Hydrochloric Acid → 2-((4-Fluoro-2-nitrophenyl)diazenyl)-6-(hydroxymethyl)-4-methoxyphenol

HRID 1691502

Reaktionsgleichung

Reaktionsgleichung von HRID 1691502
[F:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.Cl.[N:13]([O-])=O.[Na+].[OH:17][C:18]1[C:23]([CH2:24][OH:25])=[CH:22][C:21]([O:26][CH3:27])=[CH:20][C:19]=1CO.[OH-].[Na+].C1(O)C=CC=CC=1>O.S(=O)(=O)(O)N.C(O)C>[F:1][C:2]1[CH:8]=[CH:7][C:5]([N:6]=[N:13][C:19]2[CH:20]=[C:21]([O:26][CH3:27])[CH:22]=[C:23]([CH2:24][OH:25])[C:18]=2[OH:17])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1

Komponenten

10

Edukt 6

HCID 313Hydrochloric Acid2×HCID 996PhenolHCID 14798Sodium Hydroxide2×HCID 677694-Fluoro-2-nitroanilineHCID 8274592,6-Bis(hydroxymethyl)-4-methoxyphenolHCID 23668193Sodium Nitrite

Produkt 1

HCID 1363483072-((4-Fluoro-2-nitrophenyl)diazenyl)-6-(hydroxymethyl)-4-methoxyphenolAusbeute 68 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 5987Sulfamic AcidKatalysatorHCID 702EthanolLösungsmittel2×HCID 962WaterLösungsmittel5×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

In a 500 ml round bottom flask equipped with a magnetic stirrer was added 25.1 g (161 mmol) 4-fluoro-2-nitroaniline (Aldrich), HCl (aq) (J. T. Baker), 100 ml deionized water, and 100 ml absolute ethanol. The suspension was cooled to 0° C. 11.8 g (171 mmol) Sodium nitrite (Sigma-Aldrich) in 50 ml water was added dropwise over 60 minutes while keeping the reaction mixture at 0° C. The reaction mixture was stirred for an additional 1 hour. 420 mg sulfamic acid (Aldrich) was added and the reaction mixture was stirred for an additional 30 minutes and then filtered. In a 1 liter round bottom flask was combined 32.5 g (176 mmol) (2-hydroxy-5-methoxy-1,3-phenylene)dimethanol, 200 ml deionized water, and 200 ml ethanol. 32.3 g (807 mmol) NaOH (Aldrich) was dissolved in 100 ml water and approximately one-fourth of this was added to the solution containing the phenol derivative at 0° C. The diazonium salt solution and remaining sodium hydroxide solution were added dropwise to the reaction mixture at 0° C. over a 1 hour period and then allowed to stir for an additional 1 hour at 0° C. and 3 hours at ambient temperature. The reaction mixture was poured into 3 liters water and the pH was adjusted to 4 using 1N HCl. The solid was collected by filtration, washed with several liters of water, and vacuum dried (0.1 mm Hg) at 55° C. for 72 hours using P2O5 as drying agent to afford 29.9 g (68%) of a dark solid which was used in the next step without further purification.

Aufarbeitung

  1. customIn a 500 ml round bottom flask equipped with a magnetic stirrer
  2. customat 0° C
  3. stirringthe reaction mixture was stirred for an additional 30 minutes
  4. filtrationfiltered
  5. customIn a 1 liter round bottom flask was combined
  6. additionapproximately one-fourth of this was added to the solution
  7. additionwere added dropwise to the reaction mixture at 0° C. over a 1 hour period
  8. stirringto stir for an additional 1 hour at 0° C. and 3 hours at ambient temperature
  9. filtrationThe solid was collected by filtration
  10. washwashed with several liters of water, and vacuum
  11. customdried (0.1 mm Hg) at 55° C. for 72 hours
  12. customas drying agent

Quellen und Nachweise

ORD-Eintrag
ord-7f079bdc6c12490fa0adbdeee03d957a
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08153703B2

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