2,4-Dinitrophenol → 7-[o-(N-Butoxycarbonyl-N-methylaminomethyl)phenylacetamido]-3-[2-(2-carboxyethyl)-2,3-dihydro-s-triazolo[4,3-b]pyridazin-3-on-6-ylthiomethyl]-3-cephem-4-carboxylic acid

HRID 27002

反応式

HRID 27002 の反応式
[NH2:1][CH:2]1[C:29](=[O:30])[N:4]2[C:5]([C:26]([OH:28])=[O:27])=[C:6]([CH2:9][S:10][C:11]3[CH:12]=[CH:13][C:14]4[N:15]([C:17](=[O:25])[N:18]([CH2:20][CH2:21][C:22]([OH:24])=[O:23])[N:19]=4)[N:16]=3)[CH2:7][S:8][C@H:3]12.[C:31]([O:35][C:36]([N:38]([CH2:40][C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][C:42]=1[CH2:47][C:48]([O:50]C1C=CC([N+]([O-])=O)=CC=1[N+]([O-])=O)=O)[CH3:39])=[O:37])([CH3:34])(C)C.[C:63](OC(N(CC1C=CC=CC=1CC(O)=O)C)=O)(C)(C)[CH3:64].[N+](C1C=C([N+]([O-])=O)C=CC=1O)([O-])=O.C1CCC(N=C=NC2CCCCC2)CC1>C(#N)C.C1COCC1.C(N(CC)CC)C>[CH2:31]([O:35][C:36]([N:38]([CH2:40][C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][C:42]=1[CH2:47][C:48]([NH:1][CH:2]1[C:29](=[O:30])[N:4]2[C:5]([C:26]([OH:28])=[O:27])=[C:6]([CH2:9][S:10][C:11]3[CH:12]=[CH:13][C:14]4[N:15]([C:17](=[O:25])[N:18]([CH2:20][CH2:21][C:22]([OH:24])=[O:23])[N:19]=4)[N:16]=3)[CH2:7][S:8][C@H:3]12)=[O:50])[CH3:39])=[O:37])[CH2:34][CH2:63][CH3:64]

参加物

9

反応物 5

HCID 14932,4-DinitrophenolHCID 10868DicyclohexylcarbodiimideHCID 20344367o-(N-t-butoxycarbonyl-N-methylaminomethyl)phenylacetic acidHCID 203443712,4-dinitrophenyl o-(N-t-butoxycarbonyl-N-methylaminomethyl)phenylacetateHCID 1317110707-Amino-3-[2-(2-carboxyethyl)-2,3-dihydro-s-triazolo[4,3-b]pyridazin-3-on-6-ylthiomethyl]-3-cephem-4-carboxylic acid

生成物 1

HCID 1317110697-[o-(N-Butoxycarbonyl-N-methylaminomethyl)phenylacetamido]-3-[2-(2-carboxyethyl)-2,3-dihydro-s-triazolo[4,3-b]pyridazin-3-on-6-ylthiomethyl]-3-cephem-4-carboxylic acid収率 50%

試薬・触媒・溶媒 3

HCID 6342Acetonitrile溶媒HCID 8028Tetrahydrofuran溶媒HCID 8471Triethylamine溶媒

実験手順

To a mixture of 7-amino-3-[2-(2-carboxyethyl)-2,3-dihydro-s-triazolo[4,3-b]pyridazin-3-on-6-ylthiomethyl]-3-cephem-4-carboxylic acid (452 mg., 1 m.mole) and triethylamine (0.46 ml., 3.3 m.mole) in 50% aqueous acetonitrile (4 ml.) was added a THF solution (3 ml.) of 2,4-dinitrophenyl o-(N-t-butoxycarbonyl-N-methylaminomethyl)phenylacetate prepared from o-(N-t-butoxycarbonyl-N-methylaminomethyl)phenylacetic acid (283 mg., 1.1 m.mole), 2,4-dinitrophenol (202 mg., 1.1 m.mole) and DCC (227 mg., 1.1 m.mole). The mixture was stirred at room temperature overnight and concentrated under reduced pressure to remove the organic solvents. The aqueous concentrate was washed with ether (3×20 ml.), acidified with c.HCl to pH 1-2 and extracted with ethyl acetate (5×20 ml.). The combined extracts were dried with anhydrous Na2SO4 and evaporated to dryness. The residue was chromatographed on a column of silica gel (Wako gel, C-200, 10 g.) by eluting with a mixture of MeOH-CHCl3 (MeOH: 0 to 3%). The combined eluates which contained the desired product were evaporated to give 359 mg. (50%) of the title compound. M.p. >150° C. (dec.).

後処理

  1. concentrationconcentrated under reduced pressure
  2. customto remove the organic solvents
  3. concentrationThe aqueous concentrate
  4. washwas washed with ether (3×20 ml.)
  5. extractionHCl to pH 1-2 and extracted with ethyl acetate (5×20 ml.)
  6. dry with materialThe combined extracts were dried with anhydrous Na2SO4
  7. customevaporated to dryness
  8. customThe residue was chromatographed on a column of silica gel (Wako gel, C-200, 10 g.)
  9. washby eluting with a mixture of MeOH-CHCl3 (MeOH: 0 to 3%)
  10. customwere evaporated
  11. customto give 359 mg

出典と根拠

ORDレコード
ord-276df53f45614fa6b29abc2bb101bd94
出典データセット
uspto-grants-1979_04
特許番号
US04151352

関連ノート

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