Ethoxyethyl Bromide

Submitted by George C. Harrison and Harvey Diehl. Checked by R. L. Shriner and C. H. Tileord. 

In a 2-1. three-necked flask, fitted with a mechanical stirrer (Note 1), a reflux condenser, and a dropping funnel, is placed 630 g. (670 cc., 7 moles) of /3-ethoxyethyl alcohol (Note 2). The stirrer is started, and 600 g. (210 cc., 2.2 moles) (Note 3) of phosphorus tribromide is added from the dropping funnel over a period of one and one-half to two hours. The temperature is permitted to rise until the reaction mixture refluxes gently. 

The mixture is then distilled, and the distillate boiling below 150° is collected in a 2-1. flask containing 11. of water. The lower layer of crude /3-ethoxyethyl bromide is separated and dried over 10 g. of calcium chloride. The liquid is decanted and distilled through a 25-cm. fractionating column, and the fraction boiling at 125-127°/760 mm. is collected (Note 4). The yield of pure product is 660-670 g. (65-66 per cent of the theoretical amount based on the phosphorus tribromide). 

A rubber sleeve lubricated with a drop of oil provides an effective seal for the stirrer. 

Technical /3-ethoxyethyl alcohol is marketed commercially as Cellosolve it should be dried over calcium oxide and distilled. 

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Ethoxyethyl cyanide has been prepared by the action of potassium cyanide on /3-ethoxyethyl bromide.1... 

Ethoxyethyl bromide has been prepared by the action of sodium ethoxide upon ethylene bromide s by the action of bromine upon /3-ethoxyethyl iodide and by the procedure adopted here, which was first used by Chalmers.4 The action of sodium bromide and sulfuric acid on /3-ethoxyethyl alcohol cleaves the ether linkage. 

Ethane, 1-bromo-2-ethoxy-, 23, 32 Ethanolamine, 26, 38 Ethanol, 2-isopropylamino-, 26, 38 Ether, anhydrous, 22, 57 Ether, butyl o-nitrophenyl, 25, 9 /3-Ethoxyethyl alcohol, 23, 32 /3-Ethoxyethyl bromide, 23, 32, 33 /3-Ethoxyethyl cyanide, 23, 33 Ethoxymagnesiomalonic ester, 25, 73 2-Ethoxy-1-naphthaldehyde, 20,11 6-Ethoxy-8-nitroquinoline, 27, 52 /3-Ethoxypropionaldehyde acetal,... 

RC = CCH,X — RCX = C==CH,. /S.y- and 7,S-Acetylenic alcohols can be transformed to the halides in better yields by an alternative procedure, which consists in their esterification with p-toluenesulfonyl chloride and subsequent cleavage of the ester by the action of sodium iodide, lithium chloride, or calcium bromide in an appropriate solvent (60-90%). Halo ethers are prepared by the action of phosphorus tribromide on hydroxy ethers, as in the preparation of /3-ethoxyethyl bromide (66%). In a similar manner, /3-halo esters have been prepared without appreciable dehydration of the /3-hydroxy ester (40-60%). The reaction of cyanohydrins leads to a-halo nitriles. Treatment of 2-nitro-l-propanol with phosphorus pentachloride gives l-chloro-2-nitropropane (47%). ... 

The use of thiazolium salts enables the benzoin condensation to proceed at room temperature. It can also be performed in dipolar aptotic solvents or under phase transfer conditions. Thiazolium salts such as vitamin Bi, thiazolium salts attached to y-cyclodextrin, macrobicyclic thiazolium salts, thiazolium carboxylate, ° naphtho[2,l-d]thiazolium and benzothiazolium salts catalyze the benzoin condensation and quaternary salts of 1-methylbenzimidazole and 4-(4-chlorophenyl)-4//-1,2,4-triazole are reported to have similar catalytic activity. Alkylation of 2-hydroxyethyl-4-methyl-l,3-thiazole with benzyl chloride, methyl iodide, ethyl bromide and 2-ethoxyethyl bromide yields useful salts for catalyzing 1,4-addition of aldehydes to activated double bonds. Insoluble polymer-supported thiazolium salts are catalysts for the benzoin condensation and for Michael addition of aldehydes. Electron rich al-kenes such as bis(l,3-dialkylimidazolidin-2-ylidenes) bearing primary alkyl substituents at the nitrogen atoms or bis(thiazolin-2-ylidene) bearing benzyl groups at the nitrogen atoms are examples of a new class of catalyst for the conversion of ArCHO into ArCHOHCOAr. 

According to a procedure detailed in Organic Syntheses,931 2-ethoxyethyl bromide is obtained from 2-ethoxyethyl alcohol and PBr3 without addition of pyridine, the temperature being raised gradually to the boiling point, but appreciable amounts of ethyl bromide are also formed. 

Ether, butyl is-nitrophenyl, 25, 9. /3-Ethoxyethyl alcohol, 23, 32 (S-Ethoxyethyl bromide, 23, 32, 33 (3-Ethoxyethvl cyanide, 23, 33 Ethoxymagnesiomalonic ester, 25, 73... 

The coupling of Grignard reagents and alkyl halides is dramatically enhanced when the latter possesses proximate functionality capable of com-plexation, and hence of transition-state stabilization whereas neither n-pentyl nor ethoxyethyl bromide react with iodomagnesium phenylacetylide, the bromide (196) does. ... 

Cecolene, see Trichloroethylene Cekiuron, see Diuron Cekubaryl, see Carbaryl Cekusan, see Dichlorvos Celanex, see Lindane Celfume, see Methyl bromide Cellon, see 1,1,2,2-Tetrachloroethane Cellosolve, see 2-Ethoxyethanol Cellosolve acetate, see 2-Ethoxyethyl acetate Cellosolve solvent, see 2-Ethoxyethanol Celluflex DOP, see Di-rr-octyl phthalate Celluflex DPB, see Di-rr-butyl phthalate Celluflex TPP, see Triphenyl phosphate Celluphos 4, see Tributyl phosphate Celmide, see Ethylene dibromide Celthion, see Malathion... 

EDC, see 1,2-Dichloroethane Edco, see Methyl bromide Effusan, see 4,6-Dinitro-o-cresol Effusan 3436, see 4,6-Dinitro-o-cresol EGBE, see 2-Butoxyethanol EGEE, see 2-Ethoxyethyl acetate Egitol, see Hexachloroethane... 

Ethoxyethyl)-5-hydroxy-2-methylpyrazine heated in acetic acid saturated with hydrogen bromide formed a crystalline bromine-containing compound which with 5% sodium carbonate gave 5-hydroxy-2-methyl-3-vinylpyrazine (248). Heteromacrocyclic ethers have been quaternized (989). 

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