Hydrochloric Acid → 773U82 Hydrochloride

HRID 371553Notes

Reaction equation

HRID 371553 reaction equation
[CH:1]1[C:15]2=[C:16]3[C:8]([C:9]4[C:14]2=[CH:13][CH:12]=[CH:11][CH:10]=4)=[CH:7][CH:6]=[CH:5][C:4]3=C(C=O)C=1.[C:19]1([CH3:29])C=CC(S(O)(=O)=O)=CC=1.[BH3-][C:31]#[N:32].[Na+].CC1C(Br)=C(O)C(Br)=CC=1[C:44]1([C:55]2[CH:56]=C(Br)C(O)=C(Br)[C:60]=2C)[O:54]S(=O)(=O)C2C=CC=CC1=2.[ClH:65].CC[OH:68]>O.C1(C)C=CC=CC=1>[ClH:65].[CH:7]1[C:8]2=[C:16]3[C:15]([C:14]4[C:9]2=[CH:10][CH:11]=[CH:12][CH:13]=4)=[CH:1][CH:29]=[CH:19][C:4]3=[C:5]([CH2:31][NH:32][C:55]([CH3:60])([CH2:44][OH:54])[CH2:56][OH:68])[CH:6]=1

Participants

9

Reactant 6

HCID 313Hydrochloric Acid3×HCID 702Ethanol3×HCID 6101p-Toluenesulfonic acidHCID 6451Bromocresol GreenHCID 1811133-FluoranthenecarboxaldehydeHCID 5003444Sodium cyanoborohydride2×

Product 1

HCID 3024572773U82 HydrochlorideYield 66%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 1140TolueneSolvent

Procedure

To a 2 L Erlenmeyer flask was added 3-fluoranthenecarbaldehyde (11.51 g, 50 mmol) 2-methyl-2-amino-1,3-propanediol (Aldrich, 5.52 g, 52.5 mmol), p-toluenesulfonic acid.H2O (Eastman Kodak Co., Rochester, NY, 14650, 0.1 g, 0.5 mmol), and PhCH3 (500 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 (500 mL) and stirred overnight. NaBH3CN (Aldrich, 95%, 1.57 g, 25 mmol) was added to the reaction. After the NaBH3CN dissolved, an indicator (bromocresol green, Eastman, 5 mg) was added. To the resulting 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 HCl gas (10 mL) in absolute EtOH, and H2O (10 mL). The liquid was then removed by rotary evaporation to give a yellow solid. The solid was shaken with 20% HCl solution (500 mL) and collected by filtration. The resulting solid was washed with additional 20% HCl solution (250 mL) and then with CH 2 Cl2 (4×250 mL), pressed and then sucked dry. The slightly yellow solid was then recrystallized from CH3OH/Et2O to give 11.80 g (66%) of 2-((3-fluoranthenylmethyl)amino)-2-methyl-1,3-propanediol hydrochloride mp 262°-265° (dec), (,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. customThe liquid was then removed by rotary evaporation
  5. customto give a yellow solid
  6. filtrationcollected by filtration
  7. washThe resulting solid was washed with additional 20% HCl solution (250 mL)
  8. customsucked dry
  9. customThe slightly yellow solid was then recrystallized from CH3OH/Et2O

Sources & evidence

ORD record
ord-3f2fbf27a3a54242a775e795566bf64f
Source dataset
uspto-grants-1985_07
Patent number
US04532344

Reaction notes

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