Triethylamine → 1,1-dimethylethyl 4-[2-(1,1-dimethylethyl)-2H-tetrazol-5-yl]benzene propenoate

HRID 487820Notes

Reaction equation

HRID 487820 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[N:10][N:11]([C:13]([CH3:16])([CH3:15])[CH3:14])[N:12]=2)=[CH:4][CH:3]=1.[C:17]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])(=[O:20])[CH:18]=[CH2:19].C(N(CC)CC)C>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:17]([OH:21])(=[O:20])[CH:18]=[CH2:19].[CH3:23][C:22]([C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[N:10][N:11]([C:13]([CH3:16])([CH3:15])[CH3:14])[N:12]=2)=[CH:4][CH:3]=1)([CH3:25])[CH3:24]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 148887285-(4-bromophenyl)-2-(1,1-dimethylethyl)-2H-tetrazole

Product 1

HCID 867465281,1-dimethylethyl 4-[2-(1,1-dimethylethyl)-2H-tetrazol-5-yl]benzene propenoateYield 55%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
75 °C

Procedure

A solution of 5-(4-bromophenyl)-2-(1,1-dimethylethyl)-2H-tetrazole (3.0 g. 10.2 mmol), t-butyl acrylate (2.9 mL, 20.4 mmol), and triethylamine (7.9 mL, 59 mmol) in DMF (93 mL) was deoxygenated with argon, whereupon bis(triphenylphosphine)palladium dichloride (0.5 g. 0.8 mmol) was added. After heating at 75° C. for 12 hours the mixture was concentrated under reduced pressure and the brown residue was filtered through a short column of silica gel eluting with a mixture of hexanes and ethyl acetate (9:1). The eluent was concentrated and then purified by is chromatography on a Waters Prep 500 liquid chromatograph fitted with two silica gel cartridges eluting with a mixture of hexanes and ethyl acetate (9:1). The fractions containing product were pooled, concentrated and the residue was recrystallized from hexanes to give 1.1-dimethylethyl 4-[2-(1,1-dimethylethyl)-2H-tetrazol-5-yl]benzene propenoate (1.6 g. 5.6 mmol) in 55% yield, mp. 118.5°-120° C.

Workup

  1. additionwas added
  2. concentrationwas concentrated under reduced pressure
  3. filtrationthe brown residue was filtered through a short column of silica gel eluting with a mixture of hexanes and ethyl acetate (9:1)
  4. concentrationThe eluent was concentrated
  5. custompurified
  6. customfitted with two silica gel cartridges
  7. washeluting with a mixture of hexanes and ethyl acetate (9:1)
  8. additionThe fractions containing product
  9. concentrationconcentrated
  10. customthe residue was recrystallized from hexanes

Sources & evidence

ORD record
ord-e1e165040a624b758106df34b3a09a86
Source dataset
uspto-grants-1994_03
Patent number
US05296608

Reaction notes

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