Dinitrofluorobenzene → 6-(2,4-Dinitrophenylamino)-1-aminohexyl-6-(4'-azido-2'-nitrophenylamino)hexanoate

HRID 1199180Notes

Reaction equation

HRID 1199180 reaction equation
NCCCN(C)[CH2:6][CH2:7][CH2:8][NH:9][C:10]1[CH:15]=[CH:14][C:13]([N:16]=[N+:17]=[N-:18])=[CH:12][C:11]=1[N+:19]([O-:21])=[O:20].F[C:24]1[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][C:25]=1[N+:33]([O-:35])=[O:34].[N:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.[OH2:42]>>[CH:14]1[C:13]([N:16]=[N+:17]=[N-:18])=[CH:12][C:11]([N+:19]([O-:21])=[O:20])=[C:10]([NH:9][CH2:8][CH2:7][CH2:6][CH2:6][CH2:7][C:8]([NH:9][CH2:10][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][NH:36][C:24]2[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][C:25]=2[N+:33]([O-:35])=[O:34])=[O:42])[CH:15]=1

Participants

4

Reactant 3

HCID 6264DinitrofluorobenzeneHCID 54562181N-(3-aminopropyl)-N'-(4-azido-2-nitrophenyl)-N-methyl-1,3-propanediamineHCID 66926435Pyridine water2×

Product 1

HCID 30359036-(2,4-Dinitrophenylamino)-1-aminohexyl-6-(4'-azido-2'-nitrophenylamino)hexanoate

Procedure

Crude N-(3-aminopropyl)-N'-(4-azido-2-nitrophenyl)-N-methyl-1,3-propane diamine (300 mg, approx. 1 mmol) was dissolved with stirring at room temp. in 70% pyridine-water (5 ml). A solution of 1-fluoro-2,4-dinitrobenzene (110 mg, 1 mmol) in 70% pyridine water (5 ml) was added in one portion with stirring. An orange red precipitate began to form at once and the reaction mix was stirred at room temp. overnight. The mixture was then concentrated on a rotary evaporator to an oil which was dissolved in CH2Cl2 (20 ml), washed with 1M NaOH (20 ml), dried over Na2SO4 and again concentrated on a rotary evaporator to give an oily solid. Last traces of solvent were removed by evacuation with an oil pump at room temp. to give photo-DNP as an orange-red powder. Yield was 294 mg. M.p. 90°-95° C. TLC on alumina with dichloroethane was solvent showed the product to be a single spot with Rf 0.6; under these conditions, the starting amine remained at the origin.

Workup

  1. customto form at once and the reaction
  2. additionmix
  3. stirringwas stirred at room temp. overnight
  4. concentrationThe mixture was then concentrated on a rotary evaporator to an oil which
  5. dissolutionwas dissolved in CH2Cl2 (20 ml)
  6. washwashed with 1M NaOH (20 ml)
  7. dry with materialdried over Na2SO4
  8. concentrationagain concentrated on a rotary evaporator
  9. customto give an oily solid
  10. customLast traces of solvent were removed by evacuation with an oil pump at room temp.

Sources & evidence

ORD record
ord-d1d7fddf96e1417493cc2044414b85e4
Source dataset
uspto-grants-1990_02
Patent number
US04898951

Reaction notes

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