Acetic Acid → Methyl bis(4-methylphenyl)azidoacetate

HRID 2304573Notes

Reaction equation

HRID 2304573 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[CH3:11][C:12]1[CH:17]=[CH:16][C:15]([CH:18]([C:23]2[CH:28]=[CH:27][C:26]([CH3:29])=[CH:25][CH:24]=2)[C:19]([O:21][CH3:22])=[O:20])=[CH:14][CH:13]=1.C(C1C=C(C(C)C)C=C(C(C)C)C=1S([N:48]=[N+:49]=[N-:50])(=O)=O)(C)C.C(O)(=O)C>O1CCCC1.C(OCC)C>[CH3:29][C:26]1[CH:25]=[CH:24][C:23]([C:18]([C:15]2[CH:14]=[CH:13][C:12]([CH3:11])=[CH:17][CH:16]=2)([N:48]=[N+:49]=[N-:50])[C:19]([O:21][CH3:22])=[O:20])=[CH:28][CH:27]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 3717072,4,6-Triisopropylbenzenesulfonyl azideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 6452857Benzeneacetic acid, 4-methyl-alpha-(4-methylphenyl)-, methyl ester

Product 1

HCID 18435794Methyl bis(4-methylphenyl)azidoacetate

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Sodium bistrimethylsilylamide (1M solution in tetrahydrofuran, 9.82 ml) was added to a solution of methyl bis(4-methylphenyl)acetate (2.08 g, 8.18 mmol) dissolved in tetrahydrofuran(10 mL) and cooled to −78° C. under a nitrogen atmosphere. The reaction was stirred for 2.5 hours and then a solution of 2,4,6-triisopropylbenzenesulfonyl azide (2.78 g, 9 mmol) in tetrahydrofuran(6 mL) was added. This mixture was stirred for 45 minutes and then warmed to room temperature and stirred for an additional two hours. Glacial acetic acid (1.5 ml) was added and the mixture was stirred for 30 minutes. The reaction was diluted with diethyl ether and washed with saturated sodium bicarbonate and brine. The organic layer was dried over sodium sulfate, filtered and concentrated to afford crude product. This material was chromatographed on a column of silica gel eluting with 10% ethyl acetate/hexane to give the purified title compound as an oil which was used as is.

Workup

  1. stirringThis mixture was stirred for 45 minutes
  2. temperaturewarmed to room temperature
  3. stirringstirred for an additional two hours
  4. stirringthe mixture was stirred for 30 minutes
  5. washwashed with saturated sodium bicarbonate and brine
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto afford crude product
  10. customThis material was chromatographed on a column of silica gel eluting with 10% ethyl acetate/hexane
  11. customto give the
  12. custompurified title compound as an oil which

Sources & evidence

ORD record
ord-3c2ce51a24464ce488af77d507f2dc59
Source dataset
uspto-grants-2002_08
Patent number
US06436962B1

Reaction notes

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