(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

반응식

HRID 709395 반응식
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

참가 물질

4

반응물 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

생성물 1

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

시약·촉매·용매 1

HCID 702Ethanol용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-a75f2e39536243bbab832d6f98f77555
출처 데이터셋
uspto-grants-2015_11
특허 번호
US09181196B2

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