Methyl chloromethyl ether,

Alkylation. Ben2otrifluoride can also be alkylated, eg, chloromethyl methyl ether—chlorosulfonic acid forms 3-(trifluoromethyl)ben2yl chloride [705-29-3] (303,304), which can also be made from / -xylene by a chlorination—fluorination sequence (305). Exchange cyanation of this product in the presence of phase-transfer catalysts gives 3-(trifluoromethylphenyl)acetonitrile [2338-76-3] (304,305), a key intermediate to the herbicides flurtamone... 

Chloromethylation can be efficiently effected using chloromethyl methyl ether, in the presence of Lewis acids. However, due to its carcinogenic nature, extreme care should be exercised in its use (46). Alternatively, paraformaldehyde—HCl/ZnCl2 can be used as the chloromethylating agent. 

Weak Base Anion Exchangers. Both styreoic and acryHc copolymers can be converted to weak base anion-exchange resias, but differeat syathetic routes are aecessary. Styreae—DVB copolymers are chloromethylated and aminated ia a two-step process. Chloromethyl groups are attached to the aromatic rings (5) by reactioa of chloromethyl methyl ether [107-30-2] CH2OCH2CI, with the copolymer ia the preseace of a Friedel-Crafts catalyst such as aluminum chloride [7446-70-0], AlCl, iroa(III) chloride [7705-08-0], FeCl, or ziac chloride [7646-85-7], ZaCl. ... 

Fig. 1. Ion-exchange production schematic. CMME is chloromethyl methyl ether.

Isoprene reacts with a-chloroalkyl ethers in the presence of ZnCl in diethyl ether from 0—10°C. For example,a-chloromethyl methyl ether at 10°C gives a 6 1 ratio of the 1,4-adduct, (F)4-chloro-l-methoxy-2-methyl-2-butene, to the 1,2-adduct, 2-chloro-l-methoxy-2-methyl-3-butene. Other a-chloroalkyl ethers react in a similar manner to give predominately the 1,4-addition product. A wide variety of aHyUc chlorides and bromides and a-chloroethers and esters add primarily 1,4- to isoprene in the presence of acid catalysts (8). 

Tin metal also reacts directly with a number of activated organic haUdes, including aHyl bromide, benzyl chloride, chloromethyl methyl ether, and P-halocarboxyhc esters and nitriles giving fair-to-good yields of diorganotin dihaUdes (97,111—114). 

CH3OCH2CI, i-Pr2NEt, 0 , 1 h 25°, 8 h, 86% yield. This is the most commonly employed procedure for introduction of the MOM group. The reagent chloromethyl methyl ether is reported to be carcinogenic. 

CH3OCH2OCH3, Zn/BrCH2C02Et, 0° CH3COCI, 0-20°, 2 h, 75-85%. A number of methoxymethyl esters were prepared by this method, which avoids the use of the carcinogen chloromethyl methyl ether. 

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. 

Bis(chloromethyl)ether [542-88-1] and chloromethyl methyl ether [107-30-2] (technical-grade)... 

The six-position may be functionalized by electrophilic aromatic substitution. Either bromination (Br2/CH2Cl2/-5°) acetylation (acetyl chloride, aluminum chloride, nitrobenzene) " or chloromethylation (chloromethyl methyl ether, stannic chloride, -60°) " affords the 6,6 -disubstituted product. It should also be noted that treatment of the acetyl derivative with KOBr in THF affords the carboxylic acid in 84% yield. The brominated crown may then be metallated (n-BuLi) and treated with an electrophile to form a chain-extender. To this end, Cram has utilized both ethylene oxide " and dichlorodimethyl-silane in the conversion of bis-binaphthyl crowns into polymer-bound resolving agents. The acetylation/oxidation sequence is illustrated in Eq. (3.54). 

Chlorobenzene Producers Association (CPA), 270 p-Chlorobenzotrichloride, 39 Chlorobenzotrifluorides, 39 Chlorobromomethane, 39 Chlorodifluorobromomethane, 39 Chlorodifluoroethane, 39 Chlorodifluoromethane, 39 Chlorodiphenyl, 39 Chloroethanol, 39 2-Chloroethyl vinyl ether, 39 Chlorofluorocarbons, 39 Chloroform, 40 Chloromethyl anilines, 40 Chloromethyl ether, 40 Chloromethyl methyl ether, 40 2-(4-Chloro-2-methylphenoxy) propionic acid, 40 Chloromethyl phenyl isocyanate, 40... 

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 material which is collected is redistilled through a 90-cm. vacuum-jacketed column packed with glass beads (5 mm.) using a 1 10 reflux ratio. The fraction, b.p. 80-100°, is redistilled through the same column to give 353-386 g. (77-84%) of di-chloromethyl methyl ether, b.p. 82-85.5°, 20d 1.4303 (Note 5). 

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. 

The potential utility of cyclopentadienylthallium(I) in organic synthesis, and its advantages over the much more commonly employed sodium salt, have been illustrated recently 22). Treatment of (I) (Scheme 2) with chloromethyl methyl ether in dry ether resulted in smooth monoalkylation... 

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