F Chloromethyl methyl ether

Carbon tetrachloride, 0322 Carbon tetrafluoride, 0349 Carbon tetraiodide, 0525 f 1-Chlorobutane, 1637 f 2-Chlorobutane, 1638 f Chlorocyclopentane, 1923 f l-Chloro-l,l-dilluoroethane, 0731 Chlorodilluoromethane, 0369 f Chloroethane, 0848 Chloroform, 0372 f Chloromethane, 0432 f l-Chloro-3-methylbutane, 1986 f 2-Chloro-2-methylbutane, 1987 f Chloromethyl ethyl ether, 1246 f Chloromethyl methyl ether, 0850 f l-Chloro-2-methylpropane, 1639 f 2-Chloro-2-methylpropane, 1640 f 1-Chloropentane, 1988 f 1-Chloropropane, 1243 f 2-Chloropropane, 1244 f l-Chloro-3,3,3-trifluoropropane, 1127 1,2-Dibromoethane, 0785 Dibromomethane, 0395... 

Chloro-l-methylimidazolium nitrate, 1449 f Chloromethyl methyl ether, 0846... 

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). 

The kgjko isotope effect for the solvolysis of chloromethyl methyl ether in isopropyl alcohol at 0° is 1.24 + 0.08 per deuterium atom " . This is in the range of other unimolecular reactions. The values of and AS for the chloroether in isopropyl alcohol are 10.7 0.6 kcal.mole" and —28.8 + 1.6 eu, respectively. In contrast, the corresponding values for solvolysis of alkyl chlorides are in the range of about 20-25 kcal.mole and —4 to —12 eu. The lower values of A/f and AS for the solvolysis of chloromethyl methyl ether are tentatively attributed to the double bond character between oxygen and carbon at the transition state (see above) . 

The chemistry of heterocyclic compounds . Series Eds. Weissberger, A., Wipf, R, and Taylor, E. C., Vols. 1-64, Wiley-Interscience, 1950-2005. Rodd s chemistry of carbon compounds , Eds., Coffey, S. then Ansell, M. F., Vols IVa-IVl, and Supplements, 1973-1994, Elsevier, Amsterdam. United States Department of Labor, Occupational Safety Health Administration Reports Chloromethyl Methyl Ether (CMME) and Bis-Chloromethyl Ether (BCME) see also Berliner, M. and Belecki, K., Org. Synth., 2007, 84, 102 (discussion). 

CHLOROMETHYL METHYL ETHER (107-30-2) Forms explosive mixture with air (flash point 17°F/— 8°C). May be able to form unstable and explosive peroxides. Contact with oxidizers may cause fire and explosion. Decomposes on contact with water, forming hydrochloric acid and formaldehyde. Corrosive to various metals in presence of moisture. Contact with cadmium(II) acetate, cobalt(II) nitrate, copper(II) nitrate, mercury(II) chlorate, mercury(II) perchlorate, iron(II) compounds, and many other divalent metallic compounds may form highly reactive or explosive products. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

Methoxymethyl aryl ethers, Ar0CH20CH3. These ethers can be prepared by treatment of phenols with NaH in ether-DMF followed by chloromethyl methyl ether. Ronald reports that these ethers show enhanced susceptibility at the orfho-position to halogen-metal exchange, particularly with f-butyllith-ium. Thus (1) can be converted into (2) in high yield by metalation, reaction with CO2, and then reaction with diazomethane. In contrast, the methyl ether of OT-cresol under similar conditions gives less than 1% yield of carboxylic acids. 

Examples of benzylic alkylation, aromatic ring deprotonation, and nucleophilic addition to a /3-position were used in a synthesis of (-f)-20-methoxy-serrulat-14-en-7,8-diol. Deprotonation of the optically active complex (54) followed by reaction with chloromethyl methyl ether affords (55)... 

A soln. of 5.0 g. ethyl 8/, 8a/ -dimethyl-l-oxo-l,2,3,4,6,7,8,8a-octahydro-2-naph-thoate in hexamethylphosphoramide added at 5° under Ng to a stirred mixture of a 60%-dispersion ofNaHin mineral oil and hexamethylphosphoramide, stirring continued 1 hr. at room temp., cooled to 5°, 1.93 g. chloromethyl methyl ether added, and stirred 2 hrs. at room temp. 5.7 g. crude methoxymethyl enol ether dissolved in ether, added rapidly with Dry Ice-cooling under argon to a stirred dark blue soln. of Li in anhydrous NH3, and stirring continued 12 min. at -33°, the b. p. of liq. NHg 2.85 g. ethyl 8/, 8ai -dimethyl-l,2,3,4,6,7,8,8a-octahydro-2j -naphthoate. Overall Y 60%. - 0-Alkylation of the startg. -keto esters occurs under the above conditions to the complete exclusion of the C-alkylated isomer. The subsequent reduction gives the less stable axial isomer. R. M. Coates and J. E. Shaw, J. Org. Chem. 35, 2597 (1970) f. e. s. ibid. 35, 2601 carboxylic acids, also from a,/ -ethylenecarboxylic acids, cf. ibid. 36, 1151 (1971). 

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. 

AMINO GROUP Boron trifluoride ether-ate. 1-/-B utyloxy carbony ltriazole-1,2,4. Di-f-butyl dicarbonate. 4-Dimethylamino-1-f-butyloxycarbonyl pyridinium chloride. CARBONYL GROUP Ceric ammonium nitrate. 1,2-Dihydroxy-3-bromopropane. Sodium N-chloro-p-toluenesulfonamide. Thallium(III) nitrate. Trichloroethanol. Trimethylsilyl cyanide. Chloromethyl methyl sulfide. N,N -Diisopropylhydra-zine. Trichloroethanol. 

A soln. of 3,4-dimethoxyphenylpropionic acid and 2.5 moles of monochloro-methyl ether in glacial acetic acid allowed to stand 24 hrs. at room temp. 2-chloromethyl-4,5-dimethoxypropionic acid (Y 60-80%) refluxed 2 hrs. with hexamethylenetetramine in alcohol 2-formyl-4,5-dimethoxypropionic acid (Y 70%).—Direct formylation was unsuccessful. F. e. s. R. Durand-Dran, M. Lecocq, and R. Quelet, G. r. 250, 2727 (1960). 

Thiirane 1-oxide added to a soln. of chloromethyl /i-propyl ether in abs. methylene chloride, and stirred 12 hrs. under anhydrous conditions -> -propoxy-methyl 2-chlorethanesulfenate. Y 70%. F. e. s. E. Vilsmaier and B. Hloch, Synthesis 1971, 590. 

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