Methyl, alcohol phenyl ether

Acetophenone. Acetophenone [98-86-2] (methyl phenyl ketone) is a colorless Hquid that forms laminar crystals at low temperature (mp 20°C). It has a characteristic sweet orange blossom odor, and is soluble in alcohols and ethers. It is found in nature in oil of casatoreum, obtained from beavers oil of labdanum, recovered from plants and in buds of balsam poplar. It can be prepared by the Friedel-Crafts reaction (qv) of acetyl chloride with benzene in the presence of aluminum chloride however, this route is of Htde commercial significance. 

The hydroperoxide process involves oxidation of propjiene (qv) to propylene oxide by an organic hydroperoxide. An alcohol is produced as a coproduct. Two different hydroperoxides are used commercially that result in / fZ-butanol or 1-phenylethanol as the coproduct. The / fZ-butanol (TBA) has been used as a gasoline additive, dehydrated to isobutjiene, and used as feedstock to produce methyl tert-huty ether (MTBE), a gasoline additive. The 1-phenyl ethanol is dehydrated to styrene. ARCO Chemical has plants producing the TBA coproduct in the United States, Erance, and the Netherlands. Texaco has a TBA coproduct plant in the United States. Styrene coproduct plants are operated by ARCO Chemical in the United States and Japan, Shell in the Netherlands, Repsol in Spain, and Yukong in South Korea. 

Hydroperoxide Process. The hydroperoxide process to propylene oxide involves the basic steps of oxidation of an organic to its hydroperoxide, epoxidation of propylene with the hydroperoxide, purification of the propylene oxide, and conversion of the coproduct alcohol to a useful product for sale. Incorporated into the process are various purification, concentration, and recycle methods to maximize product yields and minimize operating expenses. Commercially, two processes are used. The coproducts are / fZ-butanol, which is converted to methyl tert-huty ether [1634-04-4] (MTBE), and 1-phenyl ethanol, converted to styrene [100-42-5]. The coproducts are produced in a weight ratio of 3—4 1 / fZ-butanol/propylene oxide and 2.4 1 styrene/propylene oxide, respectively. These processes use isobutane (see Hydrocarbons) and ethylbenzene (qv), respectively, to produce the hydroperoxide. Other processes have been proposed based on cyclohexane where aniline is the final coproduct, or on cumene (qv) where a-methyl styrene is the final coproduct. 

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

Methyl-phenyl nitrosamine separates as a yellow oil, which solidifies on cooling (M.P. 12°—15°). 2 gms. methyl-phenyl nitrosamine are dissolved in 4 gms. ether and 8 gms. absolute alcohol which have been saturated with hydrochloric acid gas then added. After a time needles separate out which are filtered and washed with a mixture of alcohol and ether. 

To the cold ethereal diazomethane solution prepared from 10 g of nitro-somethylurea (about 2.8 g CH2N2, 0.067 mol volume 100 ml) was added a solution of benzalacetophenone 1 (14.5 g, 0.07 mol) in 150 ml of ether (Scheme A.8). Within 5 min a precipitate formed. After 1 h at — 14°C filtration yielded 13.5 g of the colorless 3-benzoyl-4-phenyl-A1-pyrazoline 2. Partial evaporation of the ether gave an additional 3 g of the material. The total yield, based on 13.5 g of benzalacetophenone (0.065 mol), was 100%. The material may be crystallized from methyl or ethyl alcohol, a mixture of ethyl acetate and petroleum ether, a mixture of chloroform and petroleum ether, or carbon tetrachloride. The best results were obtained using methyl alcohol. Melting point 92-93°C. 

The reverse reaction consisting of the PCL-catalyzed hydrolysis of the esters of three primary alcohols 2-methyl-3-phenyl-1-propanol 4, 2-phenoxy-l-propanol 5 and solketal 6 was studied by Kazlauskas et al.61 An enhancement of the enantioselectivity E was observed when changing the solvent from ethyl ether/phosphate buffer to 30% n-propanol in phosphate buffer and when changing the substrate from 1-acetate to 1-heptanoate. The same enhancement in E value was observed with 5 but there was no significant increase towards the alcohol 9. 

The phenyl-methyl-pyrazolon is then methyl by heating with the calculated amount of me iodide in methyl alcohol at 100°—150°, in a sealed 1 for one or two hoars. The hydriodide of antipy present in the contents, is decomposed by aqu< potash, and the antipyrine obtained is then cryi lised from toluene or ether. M.p. 114°. Yi about 10 gms. 

A mixture consisting of benzyl 4-(4-iodobutyl)phenyl ether (14.29 g), 2-(2-hydroxyethyl)imidazole (13.1 g), and K2C03 was stirred in 390 ml DMF 16 hours at 60°C, then cooled, filtered, and concentrated. The residue was dissolved in EtOAc, then washed with water, brine, and reconcentrated. The residue was purified by chromatography using EtOAc/methyl alcohol, 9 1-1 9, then recrystallized using EtOAc/methyl alcohol, and 10.99 g product isolated as colorless crystals, mp = 75—77°C. 

Nitrobenzyl alcohol (200 mmol) was hydrogenated over 1.0 g 10% palladium on carbon (50% water) in 500 ml methyl t-butyl ether. After absorption of hydrogen was completed the catalyst was removed by filtration and phenyl isocyanate (200 mmol) added to the filtrate at 15 °C over 30 minutes. The product was isolated by filtration in 89% yield. 

The thermal decomposition of diazo compounds in the presence of alcohols is a reliable method for the formation of methyl," benzhydryl,"" and phenyl ethers."" Dcdiazonialion of ben-zenediazonium tetrafluoroborate (15) in the presence of 2.2.2-trifluoroethanol gives exclusively ether 16 and fluorobenzene (17) in ca. 2 1 ratio."" ""... 

Terminal 1,3-dienes. Palladium(II) acetate combined with PiCsH,), is an effective catalyst for conversion of allylic acetates or allylic phenyl ethers into terminal dienes. Allylic methyl ethers or alcohols do not undergo this elimination. Example ... 

Methoxy thoxy) ethoxy ]> ethanol Acetophenone Methyl benzoate Phenyl acetate Methyl salicylate Benzyl methyl ether Phenethyl alcohol Dimet hylaniline Isoamyl propionate Isoamyl lactate Quinoline Indene... 

Antlpyrine = Dimethylox hinizine C H, fi—is obtained by heating metbyloxychinizine with methyl iociide and methyl alcohol in sealed vessels at lOO" (212° F.) the first-named substance having been previously obtained by the action of aoetylacetio ether upon phenyl hydrazine. 

Ethyl malonate Heptyl alcohol Phenyl acetate Benzyl methyl ether Phenetole Dimethylaniline... 

---