3-Bromo-3-phenyl methyl ether

All the following have been called X-gas di-bromo(di)methyl ether, methylsulphuryl chloride, dibromomethyl ether, dichloromethyl ether, ethyl dibromoarsine, phenyl dibromoarsine, ethyl bromoacetate. 

A mixture of 14.91 g (135.324 mmol) of thiophenol and 5.5 g (137.5 mmol) of NaOH in 100 ml acetone was heated at reflux for 2.5 h and then treated dropwise with a solution of 20 g (134.19 mmol) of l-bromo-3-methyl-2-butene in 20 ml acetone. This solution was refluxed for 40 h and then stirred at room temperature for 24 h. Solvent was then removed in vacuo, the residue taken up in water, and extracted with 3 times 50 ml ether. Ether extracts were combined and washed with 3 times 30 ml of 5% NaOH solution, then water, saturated NaCI solution and dried. Solvent was then removed in vacuo and the residue further purified by kugelrohr distillation (80°C, 0.75 mm) to give the phenyl-3-methylbut-2-enylsulfide as a pale yellow oil. 

Methane, bromo-, 55,63 Methane, (4-fert-butylphenyl)-phenyl-[Methane, 4-(l,l-dimethylethyl)-phenyl-phenyl-1,55,11 Methane, iodo-, 55, 3 Methane, iodo-, hazard note, 55,134 Methane, (4-isopropylphenyl)-phenyl- [Methane, (4-( l-methylethyl)phenyl>phen-yl-l,55,ll Methane, nitio-, 55, 78 Methane, triphenyl-, 55,11 Methanesulfonyl chloride, 55, 116, 120 Methyl chloride, diphenyl- [Methane, chlo-rodiphenyl-],55, 94 Methyl ether, chloromethyl- [Methane, chloro-methoxy-], 55,94... 

A solution of N-(2-aminobenzvl)-1-phenyl-2-metKylaminoethanol-1 was prepared by the reaction of a-bromo-acetophenone and (2-nitrobenzyl)methylamine, followed by hydrogenation of the nitro group by means of nickei on diatomaceous earth at room temperature and reduction of the CO group by means of sodium borohydride. The intermediate thus produced was dissolved in 100 ml of methylene chloride and introduced dropwise into 125 ml of sulfuric acid at 10° to 15°C. After a short standing, the reaction mixture was poured onto ice and rendered alkaline by means of a sodium hydroxide solution. Dy extraction with ether, there was obtained 1,2,3,4-tetrahydro-2-methyl-4-phenyl-8-amino-iso-quinoline. The base is reacted with maleic acid to give the maleate melting point of the maleate 199° to 201°C (from ethanol). 

Pyridone IV was converted to its sodium salt by treatment with an equimolar amount of sodium methoxide in methanol (see procedure below under formation of the 3-phenyl-2(lH)pyridone sulfonates). The sodium salt was next treated with the methyl ester of a-bromo-p-toluic acid, obtained by treatment of the acid with BF3 etherate. 

A flask was charged with 4-bromo-iodobenzene (0.079 mol), 4-methoxy-2-methyl-phenyl boronic acid (0.087 mol), palladium acetate (0.004 mol), and triphenyl phosphine (0.008 mol) and then treated with 200 ml acetone and 250 ml 2M NaHCO i. The mixture was refluxed at 65°C for 18 hours and was then treated with water and diethyl ether and the organic layer isolated. This layer was washed with 40 ml saturated sodium chloride solution and water, dried over MgSC>4, filtered, and concentrated. The residue was purified by column chromatography using silica gel with CH2C12/ hexane, 1 1, and then recrystallized in / , 7 3, respectively, and 16.4 g of product isolated. 

S)-1-Phenyl-3-methyl-1-pentene. Freshly distilled benzalde-hyde (53 grams, 0.5 mole) was added slowly (2 hrs) at 0°C to a solution in ethyl ether (400 ml) of a Grignard reagent prepared from ( + )(S)-1-bromo-2-methylbutane [75.5 grams, 0.5 mole) [ ]D25 + 3.968, op 97.2% (20)] and Mg (12 grams). 

