Hydrochloric Acid → 5-Methyl-3,5,10,11a-tetrahydro-benzo[e]pyrrolo[1,2-a][1,4]diazepin-11-one

HRID 584780Notes

Reaction equation

HRID 584780 reaction equation
C([N:4]1[CH:10]([CH3:11])[C:9]2[CH:12]=[CH:13][CH:14]=[CH:15][C:8]=2[NH:7][C:6](=[O:16])[CH:5]1[CH:17]=[CH:18][C:19]1C=CC=CC=1)C=C.Cl>CCOCC.C=CC1C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Ru]Cl>[CH3:11][CH:10]1[N:4]2[CH2:19][CH:18]=[CH:17][CH:5]2[C:6](=[O:16])[NH:7][C:8]2[CH:15]=[CH:14][CH:13]=[CH:12][C:9]1=2

Participants

5

Reactant 2

HCID 313Hydrochloric Acid2×HCID 697312034-Allyl-5-methyl-3-styryl-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-one

Product 1

HCID 223418215-Methyl-3,5,10,11a-tetrahydro-benzo[e]pyrrolo[1,2-a][1,4]diazepin-11-oneYield 61%

Reagents, catalysts & solvents 2

HCID 60145889Benzylidene-bis(triphenylphosphine)ruthenium dichlorideCatalystHCID 3283Diethyl EtherSolvent

Procedure

The product of Example 15 (103 mg, 0.32 mmol) was first converted to the HCl salt with excess 1M HCl in ether, and all of the volatiles were removed. The resulting solid was then dissolved in dry dichloromethane (15 mL) and bis(tricyclohexylphosphine)benzylidine ruthenium(IV) dichloride (132 mg, 0.16 mmol) was added, and the flask was flushed with Ar(g). The reaction was allowed to proceed at room temperature for three days, after which time, the reaction was diluted with an additional 10 mL of dichloromethane, and transferred to a separatory funnel. The organic layer was washed with a saturated solution of sodium bicarbonate (3×15 mL), the aqueous layers were then combined and extracted with dichloromethane (2×10 mL). The organic layers were then combined, washed once with brine (15 mL), dried over magnesium sulfate, filtered and evaporated to yield a crude residue which was purified by flash column chromatography using ethyl acetate-hexane (3:1) to yield 32 mg (61% yield) of a dark oil. 1H NMR (360 MHz, CDCl3) δ 7.60 (bs, 1H), 7.42 (d, J=7.6 Hz, 1H), 7.32-7.19 (m, 2H), 7.00-6.95 (m, 1H), 6.16-6.10 (m, 1H), 5.88-5.82 (m, 1H), 4.34 (bs, 1H), 3.96-3.81 (m, 2H), 3.55-3.46 (m, 1H), 1.58 (d, J=6.5 Hz, 3H).

Workup

  1. customall of the volatiles were removed
  2. dissolutionThe resulting solid was then dissolved in dry dichloromethane (15 mL)
  3. customthe flask was flushed with Ar(g)
  4. additionafter which time, the reaction was diluted with an additional 10 mL of dichloromethane
  5. customtransferred to a separatory funnel
  6. washThe organic layer was washed with a saturated solution of sodium bicarbonate (3×15 mL)
  7. extractionextracted with dichloromethane (2×10 mL)
  8. washwashed once with brine (15 mL)
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. customevaporated
  12. customto yield a crude residue which
  13. customwas purified by flash column chromatography

Sources & evidence

ORD record
ord-94e5a7c6f5b84dcdb37209af95cadbb4
Source dataset
uspto-grants-2005_08
Patent number
US06927294B1

Reaction notes

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