Hydrochloric Acid → 2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepin-5(4H)one hydrochloride

HRID 1981709Notes

Reaction equation

HRID 1981709 reaction equation
Cl.[CH3:2][N:3]1C[CH2:6][CH:5]([O:8][C:9]2[C:14]([C:15]([O-:17])=O)=[CH:13][CH:12]=[CH:11][N:10]=2)[CH2:4]1.[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:38]([Cl:42])(Cl)(Cl)[Cl:39]>C(Cl)(Cl)Cl.C(O)C>[ClH:39].[Cl:42][CH2:38][CH2:6][CH:5]1[CH2:4][N:3]([CH3:2])[C:15](=[O:17])[C:14]2[CH:13]=[CH:12][CH:11]=[N:10][C:9]=2[O:8]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 5943Carbon TetrachlorideHCID 11776TriphenylphosphineHCID 23718944Sodium 2-[(1-methyl-3-pyrrolidinyl)oxy]-3-pyridinecarboxylate

Product 1

HCID 137264372-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepin-5(4H)one hydrochloride

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6212ChloroformSolvent

Procedure

Hydrogen chloride gas was bubbled into a suspension of 150 g (0.61 mole) of sodium 2-[(1-methyl-3-pyrrolidinyl)oxy]-3-pyridinecarboxylate in 1 liter of chloroform until a pH of 6 was reached. To the stirred mixture was added 350 g (1.34 mole) of triphenylphosphine and 350 g (2.3 mole) of carbon tetrachloride and the resulting cloudy solution was stirred at reflux for 1.5 hr. About 100 ml of ethanol was added and the heat removed. The solution was stirred for 1 hour while cooling and 200 ml of isooctane was added. The solution was extracted 4 times with a total of 800 ml of dilute hydrochloric acid. The acid extracts were combined, made basic with sodium hydroxide and extracted with chloroform. The chloroform layer was separated and dried over sodium sulfate and concentrated. The residue was dissolved in a mixture of 500 ml each of isopropyl alcohol and isopropyl ether and acidified with ethereal hydrogen chloride. The resulting crystals weighed 82 g (49%). A portion was recrystallized from isopropyl alcohol, m.p. 149°-153° C.

Workup

  1. temperatureat reflux for 1.5 hr
  2. customthe heat removed
  3. stirringThe solution was stirred for 1 hour
  4. temperaturewhile cooling
  5. addition200 ml of isooctane was added
  6. extractionThe solution was extracted 4 times with a total of 800 ml of dilute hydrochloric acid
  7. extractionextracted with chloroform
  8. customThe chloroform layer was separated
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated
  11. dissolutionThe residue was dissolved in a mixture of 500 ml each of isopropyl alcohol and isopropyl ether
  12. customA portion was recrystallized from isopropyl alcohol, m.p. 149°-153° C.

Sources & evidence

ORD record
ord-cb8f1470787845c9a71b4ad41876e725
Source dataset
uspto-grants-1986_06
Patent number
US04592866

Reaction notes

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