Sulfuric Acid → HCID 57440927, compound

HRID 549483Notes

Reaction equation

HRID 549483 reaction equation
S(=O)(=O)(O)O.N[C:7]1[CH:12]=[C:11]([Cl:13])[CH:10]=[CH:9][C:8]=1/[CH:14]=[C:15](\[C:19]1[CH:24]=[CH:23][C:22]([Br:25])=[CH:21][CH:20]=1)/[C:16]([OH:18])=[O:17].[OH-].[Na+].N([O-])=O.[Na+].S(=O)(=O)(O)N>O.CC(C)=O.[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Fe+2]>[Br:25][C:22]1[CH:21]=[C:20]2[C:19](=[CH:24][CH:23]=1)[C:15]([C:16]([OH:18])=[O:17])=[CH:14][C:8]1[CH:9]=[CH:10][C:11]([Cl:13])=[CH:12][C:7]2=1

Participants

9

Reactant 5

HCID 1118Sulfuric AcidHCID 5987Sulfamic AcidHCID 14798Sodium HydroxideHCID 23668193Sodium NitriteHCID 57440926HCID 57440926, compound

Product 1

HCID 57440927HCID 57440927, compound

Reagents, catalysts & solvents 3

HCID 7611Bis(eta-cyclopentadienyl) ironCatalystHCID 180AcetoneSolvent2×HCID 962WaterSolvent3×

Conditions

Temperature
0 °C

Procedure

This quinone can be obtained by following the procedure describe in Example 36, Step 1 to 3, or by the using the following procedure: to a 0° C. solution of 118 mL of concentrated sulphuric acid in 1.0 L of water was added drop wise a solution prepared as follows: 65 g of (2E)-3-(2-amino-4-chlorophenyl)-2-(4-bromophenyl)acrylic acid from Step 2 in 1 L of water followed by the addition of 11 g of NaOH, stirring for 10 minutes at 0° C., addition of NaNO2 (15 g) and stirring of the resulting solution at 0° C. for 20 minutes. After 30 minutes, sulfamic acid (12.5 g) was added to this mixture and after the gaz evolution seized, 1.3 L of acetone was added and the solution was stirred at 0° C. for 10 minutes. This mixture was then added to a solution of ferrocene (6.9 g) in 480 mL of acetone resulting in the formation of a green precipitate. After stirring for 20 minutes, water (2.0 L) was added, the solid was filtered and the 6-bromo-3-chlorophenanthrene-9-carboxylic acid was obtained and allowed to air dry. This crude phenanthrene was placed in 2.0 L of acetic acid followed by the addition of 54 g of CrO3. The reaction was placed at 110° C. and after stirring for 1 hr, 18 g of CrO3 were added. The reaction was monitored by TLC and 18 g of CrO3 were added every hour for 3 hours where 100% conversion was observed by 1H NMR. The mixture was cooled to room temperature, diluted in water (2.0 L), filtered and washed with water (1.0 L) to afford, after drying, 37 g of 3-Bromo-6-chlorophenanthrene-9,10-dione as a yellow solid.

Workup

  1. customprepared
  2. stirringstirring of the resulting solution at 0° C. for 20 minutes
  3. waitAfter 30 minutes
  4. stirringthe solution was stirred at 0° C. for 10 minutes
  5. stirringAfter stirring for 20 minutes
  6. filtrationthe solid was filtered

Sources & evidence

ORD record
ord-6b0aec460d724ebf944779429eb40406
Source dataset
uspto-grants-2011_05
Patent number
US07943649B2

Reaction notes

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