Morpholine → p-Nitrobenzyl alpha-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-alpha-(1-morpholino-2-bromoethylidene)acetate

HRID 67833

反応式

HRID 67833 の反応式
[O:1]([CH2:8][C:9]1[S:15][CH:14]2[CH:11]([C:12](=[O:33])[N:13]2[C:16](=[C:30]([OH:32])[CH3:31])[C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][C:24]([N+:27]([O-:29])=[O:28])=[CH:23][CH:22]=2)=[O:18])[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:34][S:35](Cl)(=[O:37])=[O:36].[NH:39]1[CH2:44][CH2:43][O:42][CH2:41][CH2:40]1.[Br:45]Br.C(=O)([O-])O.[Na+]>ClCCl.C(Cl)(Cl)(Cl)Cl.O.C(N(CC)CC)C>[O:1]([CH2:8][C:9]1[S:15][CH:14]2[CH:11]([C:12](=[O:33])[N:13]2[C:16](=[C:30]([N:39]2[CH2:44][CH2:43][O:42][CH2:41][CH2:40]2)[CH2:31][Br:45])[C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][C:24]([N+:27]([O-:29])=[O:28])=[CH:23][CH:22]=2)=[O:18])[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[O:1]([CH2:8][C:9]1[S:15][CH:14]2[CH:11]([C:12](=[O:33])[N:13]2[C:16]([S:35]([CH3:34])(=[O:37])=[O:36])([C:30](=[O:32])[CH3:31])[C:17]([O:19][CH2:20][C:21]2[CH:22]=[CH:23][C:24]([N+:27]([O-:29])=[O:28])=[CH:25][CH:26]=2)=[O:18])[N:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

11

反応物 5

HCID 8083MorpholineHCID 24408BromineHCID 31297Methanesulfonyl chlorideHCID 516892Sodium BicarbonateHCID 70504145p-Nitrobenzyl alpha-[3-phenoxymethyl-7-oxo4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-alpha-(1-hydroxyethylidene)acetate

生成物 2

HCID 12961193p-Nitrobenzyl alpha-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6yl]-alpha-methanesulfonyl-alpha-acetylacetate収率 12.2%HCID 54184089p-Nitrobenzyl alpha-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-alpha-(1-morpholino-2-bromoethylidene)acetate収率 69%

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 5943Carbon Tetrachloride溶媒HCID 6344Dichloromethane溶媒HCID 8471Triethylamine溶媒

実験手順

One dissolves p-nitrobenzyl α-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-α-(1-hydroxyethylidene)acetate (940 mg) in dichloromethane (14 ml), cools to -25° C., adds triethylamine (0.61 ml) and methanesulfonyl chloride (0.17 ml), and stirs for 1.5 hours. To the solution, one adds morpholine (0.209 ml), keeps at -25° C. for 1.5 hours, adds bromine (2.2 mmol) dissolved in carbon tetrachloride (2.2 ml) and after 30 minutes at -25° C., adds 5% aqueous sodium hydrogen carbonate, washes with water, dries and evaporates. Purification of the obtained residue (1.134 g) by chromatography over silica gel containing 10% water (100 g) using a mixture of benzene and ethyl acetate (3:1) gives p-nitrobenzyl α-[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-α-(1-morpholino-2-bromoethylidene)acetate (852.6 mg; 69%) and p-nitrobenzyl α -[3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-α-methanesulfonyl-α-acetylacetate (1332.2 mg; 12.2%).

後処理

  1. customcools to -25° C.
  2. customevaporates
  3. customPurification of the obtained residue (1.134 g) by chromatography over silica gel containing 10% water (100 g)
  4. additiona mixture of benzene and ethyl acetate (3:1)

出典と根拠

ORDレコード
ord-da6c52de4a3c4ddd8d07e4271ddd0713
出典データセット
uspto-grants-1982_08
特許番号
US04346218

関連ノート

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