Benzyl Alcohol → Methyl 3-(((benzyloxy)carbonyl)amino)-3-methylbutanoate

HRID 1080740ノート

反応式

HRID 1080740 の反応式
[CH3:1][O:2][C:3](=[O:11])[CH2:4][C:5]([CH3:10])([CH3:9])C(O)=O.C([N:14]([CH2:17]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:26])C=CC=CC=1.[CH2:36]([OH:43])[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>C1C=CC=CC=1>[CH2:36]([O:43][C:17]([NH:14][C:5]([CH3:9])([CH3:10])[CH2:4][C:3]([O:2][CH3:1])=[O:11])=[O:26])[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1

参加物

6

反応物 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 126021764-Methoxy-2,2-dimethyl-4-oxobutanoic acid

生成物 1

HCID 15042554Methyl 3-(((benzyloxy)carbonyl)amino)-3-methylbutanoate収率 75.1%

試薬・触媒・溶媒 1

HCID 241Benzene溶媒

実験手順

To 14.7 g (91.8 mmol) of 2,2-dimethylbutanedioic acid-4-methyl ester in 150 mL of benzene was added 13 mL of triethylamine (9.4 g, 93 mmol) followed by 21.8 mL of diphenylphosphoryl azide (27.8 g, 101 mmol). The mixture was heated under nitrogen at reflux for 45 minutes, then 19 mL (19.9 g, 184 mmol) of benzyl alcohol was added and refluxing continued for 16 hours. The mixtue was cooled, filtered and the filtrate concentrated to a minimum volume under vacuum. The residue was redissolved in 250 mL of ethyl acetate, washed with water, saturated aqueous sodium bicarbonate (2×) and brine. The organic layer was removed, dried over magnesium sulfate, filtered and the filtrate concentrated to a minimum volume under vacuum. The crude product was purified by medium pressure liquid chromatography on silica, eluting with hexane/ethyl acetate (4:1), to afford 18.27 g (68.9 mmol, 75%) of the product. 1H NMR (200 MHz, CDCl3): 1.40 (s, 6H), 2.69 (s, 2H), 3.63 (s, 3H), 5.05 (s, 2H), 5.22 (br s, 1H), 7.32 (s, 5H).

後処理

  1. temperatureThe mixture was heated under nitrogen
  2. temperatureat reflux for 45 minutes
  3. temperaturerefluxing
  4. temperatureThe mixtue was cooled
  5. filtrationfiltered
  6. concentrationthe filtrate concentrated to a minimum volume under vacuum
  7. dissolutionThe residue was redissolved in 250 mL of ethyl acetate
  8. washwashed with water, saturated aqueous sodium bicarbonate (2×) and brine
  9. customThe organic layer was removed
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationthe filtrate concentrated to a minimum volume under vacuum
  13. customThe crude product was purified by medium pressure liquid chromatography on silica
  14. washeluting with hexane/ethyl acetate (4:1)

出典と根拠

ORDレコード
ord-448666e3cca7458d8ebc86d135704f6b
出典データセット
uspto-grants-1996_12
特許番号
US05583130

反応ノート

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