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

HRID 508658노트

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HRID 508658 반응식
[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

참가 물질

8

반응물 3

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

생성물 1

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

시약·촉매·용매 4

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 6228Dimethylformamide용매HCID 81531Diisopropylethylamine용매

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온도
111 °C

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-25d58a3420ed474c929dd5f616a3bcc3
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09096544B2

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