Hydrochloric Acid → HCID 10641825, compound

HRID 1251492Notes

Reaction equation

HRID 1251492 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([CH:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][C:3]=1[N:11]1[C:19]2[C:14](=[C:15](C)[CH:16]=[C:17]([CH3:20])[N:18]=2)[C:13]([C:22]#[N:23])=[CH:12]1.COC(OC)(C)CC=O.Cl.CCCCCC.C(OCC)(=O)C>C(O)C.C(OCC)(=O)C>[Br:1][C:2]1[CH:7]=[C:6]([CH:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][C:3]=1[N:11]1[C:19]2[C:14](=[CH:15][CH:16]=[C:17]([CH3:20])[N:18]=2)[C:13]([C:22]#[N:23])=[CH:12]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 10737736HCID 10737736, compoundHCID 21226206Ethyl acetate hexaneHCID 23065701HCID 23065701, compound

Product 1

HCID 10641825HCID 10641825, compoundYield 9.8%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 1.085 g (5.07 mmole) of the product from Example 64 (part B) and 0.80 mL (0.797 g; 6.03 mmole) of acetoacetaldehyde dimethyl acetal in 20 mL of ethanol was added 0.10 mL of conc. hydrochloric acid. The mixture was refluxed for 16 hours, then cooled and evaporated to give a dark, thick oil. TLC on silica gel with 70:30 hexane-ethyl acetate showed two major spots at Rf 0.47 and 0.41. The oil was dissolved in ethyl acetate, 20 mL silica gel powder was added, and the mixture was evaporated to dryness. The powdery residue was loaded on top of a column of 60 mL of silica gel in hexane. The column was eluted in step gradients of 0, 5, 10, 15, 20, and 25% ethyl acetate in hexane. The first fraction to elute was 0.32 g of the desired 1-(2-bromo-4-isopropyl-phenyl)-3-cyano-6-methyl-7-azaindole, Rf 0.47. The material can be crystallized from hexane to give 176 mg of crystals; mp 176.0° C. Mass spec. (m+H)+=354.0595; calcd., 354.0606.

Workup

  1. temperatureThe mixture was refluxed for 16 hours
  2. temperaturecooled
  3. customevaporated
  4. customto give a dark, thick oil
  5. addition20 mL silica gel powder was added
  6. customthe mixture was evaporated to dryness
  7. washThe column was eluted in step gradients of 0, 5, 10, 15, 20, and 25% ethyl acetate in hexane
  8. washThe first fraction to elute
  9. customThe material can be crystallized from hexane

Sources & evidence

ORD record
ord-31d49ebc89004a30afb2301c1ae4c669
Source dataset
uspto-grants-2002_01
Patent number
US06342503B1

Reaction notes

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