Trimethylene chlorobromide

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. ... 

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-... 

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. 

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. 

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... 

Trimethylene chlorobromide, b257 Trimethylene chlorohydrin, c214 Trimethylenediamine, pi 93 Trimethylene dibromide, d93... 

Adipic acid is more conveniently prepared by the following method, from y-chlorobutyronitrile (C1.CH2, CH2.CH2.CN), which is itself prepared from trimethylene chlorobromide as follows ... 

To a hot solution of potassium cyanide (80 gms.) dissolved in 125 gms. of water, hot 96 per cent, alcohol is added (500 c.c,), and to this clear, hot mixture, trimethylene chlorobromide (200 gms.) is added the whole is then boiled for 1 hours on the water-bath under a reflux condenser, The alcohol is next distilled off, and carries with it most of the unchanged trimethylene chlorobromide, Water is then added to the residue in the flask to dissolve potassium salts, and the oily layer is distilled after drying over calcium chloride. After two or three fractionations the portion boiling at 192°—205° is taken as y-chloro-butyronitrile. B.p. 195°—197°. Yield, 50 per cent. 

SYNS 3-BROMOPROPYL CHLORIDE 1,3-CHBP (0-CHLOROBROMOPROPANE l-CHLORO-3-BROMOPROPANE pOT) 3-CHLOROPROPYL BROMIDE TRIMETHYLENE BROMIDE CHLORIDE TRIMETHYLENE CHLOROBROMIDE... 

Halo amines are formed by these procedures. Partial amination of trimethylene chlorobromide with diethylamine yields l-diethylamino-3 ... 

Trimethylene Chlorobromide 111-20-6 Sebacic Acid 112-80-1 Oleic Acid... 

Trimethyl-l,3-dioxane, 693 2,l -Trimethylenebenzanthrone-10,1028 Trimethylene chlorobromide, 1069 Trimethylene chlorohydrin, 733 Trimethylene dibromide, 412,1069 THmethylene oxide, 1232... 

---