Tetrahydrofuran → HCID 178421673, compound

HRID 2112525Notes

Reaction equation

HRID 2112525 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:14]2[CH:15]=[C:16]([CH3:20])[C:17]([CH3:19])=[CH:18][C:13]=2[N:12]=[C:11]2[N:21](CC=C)[NH:22][C:23]([CH3:24])=[C:10]2[N:9]=1.O1CCCC1.[H-].C([Al+]CC(C)C)C(C)C>C1(C)C=CC=CC=1.[Ni](Cl)Cl.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:14]2[CH:15]=[C:16]([CH3:20])[C:17]([CH3:19])=[CH:18][C:13]=2[N:12]=[C:11]2[NH:21][NH:22][C:23]([CH3:24])=[C:10]2[N:9]=1

Participants

6

Reactant 3

HCID 8028TetrahydrofuranHCID 21225700DiisobutylaluminumhydrideHCID 178456639HCID 178456639, compound

Product 1

HCID 178421673HCID 178421673, compoundYield 62.2%

Reagents, catalysts & solvents 2

HCID 2724937Dichloro(1,1'-(1,3-propanediyl)bis(1,1-diphenylphosphine-kappaP))nickelCatalystHCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 2.7 g (0.00716 mole) of 5-(2-chlorophenyl)-1,2-dihydro-3,7,8-trimethyl-1-(2-propenyl)-pyrazolo[3,4-b][1,4]benzodiazepine (XIVw), 0.155 g (0.00029 mole) of 1,3-bis(diphenylphosphino)propane nickel (II) chloride and 140 mL of anhydrous tetrahydrofuran at −40° C. was added 43 mL of 1M diisobutylaluminum hydride in toluene. The mixture was stirred at 0° C. for 6 hours and then quenched by the careful addition of ice water. The mixture was extracted twice with ethyl acetate. The combined ethyl acetate extracts were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography, eluting with ethyl acetate-dichloromethane (1:1) to give 1.5 g of 5-(2-chlorophenyl)-1,2-dihydro-3,7,8-trimethyl-pyrazolo[3,4-b][1,4]benzodiazepine (IVw) as an orange solid. MH+/Z=337.

Workup

  1. customquenched by the careful addition of ice water
  2. extractionThe mixture was extracted twice with ethyl acetate
  3. dry with materialThe combined ethyl acetate extracts were dried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by silica gel chromatography
  7. washeluting with ethyl acetate-dichloromethane (1:1)

Sources & evidence

ORD record
ord-f9c8b93143ed4a3fb30525e2f2e8244b
Source dataset
uspto-grants-2009_04
Patent number
US07524840B2

Reaction notes

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