Abstract
The versatile reagent chloromethyl methyl ether (MOM-Cl) is synthesized by using inexpensive
starting materials in a large scale. A modification of the existing methods reduces
material costs by more than 80%.
Key words
protecting group - MOM-Cl - alcohols - phenols - acetals
References
<A NAME="RG04204ST-1">1 </A>
Greene TW.
Wuts PGM.
Protective Groups in Organic Synthesis
3rd ed:
John Wiley and Sons;
Weinheim:
1999.
2a </A>
Amato JS.
Karady M.
Sletzinger M.
Weinstock LM.
J. Org. Chem.
1994,
59:
6499
2b </A>
Linderman RJ.
Jaber M.
Griedel BD.
J. Org. Chem.
1994,
59:
6499
2c </A>
Chong JM.
Shen L.
Synth. Commun.
1998,
28:
2801
3 </A>
Material costs are calculated from the prices quoted in the Aldrich Chemical Co. catalog
(2003). For comparison, one mole of chloromethyl methyl ether costs 229 US $. A commercial
sample of chloromethyl methyl ether contained about 4% of bis(chloromethyl)ether.
<A NAME="RG04204ST-4">4 </A>
To ensure gas tightness, PTFE-sleeves were used on all glass connections.
<A NAME="RG04204ST-5">5 </A>
All reagents were purchased by common suppliers and used as received without any further
purification.
<A NAME="RG04204ST-6">6 </A>
The integrals of the product signals (δ = 3.52 and 5.46 ppm) are compared with those
of dimethoxymethane (δ = 3.34 and 4.56 ppm).
<A NAME="RG04204ST-7">7 </A>
Without further purification, the product contains about 1% dimethoxymethane (1 H NMR, δ = 3.34 and 4.56 ppm). This is sufficient for most applications. The content
of bis(chloromethyl)ether was found to be less than 0.1% (GC, conditions 50 m × 0.32
mm FS-SE-52-CB-0.25 fused silica column, column temperature 60 °C, injector temperature
240 °C, detector temperature (FID), nitrogen flow 1 mL/min tR (MOM-Cl) = 5.79 min, tR [bis(chloromethyl)ether] = 7.97 min.
