Butyl vinyl ether → 1-(6,6-Dioxo-5,6-dihydro-6lambda*6*-thia-4,5-diaza-chrysen-12-yl)-ethanone

HRID 513796Notes

Reaction equation

HRID 513796 reaction equation
[CH:1]([O:3]CCCC)=[CH2:2].C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])([O-])=O.[K+].[K+].Br[C:44]1[CH:45]=[C:46]2[C:55](=[C:56]3[C:61]=1[CH:60]=[CH:59][CH:58]=[N:57]3)[NH:54][S:53](=[O:63])(=[O:62])[C:52]1[C:47]2=[CH:48][CH:49]=[CH:50][CH:51]=1>C1COCC1.Cl.CCOC(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2].CN(C=O)C.O>[O:62]=[S:53]1(=[O:63])[C:52]2[C:47](=[CH:48][CH:49]=[CH:50][CH:51]=2)[C:46]2[C:55](=[C:56]3[C:61](=[C:44]([C:1](=[O:3])[CH3:2])[CH:45]=2)[CH:60]=[CH:59][CH:58]=[N:57]3)[NH:54]1

Participants

10

Reactant 4

HCID 8108Butyl vinyl etherHCID 11430Potassium CarbonateHCID 812191,3-Bis(diphenylphosphino)propaneHCID 1675994412-bromo-5H-6-thia-4,5-diaza-chrysene 6,6-dioxide

Product 1

HCID 681830641-(6,6-Dioxo-5,6-dihydro-6lambda*6*-thia-4,5-diaza-chrysen-12-yl)-ethanoneYield 30.5%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 313Hydrochloric AcidSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 21962138N,N-Dimethylformamide--water (1/1)Solvent

Conditions

Temperature
90 °C

Procedure

A solution of DMF/H2O (4:1) was de-gassed for 15 min. DMF/H2O (4:1, 6 ml) and 1-vinyloxy-butane (0.59 ml, 4.53 mmol) were added to a mixture of Pd(OAc)2 (6 mg, 26 μmol), 1,3-bis(diphenylphosphino)propane (24 mg, 57 K2CO3 (150 mg, 1.01 mmol), 12-bromo-5H-6-thia-4,5-diaza-chrysene 6,6-dioxide 545 (370 mg, 0.91 mmol), under nitrogen. The mixture was heated at 90° C. for 2.5 h in the microwave. After cooling, the reaction was diluted with THF (2 ml) and 1M HCl (2 ml) and the mixture was stirred for 18 h. The mixture was further diluted with EtOAc (10 ml) and washed with water (10 ml, ×3). The precipitate formed during work-up was collected by filtration of the organic and aqueous phases and was found to be the title compound (140 mg, 40%). The organic phase was dried (Na2SO4) and concentrated in vacuo. The residue was triturated from MeOH to give the title compound (90 mg, 24%) which was used in the next step without further purification.

Workup

  1. customA solution of DMF/H2O (4:1) was de-gassed for 15 min
  2. temperatureAfter cooling
  3. washwashed with water (10 ml, ×3)
  4. customThe precipitate formed during work-up
  5. filtrationwas collected by filtration of the organic and aqueous phases
  6. dry with materialThe organic phase was dried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customThe residue was triturated from MeOH

Sources & evidence

ORD record
ord-9cf66d933baa40a1ba1220de3821cd77
Source dataset
uspto-grants-2015_08
Patent number
US09102688B2

Reaction notes

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