Methane → 5-(1-Chloro-2-methyl-2-nitropropyl)-2H-1,3-benzodioxole

HRID 616257Notes

Reaction equation

HRID 616257 reaction equation
[CH3:1][C:2]([N+:15]([O-:17])=[O:16])([CH3:14])[CH:3](O)[C:4]1[CH:9]=[CH:8][C:7]2[O:10][CH2:11][O:12][C:6]=2[CH:5]=1.S(Cl)([Cl:20])=O.C>C1C=CC=CC=1>[CH3:1][C:2]([N+:15]([O-:17])=[O:16])([CH3:14])[CH:3]([Cl:20])[C:4]1[CH:9]=[CH:8][C:7]2[O:10][CH2:11][O:12][C:6]=2[CH:5]=1

Participants

5

Reactant 3

HCID 297MethaneHCID 24386Thionyl ChlorideHCID 234548521,1-Dimethyl-2-hydroxy-2-(3,4-methylenedioxyphenyl)nitroethane

Product 1

HCID 234548395-(1-Chloro-2-methyl-2-nitropropyl)-2H-1,3-benzodioxoleYield 79.6%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 242.8 g (1.016 moles) of 1,1-dimethyl-2-hydroxy-2-(3,4-methylenedioxyphenyl)nitroethane in 500 ml of benzene was treated with 139 g (84 ml, 1.17 moles) of thionyl chloride, after which the mixture was refluxed for 4 hours, cooled slightly and concentrated to a dark yellow oil which crystallised on cooling and seeding. The resulting solid was broken up and dispersed in 150 ml of 2-propanol after which it was separated, washed twice with cold 2-propanol and dried to give crude 1,1-dimethyl-2-chloro-2-(3,4-methylenedioxyphenyl)nitroethane as a light yellow solid, m.p. 63°-66° C (Yield 230.9 g). A 201.3 g portion of the crude product was treated with "Darco" (Trade Mark) and recrystallised from 402 ml of SDA-30 to give 181.6 g (79.6%) of the pure product as a white solid, m.p. 65°-67° C.

Workup

  1. temperatureafter which the mixture was refluxed for 4 hours
  2. temperaturecooled slightly
  3. concentrationconcentrated to a dark yellow oil which
  4. customcrystallised
  5. temperatureon cooling
  6. additiondispersed in 150 ml of 2-propanol after which it
  7. customwas separated
  8. washwashed twice with cold 2-propanol
  9. customdried
  10. customto give crude 1,1-dimethyl-2-chloro-2-(3,4-methylenedioxyphenyl)nitroethane as a light yellow solid, m.p. 63°-66° C (Yield 230.9 g)
  11. customrecrystallised from 402 ml of SDA-30

Sources & evidence

ORD record
ord-23e2ec6f8c4c4aa385ddd71e7fd8a971
Source dataset
uspto-grants-1978_02
Patent number
US04073798

Reaction notes

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