1-Tetralone → (+/-) Cis 4-azido-1,2,3,4-tetrahydro-naphthalen-1-ol

HRID 1406682Notes

Reaction equation

HRID 1406682 reaction equation
[C:1]1(=[O:11])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][CH2:3][CH2:2]1.BrN1C(=O)CCC1=O.N(CCCC#N)=NCCCC#N.[N-:32]=[N+:33]=[N-:34].[Na+].[BH4-].[Na+]>C(Cl)(Cl)(Cl)Cl>[N:32]([C@@H:4]1[C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[C@H:1]([OH:11])[CH2:2][CH2:3]1)=[N+:33]=[N-:34]

Participants

7

Reactant 5

HCID 107241-TetraloneHCID 33557Sodium AzideHCID 67184N-bromobutanimideHCID 4311764Sodium borohydrideHCID 14151322Azobisbutyronitrile

Product 1

HCID 86686189(+/-) Cis 4-azido-1,2,3,4-tetrahydro-naphthalen-1-ol

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A solution of 1-tetralone (2.92 g, 20 mmol), N-bromosuccinimide (3.56 g, 20 mmol) and azodibutyronitrile (80 mg) in carbon tetrachloride (80 mL) was refluxed for 1.25h, then evaporated in vacuo. The resulting oil was dissolved in DMF (8 mL), treated with sodium azide (2.6 g, 40 mmol) and stirred at RT for 2h. The reaction mixture was partitioned between Et2O (200 mL) and H2O (50 mL). The resulting organic layer was dried (MgSO4), filtered and evaporated in vacuo. The resulting oil was dissolved in EtOH (100 mL), cooled to 0° C. under argon and treated with sodium borohydride (0.76 g, 20 mmol). The reaction mixture was stirred at RT for 1h, concentrated in vacuo to approx. 50 mL and partitioned between H2O and Et2O. The aqueous layer was extracted with DCM (100 mL) and EtOAc (100 mL) and the combined organic layers were dried (MgSO4), filtered, concentrated in vacuo and purified by FCC using 0-30% cyclohexane/diethyl ether to give the title compound at Rf 0.2 as a dark red oil (1.5 g, 40%). 1H NMR (300 MHz, CDCl3): 7.57-7.52 (1 H, m), 7.43-7.28 (3 H, m), 4.81-4.72 (1 H, m), 4.55-4.49 (1 H, m), 2.13-1.99 (3 H, m), 1.79 (1 H, m).

Workup

  1. customevaporated in vacuo
  2. dissolutionThe resulting oil was dissolved in DMF (8 mL)
  3. customThe reaction mixture was partitioned between Et2O (200 mL) and H2O (50 mL)
  4. dry with materialThe resulting organic layer was dried (MgSO4)
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. dissolutionThe resulting oil was dissolved in EtOH (100 mL)
  8. temperaturecooled to 0° C. under argon
  9. concentrationconcentrated in vacuo to approx. 50 mL
  10. custompartitioned between H2O and Et2O
  11. extractionThe aqueous layer was extracted with DCM (100 mL) and EtOAc (100 mL)
  12. dry with materialthe combined organic layers were dried (MgSO4)
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo
  15. custompurified by FCC

Sources & evidence

ORD record
ord-214819ce4d3946e98e9cd9593aa72c2b
Source dataset
uspto-grants-2014_12
Patent number
US08916708B2

Reaction notes

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