Epichlorohydrin → HCID 21536094, compound

HRID 1077296Notes

Reaction equation

HRID 1077296 reaction equation
C(OC1C=C([N+]([O-])=O)C=C(I)C=1O)C1C=CC=CC=1.C(C1OC1)Cl.OCC1OC2C=C([N+]([O-])=O)C=C(I)C=2OC1.C(OCC1OC2C=C([N+]([O-])=O)C=C(I)C=2OC1)C.[CH2:59]([O:61][CH2:62][CH:63]1[O:68][C:67]2[CH:69]=[C:70]([N+:77]([O-])=O)[CH:71]=[C:72]([C:73]([F:76])([F:75])[F:74])[C:66]=2[O:65][CH2:64]1)[CH3:60]>CN(C)C=O.[Cu].[Pd]>[NH2:77][C:70]1[CH:71]=[C:72]([C:73]([F:76])([F:75])[F:74])[C:66]2[O:65][CH2:64][CH:63]([CH2:62][O:61][CH2:59][CH3:60])[O:68][C:67]=2[CH:69]=1

Participants

9

Reactant 5

HCID 7835EpichlorohydrinHCID 215360932-(Ethoxymethyl)-2,3-dihydro-7-nitro-5-(trifluoromethyl)-1,4-benzodioxinHCID 21536097HCID 21536097, compoundHCID 21536098HCID 21536098, compoundHCID 21536100HCID 21536100, compound

Product 1

HCID 21536094HCID 21536094, compound

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 23978CopperCatalystHCID 6228DimethylformamideSolvent

Procedure

2-benzyloxy-4-nitrophenyl was iodinated to 2-benzyloxy-6-iodo-4-nitrophenol of melting point 143°C-145°C in the manner described for an analogous compound in J.Am.Chem. Soc. 75 4290 (1953). This compound was converted with epichlorohydrine into 2-(hydroxymethyl)-5-iodo-7-nitro-1,4-benzodioxane by the method described in J.Ned. Chem. 1965 page 455 for an analogous compound. The substance obtained was ethylated to 2-(ethoxymethyl)-5-iodo-7-nitro-1,4-benzodioxane (melting point of the crude product 90°--99°C), and this was converted with CF3J and powdered copper in dimethylformamide into 2-(ethoxymethyl)-7-nitro-5-(trifluoromethyl)-1,4-benzodioxan by the method described in Tetrahedron Letters 1969 pages 4095-4096. The reaction product was hydrogenated by means of a palladium on active carbon catalyst at room temperature and under a pressure of about 1.1 atmospheres to form 7-amino-2-(ethoxymethyl)-5-(trifluoromethyl)-1,4-benzodioxan, which was immediately converted with 2-(ethoxymethylene)malonic acid diethyl ester into 2- { [2-(ethoxymethyl)-5-(trifluromethyl)-1,4-benzodioxan-7-ylamino] -methylene } malonic acid diethyl ester which had a melting point of 96°-98°C.

Workup

  1. customThe substance obtained

Sources & evidence

ORD record
ord-9679caa493a64e85959235cc98127ff4
Source dataset
uspto-grants-1976_05
Patent number
US03959473

Reaction notes

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