Hydrochloric Acid → 2-(Hydroxymethyl)-6-((4-methoxyphenyl)-diazenyl)-4-methylphenol

HRID 222450

Reaction equation

HRID 222450 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([NH2:9])=[CH:5][CH:4]=1.Cl.[N:11]([O-])=O.[Na+].[OH-].[Na+].[OH:17][C:18]1[C:23](CO)=[CH:22][C:21]([CH3:26])=[CH:20][C:19]=1[CH2:27][OH:28]>O.S(=O)(=O)(O)N.C(O)C>[OH:28][CH2:27][C:19]1[CH:20]=[C:21]([CH3:26])[CH:22]=[C:23]([N:11]=[N:9][C:6]2[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=2)[C:18]=1[OH:17]

Participants

9

Reactant 5

HCID 313Hydrochloric Acid2×HCID 70392,6-Dimethylol-p-cresol2×HCID 7732P-AnisidineHCID 14798Sodium Hydroxide2×HCID 23668193Sodium Nitrite

Product 1

HCID 1359935832-(Hydroxymethyl)-6-((4-methoxyphenyl)-diazenyl)-4-methylphenolYield 81%

Reagents, catalysts & solvents 3

HCID 5987Sulfamic AcidCatalystHCID 702EthanolSolventHCID 962WaterSolvent4×

Conditions

Temperature
0 °C

Procedure

In a 250 ml round bottom flask equipped with a magnetic stirrer was added 8.91 g (72.4 mmol) p-anisidine (Aldrich), 30 ml conc. HCl(aq) (J. T. Baker), 150 ml absolute ethanol and 150 ml deionized water. Sodium nitrite (5.36 g, 77.6 mmol) in 30 ml water was added dropwise over 30 minutes while keeping the reaction mixture at −10° C. The reaction mixture was stirred for an additional 1 hour. 300 mg sulfamic acid was added and then stirred for an additional 20 minutes. The solids were filtered out and the cold diazonium solution was set aside. (2-hydroxy-5-methyl-1,3-phenylene)dimethanol was dissolved in 100 ml deionized water. Approximately one-fourth by volume of a solution comprised of 14.7 g (367 mmol) NaOH in water was added to the (2-hydroxy-5-methyl-1,3-phenylene)dimethanol solution and the reaction mixture was cooled to 0° C. The diazonium mixture and remaining NaOH solution were added simultaneously to the (2-hydroxy-5-methyl-1,3-phenylene)dimethanol mixture over 30-60 minutes and then stirred for an additional 1 hour at 0° C. and 4 hours at ambient temperature. The mixture was poured into 3 L deionized water and acidified to pH 4 with 1 N HCl. The solid was filtered and washed with several liters water and vacuum dried at 50° C. to give 15.9 g (81%) of an orange solid. 1H NMR (CDCl3) delta: 13.22 (s, 1H, Ar—OH), 7.85 (m, 2H, Ar—H), 7.66 (s, 1H, Ar—H), 7.17 (s, 1H, Ar—H), 7.03 (m, 2H, Ar—H), 4.77 (s, 2H, Ar—CH2), 3.89 (s, 3H, CH3O—Ar), 2.37 (s, 3H, Ar—CH3).

Workup

  1. customIn a 250 ml round bottom flask equipped with a magnetic stirrer
  2. customat −10° C
  3. stirringstirred for an additional 20 minutes
  4. filtrationThe solids were filtered out
  5. dissolution(2-hydroxy-5-methyl-1,3-phenylene)dimethanol was dissolved in 100 ml
  6. stirringstirred for an additional 1 hour at 0° C. and 4 hours at ambient temperature
  7. additionThe mixture was poured into 3 L
  8. filtrationThe solid was filtered
  9. washwashed with several liters water and vacuum
  10. customdried at 50° C.

Sources & evidence

ORD record
ord-0132b829bb21433283da689480b28588
Source dataset
uspto-grants-2012_06
Patent number
US08207244B2

Linked notes

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