三氯化磷 → 2-Benzhydryloxycarbonyl-3-{2-[(2-methyl-1,3,4-thiadiazol-5-yl)-thio]-prop-1-en-1-yl}-7-[2-methoxyimino-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

HRID 463581笔记

反应方程式

HRID 463581 反应方程式
[CH:1]([O:14][C:15]([C:17]1[N:18]2[CH:21]([S:22](=O)[CH2:23][C:24]=1[CH:25]=[C:26]([S:28][C:29]1[S:33][C:32]([CH3:34])=[N:31][N:30]=1)[CH3:27])[CH:20]([NH:36][C:37](=[O:67])[C:38](=[N:64][O:65][CH3:66])[C:39]1[N:40]=[C:41]([NH:44][C:45]([C:58]3[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=3)([C:52]3[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=3)[C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)[S:42][CH:43]=1)[C:19]2=[O:68])=[O:16])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CN(C)C(=O)C.P(Cl)(Cl)Cl.C(=O)(O)[O-].[Na+]>C(Cl)Cl.O.C(OCC)(=O)C>[CH:1]([O:14][C:15]([C:17]1[N:18]2[CH:21]([S:22][CH2:23][C:24]=1[CH:25]=[C:26]([S:28][C:29]1[S:33][C:32]([CH3:34])=[N:31][N:30]=1)[CH3:27])[CH:20]([NH:36][C:37](=[O:67])[C:38](=[N:64][O:65][CH3:66])[C:39]1[N:40]=[C:41]([NH:44][C:45]([C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)([C:52]3[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=3)[C:58]3[CH:59]=[CH:60][CH:61]=[CH:62][CH:63]=3)[S:42][CH:43]=1)[C:19]2=[O:68])=[O:16])([C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

参与物

8

反应物 4

HCID 24387三氯化磷HCID 31374N,N-二甲基乙酰胺HCID 516892碳酸氢钠HCID 544407692-Benzhydryloxycarbonyl-3-{2-[(2-methyl-1,3,4-thiadiazol-5-yl)-thio]-prop-1-en-1-yl}-7-[2-methoxyimino-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide

产物 1

HCID 536585572-Benzhydryloxycarbonyl-3-{2-[(2-methyl-1,3,4-thiadiazol-5-yl)-thio]-prop-1-en-1-yl}-7-[2-methoxyimino-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene收率 31.1%

试剂、催化剂与溶剂 3

HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂HCID 6344二氯甲烷溶剂HCID 8857乙酸乙酯溶剂

反应条件

温度
-10 °C

实验过程

A solution of the Z form of the syn isomer of 2-benzhydryloxycarbonyl-3-{2-[(2-methyl-1,3,4-thiadiazol-5-yl)-thio]-prop-1-en-1-yl}-7-[2-methoxyimino-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide (2.52 g) in methylene chloride (40 cc) is cooled to -10° C. N,N-Dimethylacetamide (0.95 cc) and phosphorus trichloride (0.7 g) are added successively. The solution is stirred for 20 minutes at -10° C. and then poured into a saturated aqueous solution of sodium bicarbonate (50 cc). It is diluted with distilled water (200 cc) and extraction is carried out with ethyl acetate (300 cc). The organic phase is dried over sodium sulphate and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 20° C. The residue is chromatographed on a column of Merck silica gel (0.06-0.20) (25 g) (diameter of the column: 2 cm; height: 15 cm). Elution is carried out with a 50/50 (by volume) ethyl acetate/cyclohexane mixture (500 cc), 30 cc fractions being collected. Fractions 4 to 13 are concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 20° C. This yields the Z form of the syn isomer of 2-benzhydryloxycarbonyl-3-{2-[(2-methyl-1,3,4-thiadiazol-5-yl)-thio]-prop-1-en-1-yl}-7-[2-methoxyimino-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene (0.77 g) in the form of a hard white foam.

后处理

  1. dry with materialThe organic phase is dried over sodium sulphate
  2. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 20° C
  3. customThe residue is chromatographed on a column of Merck silica gel (0.06-0.20) (25 g) (diameter of the column
  4. washElution
  5. custombeing collected
  6. concentrationFractions 4 to 13 are concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 20° C

来源与证据

ORD记录
ord-e2660ce8f61d43fca5b95acb71323d09
来源数据集
uspto-grants-1985_05
专利号
US04520193

反应笔记

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