Phosphoric Acid → HCID 57628288, compound

HRID 1692058Notes

Reaction equation

HRID 1692058 reaction equation
P(=O)(O)(O)O.CC(C)CC(=O)C.[NH2:13][C:14]1[CH:18]=[CH:17][S:16][C:15]=1/[C:19](=[CH:21]/[CH:22]([CH3:24])[CH3:23])/[CH3:20].NC1C=CSC=1/C(=C\C(C)C)/C>O>[NH2:13][C:14]1[CH:18]=[CH:17][S:16][C:15]=1[C:19]([CH2:21][CH:22]([CH3:24])[CH3:23])=[CH2:20]

Participants

6

Reactant 4

HCID 1004Phosphoric AcidHCID 7909Methyl Isobutyl KetoneHCID 44139031HCID 44139031, compoundHCID 57628287HCID 57628287, compound

Product 1

HCID 57628288HCID 57628288, compoundYield 34%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

3-aminothiophene phosphate (5.0 g, 16.1 mmol) was added into water (100 g) in an ice water bath for dissolving. Toluene (50.0 g) was added in an ice water bath, and then a 10% aqueous sodium hydroxide solution was added under stirring in an ice water bath for adjusting the reaction solution to the alkaline side. The organic layer was separated, and then the aqueous layer was further extracted with toluene. To the toluene solution of 3-aminothiophene obtained as described above were added 85% phosphoric acid (0.9 g, 8.1 mmol) and 4-methyl-2-pentanone (50.0 g, 499.2 mmol) at room temperature, and the resulting solution was stirred under reflux under nitrogen atmosphere for 5 hours with removing water. The reaction solution was cooled to room temperature, and then washed with a 10% aqueous sodium hydroxide solution two times, and the obtained organic layer was concentrated under reduced pressure to give an oily substance. The resulting concentrate was purified by silica gel column chromatography to give 1.0 g of an oily substance as a mixture of three compounds including 3-amino-2-{(E)-(4-methyl-2-penten-2-yl)}thiophene, 3-amino-2-{(Z)-(4-methyl-2-penten-2-yl)}thiophene and 3-amino-2-(4-methyl-1-penten-2-yl)thiophene (yield: 34%).

Workup

  1. washwashed with a 10% aqueous sodium hydroxide solution two times
  2. concentrationthe obtained organic layer was concentrated under reduced pressure
  3. customto give an oily substance
  4. concentrationThe resulting concentrate
  5. customwas purified by silica gel column chromatography
  6. customto give 1.0 g of an oily substance
  7. additionas a mixture of three compounds

Sources & evidence

ORD record
ord-cfa53fca085241aebc2d3a65632ae128
Source dataset
uspto-grants-2012_04
Patent number
US08153823B2

Reaction notes

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