tert-Butanol → tert-Butyl 3-methyl-4-nitrobenzoate

HRID 365639Notes

Reaction equation

HRID 365639 reaction equation
C1(S(Cl)(=O)=O)C=CC=CC=1.[CH3:11][C:12]1[CH:13]=[C:14]([CH:18]=[CH:19][C:20]=1[N+:21]([O-:23])=[O:22])[C:15]([OH:17])=[O:16].[C:24](O)([CH3:27])([CH3:26])[CH3:25]>N1C=CC=CC=1>[CH3:11][C:12]1[CH:13]=[C:14]([CH:18]=[CH:19][C:20]=1[N+:21]([O-:23])=[O:22])[C:15]([O:17][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:16]

Participants

5

Reactant 3

HCID 6386tert-ButanolHCID 7369Benzenesulfonyl chlorideHCID 183703-Methyl-4-nitrobenzoic acid

Product 1

HCID 15283350tert-Butyl 3-methyl-4-nitrobenzoate

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

Benzenesulfonyl chloride (12.8 mL, 100 mmol) was added rapidly to a solution of 3-methyl-4-nitrobenzoic acid (9.06 g, 50 mmole) in dry pyridine (25 mL) at 40° C. The reaction was mildly exothermic. The cloudy, orange solution was stirred for 5 min, then t-butanol (4.7 mL, 50 mmole, 1 eq.) was added. After 1 h, the reddish-orange mixture was poured into ice/water (200 mL), and the resulting mixture was stirred briskly for 1 h. The solid was collected by suction filtration, washed with H2O, and dissolved in toluene (200 mL). The solution was dried (MgSO4) and filtered through a pad of silica gel eluting with toluene. Concentration gave the title compound as a yellow oil which crystallized under vacuum (9.67 g, 82%). TLC Rf 0.65 (4:1 toluene:hexane); 1H NMR (250 MHz, CDCl3) δ 7.85-8.10 (m, 3H), 2.61 (s, 3H), 1.60 (s, 9H); IR (CCl4) 1724, 1531, 1372, 1308, 1295, 1164, 1120, 843 cm-1 ; MS(ES) m/e 260.0 [M+Na]+, 238.0 [M+H]+.

Workup

  1. waitAfter 1 h
  2. stirringthe resulting mixture was stirred briskly for 1 h
  3. filtrationThe solid was collected by suction filtration
  4. washwashed with H2O
  5. dissolutiondissolved in toluene (200 mL)
  6. dry with materialThe solution was dried (MgSO4)
  7. filtrationfiltered through a pad of silica gel eluting with toluene
  8. concentrationConcentration

Sources & evidence

ORD record
ord-bfbf9881f89743e98da66fecf49b429b
Source dataset
uspto-grants-2000_10
Patent number
US06127359

Reaction notes

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