Chlorobromides

Acetylene derivs. via dihalides Terminal acetylene derivs. via 1,1-chlorobromides... 

Carbon tetrachloride Ethylene chloride. Trichloroethylene. Propylene chloride. Ethylene chlorobromide 1 1 2-Trichloroethane Trimethylene chloride Tetrachloroethylene Trimethylene chlorobromide sym. Tetrachloroethane 1 4 Dichlorobutane 1 2 3-Trichloropropane Pentachloroothane. ... 

Other Bromomethanes. Bromochloromethane [74-97-5] (methylene chlorobromide), CH2BrCl, is a clear, colorless Hquid with a characteristic sweet odor and very low freezing point, —88.0°C. Its properties include bp, 68.1°C 1.9229 g/mL 1.4808 heat of vaporization at bp, 232 J /g... 

A mixture of 66.5 g. (0.5 mole) of tetrahydroquinoline and 400 g. of trimethylene chlorobromide (Note 1) is placed in a 1-1. round-bottomed flask attached to a reflux condenser, and heated in an oil bath held at 150-160° for 20 hours (Note 2). The reaction mixture is cooled, a solution of 50 ml. of concentrated hydrochloric acid in 500 ml. of water is added, and the excess trimethylene chlorobromide is removed by distillation with steam (Note 3). The acid residue from the steam distillation is made alkaline with a 40% solution of sodium hydroxide (about 75 ml.), and the julolidine is extracted with two 150-ml. portions of ether. The ethereal solution is washed with ISO ml. of water and dried over sodium hydroxide pellets. The ether is evaporated and the residue distilled under reduced pressure. The portion that boils at 105-110°/ mm. is collected (Notes 4 and 5). The yield is 67-70 g. (77-81%). 

The tetrahydroquinoline and trimethylene chlorobromide were Eastman grade materials of the Eastman Kodak Company. 

The trimethylene chlorobromide recovered may be dried over calcium chloride and used in a subsequent run. 

Julolidine has been prepared by the reaction of trimethylene chlorobromide with formanilide, aniline, methylaniline, and tetrahydroquinoline by the reduction of 8,10-diketojuloli-... 

Tetramethylene chlorohydrin may be converted to the chlorobromide in excellent yields by the action of phosphorus tribromide. ... 

As described In U.S. Patent 3,023,146, in a round-bottomed flask were placed 35 g of 2-propionyl phenothiazine (0.14 mol) 7 g of 50% sodium hydride in mineral oil (0.14 mol), and 240 cc of dimethyl formamide dried over sodium hydride. The resultant solution was stirred at room temperature for 2 hours, and then 88 g (0.56 mol) of trimethylene chlorobromide wes added at once. 

The mixture was stirred for 2 hours, heated at 60° to 70°C for 1 hour and poured into 2 liters of H O. The resulting suspension was extracted with ether, the ether layer separated and the ether removed under vacuum. A gummy mass remained which was dissolved in decalin and the solution was partly distilled to remove excess chlorobromide. After removal of most of the decalin under vacuum, the residue was treated with a large excess of N-( -hydroxyethyl)-piperazine and heated on a steam bath for 2 hours. This material was extracted with dilute aqueous HCI, this acid layer neutralized with aqueous base and the resulting oil extracted into ether. The ether layer was washed with water until the washings were neutral and dried over anhydrous potassium carbonate. On treatment with maleic acid in ether a yellow solid separated which was recrystallized from isopropanol. This yellow solid had MP 175° to 177°C. 

In a 2-1. three-neck, round-bottom flask, fitted with a stirrer, a reflux condenser and a separatory funnel are placed 82 g. (1.2 moles) of potassium cyanide (95 per cent) (Note 1) and 100 cc. of water. The mixture is warmed and stirred until the cyanide is completely dissolved. To this solution is added 350 cc. of 95 per cent alcohol, followed by 158 g. (1 mole) of trimethylene chlorobromide (Note 2), and the mixture is heated under a reflux condenser (best on a water bath) with stirring for about one and one-half hours. 

After two or three distillations the yield of pure product boiling at 93-96V26 mm. (Notes 4 and 5) is 42-49 g. (60-70 per cent of the theoretical amount based on the chlorobromide used, or 40- 47 per cent based on the total amount of chlorobromide taken). (Notes 5 and 6.)... 

The trimethylene chlorobromide used boiled at 142-1470. It may be prepared in 75-85 per cent yields from trimethylene chlorohydrin (p. 112) by the general method for the preparation of alkyl bromides described in Org. Syn. 1,1. 

The lower boiling fraction is mainly unchanged trimethylene chlorobromide and amounts to 15-20 g. It may be refractionated or used directly in a subsequent run. The high boiling residue is mainly trimethylene cyanide. If the residues from several runs are combined and redistilled an average of 6-7 g. per run of product boiling at 160-165°/26 mm. is obtained. 

Trimethylene bromohydnn, 1, 11 Tnmethylene chlonde, 8, 113 Trimethylene chlorobromide, 8, 52... 

Trimethylene chlorobromide can be obtained commercially. Material boiling at 141-1427755 mm., ng 1.4843, was used. 

Diethyl 1,1-cyclobutanedicarboxylate has been prepared by the alkylation of diethyl sodiomalonate with trimethylene dibromide 8i4>6 7 or with trimethylene chlorobromide 6-8 and by the peroxide-catalyzed addition of hydrogen bromide to diethyl allylmalonate followed by intramolecular alkylation.9 The procedure described here is that of Mariella and Raube.6... 

Human toxicity values have not been established or have not been published. However, based on available information, this material appears to be more toxic than either methylene chloride or methylene chlorobromide. It is carbon monoxide in the body. 

Synonyms AI3-15514 BRN 1730801 Bromomethyl chloride CB CBM CCRIS 817 Chlorobromomethane Chloromethyl bromide EINECS 200-826-3 Fluorocarbon 1011 Halon 1011 Methylene chlorobromide Mil-B-4394-B NSC 7294 UN 1887. 

Methylenebis(oxy) ]bis(2-chloroformaldehyde), see Bis (2-chloroethoxy) methane Methylene chlorobromide, see Bromochloromethane Methylene dichloride, see Methylene chloride Methylene dimethyl ether, see Methylal Methyl 2,2-divinyl ketone, see Mesityl oxide Methylene glycol, see Formaldehyde Methylene glycol dimethyl ether, see Methylal Methylene oxide, see Formaldehyde Methyl ethanoate, see Methyl acetate (1 -Methylethenyl)benzene, see a-Methylstyrene Methyl ethoxol, see Methyl cellosolve 1-Methylethylamine, see Isopropylamine (l-Methylethyl)benzene, see Isopropylbenzene Methylethyl carbinol, see sec-Bntyl alcohol Methyl ethylene oxide, see Propylene oxide ds-Methylethyl ethylene, see cis-2-Pentene frans-Methylethyl ethylene, see frans-2-Pentene Methyl ethyl ketone, see 2-Bntanone Methylethylmethane, see Butane... 

Reaction with phosgene yields carbonyl bromide and aluminum chlorobromide ... 

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