Sodium Iodide → 2,2-dimethylpropanoyloxymethyl (6R,7R)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-8-oxo-3-(5-oxooxolan-2-yl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate

HRID 6295

反応式

HRID 6295 の反応式
[C:1]([O:7][CH2:8]Br)(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[I-].[Na+].[I-].[NH2:13][C:14]1[S:15][CH:16]=[C:17](/[C:19](=[N:41]/[O:42][CH3:43])/[C:20]([NH:22][C@@H:23]2[C:39](=[O:40])[N:25]3[C:26]([C:36]([O-:38])=[O:37])=[C:27]([CH:30]4[O:34][C:33](=[O:35])[CH2:32][CH2:31]4)[CH2:28][S:29][C@H:24]23)=[O:21])[N:18]=1.[Na+]>CC(C)=O.C1(C)C=CC=CC=1.CN1CCCC1=O.C(OCC)(=O)C>[NH2:13][C:14]1[S:15][CH:16]=[C:17](/[C:19](=[N:41]/[O:42][CH3:43])/[C:20]([NH:22][C@@H:23]2[C:39](=[O:40])[N:25]3[C:26]([C:36]([O:38][CH2:8][O:7][C:1](=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3])=[O:37])=[C:27]([CH:30]4[O:34][C:33](=[O:35])[CH2:32][CH2:31]4)[CH2:28][S:29][C@H:24]23)=[O:21])[N:18]=1

参加物

9

反応物 4

HCID 5238Sodium IodideHCID 30165Iodide IonHCID 15916453Bromomethyl pivalateHCID 44310944sodium (6R,7R)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-8-oxo-3-(5-oxooxolan-2-yl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate

生成物 1

HCID 1415795472,2-dimethylpropanoyloxymethyl (6R,7R)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-8-oxo-3-(5-oxooxolan-2-yl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate収率 59.1%

試薬・触媒・溶媒 4

HCID 180Acetone溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒HCID 13387N-methyl-2-pyrrolidone溶媒

実験手順

Pivaloyloxymethyl bromide (0.10 g, ca. 0.5 mmol) and sodium iodide (0.1 g) in acetone (1 ml) were stirred for 0.25 h, filtered and evaporated in vacuo. The iodide in toluene (0.5 ml) was added to sodium (6R,7R)-7-[2(2-aminothiazol-4-yl)-2-(Z)-methoxyiminoacetamido]-3-[(5RS)-2-oxotetrahydrofuran-5-yl]ceph-3-em-4-carboxylate (0.124 g, 0.25 mmol) in N-methylpyrrolidone (2 ml) and stirred for 0.5 h. The reaction mixture was diluted with ethyl acetate, washed twice with water, and with brine, dried, concentrated and flash chromatographed on silica gel eluting with 80,90,100% ethyl acetate in hexane to give the title compound (86 mg, 59%), νmax (CH2Cl2) 1780, 1753, 1735, 1682, 1532, 1374, 1121, 1046 cm-1 ; δH (250 MHz, CDCl3) (9H, s), 1.9-2.2 (1H, m), 2.4-2.8 (3H, m), 3.34 and 3.64, 3.48 and 3.59 (together 2H, 2ABq, J 18.9, 18.4 Hz), 4.08 (3H, s), 5.10, 5.11 (together 1H, 2d, J 4.9 Hz), 5.35 (2H, bs), 5.5-5.95 (3H, m), 6.00, 6.10 (together 1H, 2dd, J 9, 4.9 Hz), 6.85, 6.87 (together 1H, 2s), 7.52, 7.54 (together 1H, 2d, J 9 Hz); [mass spectrum: +ve ion (3-nitrobenzyl alcohol-sodium acetate) MH+(582) MNa+(604)].

後処理

  1. filtrationfiltered
  2. customevaporated in vacuo
  3. washwashed twice with water
  4. dry with materialwith brine, dried
  5. concentrationconcentrated
  6. customflash chromatographed on silica gel eluting with 80,90,100% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-25dcd8cb6bae4c88a76e6afa5f16ed75
出典データセット
uspto-grants-1993_09
特許番号
US05246926

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