Triethylamine → tert-butyl N-(4-diazo-3-oxobutan-2-yl)carbamate

HRID 519091ノート

反応式

HRID 519091 の反応式
[C:1]([O:5][C:6]([NH:8][CH:9]([CH3:13])[C:10]([OH:12])=O)=[O:7])([CH3:4])([CH3:3])[CH3:2].CCN(CC)CC.C(Cl)(=O)OCC.[N+:27](=[CH2:29])=[N-:28]>C1COCC1.CCOCC>[C:1]([O:5][C:6](=[O:7])[NH:8][CH:9]([CH3:13])[C:10](=[O:12])[CH:29]=[N+:27]=[N-:28])([CH3:2])([CH3:3])[CH3:4]

参加物

7

反応物 4

HCID 8471TriethylamineHCID 9550DiazomethaneHCID 10928Ethyl chloroformateHCID 2684712-N-Boc-aminopropionic acid

生成物 1

HCID 56979712tert-butyl N-(4-diazo-3-oxobutan-2-yl)carbamate収率 99%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a −15° C. solution of 2-((tert-butoxycarbonyl)amino)propanoic acid (2.5 g, 13.21 mmol) in THF (66 mL) was added Et3N (1.337 g, 13.21 mmol) and ethyl carbonochloridate (1.434 g, 13.21 mmol). The reaction mixture was stirred for 15 min then allowed to warm to 0° C. A solution of diazomethane (prepared according to the standard procedure (Organic Syntheses, Coll. Vol. 5, p. 351 (1973); Vol. 41, p. 16 (1961)) in Et2O (150 mL) was added, until the rich yellow color persisted. The reaction mixture was allowed to warm to rt and stirred for 3 h. Excess CH2N2 was destroyed by the addition of a small amount of aqueous AcOH (20%, 3 mL). The reaction mixture was extracted with saturated NaHCO3 (20 mL), and the organic portion was separated and washed with saturated aqueous NH4Cl (20 mL) and brine (20 mL). The organic portion was separated, dried over Na2SO4, filtered and evaporated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 5-20% EtOAc in petroleum ether) to give (3-diazo-1-methyl-2-oxo-propyl)-carbamic acid tert-butyl ester (2.8 g, 99%) as a brown solid. 1H NMR (DMSO-d6, 400 MHz): δ 7.27 (d, J=7.2, 1H), 6.02 (s, 1H), 4.01 (m, 1H), 1.39 (s, 9H), 1.20 (m, 3H).

後処理

  1. additionwas added, until the rich yellow color
  2. temperatureto warm to rt
  3. stirringstirred for 3 h
  4. customExcess CH2N2 was destroyed by the addition of a small amount of aqueous AcOH (20%, 3 mL)
  5. extractionThe reaction mixture was extracted with saturated NaHCO3 (20 mL)
  6. customthe organic portion was separated
  7. washwashed with saturated aqueous NH4Cl (20 mL) and brine (20 mL)
  8. customThe organic portion was separated
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. customevaporated in vacuo
  12. customThe residue was purified by column chromatography on silica gel (eluting with 5-20% EtOAc in petroleum ether)

出典と根拠

ORDレコード
ord-1b7cafa19c7949d8bee5bb907e3b5d4a
出典データセット
uspto-grants-2015_08
特許番号
US09115151B2

反応ノート

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