Hydrochloric Acid → HCID 178460821, compound

HRID 1679207Notes

Reaction equation

HRID 1679207 reaction equation
Br[CH2:2][C:3]1[CH2:4][S:5][C@@H:6]2[C@H:26]([NH:27][C:28](=[O:35])[CH2:29][C:30]3[S:31][CH:32]=[CH:33][CH:34]=3)[C:25](=[O:36])[N:7]2[C:8]=1[C:9]([O:11][CH:12]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:10].C([N:39]1[C:43](=[S:44])[NH:42][N:41]=[N:40]1)C.[CH2:45](N(CC)CC)[CH3:46].Cl>O1CCCC1.[Cl-].[Na+].O.C(OCC)(=O)C.O>[CH2:45]([CH:2]([S:44][C:43]1[NH:42][N:41]=[N:40][N:39]=1)[C:3]1[CH2:4][S:5][C@@H:6]2[C@H:26]([NH:27][C:28](=[O:35])[CH2:29][C:30]3[S:31][CH:32]=[CH:33][CH:34]=3)[C:25](=[O:36])[N:7]2[C:8]=1[C:9]([O:11][CH:12]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:10])[CH3:46]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 70592080HCID 70592080, compoundHCID 178463196HCID 178463196, compound

Product 1

HCID 178460821HCID 178460821, compound

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of diphenylmethyl 3-bromomethyl-7β-(2-thienylacetamido)-ceph-3-em-4-carboxylate (11.67g) and 1-ethyltetrazoline-5-thione (2.6g) in dry tetrahydrofuran (150ml) was stirred at 0° and a solution of triethylamine (2.8ml) in tetrahydrofuran (25ml) was added, dropwise, over 5 minutes. The resulting suspension was stirred for a further 25 minutes, during which time the temperature was allowed to rise to ca. 20°, and was then added, over 5 minutes, to a stirred mixture of 2N-hydrochloric acid (50ml), water (350ml), brine (350ml), and ethyl acetate (600ml). The organic phase was separated, and washed with 2N-hydrochloric acid, saturated sodium bicarbonate, water, and brine, and dried and evaporated to a foam (11.71g). A solution of this foam in benzene (25ml) was purified by chromatography on kieselgel (200g), with benzene:ethyl acetate = 5:1 as eluant. Appropriate fractions were combined and the solvents evaporated in vacuo. The residue was dissolved in methylene dichloride, and the solution run into petroluem ether to give the ester as a pale-yellow, amorphous solid (8.585g, 68 %); [α]D23 - 131° (c 0.97, CHCl3); λmax. (EtOH) 264 nm (ε 7,300), τ (CDCl3) values include 4.12 (7-H, dd, J 5 and 9 Hz.), 5.04 (6-H, d, J 5 Hz.), 5.83 (CH3CH2 -,q, J 7 Hz.), and 8.57 (CH3CH2 --, t, J 7 Hz.).

Workup

  1. customto rise to ca. 20°
  2. customThe organic phase was separated
  3. washwashed with 2N-hydrochloric acid, saturated sodium bicarbonate, water, and brine
  4. customdried
  5. customevaporated to a foam (11.71g)
  6. customA solution of this foam in benzene (25ml) was purified by chromatography on kieselgel (200g), with benzene
  7. customthe solvents evaporated in vacuo
  8. dissolutionThe residue was dissolved in methylene dichloride

Sources & evidence

ORD record
ord-3dbaec22bf9245cd8ddb726e4f747781
Source dataset
uspto-grants-1978_03
Patent number
US04079178

Reaction notes

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