Dichloro-dimethyl ether

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

Pyridine-4-aldoxime bis-Chloromethyl ether a,a-Dichloro-dimethyl-ether... 

Experiment 5.71 DICHLOROMETHYL METHYL ETHER (1,1-dichloro-dimethyl ether)... 

Synonym BCME, Bis-CME, chloro(chloromethoxy)methane, dichloromethylether, (dichloro-dimethyl)ether, sym-dichloromethyl ether, oxybis(chloromethane)... 

Use of 1 mole of Cl2 in the liquid phase (CC14 solution or chloromethyl methyl ether) leads to l,l -dichloro- and 1,1-dichloro-dimethyl ether in the... 

SYNONYMS BCME, chloro-methyl-ether, sym-dichloro-dimethyl-ether, oxy-bis(chloromethane). 

Benzoic anhydride treated with a little ZnGl2 then dropwise with 0.625 mole a,a-dichloro-dimethyl ether, and heated 2 hrs. at 70-100° benzoyl chloride. Y 98%.—Similarly from p-toluenesulfonic acid monohydrate with 2.5 moles a,a-dichlorodimethyl ether p-toluene-sulfonyl chloride. Y 92,5%. F. e., also from carboxylic acids and alkali carboxylates, s. A. Rieche and H. Gross, B. 92, 83 (1959). 

Benzaldehyde treated with a little ZnClg then with 1.25 moles a,a-dichloro-dimethyl ether, and heated 2 hrs. at 95-100° a,a-dichlorotoluene. Y 97 %. F. e. and reactions... 

A mixture consisting of 22.7 g potassium o-bromobenzoate, 16.6 g 2,6-dichloro-3-methvlani-line, 12 ml N-ethylmorpholine, 60 ml diethylene glycol dimethyl ether, and 1.0 g anhydrous cupric bromide is heated in a nitrogen atmosphere at 145 C to 155°C for 2 hours. The reaction mixture is diluted with 60 ml diethylene glycol dimethyl ether and acidified with 25 ml concentrated hydrochloric acid. The acidic mixture is diluted with 100 ml of water and the liquid phase decanted from the insoluble oil. The insoluble oil is stirred with methanol and the crystalline N-(2,6-dichloro-3-methylphenyl)anthranilic acid which separates is collected and washed with methanol. The product, after recrystallization from acetone-water mixture melts at 248 C to 250°C. 

Synthesis By condensation of 2-bromobenzoic acid with 2,6-dichloro-3-methylaniline by means of CuBr2 in diethyleneglycol dimethyl ether containing N-ethylmorpholine, and heating at 145-155 °C (Scherrer and Short (Parke Davis), 1961 1967) Juby et al., 1968 Arrigoni-Martelli, 1978b Kleemann et al., 1999). 

Combinations of metal halides (e. g. FeCl3, A1C13) with compounds containing an active halogen atom (e. g. a-chloro-dimethyl ether, benzyl chloride, 2,3-dichloro THF). 

Activated aromatic compounds are also alkylated by 3,3-dichloro-l,2-di-phenylcyclopropene in a less usual type of reaction in the presence of boron trifluoride etherate, resorcinol dimethyl ether, for instance, gives l-(2,4-di-methoxyphenyl)-2,3-diphenylpropylium fluoroborate 540... 

Butanediol t-Butyl methacrylate Cellulose acetate propionate Chromic acid Cocamine Copper nitrate (ic) Cl 1-15 pareth-7 Cl 1-15 pareth-9 Cl 1-15 pareth-12 Cyclodextrin 3-Cyclodextrin 1,3-Dichloro-2-propanol Dicocamine Diethylene glycol dimethyl ether DImethylaminopropylmethacrylamide Dimethyl terephthalate ElemI gum Feldspar Furfuryl alcohol Gilsonite Glycerin Hexamethylenediamine Hydroxymethyl dioxoazabicyclooctane N-(2-Hydroxypropyl) benzenesulfonamide Hydroxypropyl-a-cyclodextrin Hydroxypropyi-P-cyclodextrin Hydroxypropyl-y-cyclodextrin Hydroxystearic acid Isobornyl methacrylate Lead... 

Open computer molecular models for dimethyl ether, dimethylacetylene, and OT-l,2-dichloro-l,2-difluoroethene from the 3D Molecular Models section of the book s website. By interpreting the computer molecular model for each one, draw (a) a dash formula, (b) a bond-line formula, and (c) a three-dimensional dashed-wedge formula. Draw the models in whatever perspective is most convenient—generally the perspective in which the most atoms in the chain of a molecule can be in the plane of the paper. 

