Hydrochloric Acid → 1-(2',4'-Dichlorophenyl)-1,4,5,6-tetrahydro-thieno[3',2':6,7]cyclohepta[1,2-c]pyrazol-3-carboxylic acid

HRID 709396Notes

Reaction equation

HRID 709396 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[N:9]1[C:13]2[C:14]3[S:21][CH:20]=[CH:19][C:15]=3[CH2:16][CH2:17][CH2:18][C:12]=2[C:11]([C:22]([O:24]CC)=[O:23])=[N:10]1.[OH-].[Li+].O.Cl>C1COCC1.O>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[N:9]1[C:13]2[C:14]3[S:21][CH:20]=[CH:19][C:15]=3[CH2:16][CH2:17][CH2:18][C:12]=2[C:11]([C:22]([OH:24])=[O:23])=[N:10]1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 3939Lithium HydroxideHCID 117640792Ethyl 1-(2',4'-dichlorophenyl)-1,4,5,6-tetrahydro-thieno[3',2':6,7]-cyclo-hepta[1,2-c]pyrazol-3-carboxylate

Product 1

HCID 1176407871-(2',4'-Dichlorophenyl)-1,4,5,6-tetrahydro-thieno[3',2':6,7]cyclohepta[1,2-c]pyrazol-3-carboxylic acidYield 72%

Reagents, catalysts & solvents 1

HCID 21881883Oxolane--water (1/1)Solvent

Conditions

Temperature
60 °C

Procedure

300 mg of ethyl 1-(2′,4′-dichlorophenyl)-1,4,5,6-tetrahydro-thieno[3′,2′:6,7]cyclohepta[1,2-c]pyrazol-3-carboxylate prepared in example 9e are solubilized in THF/H2O 4:1 (7 mL). Lithium hydroxide (72 mg; 2.7 mmoles) is added and the mixture is heated to 60° C. for 5 hours. After cooling at room temperature, it is diluted first by adding water (5 mL) and then a HCl 1N solution to lower the pH to 1-2. A precipitate is formed which is recovered by filtration and then washed with ethyl ether (2×10 mL). 200 mg of 1-(2′,4′-dichlorophenyl)-1,4,5,6-tetrahydro-thieno[3′,2′:6,7]cyclohepta[1,2-c]pyrazol-3-carboxylic acid are obtained (white solid; yield 72%). Rf=0.76 (chloroform/methanol 9/1 volume/volume); 1H NMR (CDCl3) δ (ppm): 7.58 (d, 1H, ArH), 7.45 (m, 2H, ArH), 7.04 (d, 1H, ArH), 6.80 (d, 1H, ArH), 3.30 (m, 2H, CH2), 3.00 (m, 2H, CH2), 2.07 (m, 2H, CH2); 13C NMR (CDCl3) δ (ppm): 163.4, 143.6, 141.3, 139.3, 137.5, 136.0, 135.0, 131.6, 130.5, 130.2, 128.2, 125.1, 123.8, 122.4, 31.0, 25.9, 24.1; FT-IR (film) νmax: 3078.0, 2929.3, 2854.1, 2715.1, 1683.4, 1450.3, 1386.6, 1251.4, 1204.2, 705.8, 665.3 cm−1.

Workup

  1. temperatureAfter cooling at room temperature
  2. additionit is diluted first
  3. customA precipitate is formed which
  4. filtrationis recovered by filtration
  5. washwashed with ethyl ether (2×10 mL)

Sources & evidence

ORD record
ord-4964f236c6744fc89bcd0cdc1de15f6f
Source dataset
uspto-grants-2015_11
Patent number
US09181196B2

Reaction notes

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