Chloromethyl phenyl ether

Chloro-3-hydroxybutyronitrile, byproduct in preparation of 3-hydroxyglu taronitrile, 46, 49 3-hydroxyglutaronitrile from, 46, 49 1-Chloro-l-methylcyclohexane as precursor of 1-methylcyclohexane-carboxylic acid, 46, 73 Chloromethyl phenyl ether, 47,... 

The activation energy for the condensation of the sodium salt of bisphenol A with bis[4-(chloromethyl)phenyl] ether has been reported [206] to be 21.2 kcalmole". At 185.5°C the second-order rate coefficient was 0.00023 mmole g sec". ... 

The carbenoid generated from chloromethyl phenyl ether with butyllithium reacts with (E)- or (Z)-2-butene in a stereospecific manner3. The simple diastereoselectivity of this and related carbenoids is generally moderate to good, favoring the formation of exo- or trans-cydoaddnets (see Vol. E 19b, p 1633)3 4. 

Cyclopropyl ethers. Ethereal ca. 1 bulyllithium soln. added dropwise at —20 to a mixture of isobutene and chloromethyl phenyl ether l-phenoxy-2,2-dimethylcyclopropane. Y 75%. F. e. s. U. Schollkopf, A. Lerch, and W. Pitteroff, Tetrah. Let. 1962, 241 1-aryl-l-chlorocyclopropanes with methyllithium s. R. A. Moss, J. Org. Chem. 27, 2683 (1962). 

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... 

Chloromethylatlon of 2,2-bls[4 -(4"-phenylsulfonylphenoxyl)phenyl] propane. A solution of 7, 40 g (0.06 mol) was blended with 400 mL of 6 M chloromethyl methyl ether solution and 0.7 mL (6 mmol) of SnCl4 in a 500 mL resin kettle, and the mixture was refluxed for 8 h under argon. The solvent was distilled until the volume was reduced to 20 mL and 300 mL of ethanol was added to produce a clear solution. The product, 2,2-bis[3-chloromethyl-4-(4-phenylsulfonyl-phenoxyl)phenyl]propane, 11, crystallized from the ice cooled solution, 40.2 g (87%) mp 182-83°C was isolated by filtration. 

Anion-exchanger. Phenyl-bonded silica gel is suspended in chloromethyl methyl ether and boiled under reflux. Then, chloromethyl methyl ether containing anhydrous ZnCl2 is added and the mixture boiled under reflux. After filtration,... 

Chlorosulfides are often used for vicinal functionalization of alkenes. Silyl enol ethers can react with a-chloromethyl phenyl sulfides (5) in the presence of ZnBr2 or TiCU to give the corresponding -keto sulfide, which could be easily transfonned into the a-methylene ketone via sulfide oxidation to sulfoxide, followed by pyrolytic elimination (Scheme 23). 

Potassium ert-butoxide, sodium hydride, butyllithium have all been used for this purpose. The alkyl(aryl)sulfanylcarbene (carbenoid) thus generated undergoes addition, often effectively, across the double bond of alkenes, enol ethers, ketene acetals and enamines. The use of chloromethyl phenyl sulfide, oxirane, tetraethylammonium bromide as a catalyst and an alkene gave phenylsulfanylcyclopropanes in rather low yield. For the synthesis of l,l-dimethyl-2-phenylsulfanylcyclopropane, see Houben-Weyl, Vol.4/3, p250 and of endoj exo-7-phenylsulfanylbicyclo[4.1.0]heptane, see Vol. E19b, pl691. 

