Chloromethyl methyl ether, reaction

Zn, (CH30)2CH2, BrCH2C02Et, 80-82% yield. Formation of the meth-oxymethyl thioether with dimethoxymethane avoids the use of the carcinogen chloromethyl methyl ether. The reaction forms an intermediate zinc thiolate, which then forms the monothioacetal. 

The chloromethylated polystyrene resin used for Merrifteld solid-phase peptide synthesis is prepared by treatment of polystyrene with chloromethyl methyl ether and a Lewis acid catalyst. Propose a mechanism for the reaction. 

The first kinetic study used chloromethyl methyl ether as chlorinating reagent and acetic acid as solvent, viz. reaction (188)381... 

Suitable precautions should be taken in utilizing this procedure, since substantial quantities of the volatile, known carcinogen, chloromethyl methyl ether, as well as the volatile and flammable methyl chloride, form under the reaction conditions. While intermediates like 15 and 16 have been postulated in a number of publications and patents in this area, no experimental evidence has been reported that describes the presence or foimation of detectable quantities of these species. 

Methoxymethylation of alcohols is generally achieved through alkylation with chloromethyl methyl ether. The procedure described here for the preparation of Bu3SnCH20CH20CH3 avoids the use of the highly toxic chloromethyl ether by employing an acid-catalyzed acetal exchange reaction with dimethoxymethane for the... 

Recently, Moody et al. reported a biomimetic synthesis of calothrixin B (378) by oxidation of Hibino s 6-formylindole[2,3-fl]carbazole 1555 (870). The key intermediate 6-formyl-indole[2,3-fl]carbazole was readily obtained in six steps from indigo (1458). Using Somei s procedure, indigo (1458) was transformed to the cis-chlorohydrin 1461 in three steps and 50% overall yield (see Scheme 5.247). The reduction of the chlorohydiin 1461 gave 5-hydroxy-indolo[2,3-fl]carbazole 1564, and subsequent Vilsmeier formylation delivered the desired 6-formyl-indole[2,3-fl]carba-zole 1565 in 45% yield. Reaction of hydroxy-indolocarbazole 1565 with an excess of chloromethyl methyl ether (MOMCI) afforded the tiis-MOM-protected compound 1555. Following Hibino s approach, the tris-MOM-protected indolocarbazole 1555... 

In the search for a reactive functional group which could be substituted on the acetylacetonate ring, chloromethylation of these chelates was attempted. The initially formed products were too reactive to be characterized directly. Treatment of rhodium acetylacetonate with chloromethyl methyl ether in the presence of boron trifluoride etherate afforded a solution of a very reactive species, apparently the chloromethyl chelate (XXX) (26). Hydrolytic workup of this intermediate yielded a polymeric mixture of rhodium chelates, but these did not contain chlorine On the basis of evidence discussed later on electrophilic cleavage of carbon from metal chelate rings and on the basis of their NMR spectra, these polymers may be of the type shown below. Reaction of the intermediate with dry ethanol afforded an impure chelate which is apparently the trisethyl ether (XXXI). Treatment of the reactive intermediate with other nucleophiles gave intractable mixtures. 

Ketoester 145 was prepared starting from Wieland-Miescher ketone in 3 stages with an overall yield of 50%. The reaction of 145 with NaH in HMPA at room temperature for 2 hours, followed by addition of chloromethyl methyl ether gives 146 in 91% yield. 

Hydroxy groups can be protected582 by reaction of their salts with chloromethyl methyl ether. 

C. The hydroxy stannane is dissolved in 100 mL of anhydrous methylene chloride in a 250-mL, one-necked, round-bottomed flask equipped with a Teflon-coated magnetic stirring bar. The yellow solution is stirred at 0°C and diisopropylethylamine (i-P NEt) (8.80 mL, 50.5 mmol) is added, followed by chloromethyl methyl ether (2.90 mL, 38.2 mmol). After 5 hr the reaction is quenched with 100 mL of aqueous saturated ammonium chloride solution. The layers are separated and the aqueous layer is extracted with two 100-mL portions of ether. The... 

Weak Base Anion Exchangers. Both styrenic and acrylic copolymers can be converted to weak base anion-exchange resins, but different synthetic routes are necessary. Styrene—DVB copolymers are chloromethylated and aminated in a two-step process. Chloromethyl groups are attached to the aromatic rings (5) by reaction of chloromethyl methyl ether [107-30-2], CH3OCH2Cl, with the copolymer in the presence of a Friedel-Crafts catalyst such as aluminum chloride [7446-70-0], A1C13, iron(III) chloride [7705-08-0]9 FeCl3, or zinc chloride [7646-85-7], ZnC. ... 

The reaction of germyllithiums with chloromethyl methyl ether gave the germylmethyl methyl ether in good yield (equation 91)9,136. 

The solution was cooled to 0° and 1.15 g (3.7 mmol) of 2e dissolved in 25 ml of THF was added dropwise during 15 min. The resulting clear brown solution was heated to reflux and treated with 350 mg (4.35 mmol) of freshly distilled chloromethyl methyl ether in 10 ml of THF. The mixture was refluxed for 1 hr and stirred at room temperature overnight. The reaction mixture was shaken with 200 g of ice and 100 ml of CHC13. The organic phase was dried (CaS04) and concentrated, and the solid residue recrystallized twice from EtOAc-petroleum ether (bp 30-60°) giving 840 mg (64%) of 20c, mp 237-239°. 

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