Lawesson's reagent → 7-Chloro-2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepin-5(4H)thione

HRID 1981723Notes

Reaction equation

HRID 1981723 reaction equation
[Cl:1][C:2]1[CH:12]=[N:11][C:10]2[O:9][CH:8]([CH2:13][CH2:14][Cl:15])[CH2:7][N:6]([CH3:16])[C:5](=O)[C:4]=2[CH:3]=1.COC1C=CC(P2(=S)SP(=S)(C3C=CC(OC)=CC=3)[S:27]2)=CC=1>C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:12]=[N:11][C:10]2[O:9][CH:8]([CH2:13][CH2:14][Cl:15])[CH2:7][N:6]([CH3:16])[C:5](=[S:27])[C:4]=2[CH:3]=1

Participants

4

Reactant 2

HCID 87949Lawesson's reagentHCID 137264457-Chloro-2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepin-5(4H)-one

Product 1

HCID 137264487-Chloro-2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepin-5(4H)thione

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

7-Chloro-2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]oxazepine-5(4H)-one, 6.0 g (0.022 mole) was suspended in 200 ml of toluene. To this suspension was added 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-dilsulfide. The mixture was heated to reflux with vigorous stirring for 2 hours. Because the reaction was not complete, an additional amount (3.0 g) of 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide was added and the mixture stirred at reflux for 2 hr and left standing for 56 hr at room temperature. The toluene layer was decanted and washed with 50 ml of dilute aqueous sodium hydroxide and 50 ml of dilute hydrochloric acid. Toluene was removed by rotary evaporation (~80° C., water aspirator). The crude oil was recrystallized from isopropyl alcohol giving 3.5 g (54%) of pale yellow crystals, m.p. 125°-127° C.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux
  3. stirringthe mixture stirred
  4. temperatureat reflux for 2 hr
  5. waitleft
  6. waitstanding for 56 hr at room temperature
  7. customThe toluene layer was decanted
  8. washwashed with 50 ml of dilute aqueous sodium hydroxide and 50 ml of dilute hydrochloric acid
  9. customToluene was removed by rotary evaporation (~80° C., water aspirator)
  10. customThe crude oil was recrystallized from isopropyl alcohol giving 3.5 g (54%) of pale yellow crystals, m.p. 125°-127° C.

Sources & evidence

ORD record
ord-0e358cbd62894df7a2d9856b9d5909e7
Source dataset
uspto-grants-1986_06
Patent number
US04592866

Reaction notes

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