4- Chloro-2-methyl -1 -chloromethyl ether

Beilstein Handbook Reference) BRN 0506943 CCRIS 138 Chlordimethylether Chlorodimethyl ether Chloromethoxymethane Chloromethyl methyl ether a,a-Dichlorodimethyl ether Dimethylchloroether EINECS 203-480-1 Ether, chloromethyl methyl Ether, dimethyl chloro Ether methylique monochlore HSDB 908 Methane, chloromethoxy- Methoxychloromethane Methoxy-methyl chloride Methyl chloromethyl ether Monochlorodimethyl ether Monochloromethyl methyl ether NSC 21208 RCRA waste number U046 UN1239, Liquid mp = -103,5° bp = 59.5° d = 1.063 soluble in EtOH, Et20, Me2CO, CHCI3. 

Related Reagents. Benzyl Chloromethyl Ether Benzyl Chloromethyl Sulfide r-Butyl Chloromethyl Ether 2-Chloro-ethyl Chloromethyl Ether Chloromethyl Methyl Sulfide Dimethoxymethane (p-Methoxybenzyloxy)methyl Chloride 2-Methoxyethoxymethyl Chloride 2-(Trimethylsilyl)ethoxymethyl Chloride. 

III-G-44. Chloro(methoxy)methane (Methyl Chloromethyl Ether, CH3OCH2CI)... 

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... 

Several chlorophyll derivatives have been prepared by electrophilic substitution, inter alia by formylation reactions. Adopting methods from corrin chemistry.50 alkylation with chloro-methyl methyl ether (caution toxic),32k chloromethyl methyl sulfide,51 and dichloromethyl methyl ether (caution toxic)52 in the presence of Lewis acids are the methods of choice to introduce carbon residues into the chlorin frame work. The compounds listed below have been prepared by these methods. 

Chloro-3-hydrox34oluene, see p-Chloro-ro-cresol 2-Chloroisopropyl ether, see Bis(2-chloroisopropyl) ether p-Chloroisopropyl ether, see Bis(2-chloroisopropyl) ether Chloromethane, see Methyl chloride (Chloromethyl)benzene, see Benzyl chloride Chloromethyl bromide, see Bromochloromethane Chloromethyl ether, see sym-Dichloromethyl ether (Chloromethyl)ethylene oxide, see Epichlorohydrin (2-Chloro-l-methylethyl) ether, see Bis(2-chloroisoprop-yl)... 

Synonyms BCME chloromethyl ether chloro(chloromethoxy)methane dichloro-methyl ether symmetrical dichloro-dimethyl ether dimethyl-1 -1dichloroether... 

S)-Pinanediol (chloromethyl)boronate is prepared by stirring 48.3 g (0.27 mol) of diisopropyl (chloro-methyl)boronate with 46.1 g (0.27 mol) of (S)-pinanediol in 200 mL of diethyl ether overnight. The solution is concentrated and the product is chromatographed on a short column of silica gel and distilled yield 58.8 g (95%) bp 95-100T (0.2 Torr). 

Chloromethylation is an efficient process but it has a serious drawback. Small amounts of the very carcinogenic (cancer-causing) bis(chloro-methyl)ether are formed in the reaction mixture so that the process has fallen out of favour. 

A complete product study was reported on the reaction of bis(chloro-methyl) ether with a-bromoisobutyrate in the presence of zinc (557). The reaction of chloromethyl benzoate with a Reformatsky reagent RCH-(ZnBr)COOR gives PhC(OH)(OCH2CHRCOOR )(CHRCOOR ) (296). 

HYDROXYL GROUPS t-Butylchlorodi-methylsilane. f-Butyldimethylsilyl perchlorate. f-Butyl chloromethyl ether. Chloromethyl methyl sulfide. 9-Chloro-9-phenylxanthene. 2-Chlorotetrahydro-furane. d-Methoxyethoxymethyl chloride. 2-Tetrahydrothicnyl diphenyl-acetate. Tris(p-bromophenyl)ammonium-yl hexachloroantimonate. 