A mixture of the crude oil of methyl 2-bromo-3- 4-[2-(5-ethyl-2-pyridyl)ethoxy]phenyl propionate (73.0 g) thiourea (14.2 g), sodium acetate (15.3 g) and ethanol (500 ml) was stirred for 3 hours under reflux. The reaction mixture was concentrated under reduced pressure, and the concentrate was neutralized with a saturated aqueous solution of sodium hydrogencarbonate, to which were added water (200 ml) and ether (100 ml). The whole mixture was stirred for 10 min to yield 5- 4-[2-(5-ethyl-2-pyridyl)ethoxy]benzyl -2-imino-4-thiazolidinone as crystals (0.3 g, 523.0%). Recrystallization from methanol gave colorless prisms, melting point 187°-188°C, dec. 

Diasteriomers were isolated by reacting the Step 5 product mixture with (—)-8-phenylmenthol chloroformate. The diasteriomers were separated by flash chromatography over silica gel using chloroform/hexanes/diethyl ether (3 2 1), and (lS,2R,5S)-5-methyl-2-(l-methyl-l-phenylethyl)-cyclohexyl-9-(3-bromo-4-fluoro phenyl)-8-oxo-2,3,5,7,8,9-hexahydro-4H-pyrano[3,4-b]thieno[2,3-e]pyridine-4-carboxylate 1,1-dioxide isolated (3). 

Two grams of 4-bromo-l-phenyl-2 3-dimethyl-5-pyrazolon.e (1 mol.) and 10 5 grams of mercuric acetate (4 mols., 90 percent.) are heated for tliirty minutes in an oil-bath at 160° C. The melt is cooled, extracted with alcohol, the solution boiled with charcoal, filtered, and treated with ether. The white precipitate is filtered, washed with ether, and dried. It is a hygroscopic substance, readily soluble in cold water, less soluble in methyl or ethyl alcohol faintly acidified with acetic acid. It decomposes with gas evolution at 225° C., and is unaffected by ammonium sulphide unless boiled. From its aqueous solution sodium chloride precipitates an insoluble chloride and sodium hydroxide the corres X)nding hydroxide. 

Photoformylation (the photo-Riemer-Tiemann reaction) of phenols (phenol, 2-methyl, 3-methyl, 4-methyl, 4-chloro, 4-bromo, 4-nitro and 4-phenyl phenol) has also been studied by irradiation in chloroform with KOH and pyridine. The yields reported are variable but formylation is reported only to occur in the 2-position ° °. This process involves the addition to phenol of radicals produced from chloroform. An electron transfer mechanism (transfer from excited state phenol to chloroform) is thought to be involved. The radical ion pair eliminates HCl and combination affords the products 232-234 (Scheme 26). The principal product is the ether and this undergoes partial conversion to the formate. The other products formed in low yield are the aldehydes . In another application of the photo-Riemer-Tiemann reaction, this time in cyclodextrin, the phenols can be converted into 4-hydroxybenzaldehydes with high selectivity . ... 

The ambident enophilic character of the resultant 3-aryl-5-bromo-2-pyrone 81 was demonstrated by the easy cycloadditions of 3-phenyl-5-bromo-2-pyrone 94 (Scheme 28) with both methyl acrylate (MA) and benzyl vinyl ether (BVE), affording the corresponding cycloadducts 95 and 96 in good yields with varying endo/exo selectivity. 

A series of 5-substituted-3-bromo-2-pyrones can be thus readily synthesized as summarized in Figure 3. The resultant 2-pyrones are expected to be potent ambident dienes as exemplified by the cycloadditions of 5-phenyl-3-bromo-2-pyrone with methyl acrylate and benzyl vinyl ether (Scheme 34). 

Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organics in the environment. A number of compounds of the chloroanisoles, bromoani-soles, and bromo-chloroanisoles have been detected in the marine atmosphere,67 in marine and freshwater fish,68 in oysters,69 in effluents of municipal wastewater treatment plants,70 and in sediments.71... 

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