Dichloromethane → HCID 13078705, compound

HRID 1731710Notes

Reaction equation

HRID 1731710 reaction equation
ClCl.P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1.P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1.ClCl.[CH:49]([O:62][C:63]([C:65]1[N:66]2[CH:69]([S:70][CH2:71][C:72]=1[CH2:73]C=O)[CH:68]([NH:76][C:77]([O:79][C:80]([CH3:83])([CH3:82])[CH3:81])=[O:78])[C:67]2=[O:84])=[O:64])([C:56]1[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=1)[C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1.[CH2:85]([Cl:87])[Cl:86]>N1C=CC=CC=1>[CH:49]([O:62][C:63]([C:65]1[N:66]2[CH:69]([S:70][CH2:71][C:72]=1[CH2:73][CH:85]([Cl:87])[Cl:86])[CH:68]([NH:76][C:77]([O:79][C:80]([CH3:83])([CH3:82])[CH3:81])=[O:78])[C:67]2=[O:84])=[O:64])([C:50]1[CH:51]=[CH:52][CH:53]=[CH:54][CH:55]=1)[C:56]1[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=1

Participants

7

Reactant 5

HCID 6344Dichloromethane3×HCID 7540Triphenyl phosphiteHCID 24526ChlorineHCID 10791754HCID 10791754, compound2×HCID 70457302HCID 70457302, compound

Product 1

HCID 13078705HCID 13078705, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A solution of the chlorine/triphenyl phosphite addition compound is prepared by adding a solution of triphenyl phosphite (1.55 g) in methylene chloride (5 cc), over a period of 15 minutes, to a 10% strength (weight/volume) solution of chlorine in methylene chloride (4 cc), cooled to -5° C. The resulting solution is added, over a period of 90 minutes, at -10° C., to a solution of 2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-8-oxo-3-(2-oxoethyl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene (product 2a) (2.4 g) and pyridine (0.4 cc) in methylene chloride (15 cc). The reaction mixture is washed with distilled water (20 cc), a saturated solution of sodium bixcarbonate (20 cc) and distilled water (2×20 cc) and then dried over magnesium sulphate and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C. This yields an equimolecular mixture (4.6 g) of 2-benzhydryloxycarbonyl-7 -t-butoxycarbonylamino-3-(2,2-dichloroethyl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene (product 2b) and triphenyl phosphate. This mixture can be used without additional purification for the remainder of the synthesis, by redissolving it in dry methylene chloride (15 cc) and adding a solution of 85% pure metachloroperbenzoic acid (1.22 g) in methylene chloride (30 cc), over a period of 20 minutes, to the above solution, cooled to -10° C. The insoluble material is removed by filtration and the filtrate is washed with a saturated solution of sodium bicarbonate (2×25 cc) and a saturated solution of sodium chloride (2×25 cc) and then dried over magnesium sulphate. The residue obtained after evaporating the solvent off under reduced pressure (30 mm Hg; 4 kPa) at 35° C. is chromatographed on a column of silica (0.04-0.06) (diameter of the column: 2 cm; height: 30 cm), elution being carried out under 50 kPa with a mixture of cyclohexane and ethyl acetate (60/40 by volume), and 30 cc fractions being collected. Fractions 6 to 12 are combined and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 40° C. This yields a hard yellow foam (1.3 g) consisting mainly of 2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-(2,2 -dichloroethyl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-5-oxide (product 2 c). Mass spectrum: molecular peak: m/e=578.

Workup

  1. customis prepared
  2. washThe reaction mixture is washed with distilled water (20 cc)
  3. distillationa saturated solution of sodium bixcarbonate (20 cc) and distilled water (2×20 cc)
  4. dry with materialdried over magnesium sulphate
  5. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C

Sources & evidence

ORD record
ord-2443a588c885427e945f8033cb9520d2
Source dataset
uspto-grants-1986_11
Patent number
US04622393

Reaction notes

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