Ammonia → (S)-8-chloro-11,12,13,13a-tetrahydro-1-vinyl-9H-imidazo[1,5-a]pyrrolo[2,1-c][1,4]benzodiazepin-9-one

HRID 1606966Notes

Reaction equation

HRID 1606966 reaction equation
[NH2-].[Na+].[Cl:3][C:4]1[C:9]2[C:10](=[O:23])[N:11]3[CH2:22][CH2:21][CH2:20][C@H:12]3[C:13]3[N:14]([CH:15]=[N:16][C:17]=3[CH:18]=O)[C:8]=2[CH:7]=[CH:6][CH:5]=1.N.O1CCC[CH2:26]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:3][C:4]1[C:9]2[C:10](=[O:23])[N:11]3[CH2:22][CH2:21][CH2:20][C@H:12]3[C:13]3[N:14]([CH:15]=[N:16][C:17]=3[CH:18]=[CH2:26])[C:8]=2[CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 4

HCID 222AmmoniaHCID 8028TetrahydrofuranHCID 24533Sodium amideHCID 22840050(S)-8-chloro-11,12,13,13a-tetrahydro-9-oxo-9H-imidazo [1,5-a]pyrrolo[2,1-c][1,4]benzodiazepine-1-carboxaldehyde

Product 1

HCID 53855314(S)-8-chloro-11,12,13,13a-tetrahydro-1-vinyl-9H-imidazo[1,5-a]pyrrolo[2,1-c][1,4]benzodiazepin-9-one

Reagents, catalysts & solvents 1

HCID 74505Methyltriphenyliphosphonium bromideCatalyst

Procedure

20.8 g of an equimolar mixture of methyltriphenylphosphonium bromide and sodium amide were stirred for 20 minutes in 80 ml of tetrahydrofuran. 15.08 g (50 mmol) of (S)-8-chloro-11,12,13,13a-tetrahydro-9-oxo-9H-imidazo[1,5-a]pyrrolo[2,1-c][1,4]benzodiazepine-1-carboxaldehyde was then added portionwise thereto, whereby the temperature rose to 43° with the evolution of ammonia. The mixture was stirred at room temperature for 1 hour, filtered and the filtrate was evaporated. After chromatography of the residue on silica gel while eluting with cyclohexane/ether/isopropanol (3:3:1) and recrystallization from ethyl acetate there was obtained (S)-8-chloro-11,12,13,13a-tetrahydro-1-vinyl-9H-imidazo[1,5-a]pyrrolo[2,1-c][1,4]benzodiazepin-9-one of melting point 213°-215°.

Workup

  1. filtrationfiltered
  2. customthe filtrate was evaporated
  3. washAfter chromatography of the residue on silica gel while eluting with cyclohexane/ether/isopropanol (3:3:1) and recrystallization from ethyl acetate

Sources & evidence

ORD record
ord-2d2e2a71fdb64b2d9ca2907ac6cb71dd
Source dataset
uspto-grants-1989_09
Patent number
US04863920

Reaction notes

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