(2,4-Dichlorophenyl)hydrazine monohydrochloride → Ethyl 1-(2',4'-dichlorophenyl)-1,4,5,6-tetrahydro-thieno[3',2':6,7]-cyclo-hepta[1,2-c]pyrazol-3-carboxylate

HRID 709395

反応式

HRID 709395 の反応式
O=[C:2]([CH:8]1[C:17](=O)[C:13]2[S:14][CH:15]=[CH:16][C:12]=2[CH2:11][CH2:10][CH2:9]1)[C:3]([O:5][CH2:6][CH3:7])=[O:4].Cl.[Cl:20][C:21]1[CH:26]=[C:25]([Cl:27])[CH:24]=[CH:23][C:22]=1[NH:28][NH2:29]>C(O)C>[Cl:20][C:21]1[CH:26]=[C:25]([Cl:27])[CH:24]=[CH:23][C:22]=1[N:28]1[C:17]2[C:13]3[S:14][CH:15]=[CH:16][C:12]=3[CH2:11][CH2:10][CH2:9][C:8]=2[C:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])=[N:29]1

参加物

4

反応物 2

HCID 2723905(2,4-Dichlorophenyl)hydrazine monohydrochlorideHCID 117640824ethyl 2-oxo-2-(8-oxo-5,6,7,8-tetrahydro-4H-cyclo hepta[b]thiophen-7-yl)acetate

生成物 1

HCID 117640792Ethyl 1-(2',4'-dichlorophenyl)-1,4,5,6-tetrahydro-thieno[3',2':6,7]-cyclo-hepta[1,2-c]pyrazol-3-carboxylate収率 35%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

560 mg of ethyl 2-oxo-2-(8-oxo-5,6,7,8-tetrahydro-4H-cyclo hepta[b]thiophen-7-yl)acetate prepared in example 9d are solubilized in absolute ethanol (11 mL). 580 mg of 2,4-dichlorophenyl-hydrazine hydrochloride are added. The reaction mixture is heated under reflux conditions for 14 hours. The solvent is removed under vacuum and the obtained residue is purified by chromatography on silica gel by using as eluent a mixture of ligroin/ethyl acetate 9:1 volume/volume. 300 mg of ethyl 1-(2′,4′-dichlorophenyl)-1,4,5,6-tetrahydro-thieno[3′,2′:6,7]-cyclo-hepta[1,2-c]pyrazol-3-carboxylate are obtained (orange solid; yield 35%). Rf=0.20 (ligroin/ethyl acetate 9/1 volume/volume); 1H NMR (CDCl3) δ (ppm): 7.55 (d, 1H, ArH), 7.48 (d, 1H, ArH), 7.42 (dd, 1H, ArH), 7.03 (d, 1H, ArH), 6.79 (d, 1H, ArH), 4.44 (q, 2H, OCH2), 3.29 (m, 2H, CH2), 2.99 (m, 2H, CH2), 2.06 (m, 2H, CH2), 1.42 (t, 3H, CH3); 13C NMR (CDCl3) δ (ppm): 162.8, 143.2, 142.4, 137.2, 136.4, 135.3, 131.9, 130.3, 130.0, 128.1, 124.8, 124.2, 122.4, 61.0, 30.9, 26.1, 24.4, 14.5; FT-IR (film) νmax: 3092.7, 2928.9, 1712.5, 1486.6, 1446.9, 1245.6, 1190.9, 1100.3, 947.0, 713.9, 641.6, 610.6 cm−1.

後処理

  1. temperatureThe reaction mixture is heated under reflux conditions for 14 hours
  2. customThe solvent is removed under vacuum
  3. customthe obtained residue is purified by chromatography on silica gel
  4. additiona mixture of ligroin/ethyl acetate 9:1 volume/volume

出典と根拠

ORDレコード
ord-a75f2e39536243bbab832d6f98f77555
出典データセット
uspto-grants-2015_11
特許番号
US09181196B2

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