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

반응식

HRID 6295 반응식
[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

참가 물질

9

반응물 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

생성물 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-carboxylate수율 59.1%

시약·촉매·용매 4

HCID 180Acetone용매HCID 1140Toluene용매HCID 8857Ethyl Acetate용매HCID 13387N-methyl-2-pyrrolidone용매

실험 절차

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)].

후처리

  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

출처 및 근거

ORD 기록
ord-25dcd8cb6bae4c88a76e6afa5f16ed75
출처 데이터셋
uspto-grants-1993_09
특허 번호
US05246926

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