Dehalo nation rranains popular as a route to fluoro-olefins. 2,3-Dichloro-trifluoropropionic esters may be dechlorinated by zinc, activated with HgCl, in polyethylene ycol dimethyl ethers. 1,2-Difluoro- and l-cbloro-2> iluoro[18]annuIenes have been prepared by the route starting from the cyclo-octatetraene dimer (11) shown in Scheme 7. They show temperature-... 

The following liquids may be used (boiling points are given in parentheses) — chlorobenzene (132-3°) bromobenzene (155°) p cymene (176°) o-dichloro-benzene (180°) aniline (184°) methyl benzoate (200°) teti-alin (207°) ethyl benzoate (212°) 1 2 4-trichlorobenzene (213°) iaopropyl benzoate (218°) methyl salicylate (223°) n-propyl benzoate (231°) diethyleneglycol (244°) n-butyl benzoate (250°) diphenyl (255°) diphenyl ether (259°) dimethyl phth ate (282°) diethyl phthalate (296°) diphenylamine (302°) benzophenone (305)° benzyl benzoate (316°). 

The addition of nucleophiles to cyclic fluoroolefins has been reviewed by Park et al. [2 ]. The reaction with alcohols proceeds by addition-elimination to yield the cyclic vinylic ether, as illustrated by tlie reaction of l,2-dichloro-3,3-di-fluorocyclopropene Further reaction results in cyclopropane ring opening at the bond opposite the difluoromethylene carbon to give preferentially the methyl and ortho esters of (Z)-3-chloro-2-fluoroacrylic acid and a small amount of dimethyl malonate [29] (equation 8). 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

To a mixture of vinyl bromide (40 mmol) and the catalyst dichloro-[(R)-Af,N-dimethyl-l-[(.S)-2-(diphenylphosphino)ferrocenyl]ethylamine]-palladium(n) (0.2 mmol) was added an ethereal solution of [a-(trimethyl-silyl)benzyl]magnesium bromide (0.6-1 m, 80 mmol) at —78 °C. The mixture was stirred at 30 °C for 4 days, and then cooled to 0 °C and hydrolysed with dilute aqueous HC1 (3 m). The organic layer was separated, and the aqueous layer was re-extracted with ether. The combined organic extracts were washed with saturated sodium hydrogen carbonate solution and water, and dried. Concentration and distillation gave the chiral allylsilane (79%, 66% ee), b.p. 55°C/0.4mmHg. 

Dibromoborane-Dimethyl sulfide, 92 Dichloro(dimethylamino)borane, 120 Diisobutylaluminum hydride-Boron trifluoride etherate, 116 Diisopinocampheylborane, 117, 182 Diisopinocampheylmethoxyborane, 86 Dimesitylmethylborane, 8 Dimethoxy[l-trimethylsilyl-l,2-buta-dienyl]borane, 218 (R,R)- and (S,S)-frans-2,5-Dimethyl-borolanes, 119... 

In a two-phase system similar to that used by Price, Stamatoff (29) obtained from 2,6-dichloro-4-bromophenol a branched polymer having approximately the statistical ratio of ortho and para ether linkages. When the reaction was carried out using the anhydrous salt of the phenol in the presence of highly polar aprotic solvents, such as dimethyl sulfoxide, the product was the linear poly(2,6-dichlorophenylene oxide) (Reaction 23). 

To a magnetically stirred solution of bromobis[2,3-butanedione dioximato(l-)]-(dimethyl sulfide)cobalt(III) (8.6 g, 0.02 mole) (see above) and dry dichloro-methane (100 mL) in a 500-mL round-bottomed flask is added 3.4 mL of 4-tert-butylpyridine (4-rm-bupy) (3.1 g, 0.02 mole). After the solution is stirred for 1 hour, the solvent is removed under reduced pressure, keeping the temperature below 25°. The resulting brown residue is triturated with diethyl ether, and the solid is collected by suction filtration and washed with additional diethyl ether. The brown powder is then stirred in 100 mL of water for 10 minutes, isolated by filtration, washed well with water, and air dried to give 9.2 g of bromobis-[2,3-butanedione dioximato(l-)] (4-rm-butylpyridine)cobalt(III) (yield is typically 90%). Anal. Calcd. for C17H27BrNs04Co C, 40.49 H, 5.40 N, 13.89 Br, 15.85. Found C, 40.51 H, 5.55 N, 14.06 Br, 16.00. 

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