Sternbach and coworkers pointed out that the reactions of the 6-chloro-2-chloromethyl-l,2-dihydro-4-phenylquinazoline 3-oxides 11 with a base gives either the 1,3-dihydro-2//-azirino[ 1,2-fl]quinazoline 4-oxides 13 or the 3H-1,4-benzodiazepine 4-oxide 15. In the first step of the reaction the anion 12 is formed by abstraction of a proton from the 1-nitrogen. The intermediate anion 12 can rearrange to the ring-chain tautomer 14. The relative stabilities of the two anions 12 and 14 are assumed to determine whether product 13 or 15 is formed. Thus when R is hydrogen or chloromethyl, the anion 12 is relatively sufficiently stable to allow the formation of the azirino-quinazoline 13. If, however, R is the electron-releasing methyl group, the anion 12 is destabilized and is converted to anion 14, which leads to benzodiazepine 15. The solvent polarity also influences the stability of the anions 12 and 14. In a nonpolar solvent (ether), the 5//-benzodiazepine 16 (R = Me) was obtained, which can be derived from anion 12 (R = Me) via the azirinoquinazoline 13 (R = Me). In a polar solvent (aqueous ethanol), however, the 3H-benzodiazepine 15 derived from anion 14 (R = Me) was the major product. As bases, potassium /er/-butoxide and sodium hydride were used. ... 

Japanese researchers recognised the herbicidal precursor activity of 4-chloro-2-methyl(phenoxyethyl)-l-chloromethyl ether (21). 

Gilman and his co-workers prepared a large number of organolithium compounds by this method.35 An analogous reaction occurs with chloro ethers, yielding, e.g., from chloromethyl ether and lithium in methylal at —25° to —30° (methoxymethyl)lithium, which is stable for days at —70° but decomposes in a few hours at 0°.36... 

The conflicting reports of the results of the chloromethylation of 2,5-dimethylthiophene with formaldehyde-hydrochloric acid have already been mentioned. With bischloromethyl ether in acetic acid this substance gives a mixture of 3-chloromethyl-2,5-dimethylthiophene (46%), 3,4-bis(chloro-methyl)-2,5-dimethylthiophene (12%), and 4-chloromethyl-5,5 -dimethyl-2,2 -dithienylmethane (15)49 (19%). 2,5-Diethylthiophene, on the other hand, yields only a very small quantity of a dithienylmethane under these conditions. The formation of a chloromethylated dithienylmethane was also observed in the bischloromethyl ether treatment of 2-ethylthiothiophene.50 The product, 16, was not actually isolated, but its presence was demonstrated by further reactions (see Section III,D) the yields in these reactions imply that 16 was a rather minor component in the crude reaction mixture. 

Bis(chloromethyl)ether and technical-grade chloro-methyl methyl ether... 

Cyclopropane derivatives have been prepared using alkenes, cm-dihalides, and copper. This is a convenient and useful procedure, e.g. cis-cyclo-octene was converted into bicyclo[6,l,0]nonane (77%) and into a mixture of endo- and cxo-9-methoxy-carbonylbicyclo[6,l,0]nonanes (71 % exo. endo = 1.3 1) using di-iodomethane and methyl dibromoacetate, respectively. An improved procedure for the conversion of alkenes into cyclopropanols uses lithium 2,2,6,6-tetramethylpiperidide and 2-chloroethyl chloromethyl ether, e.g. cycloheptene was converted into the 2-chloro-ethyl ether of bicyclo[5,l,0]octan-8-ol (62% exo.endo = 1.8 1). ... 

The situation is somewhat different in the case of chloromethylation of the same type of low cross-linked polymer in its shrunken state (nonsolvated) in n-hexane. This solvent coats but does not solvate the polymer beads. When the reactive complex of chloromethyl methyl ether/stannic tetrachloride is added, the macromolecules on the surface zone of the polymer pellets are immediately solvated due to much higher concentration of reactants at reactive phenyl moities, in contrast to the highly diluted state of the Friedel-Crafts alkylation in the first example. On the other hand, the relatively small amount of chloro-methyl-methylether/SnCl4 added in n-hexane is only sufficient to solvate and functionalize most exposed outer parts of the macromolecular thread in the shell zone of the polymer, depending on the accidental distribution of cross-links in that area of the macromolecule. 

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