Hydrochloric Acid → HCID 14973526, compound

HRID 2291385Notes

Reaction equation

HRID 2291385 reaction equation
[C:1]([C:5]1[CH2:12][N:11]2[N:7]([C:8](=[O:32])[CH:9]([NH:13][C:14](=[O:31])/[C:15](/[C:19]3[N:20]=[C:21]([NH:24]C(OCC=C)=O)[S:22][CH:23]=3)=[N:16]\[O:17][CH3:18])[CH2:10]2)[C:6]=1[C:33]([O:35]CC=C)=[O:34])(=[O:4])[CH2:2][CH3:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([SnH](CCCC)CCCC)CCC.Cl>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CC(C)=O.C(OCC)C>[C:1]([C:5]1[CH2:12][N:11]2[N:7]([C:8](=[O:32])[CH:9]([NH:13][C:14](=[O:31])/[C:15](/[C:19]3[N:20]=[C:21]([NH2:24])[S:22][CH:23]=3)=[N:16]\[O:17][CH3:18])[CH2:10]2)[C:6]=1[C:33]([OH:35])=[O:34])(=[O:4])[CH2:2][CH3:3]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 5948TributylstannaneHCID 11776TriphenylphosphineHCID 88629761HCID 88629761, compound

Product 1

HCID 14973526HCID 14973526, compoundYield 21%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 180AcetoneSolventHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

Under a nitrogen atmosphere, allyl 3-(propionyl)-7-(R,S)-[2-(2-(allyloxycarbonylamino)thiazol-4-yl)-2-(Z)-methoxyiminoacetamido]-8-oxo-1,5-diazabicyclo[3.3.0]octa-2-ene-2-carboxylate (270 mg, 0.49 mmol) was suspended in a mixture of acetonitrile (10 ml)/diethyl ether (5 ml). Palladium(II) acetate (5.5 mg, 0.0245 mmol) and triphenylphosphine (51.4 mg, 0.196 mmol) were added to the suspension then acetone (45 ml) was added to effect solution and the resultant solution was stirred for 30 minutes at room temperature then cooled to 0° C. Tri(n-butyl)tin hydride (291.05 mg, 0.27 ml, 1 mmol) was added and the resultant solution was stirred at room temperature for 3 hours. Concentrated hydrochloric acid (12M, 0.08 ml, 1 mmol) was added and the solution was concentrated in vacuo. The concentrate was dissolved in methylene chloride, precipitation was effected by the addition of diethyl ether and the precipitate was collected by filtration. The precipitate was chromatographed by medium pressure liquid chromatography on a C18 column eluted with 10% acetonitrile/1% acetic acid in water. The product-containing fractions were lyophilized to give 43 mg (21%) of 3-(propionyl)-7-(R,S)-[2-(2-aminothiazol-4-yl)-2-(Z)-methoxyiminoacetamido]-8-oxo-1,5-diazabicyclo[3.3.0]octa-2-ene-2-carboxylic acid: n.m.r. (300 MHz, DMSO-d6): δ 0.92 (t, 3, J=6), 2.97 (dd, 1, J=6, 12), 2.46-2.48 (m, 2), 3.83 (s, 3), 3.00-4.20 (m, 3), 4.92-5.06 (m, 1), 7.03 (s, 1), 7.24 (br. s, 2), 9.15 (d, 1, J=9); i.r. (KBr) 3310 (br), 1716, 1636, 1534, 1414, 1380, 1257, 1050 cm- 1 ; u.v. (EtOH) λmax =233 (ε=15992), 300 (ε=6987), 350 (ε=9801); m.p.>260° C.; f.a.b.m.s. (m/e) M+ +1=423.

Workup

  1. concentrationthe solution was concentrated in vacuo
  2. dissolutionThe concentrate was dissolved in methylene chloride
  3. customprecipitation
  4. additionwas effected by the addition of diethyl ether
  5. filtrationthe precipitate was collected by filtration
  6. customThe precipitate was chromatographed by medium pressure liquid chromatography on a C18 column
  7. washeluted with 10% acetonitrile/1% acetic acid in water

Sources & evidence

ORD record
ord-f2d303cdc5fa4969a63b8650b6602fba
Source dataset
uspto-grants-1989_01
Patent number
US04795815

Reaction notes

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