HRID325973

反应详情

EQUATION

反应方程式

REACTANTS

反应物

HCID10340

Carbonic acid sodium salt (1:2)

CNa2O3

HCID24813

Phosphoric trichloride

Cl3OP

HCID77311

未命名化合物

HCID516892

Sodium Bicarbonate

CHNaO3

HCID53744847

未命名化合物

结构：Cl.NC1C(=O)N2C(C(=O)O)=C(C[n+]3ccccc3)CS[C@H]12.O.O.[Cl-]

HCID70450238

未命名化合物

PRODUCTS

生成物

HCID77311

未命名化合物

结构：CSCON=C(C(=O)NC1C(=O)N2C(C(=O)[O-])=C(C[n+]3ccccc3)CS[C@H]12)c1csc(NC=O)n1

HCID131713490

未命名化合物

AUXILIARIES

试剂、催化剂与溶剂

溶剂HCID180

Acetone

C3H6O

溶剂HCID962

Water

H2O

2 次

溶剂HCID6228

N,N-Dimethylformamide

C3H7NO

溶剂HCID8028

Tetrahydrofuran

C4H8O

溶剂HCID8857

Ethyl acetate

C4H8O2

2 次

PROCEDURE

实验过程

Vilsmeier reagent was prepared from phosphorus oxychloride (2.0 g) and dimethylformamide (0.95 g) in ethyl acetate (2.8 ml) in a usual manner. 2-Methylthiomethoxyimino-2-(2-formamidothiazol-4-yl) acetic acid (syn isomer) (3.0 g) was added to the stirred suspension of Vilsmeier reagent in tetrahydrofuran (30 ml) under ice cooling, and stirred for 30 minutes at the same temperature to produce an activated acid solution. On the other hand, 1-[(7-amino-4-carboxy-3-cephem-3-yl)methyl]pyridinium chloride hydrochloride dihydrate (4.0 g) was dissolved to the solution of sodium bicarbonate (2.5 g) in water (20 ml) and acetone (20 ml). To the solution was added the above activated acid solution at -3° to 3° C. and the solution was stirred for 30 minutes under keeping the pH 6.5 to 7.5 with 20% aqueous solution of sodium carbonate. Water and ethyl acetate were added to the reaction mixture and a separate aqueous layer was washed with ethyl acetate. The aqueous layer was adjusted to pH 4.5 with 10% aqueous hydrochloric acid. After removing the solvent under reduced pressuer, the aqueous solution was adjusted to pH 4.0 with 10% aqueous hydrochloric acid under ice cooling. The solution was subjected to column chromatography on macroporous non-ionic adsorption resin "Diaion HP-20" (Trademark: prepared by Mitsubishi Chemical Industries) and eluted with 10% aqueous solution of iso-propyl alcohol. The fractions containing the object compound were concentrated and lyophilized to give 7-[2-methylthiomethoxyimino-2-(2-formamidothiazol-4-yl)acetamido]-3-(1-pyridiniomethyl)-3-cephem-4-carboxylate (syn isomer)(1.3 g).

WORKUP

后处理

customto produce an activated acid solution
additionTo the solution was added the above activated acid solution at -3° to 3° C.
stirringthe solution was stirred for 30 minutes
washa separate aqueous layer was washed with ethyl acetate
customAfter removing the solvent under reduced pressuer
customThe solution was subjected to column chromatography on macroporous non-ionic adsorption resin "Diaion HP-20" (Trademark: prepared by Mitsubishi Chemical Industries)
washeluted with 10% aqueous solution of iso-propyl alcohol
additionThe fractions containing the object compound
concentrationwere concentrated

来源与证据

来源类型: Open Reaction Database
ORD 记录: ord-14db42d4025a49c783c7ecca253ae496
来源数据集: uspto-grants-1984_04
DOI: 10.6084/m9.figshare.5104873.v1
专利: US04443444
来源说明: uspto-grants-1984_04

反应 SMILES

P(Cl)(Cl)([Cl:3])=O.[CH3:6][S:7][CH2:8][O:9][N:10]=[C:11]([C:15]1[N:16]=[C:17]([NH:20][CH:21]=[O:22])[S:18][CH:19]=1)[C:12]([OH:14])=O.[CH3:23][N+:24]([CH3:27])=[CH:25][Cl:26].[Cl-].O.O.Cl.[Cl-].[NH2:33][CH:34]1[C:51](=[O:52])[N:36]2[C:37]([C:48]([OH:50])=[O:49])=[C:38]([CH2:41][N+:42]3[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=3)[CH2:39][S:40][C@H:35]12.C(=O)(O)[O-].[Na+].C(=O)([O-])[O-].[Na+].[Na+]>C(OCC)(=O)C.O1CCCC1.O.CC(C)=O.CN(C)C=O>[CH3:23][N+:24]([CH3:27])=[CH:25][Cl:26].[Cl-:3].[CH3:6][S:7][CH2:8][O:9][N:10]=[C:11]([C:15]1[N:16]=[C:17]([NH:20][CH:21]=[O:22])[S:18][CH:19]=1)[C:12]([NH:33][CH:34]1[C:51](=[O:52])[N:36]2[C:37]([C:48]([O-:50])=[O:49])=[C:38]([CH2:41][N+:42]3[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=3)[CH2:39][S:40][C@H:35]12)=[O:14]