1-Fluoro-2-nitrobenzene → HCID 14625404, compound

HRID 1639005Notes

Reaction equation

HRID 1639005 reaction equation
Cl.Cl.[C:3]1([CH2:9][N:10]2[CH2:16][CH2:15][NH:14][NH:13][CH2:12][CH2:11]2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.F[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[N+:24]([O-:26])=[O:25].C(N(CC)C(C)C)(C)C>CN(C)C=O>[N+:24]([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=1[N:14]1[CH2:15][CH2:16][N:10]([CH2:9][C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH2:11][CH2:12][NH:13]1)([O-:26])=[O:25]

Participants

5

Reactant 3

HCID 738951-Fluoro-2-nitrobenzeneHCID 81531DiisopropylethylamineHCID 23046778HCID 23046778, compound

Product 1

HCID 14625404HCID 14625404, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of hexahydro-5-(phenylmethyl)-1H-1,2,5-triazepine dihydrochloride (35.0 g), 1-fluoro-2-nitrobenzene (21 ml), N,N-diisopropylethylamine (81 ml) in N,N-dimethylformamide (400 ml) was stirred and heated at 75°-80° (under reflux) under ntirogen for 5 hours. The solution was evaporated to a syrup under oil pump vacuum and the residue was mixed with chloroform and dilute sodium hydroxide. The aqueous phase was extracted several times with chloroform. The combined extracts were dried (MgSO4) and evaporated to a syrup wich was subjected to an oil pump vacuum. The syrup in toluene was applied to a column (94×8.7 cm) of dry column grade neutral alumina prepacked in toluene. Elution with toluene removed a faster moving yellow impurity. Fractions were monitored by t.l.c. on Alox-25 uv254 plates (Brinkmann) with chloroform as developer. As soon as the major component started to issue the eluting solvent was changed to toluene-chloroform (4:1), toluene-chloroform (1:1) and finally chloroform. Appropriate fractions were evaporated to a syrup which was crystallized from ether-heptane; wt. 35.7 g (86%), mp=90°-92°. Recrystallization from chloroform-ether-heptane gave pure titled product, mp=90°-92°.

Workup

  1. temperatureheated at 75°-80°
  2. temperature(under reflux) under ntirogen for 5 hours
  3. customThe solution was evaporated to a syrup under oil pump vacuum
  4. additionthe residue was mixed with chloroform and dilute sodium hydroxide
  5. extractionThe aqueous phase was extracted several times with chloroform
  6. dry with materialThe combined extracts were dried (MgSO4)
  7. customevaporated to a syrup wich
  8. washElution with toluene
  9. customremoved
  10. customAppropriate fractions were evaporated to a syrup which
  11. customwas crystallized from ether-heptane
  12. customRecrystallization from chloroform-ether-heptane

Sources & evidence

ORD record
ord-7a40a454b72c4485b290ef572709d9fa
Source dataset
uspto-grants-1989_11
Patent number
US04882323

Reaction notes

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