Ethyl Acrylate → ethyl(E)-3-(3-chloro-6-pyridazinyl)-2-propenoate

HRID 508658ノート

反応式

HRID 508658 の反応式
[Cl:1][C:2]1[N:3]=[N:4][C:5](I)=[CH:6][CH:7]=1.[C:9]([O:13][CH2:14][CH3:15])(=[O:12])[CH:10]=[CH2:11].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CN(C=O)C.C(N(C(C)C)CC)(C)C.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:1][C:2]1[N:3]=[N:4][C:5](/[CH:11]=[CH:10]/[C:9]([O:13][CH2:14][CH3:15])=[O:12])=[CH:6][CH:7]=1

参加物

8

反応物 3

HCID 8821Ethyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 154188393-Chloro-6-iodopyridazine

生成物 1

HCID 53259410ethyl(E)-3-(3-chloro-6-pyridazinyl)-2-propenoate収率 8.2%

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 81531Diisopropylethylamine溶媒

反応条件

温度
111 °C

実験手順

A suspension of 3-chloro-6-iodopyridazine (2.4 g, 10 mmol), ethyl acrylate (4.4 mL, 40 mmol), palladium(II) acetate (90 mg, 0.40 mmol) and tri(o-tolyl)phosphine (366 mg, 1.20 mmol) in DMF (10 mL) and diisopropylethyl amine (5 mL) was stirred with heating (111° C. oil-bath) for 3.5 h, cooled to room temperature, diluted with H2O (50 mL) and extracted with EtOAc (300 mL). The extract was washed (brine) and dried. After solvent removal at reduced pressure, the residue was chromatographed (14% to 20% EtOAc/hexane) to give 174 mg (8%) of ethyl(E)-3-(3-chloro-6-pyridazinyl)-2-propenoate as a brown solid, mp 106-110° C. IR 2928, 1715, 1186 cm−1; 1H NMR (CDCl3) δ 1.38 (t, J=7.5 Hz, 3H, CH2CH3), 4.33 (q, J=7.5 Hz, 2H, CH2CH3), 7.98 (d, J=16.2 Hz, 1H, CH═CHCO), 7.57 (d, J=8.4 Hz, 1H, 4-ArH), 7.63 (d, J=8.4 Hz, 1H, 5-ArH), 7.86 ppm (d, J=16.2 Hz, 1H, CH═CHCO). HRMS calcd C9H9ClN2O2 [M+H]+ 213.0425. found 213.0431.

後処理

  1. temperaturecooled to room temperature
  2. extractionextracted with EtOAc (300 mL)
  3. washThe extract was washed (brine)
  4. customdried
  5. customAfter solvent removal at reduced pressure
  6. customthe residue was chromatographed (14% to 20% EtOAc/hexane)

出典と根拠

ORDレコード
ord-25d58a3420ed474c929dd5f616a3bcc3
出典データセット
uspto-grants-2015_08
特許番号
US09096544B2

反応ノート

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