Hydrochloric Acid → t-Butyl (2-nitro-3,5,6-trichlorophenyl)acetate

HRID 1458588Notes

Reaction equation

HRID 1458588 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([Cl:9])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].Cl[CH2:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16].CC(C)([O-])C.[K+].Cl>O1CCCC1>[N+:10]([C:3]1[C:2]([Cl:1])=[CH:7][C:6]([Cl:8])=[C:5]([Cl:9])[C:4]=1[CH2:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])([O-:12])=[O:11]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 69832,4,5-TrichloronitrobenzeneHCID 66052tert-Butyl chloroacetateHCID 23665647Potassium tert-butoxide

Product 1

HCID 10688549t-Butyl (2-nitro-3,5,6-trichlorophenyl)acetateYield 59%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-40 °C

Procedure

A solution of 2,4,5-trichloronitrobenzene (Jpn. Kokai Tokyo Koho JP 81,169,651 (1980), Chem. Abstr. 1981,96, 162307 q)(103 g, 0.46 mol) and t-butyl chloroacetate (79 ml, 0.55 mol) in dry tetrahydrofuran (400 ml) was added dropwise over 30 minutes to a solution of potassium t-butoxide (128 g, 1.14 mol) in dry tetrahydrofuran (800 ml) with stirring, under nitrogen keeping the temperature at -40° C. After the addition was complete, the resulting dark blue solution was stirred for a further 30 minutes. The mixture was poured into 0.5M hydrochloric acid (2 L) and the product was extracted into ethyl acetate (2.5L and 1 L). The combined organic solutions were dried (MgSO4) and evaporated onto silica gel (70-200 m, 200 g). The silica gel was applied to the top of a silica gel chromatography column (800 g), and the product was eluted using a hexane/ethyl acetate gradient. Product-containing fractions were combined and evaporated to give a yellow solid, which was triturated with hexane to give t-butyl 2-nitro-3,5,6-trichlorophenylacetate (91.8 g, 59%) as a white solid.

Workup

  1. additionAfter the addition
  2. stirringthe resulting dark blue solution was stirred for a further 30 minutes
  3. extractionthe product was extracted into ethyl acetate (2.5L and 1 L)
  4. dry with materialThe combined organic solutions were dried (MgSO4)
  5. customevaporated onto silica gel (70-200 m, 200 g)
  6. washthe product was eluted
  7. customevaporated
  8. customto give a yellow solid, which
  9. customwas triturated with hexane

Sources & evidence

ORD record
ord-b4b864ab92d94716977a6a28b5b55e72
Source dataset
uspto-grants-1998_12
Patent number
US05852016

Reaction notes

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