Beilstein Handbook Reference) Acetophenone, 2-chloro- AI3-52322 BRN 0507950 Caswell No. 179C CCRIS 2370 Chemical mace Chloroacetophenone a-Chloroacetophenone 1-Chloroacetophenone 2-Chloro-1-phenylethanone 2-Chloroacetophenone Chloromethyl phenyl ketone CN CN (lacrimator) EINECS 208-531-1 EPA Pesticide Chemical Code 018001 Ethanone, 2-chloro-1-phenyl- HSDB 972 Mace (lacrimator) NCI-C55107 NSC 41666 ra-Chloroacetophenone Phenacyl chloride Phenacylchloride Phenylchloromethylketone UN1697. Pharmaceubcal intermediate. A lachrymator, is the primary component of Mace, a riot-control gas. Plates, mp = 56.5° bp = 247° d n 1,324 insoluble in H2O soluble in MezCO, petroleum ether, very soluble in EtOH, EtzO, C6H6, CS2 LDso (rat ori) = 127 mg/kg. Janssen Chimica Lancaster Synthesis Co. Penta Mfg. 

Chlorophenyl phenyl ether Bis(chloromethyl) ether Arsenic... 

Chloromethyl ketones, 94-95 Chloromethyl methyl ether, 387 Chloromethyl methyl sulfide, 94 Chloromethyl phenyl sulfide, 94 Chloromethyl phenyl sulfoxide, 94-95 2-ChIoro-l-methylpyridinium iodide, 95-96... 

A high-temperature-stable polyimide occurs from the reaction of pyromellitic anhydride with aromatic diamines such as p,p-diaminodi-phenyl ether. Pyromellitic acid is produced either by direct oxidation of 1,2,4,5-tetramethyl benzene (Durol) or from xylylene. The xylylene mixture is chloromethylated. Crystalline l,3-dimethyl-4,6-di(chloromethyl)-benzene (I) is separated from the two liquid isomers (II) and (III) and oxidized to pyromellitic acid with HNO3 ... 

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. 

In order to prepare the strong- or weak-base anion-exchange resins, the styrene-divinylbenzene copolymers are reacted with chloromethyl methyl ether, which converts the phenyl residues into benzyl chloride groups that are subsequently allowed to react with either secondary or tertiary amines. The chloromethyl groups supposedly become attached to the 4-position in the phenyl residues. Trimethylamine (Dowex-1, Amberlite IRA 400) and di-methylethanolamine (Dowex-2, Amberlite 410) are typical of the tertiary amines used in the preparation of commercial resins. The quaternary ammonium ion-exchange resins are highly ionized and can be used over the entire pYl range (14). 

The second order nature of quaternization reactions in our system was confirmed by rate studies on model compounds. Although benzyl chloride is usually selected as the model for chloro-methylated polymers , we chose to synthesize a difunctional model that would be sensitive to neighboring group effects. Condensation of 4-chlorophenyl phenyl sulfone with the disodlum salt of bis-phenol-A yielded an excellent model for the polysulfone segment, Quantitative chloromethylation of with a chloromethyl methyl ether/ methyl acetate mixture in the presence of stannic chloride afforded the corresponding bischloromethyl adduct,... 

Reactions of Enolates and Enolate Equivalents.—Several papers have appeared on the use of enolates released from silyl enol ethers by Lewis acids. Fleming reports the regiospecific alkylation of either the thermodynamic or the kinetic silyl enol ethers with chloromethyl phenyl sulphide in the presence of titanium(iv) chloride. Oxidative or reductive removal of the sulphur gives a-methylene- or a-methyl-ketones respectively (Scheme 69). ... 

Some typical results are shown in Table 1. Polymers are soluble in organic solvents such as benzene, toluene, THF and chlorinated hydrocarbons. The IR spectrum of these polymers displays characteristic absorption bands at 1640 cm (C=C stretching), 1600 and 1500 cm"l (phenyl ring vibrations), 1235 cm" (phenyl ether stretching) and 1015 cm (aliphatic ether stretching). The NMR spectrum of these polyethers recorded in CDCl at room temperature exhibits multiplets between 7.20 and 6.67 ppm (aromatic protons) and peaks at 6.02 ppm (-CH=CH-), at 4.50 ppm (-CH -0) and 1.60 ppm (-CH ). A small peak is observed at 4.05 ppm which can be attributed to the protons of the chloromethyl end groups. This peak is absent in the spectrum of sample 6 (Table 1). 

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