Dimethylamine → HCID 131719461, compound

HRID 1735025Notes

Reaction equation

HRID 1735025 reaction equation
[Br:1][C:2]1[CH:22]=[CH:21][C:5]2[N:6]3[CH2:20][CH2:19][C:18]4[C:7]3=[C:8]([CH:15]=[CH:16][CH:17]=4)[C:9](=[O:14])[N:10]([CH2:11][C:12]#[CH:13])[C:4]=2[CH:3]=1.[CH2:23]=O.[CH3:25][NH:26][CH3:27].[C:28]([OH:35])(=[O:34])/[CH:29]=[CH:30]/[C:31]([OH:33])=[O:32]>O1CCOCC1.ClCCl.CCOCC.C(O)C.Cl[Cu]>[C:28]([OH:35])(=[O:34])/[CH:29]=[CH:30]/[C:31]([OH:33])=[O:32].[Br:1][C:2]1[CH:22]=[CH:21][C:5]2[N:6]3[CH2:20][CH2:19][C:18]4[C:7]3=[C:8]([CH:15]=[CH:16][CH:17]=4)[C:9](=[O:14])[N:10]([CH2:11][C:12]#[C:13][CH2:25][N:26]([CH3:23])[CH3:27])[C:4]=2[CH:3]=1.[Br:1][C:2]1[CH:22]=[CH:21][C:5]2[N:6]3[CH2:20][CH2:19][C:18]4[C:7]3=[C:8]([CH:15]=[CH:16][CH:17]=4)[C:9](=[O:14])[N:10]([CH2:11][C:12]#[C:13][CH2:25][N:26]([CH3:28])[CH3:27])[C:4]=2[CH:3]=1

Participants

10

Reactant 4

HCID 674DimethylamineHCID 712FormaldehydeHCID 444972Fumaric AcidHCID 15380035HCID 15380035, compound

Product 1

HCID 131719461HCID 131719461, compoundYield 92.7%

Reagents, catalysts & solvents 5

HCID 62652Cuprous chlorideCatalystHCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 9-bromo-1,2-dihydro-7-(2-propynyl)-benzo[b]pyrrolo[3,2,1-jk][1,4]benzodiazepin-6-one (4.0 gm, 11.3 mmoles), paraformaldehyde (3 gm), dimethylamine (40% in water, 4 gm, 3 eq) and CuCl (150 mg) in 1,4-dioxane (50 ml) was stirred at room temperature for 30 minutes, then heated on a water bath (50° C.) for 2 hours. When the reaction was over, the mixture was diluted with dichloromethane (200 ml). The insolubles were filtered through a pad of celite. The solution was concentrated to a crude oil (7.5 gm). The desired product was purified by flash chromatography on a silica gel column (SiO2, 65 gm, eluted with 1% CH3OH:0.5% diethylamine:99% DCM, 1.2 l). The material thus obtained weighed 4.58 gm (98%). This oily product was dissolved in ether and added to a solution of fumaric acid (1.27 gm, 1.0 eq) in hot ethanol (15 ml). Crystals (4.75 gm) were formed slowly over a 2 hour period. Recrystallization from hot acetone (350 ml, concentrated down to 75 ml) yielded 4.21 gm, 71%, of light yellow crystals, top: 177°-179° C.

Workup

  1. temperatureheated on a water bath (50° C.) for 2 hours
  2. filtrationThe insolubles were filtered through a pad of celite
  3. concentrationThe solution was concentrated to a crude oil (7.5 gm)
  4. customThe desired product was purified by flash chromatography on a silica gel column (SiO2, 65 gm, eluted with 1% CH3OH:0.5% diethylamine:99% DCM, 1.2 l)
  5. customThe material thus obtained

Sources & evidence

ORD record
ord-7ac40929e8e44abc911943e29051796b
Source dataset
uspto-grants-1996_07
Patent number
US05536717

Reaction notes

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