Chlorosuccinimide → 2-(2,6-Dichloro-4-trifluoromethylphenylhydrazono)-methylthiopropanal-1-oxime

HRID 973683Notes

Reaction equation

HRID 973683 reaction equation
ClN1C(=O)CCC1=O.O=[C:10]([CH3:14])[CH:11]=[N:12][OH:13].[CH3:15][S-:16].[Na+].[Cl:18][C:19]1[CH:24]=[C:23]([C:25]([F:28])([F:27])[F:26])[CH:22]=[C:21]([Cl:29])[C:20]=1[NH:30][NH2:31]>CN(C)C=O.O>[Cl:18][C:19]1[CH:24]=[C:23]([C:25]([F:26])([F:28])[F:27])[CH:22]=[C:21]([Cl:29])[C:20]=1[NH:30][N:31]=[C:10]([CH2:14][S:16][CH3:15])[CH:11]=[N:12][OH:13]

Participants

7

Reactant 4

HCID 31398ChlorosuccinimideHCID 688223[2,6-Dichloro-4-(trifluoromethyl)phenyl]hydrazineHCID 4378561Sodium methanethiolateHCID 63992132-Oxopropanal-1-oxime

Product 1

HCID 1372254742-(2,6-Dichloro-4-trifluoromethylphenylhydrazono)-methylthiopropanal-1-oxime

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent2×

Procedure

N-Chlorosuccinimide (7.3 g) was added, portionwise, to a solution of 2-oxopropanal 1-oxime (4.8 g) in dimethylformamide (30 ml). The reaction was heated to 50° and hydrochloric acid gas bubbled through to initiate the reaction. The mixture was then stirred at room temperature for an hour. Poured into water, extracted with ether and the extracts worked up to give crude 1-chloro--oxopropanal 1-oxime. This (1.5 g) in dimethylformamide (25 ml) was then reacted with sodium methanethiolate (0.86 g). After 5 hours at below 5°, the mixture was poured into water and extracted with ether and the extracts worked up to give crude 1-methylthio-oxopropanal 1-oxime. This (1.0 g) was then reacted with 2,6-dichloro-4-trifluoromethylphenylhydrazine (1.84 g), in a similar to that described in Example 1, to give 2-(2,6-dichloro-4-trifluoromethylphenylhydrazono)-methylthiopropanal-1-oxime. This (1.4 g) was then reacted with acetic anhydride, in a similar manner to Example 5, to give 2-(2,6-dichloro-4-trifluoromethyl-phenylhydrazono)-1-methylthiopropanal 1-acetyloxime. This (1.4 g) was then stirred with a mixture of caesium carbonate (1.1 g) and tetrahydrofuran (40 ml) at room temperature for 2 hours. Solvent was removed and the residue worked up to give compound 3.

Workup

  1. temperatureThe reaction was heated to 50°
  2. customhydrochloric acid gas bubbled through
  3. customthe reaction
  4. extractionextracted with ether
  5. customto give crude 1-chloro--oxopropanal 1-oxime
  6. extractionextracted with ether
  7. customto give crude 1-methylthio-oxopropanal 1-oxime

Sources & evidence

ORD record
ord-2fb27871f2bc486d8c73989dad4e244d
Source dataset
uspto-grants-1991_11
Patent number
US05064844

Reaction notes

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