p-Toluenesulfonic acid monohydrate → HCID 70621000, compound

HRID 1679192Notes

Reaction equation

HRID 1679192 reaction equation
[NH2:1][C@@H:2]1[C:27](=[O:28])[N:4]2[C:5]([C:14]([O:16][CH2:17][C:18]3[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][CH:19]=3)=[O:15])=[C:6]([CH2:9][O:10][C:11](=[O:13])[CH3:12])[CH2:7][S:8][C@:3]12[O:29][CH3:30].O.[C:32]1([CH3:42])[CH:37]=[CH:36][C:35]([S:38]([OH:41])(=[O:40])=[O:39])=[CH:34][CH:33]=1>CCOC(C)=O>[C:32]1([CH3:42])[CH:33]=[CH:34][C:35]([S:38]([OH:41])(=[O:39])=[O:40])=[CH:36][CH:37]=1.[NH2:1][CH:2]1[C:27](=[O:28])[N:4]2[C:5]([C:14]([O:16][CH2:17][C:18]3[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][CH:19]=3)=[O:15])=[C:6]([CH2:9][O:10][C:11](=[O:13])[CH3:12])[CH2:7][S:8][C@:3]12[O:29][CH3:30]

Participants

5

Reactant 2

HCID 521998p-Toluenesulfonic acid monohydrateHCID 70620514HCID 70620514, compound

Product 2

HCID 6101p-Toluenesulfonic acidHCID 70621000HCID 70621000, compoundYield 31.4%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Procedure

In a separate experiment, the crude amine mixture (226 mg.) in EtOAc (1 ml.) is treated with a solution of p-toluenesulfonic acid monohydrate (98 mg., 0.52 mMol) in EtOAc (4 ml.). The resulting solution is stored at 0° C. for ca. 5 hrs., during which time a fine, white precipitate forms. The precipitate is collected, washed with cold EtOAc and hexane, and dried in vacuo to yield the p-toluenesulfonic acid salt of p-nitrobenzyl 7-amino-6-methoxy-3-acetoxymethyl-ceph-3-em-4-carboxylate (71 mg.): mp 170°-175° C. (dec.). The salt (71 mg., 0.12 mMol) is shaken with aqueous K2CO3 (18 mg., 0.13 mMol in 5 ml.) and EtOAc (5 ml.). The layers are separated and the aqueous portion is extracted with more EtOAc (3 × 3 ml.). The combined EtOAc solution is washed with brine, dried with MgSO4, filtered and evaporated in vacuo to provide the major isomer of p-nitrobenzyl 7-amino-6-methoxy-3-acetoxymethyl-ceph-3-em-4-carboxylate (53 mg.) as a pale yellow oil: ir (neat) 3.97, 5.60, 5.74, 6.55, and 7.40μ; nmr (CDCl 3) δ 1.93 (s, 2, NH2), 2.08 (s, 3, COCH3), 3.25, 3.58 (ABq, 2, J=18Hz, SCH2), 3.52 (s, 3, OCH3), 4.28 (s, 1, H7), 4.80, 5.15 (ABq, 2, J=14Hz, CH2OAc), 5.38 (s, 2, CH2Ar), and 7.60, 8.23 (ABq, 4, J=9Hz, ArH); mass spectrum m/e 437 (M+), 380, 321, 257, 186, 169, and 136.

Workup

  1. customThe precipitate is collected
  2. washwashed with cold EtOAc and hexane
  3. customdried in vacuo

Sources & evidence

ORD record
ord-1b05b7809106441eadc0a5312978c714
Source dataset
uspto-grants-1978_03
Patent number
US04079179

Reaction notes

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