Sodium Hydroxide → HCID 178507387, compound

HRID 1761701Notes

Reaction equation

HRID 1761701 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]2[C:13]3[CH:14]=[CH:15][C:16]([C:18]([C:20]4[CH:36]=[CH:35][C:23]5[C:24]([C:26]6[CH:31]=[CH:30][C:29]([N+:32]([O-])=O)=[CH:28][CH:27]=6)=[CH:25][C:22]=5[CH:21]=4)=[O:19])=[CH:17][C:12]=3[CH:11]=2)=[CH:6][CH:5]=1)([O-])=O.O.O.Cl[Sn]Cl.[BH4-].[Na+].[OH-].[Na+]>C(O)C.O>[NH2:1][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[C:13]3[CH:14]=[CH:15][C:16]([C:18]([C:20]4[CH:36]=[CH:35][C:23]5[C:24]([C:26]6[CH:31]=[CH:30][C:29]([NH2:32])=[CH:28][CH:27]=6)=[CH:25][C:22]=5[CH:21]=4)=[O:19])=[CH:17][C:12]=3[CH:11]=2)=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 14798Sodium Hydroxide2×HCID 61436Stannous chloride dihydrateHCID 4311764Sodium borohydrideHCID 178519299HCID 178519299, compound

Product 1

HCID 178507387HCID 178507387, compoundYield 53.4%

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

Into a 250 ml three neck round bottom flask equipped with a magnetic stirring bar, a reflux condensor with a nitrogen inlet and a thermometer and an equilibrating addition funnel is charged 1.0 g (3.95 mmol) of 4-nitrophenyl-4-benzocyclobutenyl ketone, 4.46 g (19.75 mmol) of (SnCl2.2H2O) and 100 ml of ethanol. Under a nitrogen atmosphere, the mixture is heated to 60° C. To the mixture, in a slow dropwise manner is added sodium borohydride, 75 mg (1.975 mmol) in 20 ml of ethanol, over a period of 20 minutes. After the addition, the temperature of the mixture is maintained at 60° C. for 30 minutes. The mixture is cooled to 10° C. and 80 ml of water previously chilled is added. Concentrated sodium hydroxide is added until the pH is 7 (4M, NaOH, about 6 ml). The mixture is transferred to a 500 ml round-bottom flask and the ethanol is removed on a rotovap. Thereafter, 100 ml of water is added to the off-while slurry and the aqueous phase is extracted with diethyl ether four times with 100 ml aliquots. The ether extracts are dried over sodium sulfate overnight. The sodium sulfate is filtered from the diethyl ether extracts and the diethyl ether is removed on a rotovap. A bright orange solid (0.87 g) is obtained. The solid is recrystallized using carbon tetrachloride (200 ml) and decolorizing charcoal. The first crop of crystals is a pale yellow solid 0.54 g (61.3%). The carbon tetrachloride is concentrated to 50 ml and left standing overnight. NMR and IR indicate the product is 4-aminophenyl-4-benzocyclobutenyl ketone.

Workup

  1. additiona reflux condensor with a nitrogen inlet and a thermometer and an equilibrating addition funnel
  2. additionAfter the addition
  3. temperaturethe temperature of the mixture is maintained at 60° C. for 30 minutes
  4. temperatureThe mixture is cooled to 10° C.
  5. additionis added
  6. customThe mixture is transferred to a 500 ml round-bottom flask
  7. customthe ethanol is removed on a rotovap
  8. additionThereafter, 100 ml of water is added to the off-while slurry
  9. extractionthe aqueous phase is extracted with diethyl ether four times with 100 ml aliquots
  10. dry with materialThe ether extracts are dried over sodium sulfate overnight
  11. filtrationThe sodium sulfate is filtered from the diethyl ether extracts
  12. customthe diethyl ether is removed on a rotovap

Sources & evidence

ORD record
ord-31b31de3cf194305999f7d250ee9ada1
Source dataset
uspto-grants-1989_05
Patent number
US04826997

Reaction notes

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