Potassium Iodide → HCID 21471883, compound

HRID 2294863Notes

Reaction equation

HRID 2294863 reaction equation
Cl[CH2:2][CH2:3][CH2:4][S:5][C:6]1[S:10][C:9]2[CH2:11][CH2:12][CH2:13][C:14](=[O:15])[C:8]=2[CH:7]=1.Cl.[F:17][C:18]1[CH:32]=[CH:31][C:21]2[C:22]([CH:25]3[CH2:30][CH2:29][NH:28][CH2:27][CH2:26]3)=[N:23][O:24][C:20]=2[CH:19]=1.C(=O)([O-])[O-].[K+].[K+].[I-].[K+]>CN(C)C=O.C1(C)C=CC=CC=1.O>[F:17][C:18]1[CH:32]=[CH:31][C:21]2[C:22]([CH:25]3[CH2:26][CH2:27][N:28]([CH2:2][CH2:3][CH2:4][S:5][C:6]4[S:10][C:9]5[CH2:11][CH2:12][CH2:13][C:14](=[O:15])[C:8]=5[CH:7]=4)[CH2:29][CH2:30]3)=[N:23][O:24][C:20]=2[CH:19]=1

Participants

8

Reactant 4

HCID 4875Potassium IodideHCID 11430Potassium CarbonateHCID 11334359R-56109 hydrochlorideHCID 21471886HCID 21471886, compound

Product 1

HCID 21471883HCID 21471883, compoundYield 58.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of 0.5 g of 2-((3-chloropropyl)thio)-4-oxo-4,5,6,7-tetrahydrobenzo(b)thiophene, 0.5 g of 4-(6-fluoro-1,2-benzisoxazol-3-yl)piperidine hydrochloride, 0.6 g of potassium carbonate and 0.4 g of potassium iodide in 10 ml of dimethylformamide and 10 ml of toluene was mixed at 100° C. for 4 hours and poured into water. The toluene layer was washed with water, dried over magnesium sulfate and concentrated. The residue was purified by column chromatography on a silica gel to give 0.5 g of 2-(3-(4-(6-fluoro-1,2-benzisoxazol-3-yl)piperidin-1-yl)propylthio)-4-oxo-4,5,6,7-tetrahydrobenzo(b)-thiophene. The resulting compound was dissolved in 20 ml of ethanol, and 0.1 g of hydroxylamine hydrochloride and 0.12 g of sodium hydrogencarbonate were added thereto. After the mixture was refluxed for 3 hours, the solvent was distilled away in vacuo and water was added to the residue, and then extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated. To the residue was added isopropyl ether to give 0.5 g of an oxime compound as crystals. A mixture of 0.35 g of the oxime compound and 3.5 g of 115% polyphosphoric acid was stirred at 100° C. for 5 hours, poured into water and extracted with chloroform. The extract was washed with water, dried and concentrated. The residue was separated and purified by column chromatography on a silica gel and each of resulting crystals was recrystallized from isopropyl ether to give 0.06 g of 2-(3-(4-(6-fluoro-1,2-benzisoxazol-3-yl)piperidin-1-yl)propylthio)-5,6,7,8-tetrahydro-4H-thieno[3,2-c]azepin-4-one, m.p. 119°-121° C. and 0.019 g of 2-(3-(4-(6-fluoro-1,2-benzisoxazol-3-yl)piperidin-1-yl)propylthio)-4,6,7,8-tetrahydro-5H-thieno[3,2-b]azepin-5-one, m.p. 125°-127° C.

Workup

  1. additionwas mixed at 100° C. for 4 hours
  2. washThe toluene layer was washed with water
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated
  5. customThe residue was purified by column chromatography on a silica gel

Sources & evidence

ORD record
ord-02f0f54cdceb42a9b18b61747375b858
Source dataset
uspto-grants-1997_11
Patent number
US05691330

Reaction notes

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