Toluene → Methyl cis-3-t-butoxycarbonylamino-1-(2,4-dimethoxybenzyl)-4-oxoazetidine-2-carboxylate

HRID 127891

反応式

HRID 127891 の反応式
[NH2:1][C@H:2]1[C:5](=[O:6])[N:4]([CH2:7][C:8]2[CH:13]=[CH:12][C:11]([O:14][CH3:15])=[CH:10][C:9]=2[O:16][CH3:17])[C@H:3]1[C:18]([O:20][CH3:21])=[O:19].C(N(CC)CC)C.C(Cl)(Cl)=O.C(#N)C.[C:36](=[O:38])=[O:37].[C:39]1([CH3:45])[CH:44]=CC=C[CH:40]=1>C1C=CC=CC=1>[C:39]([O:37][C:36]([NH:1][C@H:2]1[C:5](=[O:6])[N:4]([CH2:7][C:8]2[CH:13]=[CH:12][C:11]([O:14][CH3:15])=[CH:10][C:9]=2[O:16][CH3:17])[C@H:3]1[C:18]([O:20][CH3:21])=[O:19])=[O:38])([CH3:45])([CH3:44])[CH3:40]

参加物

7

反応物 5

HCID 1140TolueneHCID 6371PhosgeneHCID 8471TriethylamineHCID 18632686Methyl cis-1-(2,4-Dimethoxybenzyl)-3-amino-4-oxoazetidine-2-carboxylateHCID 86587134Acetonitrile dry ice

生成物 1

HCID 70577863Methyl cis-3-t-butoxycarbonylamino-1-(2,4-dimethoxybenzyl)-4-oxoazetidine-2-carboxylate収率 52%

試薬・触媒・溶媒 1

HCID 241Benzene溶媒

実験手順

A solution of 5.5 g (18.8 mmole) of methyl cis-3-amino-1-(2,4-dimethoxybenzyl)-4-oxoazetidine-2-carboxylate in 100 ml of dry toluene is cooled to -78°; 2.5 ml (18.8 mmole) of triethylamine is added followed by rapid addition of 35 ml (42 mmole) of a 12% solution of phosgene in benzene. The mixture is stirred 15 min at -78°, 3 hr at -45° (acetonitrile-dry ice), then warmed to room temperature and concentrated to half volume in vacuum. To the resulting solution is added 50 ml of t-butanol and the mixture is stirred at room temperature overnight. The solvents are removed in vacuum, the residue is diluted with ethyl acetate and filtered. The filtrate is transferred to a separatory funnel and washed with 5% NaHCO3, 5% HCl and brine; dried over magnesium sulfate and evaporated to dryness. Recrystallization of the crude, crystalline product affords 3.8 g (52%) of the title compound. Recrystallization from ether gives an analytical sample.

後処理

  1. concentrationconcentrated to half volume in vacuum
  2. additionTo the resulting solution is added 50 ml of t-butanol
  3. customThe solvents are removed in vacuum
  4. additionthe residue is diluted with ethyl acetate
  5. filtrationfiltered
  6. customThe filtrate is transferred to a separatory funnel
  7. washwashed with 5% NaHCO3, 5% HCl and brine
  8. dry with materialdried over magnesium sulfate
  9. customevaporated to dryness
  10. customRecrystallization of the crude, crystalline product

出典と根拠

ORDレコード
ord-639101b47b35420db9b63f4f96bb27c1
出典データセット
uspto-grants-1981_03
特許番号
US04257947

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