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

HRID 1981052

반응식

HRID 1981052 반응식
[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]

참가 물질

11

반응물 6

HCID 313Hydrochloric Acid2회HCID 15312-Amino-2-methyl-1,3-propanediolHCID 6101p-Toluenesulfonic acidHCID 6451Bromocresol GreenHCID 78437Phenanthrene-9-carbaldehydeHCID 5003444Sodium cyanoborohydride2회

생성물 1

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

시약·촉매·용매 4

HCID 702Ethanol용매3회HCID 962Water용매2회HCID 1140Toluene용매HCID 3283Diethyl Ether용매

실험 절차

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).

후처리

  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×)

출처 및 근거

ORD 기록
ord-5dfd6b267c3a49948c3bc185447c1251
출처 데이터셋
uspto-grants-1985_04
특허 번호
US04511582

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