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Dimethylformamide → 1-ethyl-3,3,5-trimethyl-2,4-dioxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepine-7-carbonitrile

HRID 1504114
Notes
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Reaction equation

HRID 1504114 reaction equation
[CH2:1]([N:3]1[C:9](=[O:10])[C:8]([CH3:12])([CH3:11])[C:7](=[O:13])[N:6]([CH3:14])[C:5]2[CH:15]=[C:16](OS(C(F)(F)F)(=O)=O)[CH:17]=[CH:18][C:4]1=2)[CH3:2].[CH3:27][N:28](C=O)C>[C-]#N.[Zn+2].[C-]#N.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].[Zn]>[CH2:1]([N:3]1[C:9](=[O:10])[C:8]([CH3:12])([CH3:11])[C:7](=[O:13])[N:6]([CH3:14])[C:5]2[CH:15]=[C:16]([C:27]#[N:28])[CH:17]=[CH:18][C:4]1=2)[CH3:2]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 2

HCID 6228DimethylformamideHCID 86670475Trifluoromethanesulfonic acid 1-ethyl-3,3,5-trimethyl-2,4-dioxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepine-7-yl ester

Product 1

HCID 669604771-ethyl-3,3,5-trimethyl-2,4-dioxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepine-7-carbonitrile

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)Catalyst
HCID 23994
Zinc
Catalyst
HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)Catalyst
HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalyst

Conditions

Temperature
170 °C

Procedure

Trifluoromethanesulfonic acid 1-ethyl-3,3,5-trimethyl-2,4-dioxo-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepine-7-yl ester(0.12 g), zinc cyanide(70 mg), tris(dibenzylideneacetone) dipalladium 7 mg), 1,1′-bis(diphenylphosphino) ferrocene(8 mg), and zinc powder(2 mg) were added to DMF (1 ml), and the mixture was heated for 20 minutes at 170° C. (microwave reactor). The reaction liquid was cooled to room temperature, and subjected to celite filtration. The filtrate was condensed under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate=50:50→0:100). The purified product was condensed under reduced pressure to give the title compound(77 mg) as a white solid.

Workup

  1. customThe reaction liquid
  2. temperaturewas cooled to room temperature
  3. filtrationsubjected to celite filtration
  4. customcondensed under reduced pressure
  5. customthe residue was purified by silica gel column chromatography (hexane: ethyl acetate=50:50→0:100)
  6. customcondensed under reduced pressure

Sources & evidence

ORD record
ord-a0dd4503c302459c83027fdc64e11a03
Source dataset
uspto-grants-2015_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09212187B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes