Sodium Azide → HCID 86728458, compound

HRID 571568Notes

Reaction equation

HRID 571568 reaction equation
[CH3:1][C:2]1[NH:3][C:4]2[C:9]([CH:10]=1)=[CH:8][C:7]([NH2:11])=[CH:6][CH:5]=2.N([O-])=O.[Na+].[N-:16]=[N+:17]=[N-].[Na+]>CC(O)=O.O>[CH3:1][C:2]1[NH:3][C:4]2[C:9]([CH:10]=1)=[CH:8][C:7]([N:11]=[N+:16]=[N-:17])=[CH:6][CH:5]=2

Participants

6

Reactant 3

HCID 33557Sodium AzideHCID 27339925-Amino-2-methylindoleHCID 23668193Sodium Nitrite

Product 1

HCID 86728458HCID 86728458, compoundYield 66%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent3×

Procedure

In an oven dried, 250 mL round bottom flask flushed with argon, compound 33 (400 mg, 2.74 mmol, 146.19 MW) was dissolved in 90% AcOH (20 mL). After complete solvation, the reaction was placed at 0° C. and protected from light with foil. NaNO2 (1.1×, 3.01 mmol, 208 mg, 69.00 MW) dissolved in cold H2O (2 mL) was added dropwise and stirred for ten minutes. NaN3 (1.1×, 3.01 mmol, 196 mg, 65.01 MW) dissolved in cold H2O (2 mL) was added dropwise. After one hour the reaction was poured into water (40 mL), which was extracted 3 times with CH2Cl2 (40 mL each). The extracts were washed with sodium bicarbonate and brine (100 mL each), dried with sodium sulfate, filtered and concentrated. Purification by silica flash chromatography (100% CH2Cl2) yielded the azide as a light brown solid (310 mg, 66%). 1H NMR (600 MHz, d6-DMSO): δ 11.025 (s, 1H, N—H), 7.295-7.281 (d, J=8.4, 1H, indole-7H), 7.131-7.127 (d, J=2.4, 1H, indole-4H), 6.737-6.719 (dd, J1=8.4, J2=2.4, 1H, indole-6H), 6.108-6.106 (d, J=1.2, 1H, indole-3H), 2.369 (s, 1H, methyl). 13C NMR (150 MHz, d6-DMSO): δ 137.5, 133.9, 130.0, 129.5, 111.7, 111.6, 108.5, 99.0, 13.4. Melting point: 57-60° C. TLC (in 1:1 ethyl acetate:hexanes) Rf=0.56. IR (film): 3409 cm.−1, 2111 (aryl-azide). Elemental analysis calculated for C9H8N4: C, 62.78; H, 4.68; N, 32.54. found: C, 62.95; H, 4.68; N, 32.53.

Workup

  1. customIn an oven dried
  2. customwas placed at 0° C.
  3. additionwas added dropwise
  4. additionwas added dropwise
  5. extractionwas extracted 3 times with CH2Cl2 (40 mL each)
  6. washThe extracts were washed with sodium bicarbonate and brine (100 mL each)
  7. dry with materialdried with sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by silica flash chromatography (100% CH2Cl2)

Sources & evidence

ORD record
ord-5df61970204d459eaaa33dcc0ce7fc7a
Source dataset
uspto-grants-2015_05
Patent number
US09028796B2

Reaction notes

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