Sodium Chloride → N-(3,4-Dichloro-benzyl)-2-(2,2-dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-methyl-acetamide

HRID 2214533

反応式

HRID 2214533 の反応式
[CH3:1][C:2]1([CH3:12])[O:6][C:5](=[CH:7][C:8]([OH:10])=O)[C:4](=[O:11])[O:3]1.C(Cl)(=O)C(Cl)=O.Cl.[Cl:20][C:21]1[CH:22]=[C:23]([CH:27]=[CH:28][C:29]=1[Cl:30])[CH2:24][NH:25][CH3:26].[Cl-].[Na+]>C1C=CC=CC=1.C(Cl)Cl.N1C=CC=CC=1.Cl>[Cl:20][C:21]1[CH:22]=[C:23]([CH:27]=[CH:28][C:29]=1[Cl:30])[CH2:24][N:25]([CH3:26])[C:8](=[O:10])[CH:7]=[C:5]1[C:4](=[O:11])[O:3][C:2]([CH3:1])([CH3:12])[O:6]1

参加物

9

反応物 4

HCID 5234Sodium ChlorideHCID 65578Oxalyl chlorideHCID 172938771-(3,4-Dichlorophenyl)-N-methylmethanamine hydrochlorideHCID 68860642(2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-acetic acid

生成物 1

HCID 69655735N-(3,4-Dichloro-benzyl)-2-(2,2-dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-methyl-acetamide収率 82%

試薬・触媒・溶媒 4

HCID 241Benzene溶媒HCID 313Hydrochloric Acid溶媒HCID 1049Pyridine溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

To a suspension of (2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-acetic acid, Compound III-A, (4.5 g, 26.2 mmol) in benzene (30 mL) was added oxalyl chloride (15 mL) and the resulting mixture was heated at reflux for 1 h. The mixture was cooled to room temp. and concentrated. The residue was dissolved in methylene chloride (30 mL) and cooled to 0° C. To this was added a suspension of (3,4-dichloro-benzyl)-methyl-amine hydrochloride salt (5.0 g, 22.1 mmol) in methylene chloride (30 mL) and pyridine (18 mL). The resulting mixture was stirred at room temp for 18 h then diluted with 1N HCl. The aqueous phase was saturated with sodium chloride and extracted with methylene chloride (3 times). The organic layers were combined, dried (Na2SO4), and concentrated. The brown oil was purified over silica gel eluting with ethyl acetate/hexane (1:1) to give the title compound as a pale yellow oil that solidified to a white solid upon standing (6.2 g, 82% yield). 1H NMR (300 MHz, DMSO) δ: 7.44–7.10 (m, 3H), 6.16 (s, 0.66H), 6.08 (s, 0.33H), 4.59 (s, 1.33H), 4.53 (s, 0.67H), 3.02 (s, 2H), 2.97 (s, 1H), 1.74 (s, 4H), 1.69 (s, 2H).

後処理

  1. temperaturethe resulting mixture was heated
  2. temperatureat reflux for 1 h
  3. temperatureThe mixture was cooled to room temp.
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in methylene chloride (30 mL)
  6. additionTo this was added
  7. extractionextracted with methylene chloride (3 times)
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated
  10. customThe brown oil was purified over silica gel eluting with ethyl acetate/hexane (1:1)

出典と根拠

ORDレコード
ord-ca545db157cc491aace4a2e01517f5f2
出典データセット
uspto-grants-2006_09
特許番号
US07109186B2

関連ノート

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