Bromotrimethylsilane → HCID 178502819, compound

HRID 894827Notes

Reaction equation

HRID 894827 reaction equation
Br[Si](C)(C)C.C[O:7][P:8]([NH:12][C:13]([O:15][CH2:16][C:17]1[CH2:18][S:19][C@@H:20]2[C@H:33]([NH:34][C:35](=[O:45])/[C:36](/[C:40]3[O:41][CH:42]=[CH:43][CH:44]=3)=[N:37]\[O:38][CH3:39])[C:32](=[O:46])[N:21]2[C:22]=1[C:23]([O:25][CH:26]([O:28][C:29](=[O:31])[CH3:30])[CH3:27])=[O:24])=[O:14])([O:10]C)=[O:9].[CH3:47][Si](NC(OCC)=O)(C)C>ClCCl>[CH:42]([O:41][CH:40]([CH3:36])[CH3:44])([CH3:43])[CH3:47].[P:8]([NH:12][C:13]([O:15][CH2:16][C:17]1[CH2:18][S:19][C@@H:20]2[C@H:33]([NH:34][C:35](=[O:45])/[C:36](/[C:40]3[O:41][CH:42]=[CH:43][CH:44]=3)=[N:37]\[O:38][CH3:39])[C:32](=[O:46])[N:21]2[C:22]=1[C:23]([O:25][CH:26]([O:28][C:29](=[O:31])[CH3:30])[CH3:27])=[O:24])=[O:14])([OH:9])([OH:10])=[O:7]

Participants

6

Reactant 3

HCID 76113BromotrimethylsilaneHCID 11355656N-trimethylsilylurethaneHCID 178502818HCID 178502818, compound

Product 2

HCID 7914Diisopropyl EtherHCID 178502819HCID 178502819, compoundYield 133.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Bromotrimethylsilane (0.31 g) in dichloromethane (3 ml) was added to a cooled (0°) stirred mixture of (R and S)-1-acetoxyethyl (6R,7R)-3-dimethoxyphosphorylcarbamoyloxymethyl-7-[Z-2-(fur-2-yl)-2-methoxyiminoacetamido]ceph-3-em-4-carboxylate (0.62 g) and trimethylsilylurethane (0.16 g) in dry dichloromethane (12 ml) in a nitrogen atmosphere. After 2.5 hours the reaction mixture was evaporated in vacuo to a foam. This foam was dissolved in ethyl acetate (30 ml) although a slight precipitate remained. The filtered organic solution was treated with saturated aqueous sodium bicarbonate solution (30 ml) and the aqueous solution was layered with butan-1-ol (20 ml) and acidified to pH 0.5 by addition of concentrated hydrochloric acid. The aqueous phase was extracted with butan-1-ol (2×15 ml) and the combined organic extracts were evaporated in vacuo to give a solid. Trituration of this solid with di-isopropyl ether afforded the title ester (0.396 g) as a solid; νmax (Nujol) 3270 (NH), 1788 (β-lactam), 1734 (CO2R) and 1684 and 1540 cm-1 (CONH); τ (DMSO-d6) 0.18 (d, J 8 Hz, NH), 2.9 to 3.4 (broad m, 2 superimposed q, CHCH3), 4.14 (m, 7-H, mixture of diastereoisomers), 4.76 (m, 6-H, mixture of diastereoisomers), 7.92 (s, OCOCH3) and 8.52 (d, J 5 Hz, CHCH3).

Workup

  1. temperaturea cooled (0°)
  2. customAfter 2.5 hours the reaction mixture was evaporated in vacuo to a foam
  3. dissolutionThis foam was dissolved in ethyl acetate (30 ml) although a slight precipitate
  4. additionThe filtered organic solution was treated with saturated aqueous sodium bicarbonate solution (30 ml)
  5. additionacidified to pH 0.5 by addition of concentrated hydrochloric acid
  6. extractionThe aqueous phase was extracted with butan-1-ol (2×15 ml)
  7. customthe combined organic extracts were evaporated in vacuo
  8. customto give a solid

Sources & evidence

ORD record
ord-19471d4147dd4292a9ec51c979856bb4
Source dataset
uspto-grants-1981_08
Patent number
US04284766

Reaction notes

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