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Dicyclohexylcarbodiimide → 2-Benzhydryloxycarbonyl-7-[2-(1-t-butoxycarbonylcyclobutoxyimino)-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-3-(2-tosyloxyvinyl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide

HRID 1649267
ノート
印刷プレビュー

反応式

HRID 1649267 の反応式
[C:1]([O:5][C:6]([C:8]1([O:12][N:13]=[C:14]([C:18]2[N:19]=[C:20]([NH:23][C:24]([C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)([C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[S:21][CH:22]=2)[C:15]([OH:17])=O)[CH2:11][CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[NH2:43][CH:44]1[C:51](=[O:52])[N:50]2[CH:45]1[S:46](=[O:82])[CH2:47][C:48]([CH:69]=[CH:70][O:71][S:72]([C:75]1[CH:81]=[CH:80][C:78]([CH3:79])=[CH:77][CH:76]=1)(=[O:74])=[O:73])=[C:49]2[C:53]([O:55][CH:56]([C:63]1[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=1)[C:57]1[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=1)=[O:54].C1(N=C=NC2CCCCC2)CCCCC1>CN(C)C1C=CN=CC=1.C(Cl)Cl>[CH:56]([O:55][C:53]([C:49]1[N:50]2[CH:45]([S:46](=[O:82])[CH2:47][C:48]=1[CH:69]=[CH:70][O:71][S:72]([C:75]1[CH:76]=[CH:77][C:78]([CH3:79])=[CH:80][CH:81]=1)(=[O:73])=[O:74])[CH:44]([NH:43][C:15](=[O:17])[C:14](=[N:13][O:12][C:8]1([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH2:11][CH2:10][CH2:9]1)[C:18]1[N:19]=[C:20]([NH:23][C:24]([C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=3)([C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[C:37]3[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=3)[S:21][CH:22]=1)[C:51]2=[O:52])=[O:54])([C:63]1[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=1)[C:57]1[CH:58]=[CH:59][CH:60]=[CH:61][CH:62]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 3

HCID 10868DicyclohexylcarbodiimideHCID 539396637-Amino-2-benzhydryloxycarbonyl-8-oxo-3-(2-tosyloxyvinyl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide2 回HCID 542728042-(1-t-Butoxycarbonylcyclobutoxyimino)-2-(2-tritylaminothiazol-4-yl)-acetic acid

生成物 1

HCID 543494522-Benzhydryloxycarbonyl-7-[2-(1-t-butoxycarbonylcyclobutoxyimino)-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-3-(2-tosyloxyvinyl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
5 °C

実験手順

The syn isomer of 2-(1-t-butoxycarbonylcyclobutoxyimino)-2-(2-tritylaminothiazol-4-yl)-acetic acid prepared according to Belgian Patent 876,541 (4.42 g) and 4-dimethylaminopyridine (0.25 g) are added to a solution of the E form of 7-amino-2-benzhydryloxycarbonyl-8-oxo-3-(2-tosyloxyvinyl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide (product 7d) (4.34 g) in methylene chloride (50 cc). The mixture is cooled to 5° C. and a solution of N,N'-dicyclohexylcarbodiimide (1.69 g) in methylene chloride (30 cc) is added dropwise in the course of 10 minutes. The temperature is left to rise, the mixture is stirred for 4 hours at 20° C. and concentrated to dryness at 20° C. under 20 mm Hg (2.7 kPa) and the residue is taken up in ethyl acetate (200 cc). The solution is washed with water (2×100 cc), 0.1 N hydrochloric acid (100 cc), a saturated aqueous solution of sodium bicarbonate (100 cc) and water (100 cc), dried over sodium sulphate and filtered and the filtrate is concentrated to dryness at 25° C. under 20 mm Hg (2.7 kPa). The residue is chromatographed on a column of Merck silica gel (0.06-0.2) (180 g) (diameter of the column: 3 cm, height: 60 cm). Elution is carried out with a 70/30 (by volume) cyclohexane/ethyl acetate mixture (1 liter), 60 cc fractions being collected. Fractions 6 to 10 are concentrated to dryness at 20° C. under 20 mm Hg (2.7 kPa) and this yields a product (7a) (2.7 g) in the form of a cream-coloured powder.

後処理

  1. waitThe temperature is left
  2. concentrationconcentrated to dryness at 20° C. under 20 mm Hg (2.7 kPa)
  3. washThe solution is washed with water (2×100 cc), 0.1 N hydrochloric acid (100 cc)
  4. dry with materiala saturated aqueous solution of sodium bicarbonate (100 cc) and water (100 cc), dried over sodium sulphate
  5. filtrationfiltered
  6. concentrationthe filtrate is concentrated to dryness at 25° C. under 20 mm Hg (2.7 kPa)
  7. customThe residue is chromatographed on a column of Merck silica gel (0.06-0.2) (180 g) (diameter of the column
  8. washElution
  9. custombeing collected
  10. concentrationFractions 6 to 10 are concentrated to dryness at 20° C. under 20 mm Hg (2.7 kPa)

出典と根拠

ORDレコード
ord-d31642104a1b4e7693acf6c9e81deeb3
出典データセット
uspto-grants-1983_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04415562

反応ノート

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このページの内容参加物反応条件実験手順後処理出典と根拠反応ノート