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Sodium Azide → 5-(Azidomethyl)-1,6-diethyl-N-(tetrahydro-2H-pyran-4-yl)-1H-pyrazolo[3,4-b]pyridin-4-amine

HRID 662016
Notes
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Reaction equation

HRID 662016 reaction equation
[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([CH2:21][CH3:22])=[C:10]([CH2:19]O)[C:11]([NH:12][CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[C:6]2[CH:5]=[N:4]1)[CH3:2].[N-:23]=[N+:24]=[N-:25].[Na+]>CS(C)=O.S(Cl)(Cl)=O>[N:23]([CH2:19][C:10]1[C:9]([CH2:21][CH3:22])=[N:8][C:7]2[N:3]([CH2:1][CH3:2])[N:4]=[CH:5][C:6]=2[C:11]=1[NH:12][CH:13]1[CH2:18][CH2:17][O:16][CH2:15][CH2:14]1)=[N+:24]=[N-:25]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 2

HCID 33557Sodium AzideHCID 59683222[1,6-Diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methanol

Product 1

HCID 596832325-(Azidomethyl)-1,6-diethyl-N-(tetrahydro-2H-pyran-4-yl)-1H-pyrazolo[3,4-b]pyridin-4-amineYield 218.1%

Reagents, catalysts & solvents 2

HCID 24386Thionyl ChlorideCatalyst
HCID 679
Dimethyl Sulfoxide
Solvent

Conditions

Temperature
80 °C

Procedure

To [1,6-diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methanol (24.9 g, 82 mmol) was added thionyl chloride (90 mL, 1.23 mmol) and the mixture was heated to 80° C. under an atmosphere of nitrogen. After 2 h the mixture was cooled, evaporated and the residue azeotroped with toluene. The residue was then dissolved in a solution of sodium azide (7.98 g, 123 mmol) in DMSO (120 mL). The mixture was stirred for 16 h. The above procedure was repeated on the same scale and the 2 reactions combined for work-up. The combined DMSO mixture was partitioned between ethyl acetate and aqueous sodium bicarbonate. The aqueous phase was extracted thoroughly with ethyl acetate and the combined organics were washed with water, then brine, dried and evaporated to afford 58.9 g of a brown solid. The product was purified by flash chomatography on 1.5 kg of silica using a step gradient from 3:1 to 2:1 cyclohexane/ethyl acetate to afford 39.94 g of the title compound. LC-MS m/z 330 (M+H)+, 2.21 min (ret time).

Workup

  1. temperatureAfter 2 h the mixture was cooled
  2. customevaporated
  3. customthe residue azeotroped with toluene
  4. customThe combined DMSO mixture was partitioned between ethyl acetate and aqueous sodium bicarbonate
  5. extractionThe aqueous phase was extracted thoroughly with ethyl acetate
  6. washthe combined organics were washed with water
  7. dry with materialbrine, dried
  8. customevaporated

Sources & evidence

ORD record
ord-b3c3c1f8012940c6aa74fd9fb268e2df
Source dataset
uspto-grants-2011_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08084449B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes