Diallylamine → HCID 86753944, compound

HRID 1737322Notes

Reaction equation

HRID 1737322 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]=[C:20]([Cl:21])[C:15]=3[C:14](=[O:22])[N:13]3[CH2:23][CH2:24][CH2:25][C@H:12]3[C:11]=12)=[O:6])[C:2]#[CH:3].IN1C(=O)CCC1=O.[CH2:34]([NH:37][CH2:38][CH:39]=[CH2:40])[CH:35]=[CH2:36]>C(O)(=O)C>[Cl:21][C:20]1[C:15]2[C:14](=[O:22])[N:13]3[CH2:23][CH2:24][CH2:25][C@H:12]3[C:11]3[N:10]([CH:9]=[N:8][C:7]=3[C:5]3[O:6][C:2]([CH2:3][N:37]([CH2:38][CH:39]=[CH2:40])[CH2:34][CH:35]=[CH2:36])=[CH:1][N:4]=3)[C:16]=2[CH:17]=[CH:18][CH:19]=1

Participants

5

Reactant 3

HCID 31279DiallylamineHCID 120273N-IodosuccinimideHCID 86753943HCID 86753943, compound

Product 1

HCID 86753944HCID 86753944, compoundYield 29%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A solution of 7.95 g (0.0224 mol) of (S)-8-chloro-9-oxo-11,12,13,13a-tetrahydro-9H-imidazo[1,5-a]pyrrolo[2,1-c][1,4]benzodiazepine-1-carboxylic acid prop-2-ynylamide in 200 ml of acetic acid was treated with 7.56 g (0.0336 mol) of N-iodosuccinimide while gassing with argon. After stirring at room temperature for 19 hrs. and at 50° for 4 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 23.9 ml (0.194 mol) of diallylamine and stirred at room temperature for 48 hrs. The solution 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 ethyl acetate. The organic phase was concentrated, the dark 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 2.89 g (29%) of (S)-8-chloro-1-(5-diallylaminomethyl-oxazol-2-yl)-11,12,13,13a-tetrahydro-9H-imidazo[1,5-a]pyrrolo[2,1-c][1,4]benzodiazepin-9-one as a yellow foam; [α]D20 =+11.3° (MeOH, c=1%).

Workup

  1. waitand at 50° for 4 hrs
  2. customthe dark brown suspension obtained
  3. dry with materialdried azeotropically several times with toluene
  4. dissolutionThe red-brown solid residue was dissolved in 100 ml of THF
  5. stirringstirred at room temperature for 48 hrs
  6. customThe solution obtained
  7. customthe residue was partitioned between ethyl acetate and 1N aqueous hydrochloric acid
  8. extractionextracted
  9. extractionextracted with ethyl acetate
  10. concentrationThe organic phase was concentrated
  11. customthe dark brown product was chromatographed over basic Alox (grade III) with dichloromethane/ethyl acetate 4:1 as the eluent
  12. customrecrystallized from hot isopropyl ether

Sources & evidence

ORD record
ord-84bd979a6ec84b72a74d010ba2d85f52
Source dataset
uspto-grants-1999_10
Patent number
US05962450

Reaction notes

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