Methanol → HCID 131710423, compound

HRID 1282995Notes

Reaction equation

HRID 1282995 reaction equation
P(Cl)(Cl)(Cl)(Cl)Cl.N1C=CC=CC=1.[C:13]([CH2:15][CH2:16][C:17]1[CH2:18][S:19][C@@H:20]2[C@H:40]([NH:41]C(=O)CC3SC=CC=3)[C:39](=[O:50])[N:21]2[C:22]=1[C:23]([O:25][CH:26]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[O:24])#[N:14].CO>C(Cl)Cl>[NH2:41][C@@H:40]1[C:39](=[O:50])[N:21]2[C:22]([C:23]([O:25][CH:26]([C:33]3[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=3)[C:27]3[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=3)=[O:24])=[C:17]([CH2:16][CH2:15][C:13]#[N:14])[CH2:18][S:19][C@H:20]12

Participants

6

Reactant 4

HCID 887MethanolHCID 1049PyridineHCID 24819Phosphorus pentachloride2×HCID 131710419HCID 131710419, compound

Product 1

HCID 131710423HCID 131710423, compoundYield 82.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

A suspension of phosphorus pentachloride (606 mg., ca 2.9 mmole) in methylene dichloride (5 ml) was warmed until most of the phosphorus pentachloride had dissolved. A solution of pyridine in methylene dichloride (4.6 ml., as a 10% v/v solution, ca 5.7 mmole) was added, and the mixture cooled to 0°. A solution of diphenylmethyl 3-(2-cyanoethyl)-7β-(2-thienylacetamido)ceph-3-em-4-carboxylate (700 mg ca 1.3 mmole) in methylene dichloride (9 ml) was added and the mixture was stirred at 0° for 30 minutes. After a further 30 minutes at 25° the solution was run into a vigorously stirred mixture of methanol (2 ml.) and methylene dichloride (10 ml). the resulting solution was washed with dilute aqueous sodium bicarbonate solution and water, and dried and evaporated in vacuo the residue was triturated with petroleum to remove traces of pyridine and the resulting solid (500 mg) dissolved in ethyl acetate. The solvent was removed in vacuo and the residue washed with ether to give the title compound (450 mg) as small needles m.p. 118° to 122° (decomp) [α]D25 49.1° (c 1.3, CHCl3) λmax. (CHCl3) 258.5 nm (ε 5,950) νmax. (CHBr3) 3450 and 3380 (NH2), 1780 (β-lactam) 1728 CO2R) and 758 and 740 (CHPh2) cm.-1 τ (CDCl3) 2.62 (Ph), 3.05 (CHPh2) 5.06 and 5.23 (C6 and C7 --H, two doublets J 5 Hz.) 6.48 and 6.65 (C2 --CH2AB-quartet, J 18 Hz.) 7.1 to 7.6 (CH2CH2CN complex) 7.5 (NH2). The compound ran to the cathode on electrophoresis at pH 1.9

Workup

  1. dissolutionhad dissolved
  2. addition, as a 10% v/v solution, ca 5.7 mmole) was added
  3. temperaturethe mixture cooled to 0°
  4. washthe resulting solution was washed with dilute aqueous sodium bicarbonate solution and water
  5. customdried
  6. customevaporated in vacuo the residue
  7. customwas triturated with petroleum
  8. customto remove traces of pyridine
  9. dissolutionthe resulting solid (500 mg) dissolved in ethyl acetate
  10. customThe solvent was removed in vacuo
  11. washthe residue washed with ether

Sources & evidence

ORD record
ord-995ccad097f942a7afa3c1e687c30345
Source dataset
uspto-grants-1976_08
Patent number
US03974152

Reaction notes

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