Sodium Azide → HCID 69059203, compound

HRID 1295063Notes

Reaction equation

HRID 1295063 reaction equation
[CH2:1]([N:8]1[C:15]2[CH:14]3[CH2:16][CH:13]3[CH2:12][C:11]=2[C:10]([C:17]#[N:18])=[N:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N-:19]=[N+:20]=[N-:21].[Na+]>CN(C=O)C.[Zn+2].[Br-].[Br-]>[CH2:1]([N:8]1[C:15]2[CH:14]3[CH2:16][CH:13]3[CH2:12][C:11]=2[C:10]([C:17]2[N:19]=[N:20][NH:21][N:18]=2)=[N:9]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 33557Sodium AzideHCID 69063025HCID 69063025, compound

Product 1

HCID 69059203HCID 69059203, compound

Reagents, catalysts & solvents 2

HCID 10421208Zinc bromideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of 2-benzyl-1a,2,5,5a-tetrahydro-1H-2,3-diaza-cyclopropa[a]pentalene-4-carbonitrile (11.1 g, 47.2 mmol) in DMF (125 mL) was added ZnBr2 (18.4 g, 70.6 mmol) followed by NaN3 (12.2 g, 188 mmol). The mixture was heated to 120° C. and stirred for 18 h under N2 atmosphere. The reaction was cooled to rt and the DMF was removed in vacuo. The crude residue was diluted with EtOAc (200 mL) and HCl (3N aq., ˜100 mL) and stirred for 10 min. The layers were separated and the aqueous phase was back-extracted with EtOAc (150 mL). The combined organics were washed with NaOH (1M aq., 2×250 mL) and the organic layers were discarded. The basic aqueous phase was acidified with 6 N HCl to pH ˜2 and was extracted with EtOAc (2×250 mL). The extracts were washed with brine (150 mL), dried over MgSO4, filtered, and concentrated to give 2-benzyl4-(2H-tetrazol-5-yl)-1a,2,5,5a-tetrahydro-1H-2,3-diaza-cyclopropa[a]pentalene as a light brown solid. 1H NMR (400 MHz, MeOD): δ 7.33 (5H, m), 5.42 (1H, d, J=14.8 Hz), 5.35 (1H, d, J=15.2 Hz), 3.01 (1H, dd, J=16.4, 6.4 Hz), 2.88 (1H, d, J=17.6 Hz), 2.28 (1H, m), 2.11 (1H, M), 1.14 (1H, m), 0.33 (1H, m). HPLC/MS: Alltech® Prevail C18 column (5μ, 50×4.6 mm), 5% v/v CH3CN (containing 1% v/v TFA) in H2O (containing 1% v/v TFA) gradient to 99% v/v CH3CN in H2O, 3.5 ml/min, tr=2.14 min, ESI+=279.3 (M+H).

Workup

  1. temperatureThe reaction was cooled to rt
  2. customthe DMF was removed in vacuo
  3. additionThe crude residue was diluted with EtOAc (200 mL) and HCl (3N aq., ˜100 mL)
  4. stirringstirred for 10 min
  5. customThe layers were separated
  6. extractionthe aqueous phase was back-extracted with EtOAc (150 mL)
  7. washThe combined organics were washed with NaOH (1M aq., 2×250 mL)
  8. extractionwas extracted with EtOAc (2×250 mL)
  9. washThe extracts were washed with brine (150 mL)
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-41d0a7ab76f04dda94d4ac826691cb8e
Source dataset
uspto-grants-2007_07
Patent number
US07241792B2

Reaction notes

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