4-Nitrophenol → Carbonic acid, 1,1-dimethylethyl 4-nitrophenyl ester

HRID 51174Notes

Reaction equation

HRID 51174 reaction equation
[C:1](=[O:4])([O-:3])[O-:2].[Na+].[Na+].[N+:7]([C:10]1[CH:15]=[CH:14][C:13](O)=[CH:12][CH:11]=1)([O-:9])=[O:8].[CH2:17](OC(NC1C=CNC(=O)N=1)=O)[C:18]1[CH:23]=CC=C[CH:19]=1.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.O1CCOCC1>[C:1](=[O:3])([O:2][C:13]1[CH:14]=[CH:15][C:10]([N+:7]([O-:9])=[O:8])=[CH:11][CH:12]=1)[O:4][C:18]([CH3:23])([CH3:19])[CH3:17]

Participants

7

Reactant 4

HCID 9804-NitrophenolHCID 10340Sodium CarbonateHCID 11430Potassium CarbonateHCID 178522340HCID 178522340, compound

Product 1

HCID 83324Carbonic acid, 1,1-dimethylethyl 4-nitrophenyl ester

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Sodium carbonate (29.14 g; 0.275 mol) and 4-nitrophenol (12.75 g; 91.6 mmol) were mixed with dioxane (250 ml). Boc-anhydride (20.0 g; 91.6 mmol) was transferred to the mixture with dioxane (50 ml). The mixture was refluxed for 1 h, cooled to 0° C., filtered and concentrated to ⅓, and then poured into wat.82 ml;82.6 mmol) and a suspension of N4-benzyloxycarbonyl-cytosine (9, 21.0 g;82.6 mmol) and potassium carbonate (11.4 g;82.6 mmol) in dry DMF (900 ml). The mixture was stirred vigorously overnight, filtered, and evaporated to dryness, in vacuo. Water (300 ml) and 4 N hydrochloric acid (10 ml) were added, the mixture was stirred for 15 minutes at 0° C., filtered, and washed with water (2×75 ml). The isolated precipitate was treated with water (120 ml), 2N sodium hydroxide (60 ml), stirred for 30 min, filtered, cooled to 0° C., and 4 N hydrochloric acid (35 ml) was added. The title compound was isolated by filtration, washed thoroughly with water, recrystallized from methanol (1000 ml) and washed thoroughly with ether. This afforded 7.70 g (31%) of pure compound. The mother liquor from the recrystallization was reduced to a volume of 200 ml and cooled to 0° C. This afforded an additional 2.30 g of a material that was pure by tlc but had a reddish color. M.p. 266-274° C. Anal., for C14H13N3O5. Found(calc.); C, 55.41(55.45); H, 4.23(4.32); N, 14.04(13.86) 1H-NMR (90 MHz; DMSO-d6): 8.02 ppm (d,J=7.32 Hz,1H,H-6); 7.39 (s,5H,Ph); 7.01 (d,J=7.32 Hz,1H,H-5); 5.19 (s,2H,PhCH2—); 4.52. (s,2H).

Workup

  1. temperatureThe mixture was refluxed for 1 h
  2. filtrationfiltered
  3. concentrationconcentrated
  4. additionpoured into wat
  5. filtrationfiltered
  6. customevaporated to dryness, in vacuo
  7. additionWater (300 ml) and 4 N hydrochloric acid (10 ml) were added
  8. stirringthe mixture was stirred for 15 minutes at 0° C.
  9. filtrationfiltered
  10. washwashed with water (2×75 ml)
  11. additionThe isolated precipitate was treated with water (120 ml), 2N sodium hydroxide (60 ml)
  12. stirringstirred for 30 min
  13. filtrationfiltered
  14. temperaturecooled to 0° C.
  15. addition4 N hydrochloric acid (35 ml) was added

Sources & evidence

ORD record
ord-2cfafea65947482e90e3381fd1b1ca82
Source dataset
uspto-grants-2004_03
Patent number
US06713602B1

Reaction notes

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