Methanol → HCID 131710408, compound

HRID 918598Notes

Reaction equation

HRID 918598 reaction equation
N1C=CC=CC=1.P(Cl)(Cl)(Cl)(Cl)Cl.[CH2:13]([N:15]1[C:19]([S:20][CH2:21][C:22]2[CH2:23][S:24][C@@H:25]3[C@H:45]([NH:46]C(=O)CC4SC=CC=4)[C:44](=[O:55])[N:26]3[C:27]=2[C:28]([O:30][CH:31]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)=[O:29])=[N:18][N:17]=[N:16]1)[CH3:14].CO>C(Cl)Cl>[NH2:46][C@@H:45]1[C:44](=[O:55])[N:26]2[C:27]([C:28]([O:30][CH:31]([C:38]3[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=3)[C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)=[O:29])=[C:22]([CH2:21][S:20][C:19]3[N:15]([CH2:13][CH3:14])[N:16]=[N:17][N:18]=3)[CH2:23][S:24][C@H:25]12

Participants

6

Reactant 4

HCID 887MethanolHCID 1049PyridineHCID 24819Phosphorus pentachlorideHCID 131710409HCID 131710409, compound

Product 1

HCID 131710408HCID 131710408, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

A solution of pyridine (2.13ml) in dry methylene dichloride (10ml) was added, over 5 minutes, to a stirred suspension of phosphorus pentachloride (5.47g) in methylene dichloride (20ml). After 10 minutes, the suspension was cooled to 0°, and a solution of diphenylmethyl 3-(1-ethyltetrazol-5-yl-thiomethyl)-7β-(2-thienylacetamido)-ceph-3-em-4-carboxylate (8.3g) in methylene dichloride (40ml) was added, dropwise, over 10 minutes. The resulting solution was stirred for a further 1 hour, during which time the temperature was allowed to rise to ca. 23°, and then added, over 10 minutes, to a stirred and cooled (0°) mixture of methanol (30 ml) and methylene dichloride (60ml). After 15 minutes, N-hydrochloric acid (50ml) was added, and stirring continued for a further 10 minutes. The organic phase was separated, stirred for 30 minutes with saturated sodium bicarbonate (200ml), and washed with saturated sodium bicarbonate and brine and treated with some charcoal. The suspension was filtered through a kieselguhr pad, the filtrate dried and evaporated to an oily solid (7.47 g). This material was triturated with ethyl acetate (15ml) to give the amine as a pale-yellow solid (3.854g. 58%); [α]D23 - 213° (c 1.14, CHCL3); λmax. (CHCL3) 265nm. (ε 7,900); 268.5 nm. (ε 7,900), and 279.5nm (ε 7,800); τ (DMSO-d6) values include 4.92 (d, J 5 Hz.) and 5.11 (d, J 5 Hz.), (6-H and 7H), and 5.72 (q, J 7 Hz.) and 8.61 (t, J 7 Hz.), (CH3CH2 --).

Workup

  1. temperaturethe suspension was cooled to 0°
  2. waitdropwise, over 10 minutes
  3. customto rise to ca. 23°
  4. additionadded, over 10 minutes
  5. stirringto a stirred
  6. temperaturecooled
  7. waitAfter 15 minutes
  8. stirringstirring
  9. waitcontinued for a further 10 minutes
  10. customThe organic phase was separated
  11. stirringstirred for 30 minutes with saturated sodium bicarbonate (200ml)
  12. washwashed with saturated sodium bicarbonate and brine
  13. additiontreated with some charcoal
  14. filtrationThe suspension was filtered through a kieselguhr pad
  15. customthe filtrate dried
  16. customevaporated to an oily solid (7.47 g)
  17. customThis material was triturated with ethyl acetate (15ml)

Sources & evidence

ORD record
ord-f2682286c1cb4f0183af20134acdafb0
Source dataset
uspto-grants-1976_07
Patent number
US03971778

Reaction notes

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