Diphenylphosphoryl azide → 17-Aminoheptadecanoic acid tert-butyl ester

HRID 2369794Notes

Reaction equation

HRID 2369794 reaction equation
[C:1]([O:5][C:6](=[O:26])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22]C(O)=O)([CH3:4])([CH3:3])[CH3:2].C1C=CC(OP(OC2C=CC=CC=2)([N:36]=[N+]=[N-])=O)=CC=1>C(#N)C>[C:1]([O:5][C:6](=[O:26])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][NH2:36])([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 123414Diphenylphosphoryl azideHCID 2728247318-(Tert-butoxy)-18-oxooctadecanoic acid

Product 1

HCID 8664712917-Aminoheptadecanoic acid tert-butyl esterYield 31.5%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

Acetonitrile (10 mL) was added to octadecanedioic acid mono-tert-butyl ester (500 mg, 1.3 mmol) and TEA (0.226 mL, 1.6 mmol) was added. Diphenylphosphonic azide (0.37 g, 1.3 mmol) was added in a solution of acetonitrile (1 mL). The mixture was stirred at reflux for 2 h, and at RT for 16 h. The reaction was concentrated under vacuum, and suspended/dissolved in 1:2, AcOEt:heptane (2 mL) and applied to a dry bed of silica (2×4 cm dia). It was eluated with 1:2 AcOEt:heptane (2 mL) and 1:1 AcOEt:heptane (60 mL). The eluate was concentrated to dryness. The residue was partly suspended in THF (2 mL) and 1 N NaOH (2 mL) was added. The turbid solution/suspension was stirred for 1 h at RT. Water (15 mL) was added and this was extracted with AcOEt (2×25 mL), adding some brine to aid separation. The organic phase was washed with sat. NaCl, dried, filtered and conc. to dryness. To the residue was added 20% acetonitrile/water (15 mL), TFA (15-20 ul) and DMSO (1 mL). A filtration of the mixture failed, so the filter and the solution were extracted with DCM (2×60 mL). The organic extracts were concentrated to yield the crude product (0.14 g),

Workup

  1. additionwas added
  2. temperatureat reflux for 2 h
  3. concentrationThe reaction was concentrated under vacuum
  4. dissolutionsuspended/dissolved in 1:2, AcOEt
  5. concentrationThe eluate was concentrated to dryness
  6. addition1 N NaOH (2 mL) was added
  7. stirringThe turbid solution/suspension was stirred for 1 h at RT
  8. additionWater (15 mL) was added
  9. extractionthis was extracted with AcOEt (2×25 mL)
  10. additionadding some brine
  11. customseparation
  12. washThe organic phase was washed with sat. NaCl
  13. customdried
  14. filtrationfiltered and conc. to dryness
  15. additionTo the residue was added 20% acetonitrile/water (15 mL), TFA (15-20 ul) and DMSO (1 mL)
  16. filtrationA filtration of the mixture
  17. filtrationso the filter
  18. extractionthe solution were extracted with DCM (2×60 mL)
  19. concentrationThe organic extracts were concentrated

Sources & evidence

ORD record
ord-ba5cec2b9a024f719afd1d50d3a6655c
Source dataset
uspto-grants-2014_04
Patent number
US08710000B2

Reaction notes

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