Potassium Iodide → HCID 11560423, compound

HRID 380353Notes

Reaction equation

[OH:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[CH2:15][C:16]([O:18]C)=[O:17])=[CH:4][CH:3]=1.Cl[CH2:21][C:22]1[CH:31]=[CH:30][C:29]2[C:24](=[CH:25][CH:26]=[CH:27][CH:28]=2)[N:23]=1.C(=O)([O-])[O-].[K+].[K+].[I-].[K+].[OH-].[K+].N1C2C(=CC=CC=2)C=CC=1>C(O)C.O.CC(=O)CC>[N:23]1[C:24]2[C:29](=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH:30]=[CH:31][C:22]=1[CH2:21][O:1][C:2]1[CH:3]=[CH:4][C:5]([S:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[CH2:15][C:16]([OH:18])=[O:17])=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 5 °C

Procedure

A stirred mixture of methyl 2-(4-hydroxyphenylsulfanyl)phenylacetate (5.0 g, 18.0 mmol), 2-chloromethylquinoline (3.2 g, 18.0 mmol), anhydrous potassium carbonate (6.5 g), potassium iodide (0.2 g), and butan-2-one (70 ml) was refluxed for 8 h. The hot mixture was filtered, the filtration cake was washed with boiling butan-2-one (2×15 ml) and the filtrate was again filtered with charcoal. The solution was evaporated under reduced pressure. The crystalline residue was mixed with methanol (15 ml) and left to stand overnight in a refrigerator. The crystalline methyl ester of the title acid was filtered (5.9 g, 80.8%), m.p. 100-102. 1H NMR spectrum (CDCl3): CH3(OCO) 3.64 s; CH2(COO) 3.83 s; CH2(O) 5.36 s; aromatic H of the quinoline nucleus: H(3) 7.64 d, J=8.8 Hz; H(4) 8.18 d, J=8.8 Hz; H(5) 7.82 dd, J=1.3, 8.5 Hz; H(6) 7.54 m: H(7) 7.73 m; H(8) 8.08 d, J=8.5 Hz; This ester (5.9 g, 14.2 mmol) was suspended in ethanol (75 ml), a solution of potassium hydroxide (1.5 g, 27 mmol) in water (10 ml) was added and the mixture was refluxed 30 min. Then ethanol was evaporated under reduced pressure, the mixture was diluted with water (100 ml) and the cloudy solution was filtered with charcoal. The filtrate was acidified with acetic acid to pH 4.5, the mixture was cooled to 5° C. and the formed precipitate was filtered. The crude product was purified by crystallization from ethanol (120 ml) to give the title acid (3.0 g, 52.6%), m.p. 179-181° C. For C24H19NO3S (401.5) calculated: 71.80% C, 71.80% C, 4.77% H, 3.49% N, 7.99% S; found: 71.67% C, 4.94% H, 3.41% N, 7.77% S. 1H NMR spectrum (DMSO-d6, 60° C.): CH2(COO) 3.77 s; CH2(O) 5.38 s; aromatic H of the quinoline nucleus: H(3) 7.67 d, J=8.2 Hz; H(4) 8.40 d, J=8.2 Hz; H(5) 8.03 d, J=8.5 Hz; H(6) 7.78 m; H(7) 7.61 m; H(8) 7.98 dd, J=0.9, 8.5 Hz;

Workup

temperaturewas refluxed for 8 h
filtrationThe hot mixture was filtered
washthe filtration cake was washed with boiling butan-2-one (2×15 ml)
filtrationthe filtrate was again filtered with charcoal
customThe solution was evaporated under reduced pressure
additionThe crystalline residue was mixed with methanol (15 ml)
waitleft
filtrationThe crystalline methyl ester of the title acid was filtered (5.9 g, 80.8%)
customCH3(OCO) 3.64 s
customCH2(COO) 3.83 s
customCH2(O) 5.36 s
custom7.64 d, J=8.8 Hz
customH(4) 8.18 d, J=8.8 Hz
customH(8) 8.08 d, J=8.5 Hz
temperaturethe mixture was refluxed 30 min
customThen ethanol was evaporated under reduced pressure
additionthe mixture was diluted with water (100 ml)
filtrationthe cloudy solution was filtered with charcoal
filtrationthe formed precipitate was filtered
customThe crude product was purified by crystallization from ethanol (120 ml)
customto give the title acid (3.0 g, 52.6%), m.p. 179-181° C
custom1H NMR spectrum (DMSO-d6, 60° C.)
customCH2(O) 5.38 s
custom7.67 d, J=8.2 Hz
customH(4) 8.40 d, J=8.2 Hz
customH(5) 8.03 d, J=8.5 Hz

Sources & evidence

ORD record: ord-4005839efd3142acb591de47982e977a
Source dataset: uspto-grants-2001_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06303612B1

Reaction notes

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