Chloromethyl Methyl Ether → HCID 19595205, compound

HRID 612456Notes

Reaction equation

HRID 612456 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH2:17][CH2:18][CH2:19][NH:20][NH:21][C:22]2[CH:27]=[CH:26][N:25]=[CH:24][CH:23]=2)[CH:6]=[CH:7][C:8]=1[O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11].[CH3:28]OCCl>C(O)(=O)C>[CH3:1][O:2][C:3]1[C:8]([O:9][Si:10]([C:13]([CH3:16])([CH3:14])[CH3:15])([CH3:11])[CH3:12])=[CH:7][C:6]2[CH2:28][N:20]([NH:21][C:22]3[CH:23]=[CH:24][N:25]=[CH:26][CH:27]=3)[CH2:19][CH2:18][CH2:17][C:5]=2[CH:4]=1

Participants

4

Reactant 2

HCID 7864Chloromethyl Methyl EtherHCID 19595284HCID 19595284, compound

Product 1

HCID 19595205HCID 19595205, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution of N-[3-(3-methoxy-4,6-butyldimethylsilyloxyphenyl)propylidene]-N'-pyridin-4-yl-hydrazine (5.81 g) in tetrahydrofuran (150 ml) was added lithium aluminum hydride in small portions at ambient temperature. The reaction mixture was stirred for 1.5 hrs at ambient temperature, sodium sulfate decahydrate was added. Ethyl acetate was added, and the mixture was filtered over celite. The filtrate was concentrated in vacuo to afford 5.81 g (75%) of N-[3-(3-methoxy-4-t-butyldimethylsilyloxyphenyl)propyl]-N'-pyridin-4-yl hydrazine. To a solution of N-[3-(3-methoxy-4-t-butyldimethylsilyloxyphenyl)propyl]-N'-pyridin-4-yl hydrazine in glacial acetic acid (50 ml) was added chloromethyl methyl ether (1.42 g). The reaction mixture was stirred overnight, then partitioned between 10% aqueous sodium hydroxide (500 ml) and ethyl acetate (500 ml). The organic extract was separated, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated in vacuo. This residue was chromatographed over silica gel, eluting with dichloromethane/methanol (9:1). The appropriate fractions were collected and evaporated to afford 3.61 g (60%) of product, mp 149-150° C.

Workup

  1. custompartitioned between 10% aqueous sodium hydroxide (500 ml) and ethyl acetate (500 ml)
  2. extractionThe organic extract
  3. customwas separated
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated in vacuo
  7. customThis residue was chromatographed over silica gel
  8. washeluting with dichloromethane/methanol (9:1)
  9. customThe appropriate fractions were collected
  10. customevaporated

Sources & evidence

ORD record
ord-dbac2bcf98b24183a049a10f9a6cd4e2
Source dataset
uspto-grants-1999_12
Patent number
US06004977

Reaction notes

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