Sodium Hydroxide → HCID 70388848, compound

HRID 620920Notes

Reaction equation

HRID 620920 reaction equation
Cl.[CH2:2]([O:9][CH2:10][CH2:11][C:12]1[C:18]([F:19])=[CH:17][CH:16]=[CH:15][C:13]=1[NH2:14])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[N:20]([O-])=O.[Na+].O.O.[Sn](Cl)[Cl:27].[OH-].[Na+]>O.Cl.CC(O)=O>[ClH:27].[CH2:2]([O:9][CH2:10][CH2:11][C:12]1[C:18]([F:19])=[CH:17][CH:16]=[CH:15][C:13]=1[NH:14][NH2:20])[C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 61436Stannous chloride dihydrateHCID 21245478HCID 21245478, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 70388848HCID 70388848, compoundYield 96.9%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolvent2×

Conditions

Temperature
-10 °C

Procedure

A mechanically stirred suspension of 2-(2-benzyloxyethyl)-3-fluoroaniline hydrochloride (53 g, 0.188 mole) in a mixture of water (30 mL), concentrated HCl (127 mL) and glacial HOAc (127 mL) was cooled to -10° C. (internal temperature). A solution of NaNO2 (14.27 g, 0.206 mole) in water (52 mL) was added dropwise while maintaining the internal temperature at -10° C. The resulting red solution was stirred an additional 75 minutes at -10° C. and then treated dropwise (over 30 minutes) with a solution of tin (II) chloride dihydrate (84.8 g, 0.376 mole) in concentrated HCl (97 mL) precooled to -40° C. The mixture was stirred an additional 75 minutes at -10° C. and then cooled at -15° C. and basified (to pH 14) with 50% NaOH (about 320 mL). The internal temperature was kept at - 8°/-10° C. during the addition of the base. The mixture was extracted with ether (3×). The combined extracts were washed with brine, dried (anhydrous K2CO3) and carefully acidified with ethereal HCl. Removal of the solvent provided the title compound as a tan solid (54 g, 96.9%). Trituration with light petroleum ether removed the less polar impurities and provided pure product (48.4 g, 86.8%).

Workup

  1. temperaturewhile maintaining the internal temperature at -10° C
  2. customprecooled to -40° C
  3. stirringThe mixture was stirred an additional 75 minutes at -10° C.
  4. temperaturecooled at -15° C.
  5. custom8°/-10° C.
  6. additionduring the addition of the base
  7. extractionThe mixture was extracted with ether (3×)
  8. washThe combined extracts were washed with brine
  9. dry with materialdried (anhydrous K2CO3)
  10. customRemoval of the solvent

Sources & evidence

ORD record
ord-a36af60931a646859a721bdeb1d92520
Source dataset
uspto-grants-1989_04
Patent number
US04822893

Reaction notes

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