Triphenylphosphine → 9-[2-[2-aminoethyl(triphenylmethyl)amino]ethyl]-9H-pyrido[3,4-b]indole

HRID 379615Notes

Reaction equation

HRID 379615 reaction equation
[CH:1]1[CH:2]=[CH:3][C:4]2[NH:13][C:12]3[CH:11]=[N:10][CH:9]=[CH:8][C:7]=3[C:5]=2[CH:6]=1.[H-].[Na+].Cl[CH2:17][CH2:18][N:19]([CH2:39][CH2:40]Cl)[C:20]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[N-:42]=[N+]=[N-].[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C)C=O.C1(C)C=CC=CC=1>[NH2:42][CH2:17][CH2:18][N:19]([C:20]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[CH2:39][CH2:40][N:13]1[C:4]2[C:5](=[CH:6][CH:1]=[CH:2][CH:3]=2)[C:7]2[CH:8]=[CH:9][N:10]=[CH:11][C:12]1=2

Participants

8

Reactant 5

HCID 11776TriphenylphosphineHCID 24758Sodium hydrideHCID 33557Sodium AzideHCID 64961Beta-CarbolineHCID 4195463Bis(2-chloroethyl)(triphenylmethyl)amine

Product 1

HCID 183665539-[2-[2-aminoethyl(triphenylmethyl)amino]ethyl]-9H-pyrido[3,4-b]indoleYield 20.5%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 506 mg (3.01 mmol) of norharman in N,N-dimethylformamide (15 ml) was added 132 mg (3.3 mmol) of sodium hydride in small portions under ice cooling, followed by stirring at room temperature for 30 minutes. To the reaction mixture was added 3.84 g (10 mmol) of bis(2-chloroethyl)(triphenylmethyl)amine and the mixture was reacted at 110° C. for 3 hours. Then, 650 mg (10 mmol) of sodium azide was added, followed by reaction at 100° C. for 2 hours. After cooling to room temperature, the resulting suspension was diluted with toluene and then washed with water and saturated saline. The toluene layer was dried over sodium sulfate and then concentrated under reduced pressure. The residue was added with tetrahydrofuran (3 ml) and water (1 ml) to dissolve the former in the latter. To the resulting solution was added 787 mg (3.0 mmol) of triphenylphosphine and the mixture was reacted at 50° C. for 2 hours. Generation of a gas was observed for a while after the initiation of the reaction and it lasted for about 1.5 hours. After completion of the reaction, the reaction mixture was concentrated, followed by purification through chromatography on a silica gel column (mobile phase; chloroform:methanol:aqueous ammonia=90:9.7:0.3 (v/v)), whereby 306 mg (20.5%) of the title compound was obtained. The physical properties of the resulting compound are as follows:

Workup

  1. customthe mixture was reacted at 110° C. for 3 hours
  2. customfollowed by reaction at 100° C. for 2 hours
  3. temperatureAfter cooling to room temperature
  4. washwashed with water and saturated saline
  5. dry with materialThe toluene layer was dried over sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. additionThe residue was added with tetrahydrofuran (3 ml) and water (1 ml)
  8. dissolutionto dissolve the former in the latter
  9. customthe mixture was reacted at 50° C. for 2 hours
  10. customafter the initiation of the reaction and it
  11. waitlasted for about 1.5 hours
  12. customAfter completion of the reaction
  13. concentrationthe reaction mixture was concentrated
  14. customfollowed by purification through chromatography on a silica gel column (mobile phase; chloroform:methanol:aqueous ammonia=90:9.7:0.3 (v/v))

Sources & evidence

ORD record
ord-c7b9105a8c4041c08a1b32d7bff0bcd8
Source dataset
uspto-grants-2001_10
Patent number
US06300331B1

Reaction notes

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