Sulfuryl chloride → 7-Chloro-2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepin-5(4H)-one

HRID 1981722Notes

Reaction equation

HRID 1981722 reaction equation
Cl.[Cl:2][CH2:3][CH2:4][CH:5]1[CH2:11][N:10]([CH3:12])[C:9](=[O:13])[C:8]2[CH:14]=[CH:15][CH:16]=[N:17][C:7]=2[O:6]1.S(Cl)([Cl:21])(=O)=O>CN(C)C=O>[Cl:21][C:15]1[CH:16]=[N:17][C:7]2[O:6][CH:5]([CH2:4][CH2:3][Cl:2])[CH2:11][N:10]([CH3:12])[C:9](=[O:13])[C:8]=2[CH:14]=1

Participants

4

Reactant 2

HCID 24648Sulfuryl chlorideHCID 137264372-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepin-5(4H)one hydrochloride

Product 1

HCID 137264457-Chloro-2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepin-5(4H)-oneYield 6.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A sample of 2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]-oxazepin-5-(4H)-one hydrochloride (10 g, 136 mole) was dissolved in dimethylformamide (150 ml) and heated to reflux. Sulfuryl chloride (20 g, 0.148 mole) was then added dropwide over a period of 40-50 minutes. The reaction was allowed to stir at reflux for 30 minutes following the addition of SO2CL2. After cooling, the contents of the flask were partitioned between water (150 ml) and benzene (150 ml). The benzene layer was saved and the water layer extracted with an additional amount of benzene (2×50 ml). The benzene extracts were combined and washed with dilute aqueous potassium hydroxide (2×50 ml) followed by dilute aqueous hydrochloric acid (2×50 ml). The benzene layer was dried over sodium sulfate and concentrated by rotary evaporation (~70° C., water aspirator) yielding 2.61 g of the crude material. The crude material was recrystallized from isopropyl ether giving 1.25 g (12.6%) of off-white crystals, m.p. 78°-79° C.

Workup

  1. temperatureheated to reflux
  2. temperatureat reflux for 30 minutes
  3. additionthe addition of SO2CL2
  4. temperatureAfter cooling
  5. customthe contents of the flask were partitioned between water (150 ml) and benzene (150 ml)
  6. extractionthe water layer extracted with an additional amount of benzene (2×50 ml)
  7. washwashed with dilute aqueous potassium hydroxide (2×50 ml)
  8. dry with materialThe benzene layer was dried over sodium sulfate
  9. concentrationconcentrated by rotary evaporation (~70° C., water aspirator)

Sources & evidence

ORD record
ord-4f90114c07f142ffac73472a2305b0a1
Source dataset
uspto-grants-1986_06
Patent number
US04592866

Reaction notes

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