Tetramethylene dichloride

For recovery of tetrahydrofuran, the condensate from the cooling traps and the low-boiling material from the fractionations are combined, cooled in an ice bath, and treated carefully with 15-20 cc. of 40 per cent alkali. The upper layer is separated, dried with a little calcium chloride, and distilled. The recovered tetrahydrofuran, b.p. 64-67°, weighs 20-22 g. (17-19 per cent of the original material). The residue (12-14 g-) remaining after disdllation of the tetrahydrofuran distils at 43-45°/io mm. and is tetramethylene dichloride. 

Dimethoxybenzoic acid Tetramethylene dichloride p-Methoxyphenyl acetone Ethylamine... 

B) 4 -Chlorobutyl-3,4-Dimethoxybenzoate 92 g of the sodium salt described under (A) (it contains at the most 81.5 g of sodium 3,4-dimethoxybenzoate) was boiled in 900 ml of tetramethylene dichloride for 90 hours after cooling the mixture was filtered and the residue washed with 3 x 50 ml of ether. The filtrate was evaporated to dryness in vacuo and the residue (102 g) was distilled in vacuo. Fraction 1 50° to 55°C/0.5 mm 19 g (probably tetramethylene dichloride). Fraction 2 175° to 184°C/0.5 mm 77.5 g (=71%) Cl= 12.6% (calculated 13.0%). Remark The second fraction partially solidified or became more viscous on standing, and even during the distillation. 

TETRAMETHYLENE DICHLORIDE, DCB (764-41-0) Forms explosive mixture with air (flash point 126°F/52°C). Water contact produces hydrogen chloride. Violent reaction with strong oxidizers. Incompatible with alkalis, alkali metals. May slowly form explosive compounds with metallic azides. Corrodes metals in the presence of moisture. 

The importance of the solvent, in many cases an excess of the quatemizing reagent, in the formation of heterocyclic salts was recognized early. The function of dielectric constants and other more detailed influences on quatemization are dealt with in Section VI, but a consideration of the subject from a preparative standpoint is presented here. Methanol and ethanol are used frequently as solvents, and acetone,chloroform, acetonitrile, nitrobenzene, and dimethyl-formamide have been used successfully. The last two solvents were among those considered by Coleman and Fuoss in their search for a suitable solvent for kinetic experiments both solvents gave rise to side reactions when used for the reaction of pyridine with i-butyl bromide. Their observation with nitrobenzene is unexpected, and no other workers have reported difficulties. However, tetramethylene sulfone, 2,4-dimethylsulfolane, ethylene and propylene carbonates, and salicylaldehyde were satisfactory, giving relatively rapid reactions and clean products. Ethylene dichloride, used quite frequently for Friedel-Crafts reactions, would be expected to be a useful solvent but has only recently been used for quatemization reactions. ... 

The preparation and purification of this compound is identical with that of cycZoselenobutane, the aS-tetramethylene dibromide in the latter case now being replaced by 27 grams of ae-pentamethylene dibromide. The product need only be distilled under ordinary pressure in a stream of carbon dioxide to effect purification. It is a colourless or very faintly yellow liquid, B.pt. 158° C. at 759 mm., nv 1 5475 at 18° C., density 1 409 at 12 5° C., 1 899 at 20° C., 1 892 at 26° C., and 1 884 at 32 2° C., whence d ° - 1 424 0-001236f. The compound has similar properties to those described for o/cZoselenobutane. The mercurichloride, C6H10Se. HgCl2, forms white, feathery needles, M.pt. 175° to 176° C. cycloSelenipentane I 1 -dichloride,... 

The cleavage of tetrahydrofuran and its alkylated derivatives with halogen acids is an excellent method for the preparation of, A-dihalo-alkanes.The reaction of tetrahydrofuran with the less-reactive hydrogen chloride stops at the chlorohydrin stage, whereas the reaction in the presence of zinc chloride catalyst leads to the formation of the dichloride. The crude reaction mixture containing the intermediate chlorohydrin may be treated directly with phosphorus tribromide, yielding tetramethylene chlorobromide. The preparation of dibromides can be accomplished easily with hydrogen bromide or phosphorus and bromine and diiodides, by the action of potassium iodide and orthophosphoric acid. ... 

AO containing various phenolic moieties were prepared by transesterification in the presence of tetraalkyl titanates. Randomly distributed -active moieties are characteristic of 140 (only the hard polyester segment is given) prepared from dimethyl terephthalate, 1,4-butanediol, poly(tetramethylene oxide)diol and dimethyl 5-(3,5-di-tm-butyl-4-hydroxybenzenepropaneamido)isophthalate [181]. The mentioned polymeric AO was used for stabilization of polyether-polyester elastomers. A partial attachement of tetrakis[methylene 3(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate]methane (3) via transesterification reaction was expected in the synthesis of another polyether-polyester elastomer by [182]. A reversible redox polyester was formed from 2,5-bis(2-hydroxyethyl)hydroquinone and dichlorides of aliphatic dicarboxylic acids [137],... 

Tetrahalides are known. SF, b.p. —40.5°, is made by the direct fluorination of sulphur at —75° (Brown and Robinson, 1955). It is more conveniently prepared by the action of sulphur dichloride on a suspension of sodium fluoride in acetonitrile or tetramethylene sulphone at 70°. A medium offering some chance of ionisation is necessary. 

Ethylene diamine tetra (methylene phosphonic acid), pentasodium sah. See Pentasodium ethylene diamine tetramethylene phosphonate Ethylenediammonium chloride. See Ethylenediamine dihydrochloride Ethylene dichloride... 

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