Nitric Acid → Methyl 2-[(2-bromoethyl)oxy]-5-nitro-3-[(phenylcarbonyl)oxy]benzoate

HRID 253292Notes

Reaction equation

HRID 253292 reaction equation
[N+:1]([O-:4])(O)=[O:2].S(=O)(=O)(O)O.[Br:10][CH2:11][CH2:12][O:13][C:14]1[C:23]([O:24][C:25]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[O:26])=[CH:22][CH:21]=[CH:20][C:15]=1[C:16]([O:18][CH3:19])=[O:17]>>[Br:10][CH2:11][CH2:12][O:13][C:14]1[C:23]([O:24][C:25]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[O:26])=[CH:22][C:21]([N+:1]([O-:4])=[O:2])=[CH:20][C:15]=1[C:16]([O:18][CH3:19])=[O:17]

Participants

4

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 66891818Methyl 2-[(2-bromoethyl)oxy]-3-[(phenylcarbonyl)oxy]benzoate

Product 1

HCID 66889528Methyl 2-[(2-bromoethyl)oxy]-5-nitro-3-[(phenylcarbonyl)oxy]benzoateYield 87%

Procedure

A solution of fuming nitric acid (55 mL) and concentrated sulfuric acid (11 mL) was cooled to −5° C. Powdered methyl 2-[(2-bromoethyl)oxy]-3-[(phenylcarbonyl)oxy]benzoate (30 g, 79.1 mmol) was slowly added over a period of 30 min. After an additional stirring time of 30 min., the reaction mixture was quickly poured over ice, which was then extracted with dichloromethane (2×400 mL). The combined organic layers were washed with water (400 mL) and aqueous saturated sodium bicarbonate (200 mL). The organic solution was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The crude precipitate was triturated with diethyl ether (200 mL) to give 29.1 g (87%) of methyl 2-[(2-bromoethyl)oxy]-5-nitro-3-[(phenylcarbonyl)oxy]benzoate as an off-white powder: 1H NMR (400 MHz, CDCl3): 9.06 (t, J=2.2 Hz, 1H), 8.72 (d, J=3.2 Hz, 1H), 8.57-8.53 (m, 3H), 8.32 (d, J=3.2 Hz, 1H), 7.79 (t, J=8.0 H, 1H), 4.43 (t, J=5.8 Hz, 2H), 4.00 (s, 3H), 3.57 (t, J=5.6 Hz, 2H).

Workup

  1. additionAfter an additional stirring time of 30 min., the reaction mixture was quickly poured over ice, which
  2. extractionwas then extracted with dichloromethane (2×400 mL)
  3. washThe combined organic layers were washed with water (400 mL) and aqueous saturated sodium bicarbonate (200 mL)
  4. washThe organic solution was washed with brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated
  7. customThe crude precipitate was triturated with diethyl ether (200 mL)

Sources & evidence

ORD record
ord-dc76e12e8b554355b38791b50251498e
Source dataset
uspto-grants-2011_01
Patent number
US07872014B2

Reaction notes

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