Ethylene chlorohydrin derivatives

Ethylene oxide [75-21-8] was first prepared in 1859 by Wurt2 from 2-chloroethanol (ethylene chlorohydrin) and aqueous potassium hydroxide (1). He later attempted to produce ethylene oxide by direct oxidation but did not succeed (2). Many other researchers were also unsuccesshil (3—6). In 1931, Lefort achieved direct oxidation of ethylene to ethylene oxide using a silver catalyst (7,8). Although early manufacture of ethylene oxide was accompHshed by the chlorohydrin process, the direct oxidation process has been used almost exclusively since 1940. Today about 9.6 x 10 t of ethylene oxide are produced each year worldwide. The primary use for ethylene oxide is in the manufacture of derivatives such as ethylene glycol, surfactants, and ethanolamines. 

Treatment of the triazine derivative 534 with ethylene chlorohydrin gave 535, whose thermolysis gave (81 KGS 1125) the triazinotriazine derivative 536. 

The petrochemical industry had its birth in the early 1900s. In 1913 propylene, a by-product of cracking, was introduced. In 1920 isopropyl alcohol was made from petroleum. In 1923 the first derivatives of ethylene were commercialized ethylene chlorohydrin, ethylene glycol, and dichloroethane. By the 1940s petrochemicals were fully developed in the... 

The solvents more generally used are oil of turpentine, pinewood oil, methyl, ethyl or amyl alcohol, amyl acetate, acetone, ether, carbon disulphide, carbon tetrachloride, chloro-derivatives of ethane and ethylene, chlorohydrins, light mineral oils, light oils from tar, from resin or from shale, and camphor oil. 

Two hundred twenty-six milliliters of silicon tetrachloride (2.0 mols) is allowed to react with 68 ml. of ethylene chlorohydrin (1.0 mol). This excess of silicon tetrachloride is used to reduce the probability of secondary reactions which might produce di-, tri-, and/or tetraalkoxy derivatives. 

Ethylene Glycols. Monoethylene glycol or ethylene glycol is the major derivative of ethylene oxide. Ethylene glycol was initially made commercially by hydrolysis of ethylene chlorohydrin. Today, hydrolysis of ethylene oxide is the preferred route. 

Alkylation of 3-piperideines at the nitrogen atom is usually performed by the action of alkyl halides on the corresponding sodium derivatives. Thus, l-(2-hydroxyethyl)-3-piperideine (141) was obtained from ethylene chlorohydrin and 3-piperideine pretreated with sodium ethoxide in ethanol,122 or by refluxing a mixture of 3-piperi-... 

Local anesthetics make use of the lipophobic property of an aromatic amine moiety, or its acyl derivative, that links with a hydrophilic amino acid. The products include the anilide lidocaine, or 2-(diethylamino)-A-(2,6-dimethylphenyl)acetamide (153), the toluidine derivative prilocaine and the century-old procaine, 2-diethylaminoethyl 4-aminobenzoate (154)84. The ester is prepared by reacting p-aminobenzoic acid with ethylene chlorohydrin and diethylamine. 

Properties Colorless liquid. D 1.3825 (20C), bp 152.5C (752 mm Hg). Decomposed by alkaline solutions and hot water. Insoluble in cold water. Derivation By bubbling gaseous phosgene into ethylene chlorohydrin at 0C. 

Derivation Interaction of sulfuryl chloride and ethylene chlorohydrin. Also from action of sulfur trioxide on ethylene chloride below 45C. 

Derivation By heating ethylene chlorohydrin and trichloromethylchloroformate together (under reflux). 

Derivation (1) Oxidation of ethylene in air or oxygen with silver catalyst (2) action of an alkali on ethylene chlorohydrin. 

Derivation (1) By heating chloroethyl-p-nitroben-zoic ester with diethylamine for 24 hours under pressure at 120C. The product is then reduced with tin and hydrochloric acid. (2) By condensation of ethylene chlorohydrin with diethylamine. The chlo-roethyldiethylamine formed is heated with sodi-u m-p-am i nobenzoate. 

Properties Syrupy, colorless liquid characteristic odor. D 1.1852 (20C), bp 283C, fp -10C, viscosity 0.652 cP (20C), flash p 320F (160C), bulk d 9.85 lb/ gal, refr index 1.5217 (20C). Soluble in acetone, alcohol, chloroform, water slightly soluble in benzene, carbon tetrachloride, and ether. Combustible. Derivation Hydrolysis of dichloroethyl sulfide, interaction of ethylene chlorohydrin and sodium sulfide. 

The second reaction step in the preparation of chlorophenoxyethanols is condensation with ethylene oxide, ethylene chlorohydrin or diethyl carbonate. Reduction of the respective acetic acid derivative is also feasible but uneconomical. 

The monomers may be prepared by the reaction of the 5-(2H-benzo-triazole-2-yl)-2,2, 4,4 -tetrahydroxybenzophenone and its chloro and meth-oxy derivatives with allyl bromide, acryloyl chloride, methacryloyl chloride, glycidyl acrylate, and ethylene chlorohydrin. °... 

Uses Intermediate for prod, of vinylcyclohexene dioxide comonomer in polymerization of other monomers in halogenation to polyhalogenated derivs. used as flame retardants prod, of insecticides with ethylene chlorohydrin organic synthesis Manuf./Distrib. Aldrich http //www.sigma-aldrich.com, Fluka http //www.sigma-aldrich.com, Sigma... 

Numerous ethers of cellulose, starch, and bacterial dextran are of established or potential industrial importance. (See also Chapter XII.) Treatment of the polysaccharides with alkali and methyl chloride, ethyl chloride, benzyl chloride, ethylene oxide (or ethylene chlorohydrin), sodium chloro-acetate, and allyl bromide gives, respectively, the methyl, ethyl, benzyl, hydroxy ethyl, carboxy methyl, and allyl ethers. The cellulose derivatives... 

The IR spectra of PEO in the liquid state or in solution may be interpreted by comparing them with the assigned bands in the vibrational spectra of crystalline PEO [20, 26, 27] and structurally related compounds such as 1,2-dichlorethane, [19, 21-23]. ethylene chlorohydrin [30], metal-ethylenediamine complexes [31, 32] ester and ether derivative of ethylene glycol [33], crystalline polyesters [34], and metal-ethylene glycol complexes [35]. 

Ethylene and Propylene Oxides. Ethylene oxide (26) and its derivatives are among the important aliphatic chemicals the 1950 production amounted to between 400,000,000 and 500,000,000 pounds. The chlorohydrin process was introduced in the early 1920 s and the direct oxidation process in the 1930 s, both based on ethylene. In the older process, the one most used today, the ethylene reacts in solution with hypo-chlorous acid at room temperature. 

B) Examination of the Solvents insoluble in Water. These may be carbon disulphide, chloroform, carbon tetrachloride, a chloro-derivative of ethane or ethylene, a chlorohydrin, amyl alcohol, amyl acetate, ether, benzene or a homologue, oil of turpentine, pinewood oil, light mineral oil, resin oil, tar oil, shale oil, or camphor oil. 

As early as in 1904 the substance was proposed [35] as an additive to lower the freezing temperature of nitroglycerine, but its practical application on a large scale was hindered by lack of the raw material, propan-1,2-diol. It is only recently that the synthesis of ycol from ethylene led to the development of a method for producing methyl glycol from propylene via chlorohydrin. Even so, propylene-1,2-glycol is somewhat more expensive than glycols derived from ethylene. 

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