Dipropylamine → HCID 86753938, compound

HRID 1737315Notes

Reaction equation

HRID 1737315 reaction equation
[CH2:1]([NH:4][C:5]([C:7]1[N:8]=[CH:9][N:10]2[C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[C:14](=[O:21])[N:13]3[CH2:22][CH2:23][C@H:12]3[C:11]=12)=[O:6])[C:2]#[CH:3].IN1C(=O)CCC1=O.[CH2:32]([NH:35][CH2:36][CH2:37][CH3:38])[CH2:33][CH3:34]>C(O)(=O)C>[CH2:32]([N:35]([CH2:3][C:2]1[O:6][C:5]([C:7]2[N:8]=[CH:9][N:10]3[C:16]4[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=4[C:14](=[O:21])[N:13]4[CH2:22][CH2:23][C@H:12]4[C:11]=23)=[N:4][CH:1]=1)[CH2:36][CH2:37][CH3:38])[CH2:33][CH3:34]

Participants

5

Reactant 3

HCID 8902DipropylamineHCID 120273N-IodosuccinimideHCID 86753939HCID 86753939, compound

Product 1

HCID 86753938HCID 86753938, compoundYield 27%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A solution of 3.06 g (0.010 mol) of (S)-9-oxo-12,12a-dihydro-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepine-1-carboxylic acid prop-2-ynylamide in 200 ml of acetic acid was treated with 3.36 g (0.015 mol) of N-iodosuccinimide while gassing with argon. After stirring at room temperature for 47 hrs. the dark brown suspension obtained was completely freed from the solvents and dried azeotropically several times with toluene. The red-brown solid residue was dissolved in 100 ml of THF, treated with 11.9 ml (0.0865 mol) of dipropylamine and stirred at room temperature for 17 hrs. The suspension obtained was completely freed from the solvents, the residue was partitioned between ethyl acetate and 1N aqueous hydrochloric acid and extracted. The aqueous-acidic phase was made basic and extracted with dichloromethane. The organic phase was concentrated, the brown product was chromatographed over basic Alox (grade III) with dichloromethane/ethyl acetate 4:1 as the eluent and recrystallized from hot isopropyl ether. There were obtained 1.09 g (27%) of (S)-1-(5-dipropylaminomethyl-oxazol-2-yl)-12,12a-dihydro-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepin-9-one as yellowish crystals; m.p. 132-134° and [α]D20 =-187.8° (MeOH, c=1%).

Workup

  1. customthe dark brown suspension obtained
  2. dry with materialdried azeotropically several times with toluene
  3. dissolutionThe red-brown solid residue was dissolved in 100 ml of THF
  4. stirringstirred at room temperature for 17 hrs
  5. customThe suspension obtained
  6. customthe residue was partitioned between ethyl acetate and 1N aqueous hydrochloric acid
  7. extractionextracted
  8. extractionextracted with dichloromethane
  9. concentrationThe organic phase was concentrated
  10. customthe brown product was chromatographed over basic Alox (grade III) with dichloromethane/ethyl acetate 4:1 as the eluent
  11. customrecrystallized from hot isopropyl ether

Sources & evidence

ORD record
ord-25ab6d1d6c624c5491e3b2aed701ae84
Source dataset
uspto-grants-1999_10
Patent number
US05962450

Reaction notes

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