tert-Butanol → [7-(2-chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridin-3-yl]carbamic acid tert-butyl ester

HRID 916214

Reaktionsgleichung

Reaktionsgleichung von HRID 916214
[Cl:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4]([CH3:9])[C:3]=1[N:10]1[CH2:15][CH2:14][CH2:13][C:12]2=[C:16](C(O)=O)[N:17]([CH3:19])[N:18]=[C:11]12.[C:23]([OH:27])([CH3:26])([CH3:25])[CH3:24].C([N:30]([CH2:33]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:42])C=CC=CC=1>C(OCC)(=O)C.CCCCCC>[C:23]([O:27][C:33](=[O:42])[NH:30][C:16]1[N:17]([CH3:19])[N:18]=[C:11]2[C:12]=1[CH2:13][CH2:14][CH2:15][N:10]2[C:3]1[C:4]([CH3:9])=[CH:5][C:6]([CH3:8])=[CH:7][C:2]=1[Cl:1])([CH3:26])([CH3:25])[CH3:24]

Komponenten

7

Edukt 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 221362637-(2-chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-3-carboxylic acid

Produkt 1

HCID 23527225[7-(2-chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridin-3-yl]carbamic acid tert-butyl ester

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8058HexaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

A 159 mg sample of 7-(2-chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridine-3-carboxylic acid was combined with 2.5 mL of t-butanol and 140 μL of triethylamine was added. Then 129 μL of diphenylphosphoryl azide was added and the reaction mixture was heated to 85° C. for 2 h. After cooling to room temperature, the reaction mixture was dissolved in ethyl acetate and washed with 1M aqueous sodium bisulfate, aqueous sodium bicarbonate, water, and brine. The ethyl acetate solution was dried with magnesium sulfate and concentrated to give material which was chromatographed on silica gel eluting with an acetone/hexane gradient. Product containing fractions were concentrated to give a solid residue which was slurried in a small amount of boiling hexane. After the mixture cooled to room temperature, the solids were collected by filtration to provide 71 mg of [7-(2-chloro-4,6-dimethylphenyl)-2-methyl-4,5,6,7-tetrahydro-2H-pyrazolo[3,4-b]pyridin-3-yl]carbamic acid tert-butyl ester, mp 171.4-175.7° C.

Aufarbeitung

  1. additionwas added
  2. temperatureAfter cooling to room temperature
  3. washwashed with 1M aqueous sodium bisulfate, aqueous sodium bicarbonate, water, and brine
  4. dry with materialThe ethyl acetate solution was dried with magnesium sulfate
  5. concentrationconcentrated
  6. customto give material which
  7. customwas chromatographed on silica gel eluting with an acetone/hexane gradient
  8. additionProduct containing fractions
  9. concentrationwere concentrated
  10. customto give a solid residue which
  11. temperatureAfter the mixture cooled to room temperature
  12. filtrationthe solids were collected by filtration

Quellen und Nachweise

ORD-Eintrag
ord-8860be654ed245ea95e46415e8a4570b
Quelldatensatz
uspto-grants-2007_09
Patentnummer
US07268146B2

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