Hydrochloric Acid → 1,3-Propanediol, 2-methyl-2-((9-phenanthrenylmethyl)amino)-, hydrochloride

HRID 1981052

反応式

HRID 1981052 の反応式
[CH:1]1[C:14]2[CH:13]=[C:12]([CH:15]=O)[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[CH3:17][C:18]([NH2:23])([CH2:21][OH:22])[CH2:19][OH:20].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:70]>CCO.CCOCC.O.C1(C)C=CC=CC=1>[ClH:70].[CH3:17][C:18]([NH:23][CH2:15][C:12]1[C:11]2[C:6]([C:5]3[CH:4]=[CH:3][CH:2]=[CH:1][C:14]=3[CH:13]=1)=[CH:7][CH:8]=[CH:9][CH:10]=2)([CH2:21][OH:22])[CH2:19][OH:20]

参加物

11

反応物 6

HCID 313Hydrochloric Acid2 回HCID 15312-Amino-2-methyl-1,3-propanediolHCID 6101p-Toluenesulfonic acidHCID 6451Bromocresol GreenHCID 78437Phenanthrene-9-carbaldehydeHCID 5003444Sodium cyanoborohydride2 回

生成物 1

HCID 1504171,3-Propanediol, 2-methyl-2-((9-phenanthrenylmethyl)amino)-, hydrochloride収率 36%

試薬・触媒・溶媒 4

HCID 702Ethanol溶媒3 回HCID 962Water溶媒2 回HCID 1140Toluene溶媒HCID 3283Diethyl Ether溶媒

実験手順

To a 2 L Erlenmeyer flask was added 9-phenanthrenecarbaldehyde (Aldrich Chemical Co., Milwaukee, WI, 53201, 20.63 g, 0.1 mol), 2-methyl-2-amino-1,3-propanediol (Aldrich, 9.13 g, 86.8 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%, 4.40 g, 70 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. The reaction was diluted to 4 L with absolute ether and stirred for 1 h. The precipitate was then collected by filtration using a medium porosity glass fritted funnel and pressed dry. The filter cake was washed thoroughly with CH2Cl2 (4×500 mL), pressed, sucked dry, and dried overnight (100°). Recrystallization from EtOH/Et2O (3×) gave 11.84 g (36%) of 2-methyl-2-((9-phenanthrylmethyl)amino)-1,3-propanediol hydrochloride mp 144°-146°, (C,H,Cl,N).

後処理

  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
  6. custompressed dry
  7. washThe filter cake was washed thoroughly with CH2Cl2 (4×500 mL)
  8. customsucked dry
  9. customdried overnight (100°)
  10. customRecrystallization from EtOH/Et2O (3×)

出典と根拠

ORDレコード
ord-5dfd6b267c3a49948c3bc185447c1251
出典データセット
uspto-grants-1985_04
特許番号
US04511582

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