Water → HCID 86735598, compound

HRID 2082779Notes

Reaction equation

HRID 2082779 reaction equation
[Na].O[C:3]1[CH:26]=[CH:25][C:24]([N+:27]([O-:29])=[O:28])=[CH:23][C:4]=1[NH:5][C:6](=[O:22])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH3:21].[Br:30][CH2:31][CH2:32][P:33](Cl)(Cl)=[O:34].O>C1C=CC=CC=1>[Br:30][CH2:31][CH2:32][P:33](=[C:3]1[CH:26]=[CH:25][C:24]([N+:27]([O-:29])=[O:28])=[CH:23][CH:4]1[NH:5][C:6](=[O:22])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH3:21])=[O:34]

Participants

6

Reactant 4

HCID 962WaterHCID 283495(2-bromoethyl)phosphonic dichlorideHCID 34841452-(n-Hexadecanoylamino)-4-nitrophenolHCID 5360545Sodium

Product 1

HCID 86735598HCID 86735598, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Conditions

Temperature
10 °C

Procedure

In 400 ml of benzene was suspended 4.15 g (10 mmol) of the sodium salt of 2'-hydroxy-5'-nitrohexadecananilide. The suspension was stirred and heated to boiling. Benzene, 100 ml was collected through a concentrator condenser. The condenser was then replaced with a reflux condenser on which a drying tube was mounted. The temperature of the mixture was lowered to 25° C and 4.84 g (20 mmol; 2.64 ml) of β-bromoethylphosphoryl dichloride was added. The slightly yellow solution was stirred for 1 hour at room temperature and then it was heated under reflux for 24 hours. After cooling to 10° C, 10 ml (0.56 mol) of water was added and the stirring was continued for 72 hours at room temperature. The precipitate 4.2 g was filtered from the mother liquor and washed with 100 ml of benzene. (Subsequent treatment of the mother liquor is described in part (d) of this example.) The dried and pulverized product was then suspended in 90 ml of 0.2 M sodium acetate buffer (pH 5.0) and stirred for 3 hours. The mixture was filtered through a coarse filter paper and the filtrate was acidified with 90 ml of 1 N hydrochloric acid and extracted twice with 180 ml of ethyl acetate. After evaporation of the solvent the residue (2.7 g) was recrystallized from 70 ml of acetone to yield 2.2 g (38%) of 2'-(β-bromoethylphosphoryl)-5'-nitrohexadecananilide. Mp 117°-118° C. The compound was water soluble as a sodium salt, 10-4M pH 3.7, and in 0.2 M sodium acetate buffer (pH 5.0), 100 mg per ml. It was insoluble in water; slightly soluble in ethyl ether; soluble in methyl and ethyl alcohol, ethyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, benzene and chloroform. Thin-layer chromatography: Chloroform-methanol-water (75:25:3). Rf 0.5. 2'-hydroxy-5'-nitrohexadecananilide, Rf 0.95). The ir spectrum displayed the following additional bands when compared with the spectrum of 2'-hydroxy-5'-nitrohexadecananilide, 1210 (P=0 str.), 1005, 950, 920 (P=0 (OH)), 730, 560 cm-1 (bromine ?).

Workup

  1. temperatureheated to boiling
  2. customBenzene, 100 ml was collected through a concentrator condenser
  3. customThe condenser was then replaced with a reflux condenser on which a drying tube
  4. customwas lowered to 25° C
  5. stirringThe slightly yellow solution was stirred for 1 hour at room temperature
  6. temperatureit was heated
  7. temperatureunder reflux for 24 hours
  8. filtrationThe precipitate 4.2 g was filtered from the mother liquor
  9. washwashed with 100 ml of benzene
  10. custom) The dried
  11. stirringstirred for 3 hours
  12. filtrationThe mixture was filtered through
  13. filtrationa coarse filter paper
  14. extractionextracted twice with 180 ml of ethyl acetate
  15. customAfter evaporation of the solvent the residue (2.7 g)
  16. customwas recrystallized from 70 ml of acetone

Sources & evidence

ORD record
ord-9f7de3df8d91401b93addca2220558d9
Source dataset
uspto-grants-1978_04
Patent number
US04082781

Reaction notes

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