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

HRID 2107816Notes

Reaction equation

HRID 2107816 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 nitrogen 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 nitrogen 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-a8b7b9053fe7409d9afc0db7feb5fc4c
Source dataset
uspto-grants-1990_06
Patent number
US04935515

Reaction notes

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