Ethyl 2-Cyano-2-methylpropionate → Ethyl 2-carbamothioyl-2,2-dimethylacetate

HRID 38681ノート

反応式

HRID 38681 の反応式
C1([S:7]P(C2C=CC=CC=2)(=S)O)C=CC=CC=1.[CH2:17]([O:19][C:20](=[O:26])[C:21]([C:24]#[N:25])([CH3:23])[CH3:22])[CH3:18]>C(O)(C)C>[NH2:25][C:24](=[S:7])[C:21]([CH3:23])([CH3:22])[C:20]([O:19][CH2:17][CH3:18])=[O:26]

参加物

4

反応物 2

HCID 344887Ethyl 2-Cyano-2-methylpropionateHCID 22486041Diphenyl-sulfanyl-sulfanylidene-$l^{5-phosphane

生成物 1

HCID 12409835Ethyl 2-carbamothioyl-2,2-dimethylacetate収率 22.2%

試薬・触媒・溶媒 1

HCID 3776Isopropanol溶媒

実験手順

A mixture of diphenyldithiophosphonic acid (ALFAAESAR, 1.42 g, 5.67 mmol) and 2-cyano-2-methylpropionic acid ethyl ester (ABCR, 0.412 mL, 2.83 mmol) in isopropanol (30 mL) was heated under reflux for 4 h. Reaction mixture was cooled to room temperature and a precipitate was formed. Reaction flask was placed in the freezer for 1 h. Reaction mixture was filtered and filtrate was concentrated. Residue was taken up in DCM (100 mL) and washed with water (20 mL), 1N NaOH (20 mL), saturated NaHCO3 (20 mL) and dried over sodium sulfate and concentrated. The resulting oil was loaded on a 25 g silica cartridge and eluted with linear gradient 0-50% hexane-ethyl acetate to yield the title compound (110 mg, 0.628 mmol, 22.2% yield). Another impure batch was loaded on a 10 g silica cartridge and eluted with linear gradient 0-50% hexane-ethyl acetate to recover the title compound (120 mg, 0.685 mmol, 24.17% yield). Total yield: (230 mg, 1.313 mmol, 46.32%). 1H NMR (300 MHz, DMSO-d6) δ ppm: 9.70 (br s, 1H), 8.86 (br s, 1H), 4.05 (q, 2H), 1.39 (s, 6H), 1.15 (t, 3H). [ES+MS] m/z 176 (MH+).

後処理

  1. temperaturewas heated
  2. temperatureunder reflux for 4 h
  3. customReaction mixture
  4. customa precipitate was formed
  5. customReaction flask
  6. customReaction mixture
  7. filtrationwas filtered
  8. concentrationfiltrate was concentrated
  9. washwashed with water (20 mL), 1N NaOH (20 mL), saturated NaHCO3 (20 mL)
  10. dry with materialdried over sodium sulfate
  11. concentrationconcentrated
  12. washeluted with linear gradient 0-50% hexane-ethyl acetate

出典と根拠

ORDレコード
ord-0fa2f6cbb20a4225beef7778b22e2246
出典データセット
uspto-grants-2013_09
特許番号
US08524750B2

反応ノート

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