Morpholine → p-Nitrobenzyl alpha-(3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo(3,2,0)hept-2-en-6-yl)-alpha-(1-morpholinoethylidene)acetate

HRID 1155431Notes

Reaction equation

HRID 1155431 reaction equation
[O:1]([CH2:8][C:9]1[S:15][CH:14]2[CH:11]([C:12](=[O:33])[N:13]2[C:16](=[C:30](O)[CH3:31])[C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][C:24]([N+:27]([O-:29])=[O:28])=[CH:23][CH:22]=2)=[O:18])[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.P(Cl)(Cl)(OC1C=CC=CC=1)=O.[NH:52]1[CH2:57][CH2:56][O:55][CH2:54][CH2:53]1>O1CCCC1>[O:1]([CH2:8][C:9]1[S:15][CH:14]2[CH:11]([C:12](=[O:33])[N:13]2[C:16](=[C:30]([N:52]2[CH2:57][CH2:56][O:55][CH2:54][CH2:53]2)[CH3:31])[C:17]([O:19][CH2:20][C:21]2[CH:22]=[CH:23][C:24]([N+:27]([O-:29])=[O:28])=[CH:25][CH:26]=2)=[O:18])[N:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 8083MorpholineHCID 8471TriethylamineHCID 13038Phosphorodichloridic acid, phenyl esterHCID 70504145p-Nitrobenzyl alpha-[3-phenoxymethyl-7-oxo4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl]-alpha-(1-hydroxyethylidene)acetate

Product 1

HCID 54060416p-Nitrobenzyl alpha-(3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo(3,2,0)hept-2-en-6-yl)-alpha-(1-morpholinoethylidene)acetate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
20 °C

Procedure

To a stirred solution of p-nitrobenzyl α-(3-phenoxymethyl-7-oxo-4-thia-2,6-diazabicyclo(3,2,0)hept-2-en-6-yl)-α-(1-hydroxyethylidene)acetate (4.69 g.) in tetrahydrofuran (60 ml.) under a nitrogen atmosphere at 0°-5° C. was added triethylamine (1.6 ml.) followed by dropwise addition of phenyl dichlorophosphate (1.72 ml.) over 5 minutes. After stirring for 3 hours at 20° C., the reaction mixture was cooled to 0° C. and morpholine (4.0 ml.) was added dropwise over 10 minutes with the reaction temperature maintained at 0°-5° C. After stirring for 3 hours at this temperature, the tetrahydrofuran was evaporated and the residue dissolved in dichloromethane. The resulting solution was washed with water and then with saturated sodium chloride solution, dried with magnesium sulphate and evaporated to give the title compound as a yellow foam in essentially quantitative yield. The product obtained was a mixture of geometric isomers (ca. 1:1.4) about the enamine double bond and was identical to that produced in example 8.

Workup

  1. temperaturethe reaction mixture was cooled to 0° C.
  2. temperaturemaintained at 0°-5° C
  3. stirringAfter stirring for 3 hours at this temperature
  4. customthe tetrahydrofuran was evaporated
  5. dissolutionthe residue dissolved in dichloromethane
  6. washThe resulting solution was washed with water
  7. dry with materialwith saturated sodium chloride solution, dried with magnesium sulphate
  8. customevaporated

Sources & evidence

ORD record
ord-47624b9048484259b6a2c4d06b784295
Source dataset
uspto-grants-1981_11
Patent number
US04301280

Reaction notes

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