Methanethiol → HCID 131710686, compound

HRID 597153Notes

Reaction equation

HRID 597153 reaction equation
C(O[CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:16]([NH:17][CH:18]=[O:19])[C:15](=[O:20])[N:10]2[C:11]=1[C:12]([O-:14])=[O:13])(=O)C.[Na+].[CH3:22][SH:23]>O>[CH:18]([NH:17][C@@H:16]1[C:15](=[O:20])[N:10]2[C:11]([C:12]([OH:14])=[O:13])=[C:6]([CH2:5][S:23][CH3:22])[CH2:7][S:8][C@H:9]12)=[O:19]

Participants

4

Reactant 2

HCID 878MethanethiolHCID 44573463HCID 44573463, compound

Product 1

HCID 131710686HCID 131710686, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Sodium 3-acetoxymethyl-7β-formamidoceph-3-em-4-carboxylate (3.22 g., 0.01 mole) in water (50 ml.) was treated with methanethiol (1.44 g., 0.03 mole) in a sealed glass tube at 70° for 2 hr. The contents of the tube were transferred to an open vessel and stirred at room temperature for 15 min. to allow the excess thiol to evaporate off. The solution was covered with ethyl acetate (50 ml.) and the pH of the aqueous layer adjusted to 1. The ethyl acetate layer was collected and combined with further ethyl acetate extracts (2 × 50 ml.) of the aqueous layer. The combined extract was washed successively with water (50 ml.) and brine (50 ml.), dried, and the solution evaporated, leaving impure 7β-formamido-3-methylthiomethylceph-3-em-4-carboxylic acid as a colourless foam (2.22 g.), which was dissolved in acetone (12 ml.) and ether (12 ml.), and a 10% w/v solution of sodium 2 -ethylhexanoate in acetone (12 ml.) was added. After refrigeration for 1 hr. the precipitate was collected by filtration, washed with acetone:ether (1:1, 2 × 10 ml.) and ether (2 × 20 ml.), and dried in vacuo giving sodium 7β-formamido-3-methylthiomethylceph-3-em-4-carboxylate as a colourless solid (1.69 g.), essentially homogeneous by thin-layer chromatography (trace of starting cephalosporanic acid), [α]D20 + 75.5° (c 1.00, water), λmax. (pH 6 buffer) 263 nm. (ε 7,760), νmax. (Nujol) 1760 (β-lactam), 1680, 1540 (amide), 1608 cm.-1 (CO2-), τ(D2O) 1.78 (1-proton singlet, CHO), 4.31 (1-proton doublet, J 4.5 Hz.: C-7H), 4.84 (1-proton doublet, J 4.5 Hz.: C-6 H) 6.20, 6.65 [two 1-proton doublets (branches or a quartet) J 17 Hz.: C-2 H2 ], 6.22, 6.69 [two 1-proton doublets (branches of a quartet), J 14 Hz.: C-3 CH2 ], 7.98 (3-proton singlet; SCH3)

Workup

  1. customThe contents of the tube were transferred to an open vessel
  2. customto evaporate off
  3. customThe ethyl acetate layer was collected
  4. extractionThe combined extract
  5. washwas washed successively with water (50 ml.) and brine (50 ml.)
  6. customdried
  7. customthe solution evaporated

Sources & evidence

ORD record
ord-c8e39d1f85134388b38f1fbb1a401472
Source dataset
uspto-grants-1977_03
Patent number
US04013645

Reaction notes

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