solvents 4

HCID 702EthanolSolvent3×HCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

To a 1 L Erlenmeyer flask was added 2-triphenylenecarbaldehyde 5.13 g, (20 mmol), 2-methyl-2-amino-1,3-propanediol (Aldrich, 2.2 g, 21 mmol), p-toluenesulfonic acid.H2O (Eastman Kodak Co., Rochester, NY, 14650, 0.1 g, 0.5 mmol), and PhCH3 (250 mL). The mixture was warmed to reflux for a few minutes and H2O (2-3 mL) was driven off. The resulting golden colored solution was allowed to cool to RT, diluted with absolute EtOH (250 mL) and stirred overnight. NaBH3CN (Aldrich, 95%, 0.63 g, 10 mmol) was added to the reaction. After the NaBH3CN dissolved, an indicator (bromocresol green, Eastman, 5 mg) was added. To the ressulting blue solution was added 5 drops of 1M solution of HCl gas in absolute EtOH every 15 minutes. After 3 days the indicator turned green then yellow and voluminous white precipitate was present in the flask. To the flask was then added 1M gas HCl (10 mL) in absolute EtOH. The reaction was diluted to 2 L with absolute ether and stirred for 1 h. The precipitate was then collected by filtration through a medium porosity glass fritted funnel and pressed dry. The filter cake was washed thoroughly with 20% HCl (2×250 mL), pressed dry and then washed with CH2Cl2 (4×500 mL), pressed and sucked dry. The crude off-white solid was then recrystallized (EtOH/Et2O) 3x to give after drying (100°) 3.34 g (43%) of 2-methyl-2-((2-triphenylenylmethyl)amino)-1,3-propanediol hydrochloride.1/2 H2O mp 207°-208.5° (dec), (C,H,Cl,N).

Workup

  1. temperatureThe mixture was warmed
  2. temperatureto reflux for a few minutes
  3. waitAfter 3 days the indicator turned green
  4. stirringstirred for 1 h
  5. filtrationThe precipitate was then collected by filtration through a medium porosity glass fritted funnel
  6. custompressed dry
  7. washThe filter cake was washed thoroughly with 20% HCl (2×250 mL)
  8. custompressed dry
  9. washwashed with CH2Cl2 (4×500 mL)
  10. customsucked dry
  11. customThe crude off-white solid was then recrystallized (EtOH/Et2O) 3x
  12. customto give
  13. dry with materialafter drying (100°) 3.34 g (43%) of 2-methyl-2-((2-triphenylenylmethyl)amino)-1,3-propanediol hydrochloride

Sources & evidence

ORD record
ord-5df8f7707a9d49fa9e0dbb26e413d260
Source dataset
uspto-grants-1985_11
Patent number
US04551282

Reaction notes

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