Sulfuric Acid → 2-(2-Nitro-4-trifluoromethyl-phenylazo)-6-(1-methyl-1-phenyl-ethyl)-4-(1,1,3,3-tetramethyl-butyl)-phenol

HRID 395919Notes

Reaction equation

HRID 395919 reaction equation
[F:1][C:2]([F:14])([F:13])[C:3]1[CH:9]=[CH:8][C:6]([NH2:7])=[C:5]([N+:10]([O-:12])=[O:11])[CH:4]=1.[C:15]([C:24]1[CH:29]=[C:28]([C:30]([CH2:33][C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:32])[CH3:31])[CH:27]=[CH:26][C:25]=1[OH:38])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)([CH3:17])[CH3:16].S(=O)(=O)(O)O.[N:44](OS(=O)(=O)O)=O>O>[N+:10]([C:5]1[CH:4]=[C:3]([C:2]([F:13])([F:14])[F:1])[CH:9]=[CH:8][C:6]=1[N:7]=[N:44][C:26]1[CH:27]=[C:28]([C:30]([CH3:31])([CH3:32])[CH2:33][C:34]([CH3:37])([CH3:36])[CH3:35])[CH:29]=[C:24]([C:15]([CH3:17])([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[CH3:16])[C:25]=1[OH:38])([O-:12])=[O:11]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 67865Benzenamine, 2-nitro-4-(trifluoromethyl)-HCID 82157Nitrosylsulfuric acidHCID 22644018Phenol, 2-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)-

Product 1

HCID 1358041322-(2-Nitro-4-trifluoromethyl-phenylazo)-6-(1-methyl-1-phenyl-ethyl)-4-(1,1,3,3-tetramethyl-butyl)-phenolYield 77%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
5 °C

Procedure

To a 1 L lab flask are added 54.6 g (0.26 mol, 99.9%) of 4-trifluoromethyl-2-nitroaniline, PETROSUL H-60 (5.3 g dissolved in 121.4 g water), 2-cumyl-4-tert-octylphenol (80.9 g, 0.25 mol, 92.5%) and ligroine (241.7 g, bp 90-110° C.). Sulfuric acid (32.7g, 93%) is charged to the reactor with stirring. The reaction mass is cooled to 5° C. Nitrosylsulfuric acid (94.4 g, 0.30 mol, 40% in sulfuric acid) and water (84.5 g) are added via a peristaltic pump over 8 hours. The cooling bath is removed and the reaction mass is allowed to warm to room temperature overnight. The reaction mass is heated to 40° C. Stirring is stopped and the two phases separate. Removed the aqueous layer. The ligroine layer weighed 373.8 g and contained 25.73 weight % of desired product (96.2 g of monoazo corresponding to a yield of 77% based on phenol as determined by calibrated HPLC analysis). The product may be crystallized from hot methanol, resulting in a burgundy solid with a melting point of 101-105° C. as per co-pending application 09/632217 example 10. 1H-NMR (CDCl3; 499.8494 MHz): δ 0.85 (s, 9H); δ 1.42 (s, 6H); δ 1.77 (s, 2H); δ 1.78 (s, 6H); δ 7.14-7.30 (multiplet, 5H); δ 7.50 (d, 1H); δ 7.90 (d, 1H); δ 8.15 (d, 1H); δ 8.37 (s, 1H).

Workup

  1. additionTo a 1 L lab flask are added
  2. customThe cooling bath is removed
  3. temperatureto warm to room temperature overnight
  4. temperatureThe reaction mass is heated to 40° C
  5. stirringStirring
  6. customthe two phases separate
  7. customRemoved the aqueous layer
  8. customThe product may be crystallized from hot methanol
  9. customresulting in a burgundy solid with a melting point of 101-105° C. as per co-pending application 09/632217 example 10

Sources & evidence

ORD record
ord-7908ab695b4f4da7a8a0616e40211da6
Source dataset
uspto-grants-2003_08
Patent number
US06605727B2

Reaction notes

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