Trimethylene chloride

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. ... 

The portion boiling up to 5 5 °/10 mm., obtained after the second fractionation, was washed with concentrated sulfuric acid, then water, and finally dried and distilled. A certain amount of trimethylene chloride was sometimes obtained, boiling at 115-120° and amounting to about 30 per cent of the total fraction. 

The chlorohydrin contains a very small amount (less than 0.5 per cent) of water-insoluble material, which is probably trimethylene chloride and di- y-chloropropy 1 ether. 

Trimethylene bromohydrin, 1, 11 Trimethylene chloride, 8, 113 Trimethylene chlorobromide, 8, 52... 

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

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

Thionyl chloride Thiophosgene Titanium tetrachloride Trichloromethyl perchlorate Triformoxime trinitrate Trimethylacetyl chloride Trimethylene glycol diperchlorate Trimethylol nitromethane trinitrate... 

To obtain the trimethylene chlorohydrin, the distillate from this operation is heated for about one hour on a steam bath in order to drive out most of the excess hydrogen chloride. The distillate is then fractionated under reduced pressure (Note 3) in a modified Claisen flask (Org. Syn. 1, 40). The fractionating side arm should be 25 cm. in length. The fractions collected under 10 mm. are to 55°, 55-57°, 57-65°, 65-85°, 85-105°, residue. 

Trimethylene chlorohydrin cannot be distilled under atmospheric pressure without some decomposition. The fractionation can be carried out at ordinary pressures when the fractions collected are up to 1250, 125-158°, 158-164°, 164-190°, 190-210° and residue. This procedure is less desirable as some hydrogen chloride is evolved and the product turns dark on standing. 

The general plan of Organic Syntheses has been discussed in the prefaces of the previous volumes. In this volume are published two distinctly different methods of preparation for each of two compounds. The directions for producing /3-chloro-propionic acid first from acrolein and second from trimethylene chlorohydrin, and for producing trimethylacetic acid first from terJ-butyl chloride and second from pinacolone, have been included. This has been deemed advisable since in some countries one raw material is more readily available than the other. 

B. 2,2-(Trimethylenedithio)cyclohexanone. A solution of 3.02 g. (0.02 mole) of freshly distilled 1-pyrrolidinocyclohexene, 8.32 g. (0.02 mole) of trimethylene dithiotosylate4 (Note 2), and 5 ml. of triethylamine (Note 3) in 40 ml. of anhydrous acetonitrile (Note 4), is refluxed for 12 hours in a 100-ml., round-bottom flask under a nitrogen atmosphere. The solvent is removed under reduced pressure on a rotary evaporator, and the residue is treated with 100 ml. of aqueous 0.1 N hydrochloric acid for 30 minutes at 50° (Note 5). The mixture is cooled to ambient temperature and extracted with three 50-ml. portions of ether. The combined ether extracts are washed with aqueous 10% potassium bicarbonate solution (Note 6) until the aqueous layer remains basic to litmus, and then with saturated sodium chloride solution. The ethereal solution is dried over anhydrous sodium sulfate, filtered, and concentrated on a rotary evaporator. The resulting oily residue is diluted with 1 ml. of benzene and then with 3 ml. of cyclohexane. The solution is poured into a chromatographic column (13 x 2.5 cm.), prepared with 50 g. of alumina (Note 7) and a 3 1 mixture of cyclohexane and benzene. With this solvent system, the desired product moves with the solvent front, and the first 250 ml. of eluent contains 95% of the total product. Elution with a further 175 ml. of solvent removes the remainder. The combined fractions are evaporated, and the pale yellow, oily residue crystallizes readily on standing. Recrystallization of this material from pentane gives 1.82 g. of white crystalline 2,2-(trimethylenedithio)cyclo-hexanone, m.p. 52-55° (45% yield) (Note 8). 

Hydrogen sulfide is undesirable because its presence can lead to the formation of potassium p-toluenesulfinate. The latter can be formed by the desulfurization of thiotosylate by hydrogen sulfide generated in the reaction of potassium hydrosulfide with tosyl chloride. Attention should be directed toward control of the reaction temperature so that hydrogen sulfide is rapidly removed, thereby ensuing survival of the S—S bond of the thiotosylate. p-Toluenesulfinate ion can displace bromide to form stable sulfones which are less soluble in common solvents, such as benzene, than trimethylene dithiotosylate. Therefore, purification of the dithiotosylate contaminated with the sulfones is difficult to achieve by means of fractional recrystallization. 

D-4 1814 TMB-4 1,1 -trimethylene- 56-97-3 bis(4-formyl-pyridinium) bromide (bromide) (or chloride) dioxime 3613-81-9 trimedoxime 1,3-bis (chloride) (4-formylpyridinium)propane dibromide (or dichloride) blsoxime 32... 

Carbamic acid 2-methyl-2-propyl -trimethylene ester, AQlA Carbamylcyclopentadienyl cyclo-pentadtenyl iron, AT31 U-Carbamyl-1-ethylpyrIdi n ium chloride, AN76 Carbamylferrocene, AT31 Carbamylhydrazlne, AA3 ... 

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. 

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