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

HRID 1421799ノート

反応式

HRID 1421799 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:40]/[O:41][CH3:42])/[C:20]([NH:22][C@@H:23]2[C:38](=[O:39])[N:25]3[C:26]([C:35]([O-:37])=[O:36])=[C:27]([C@H:30]4[CH2:34][CH2:33][CH2:32][O: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:40]/[O:41][CH3:42])/[C:20]([NH:22][C@@H:23]2[C:38](=[O:39])[N:25]3[C:26]([C:35]([O:37][CH2:8][O:7][C:1](=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3])=[O:36])=[C:27]([C@H:30]4[CH2:34][CH2:33][CH2:32][O: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 88280324sodium (6R,7R)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-8-oxo-3-[(2R)-oxolan-2-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate

生成物 1

HCID 882588472,2-dimethylpropanoyloxymethyl (6R,7R)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-8-oxo-3-[(2R)-oxolan-2-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate収率 78.1%

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 (247 mg, 1.27 mmol) and sodium iodide (247 mg, 1.65 mmol) in acetone (5 ml) were stirred for 30 min., filtered, and the filtrate concentrated in vacuo. The resulting iodide in toluene (3 ml) was added to a solution of sodium (6R,7R)-7-[2-(2-aminothiazol-4-yl)-2-(Z)-methoxyiminoacetamido]-3-[(R)-tetrahydrofuran-2-yl]ceph-3-em-4-carboxylate (320 mg, 0.67 mmol) in N-methylpyrrolidinone (5 ml). After stirring for 30 min. at room temperature, the reaction mixture was diluted with ethyl acetate, washed successively with water (×3) and brine, dried over MgSO4 and concentrated in vacuo. The residue was chromatographed on silica gel eluting with 80% ethyl acetate in hexane to give the title compound as a yellow foam (297 mg, 78%); νmax (CH 2Cl2) 3387, 1786, 1752, 1735, 1686, 1605 cm-1 ; δH (CDCl3, 250 MHz) 1.22 (9H, s), 1.69 (1H, m), 1.98 (2H, m), 2.18 (1H, m), 3.43 and 3.62 (2H, ABq, J 18.0 Hz), 3.80-3.96 (2H, m), 4.10 (3H, s), 5.08 (1H, d, J 4.7 Hz), 5.19 (1H, m), 5.83-5.92 (3H, m), 6.32 (2H, br. s, exch), 7.02 (1H, s), 7.63 (1H, br. d, exch., J 8.6 Hz). [Mass spectrum: +ve ion (thioglycerol) MH+ (568)].

後処理

  1. filtrationfiltered
  2. concentrationthe filtrate concentrated in vacuo
  3. washwashed successively with water (×3) and brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was chromatographed on silica gel eluting with 80% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-0d53ad015d52497d9d2929991b7dcec1
出典データセット
uspto-grants-2000_06
特許番号
US06077952

反応ノート

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