1,1'-(Diazomethylene)bis(benzene) → HCID 12764268, compound

HRID 1283079Notes

Reaction equation

HRID 1283079 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:16]([NH:17][CH:18]=[O:19])[C:15](=[O:20])[N:10]2[C:11]=1[C:12]([OH:14])=[O:13])(=[O:3])[CH3:2].[C:21]1([C:27]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[N+]=[N-])[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>O1CCCC1.CCOCC>[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:16]([NH:17][CH:18]=[O:19])[C:15](=[O:20])[N:10]2[C:11]=1[C:12]([O:14][CH:27]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)=[O:13])(=[O:3])[CH3:2]

Participants

5

Reactant 2

HCID 612301,1'-(Diazomethylene)bis(benzene)HCID 12764266HCID 12764266, compound

Product 1

HCID 12764268HCID 12764268, compoundYield 40%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of (6R,7R)-3-acetoxymethyl-7-formamidoceph-3-em-4-carboxylic acid (6.20g, 20 mmole) in dry tetrahydrofuran (150 ml) was stirred with a solution of diphenyldiazomethane (20 mmole; prepared in ether solution, then evaporated) in dry tetrahydrofuran (20 ml) at +20° to +25° for 16 hrs. The solvent was evaporated and the solution of the residue in methylene chloride (150 ml) was washed successively with 2N-hydrochloric acid 3%-aqueous sodium bicarbonate solution. The solution was dried and evaporated leaving a foam which was chromatographed on kieselgel G (250g) in benzeneethyl acetate (9:1, then 1:1). The appropriate fractions were combined, evaporated, and triturated with ethyl acetate to give the title compound as a crystalline solid (3.789g, 8.1 mmole, 40%), m.p. 158.6 to 160.4(cap.); [α]D +32.8; λmax 261 nm (ε7,750); νmax 3410 (NH), 1788 (azetidin-2-one), 1732 (OCOCH3), 1705 (CO2R) and 1698 and 1502 cm-1 (CONH); τ 1.80 (1H,d,J9Hz, NH), 2.70(10H,m, [C6H5 ]CH), 3.03(1H,s, [C6H5 ]2CH), 4.10 (1H, dd,J9 and 4.5Hz, C7 -H), 4.90 and 5.23 (2H, ABq, J14Hz, CH 2 OCOCH3), 5.04 (1H, d, J5Hz, C6 -H), 6.38 and 6.72 (2H, ABq, J18Hz, C2 -H2), 8.00 (3H,s, OCOCH3). (Found: C, 62.1; H, 4.8; N, 5.8; S, 6.9. C24H22N2O6S(466.5) requires C, 61.8; H, 4.8; N, 6.0; S, 6.9%).

Workup

  1. customevaporated) in dry tetrahydrofuran (20 ml) at +20° to +25° for 16 hrs
  2. customThe solvent was evaporated
  3. washthe solution of the residue in methylene chloride (150 ml) was washed successively with 2N-hydrochloric acid 3%-aqueous sodium bicarbonate solution
  4. customThe solution was dried
  5. customevaporated
  6. customleaving a foam which
  7. customwas chromatographed on kieselgel G (250g) in benzeneethyl acetate (9:1
  8. customevaporated
  9. customtriturated with ethyl acetate

Sources & evidence

ORD record
ord-187b15fc569942d58eb53274f1349c82
Source dataset
uspto-grants-1976_08
Patent number
US03974150

Reaction notes

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