Hydrochloric Acid → HCID 10373871, compound

HRID 1707451Notes

Reaction equation

HRID 1707451 reaction equation
[C:1]1([CH:7]([O:14][C:15]([C:17]2[N:22]3[C:23](=[O:63])[C@@H:24]([NH:25][C:26](=[O:62])/[C:27](/[C:49]4[N:50]=[C:51]([NH:54][C:55]([O:57][C:58]([CH3:61])([CH3:60])[CH3:59])=[O:56])[S:52][CH:53]=4)=[N:28]\[O:29][C:30]([C:43]4[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=4)([C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=4)[C:31]4[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=4)[C@H:21]3[S:20](=[O:64])[CH2:19][C:18]=2[S:65][CH2:66][S:67][C:68]2[N:72]=[CH:71][NH:70][N:69]=2)=[O:16])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:73][Si]([N-][Si](C)(C)C)(C)C.[Li+].COS(C(F)(F)F)(=O)=O.Cl>O1CCCC1.O>[C:1]1([CH:7]([O:14][C:15]([C:17]2[N:22]3[C:23](=[O:63])[C@@H:24]([NH:25][C:26](=[O:62])/[C:27](/[C:49]4[N:50]=[C:51]([NH:54][C:55]([O:57][C:58]([CH3:61])([CH3:60])[CH3:59])=[O:56])[S:52][CH:53]=4)=[N:28]\[O:29][C:30]([C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=4)([C:43]4[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=4)[C:31]4[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=4)[C@H:21]3[S:20](=[O:64])[CH2:19][C:18]=2[S:65][CH2:66][S:67][C:68]2[N:72]([CH3:73])[CH:71]=[N:70][N:69]=2)=[O:16])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 9526Methyl triflateHCID 2733832Lithium HexamethyldisilazideHCID 178452986HCID 178452986, compound

Product 1

HCID 10373871HCID 10373871, compoundYield 27%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of 7β-[(Z)-2-(2-t-butoxycarbonylaminothiazol-4-yl)-2-trityloxyiminoacetylamino]-3-(1,2,4-triazol-3-ylthiomethylthio)-3-cephem-4-carboxylic acid diphenylmethyl ester 1-oxide (2.71 g: 2.63 mMol.) in tetrahydrofuran (50 ml) at -78° C. is added a solution of lithium bis(trimethylsilyl)amide in tetrahydrofuran (1M: 2.9 ml), and the mixture is stirred at -78° C. for 10 minutes, mixed with trifluoromethanesulfonic acid methyl ester (0.33 ml: 2.92 mMol.), and stirred at -78° C. for 30 minutes. The reaction mixture is mixed with 10% hydrochloric acid (2.1 ml), diluted with water, and extracted with ethyl acetate. The extract is washed with aqueous sodium hydrogen carbonate and brine, dried over sodium sulfate, and concentrated. The residue is purified by silica gel chromatography (ethyl acetate) to give 7β-[(Z)-2-(2-t-butoxycarbonylaminothiazol-4-yl)-2-trityloxyiminoacetylamino]-3-(4-methyl-1,2,4-triazol-3-ylthiomethylthio)-3-cephem-4-carboxylic acid diphenylmethyl ester 1 -oxide (0.73 g) as pale brown foam. Yield: 27%. NMR δ(CDCl3 -CD3OD) ppm: 1.51(s, 9H), 3.31(s, 3H), 3.85(s, 2H), 4.12, 4.70(ABq, J=14.6 Hz, 2H), 4.74(d, J=4.8 Hz, 1H), 6.26(d, J=4.8 Hz, 1H), 6.96(s, 1H), 7.01(s, 1H), 7.2-7.5(m, 25H), 8.11(brs, 1H). IR ν(CHCl3) cm-1 : 3400, 1805, 1722, 1690, 1545, 1507, 1497, 1450, 1372, 1040.

Workup

  1. stirringstirred at -78° C. for 30 minutes
  2. extractionextracted with ethyl acetate
  3. washThe extract is washed with aqueous sodium hydrogen carbonate and brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue is purified by silica gel chromatography (ethyl acetate)

Sources & evidence

ORD record
ord-0ecb271c7125481d8b349661e46a35f8
Source dataset
uspto-grants-1994_10
Patent number
US05352792

Reaction notes

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