Nitric Acid → HCID 58368547, compound

HRID 1192716Notes

Reaction equation

HRID 1192716 reaction equation
[Cl:1][C:2]1[C:3]([C:13]#[C:14][Si:15]([CH3:18])([CH3:17])[CH3:16])=[CH:4][C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[N+:19]([O-])([OH:21])=[O:20].O>C(O)(=O)C>[Cl:1][C:2]1[C:3]([C:13]#[C:14][Si:15]([CH3:16])([CH3:18])[CH3:17])=[C:4]([N+:19]([O-:21])=[O:20])[C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 962WaterHCID 58368507HCID 58368507, compound

Product 1

HCID 58368547HCID 58368547, compoundYield 72.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

A solution of methyl 5-chloro-2-hydroxy-4-[(trimethylsilyl)ethynyl]benzoate (540 g, 1.9 mol) in acetic acid (3.7 L) was heated at 55-59° C. The heating was discontinued and the reaction mixture was flushed with nitrogen and treated with a solution of nitric acid (120 mL, 2.9 mol) in acetic acid (200 mL, 3.6 mol) over 30 minutes. The reaction temperature reached 98.9° C. The resulting solution was stirred for 30 minutes at which time the temperature went from 98.9 to 87.5° C. The reaction was cooled to room temperature and treated with crushed ice (3.5 kg) in one portion. The reaction mixture temperature dropped to −12° C. The reaction mixture was treated with water (3.5 kg) and and stirred at room temperature for 1 hour. The product was filtered, rinsed with water (2 L), and dried on the filter under vacuum overnight to give the desired product (450 g, 72%) as a yellow solid. HPLC 92.9% pure @ 220 nm. LCMS for C13H15ClNO5Si (M+H)+: m/z=328.0; Found: 327.9; 1H NMR (300 MHz, DMSO-d6): δ 11.2 (br s, 1 H), 8.00 (s, 1 H), 3.89 (s, 3 H), 0.23 (s, 9 H).

Workup

  1. customthe reaction mixture was flushed with nitrogen
  2. customreached 98.9° C
  3. customwent from 98.9 to 87.5° C
  4. additionThe reaction mixture temperature dropped to −12° C
  5. stirringstirred at room temperature for 1 hour
  6. filtrationThe product was filtered
  7. washrinsed with water (2 L)
  8. customdried on the
  9. filtrationfilter under vacuum overnight

Sources & evidence

ORD record
ord-870d211d13d8481aa5fa86f818016d5f
Source dataset
uspto-grants-2014_03
Patent number
US08680108B2

Reaction notes

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