N,N-Dimethylaniline → 2-(4-Methoxybenzyloxycarbonyloxyimino)-2-phenylacetonitrile

HRID 596220Notes

Reaction equation

HRID 596220 reaction equation
CN(C)C1C=CC=CC=1.ON=C(C1C=CC=CC=1)C#N.C(Cl)(Cl)=O.Cl[C:26]([O:28][N:29]=[C:30]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:31]#[N:32])=[O:27].[CH3:39][O:40][C:41]1[CH:48]=[CH:47][C:44]([CH2:45][OH:46])=[CH:43][CH:42]=1>C1C=CC=CC=1.N1C=CC=CC=1>[CH3:39][O:40][C:41]1[CH:48]=[CH:47][C:44]([CH2:45][O:46][C:26]([O:28][N:29]=[C:30]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C:31]#[N:32])=[O:27])=[CH:43][CH:42]=1

Participants

8

Reactant 5

HCID 949N,N-DimethylanilineHCID 6371PhosgeneHCID 77384-Methoxybenzyl alcoholHCID 699982-(Hydroxyimino)-2-phenylacetonitrileHCID 536547752-Chlorocarbonyloxyimino-2-phenylacetonitrile

Product 1

HCID 39162272-(4-Methoxybenzyloxycarbonyloxyimino)-2-phenylacetonitrile

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent3×HCID 1049PyridineSolvent

Procedure

A solution of dimethylaniline (6.0 ml.) in benzene (15 ml.) was dropwise added to a suspension of 2-hydroxyimino-2-phenylacetonitrile (7.3 g.) and phosgene (5.0 g.) in benzene (50 ml.) over 40 minutes under ice-cooling. The mixture was stirred for 2 hours at the same temperature and allowed to stand overnight. To the mixture containing 2-chlorocarbonyloxyimino-2-phenylacetonitrile was dropwise added a solution of 4-methoxybenzyl alcohol (6.9 g.) and pyridine (4.0 ml.) in benzene (20 ml.) over 30 minutes under ice-cooling, and the mixture was stirred for 7 hours at room temperature. The reaction mixture was in turn washed with water, 1N hydrochloric acid, water, a sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate. The solution was concentrated, and the residual crystals were triturated in n-hexane and collected by filtration. The crystals were recrystallized from a mixture of ethyl acetate and n-hexane to give 2-(4-methoxybenzyl)oxycarbonyloxyimino-2-phenylacetonitrile (3.1 g.). Mp 112° to 113° C. The mother liquor was concentrated to give the object compound (2.4 g.). Total yield (5.5 g.).

Workup

  1. temperaturecooling
  2. waitto stand overnight
  3. temperaturecooling
  4. stirringthe mixture was stirred for 7 hours at room temperature
  5. washwashed with water, 1N hydrochloric acid, water
  6. dry with materiala sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate
  7. concentrationThe solution was concentrated
  8. customthe residual crystals were triturated in n-hexane
  9. filtrationcollected by filtration
  10. customThe crystals were recrystallized from a mixture of ethyl acetate and n-hexane

Sources & evidence

ORD record
ord-f2b1f41920a7439c804b314defcfe8c1
Source dataset
uspto-grants-1977_03
Patent number
US04010178

Reaction notes

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