Chloroethanol oxidations

Virtually all of the organo derivatives of CA are produced by reactions characteristic of a cycHc imide, wherein isocyanurate nitrogen (frequendy as the anion) nucleophilically attacks a positively polarized carbon of the second reactant. Cyanuric acid and ethylene oxide react neady quantitatively at 100°C to form tris(2-hydroxyethyl)isocyanurate [839-90-7] (THEIC) (48—52). Substitution of propylene oxide yields the hydroxypropyl analogue (48,49). At elevated temperatures (- 200° C). CA and alkylene oxides react in inert solvent to give A/-hydroxyalkyloxazohdones in approximately 70% yield (53). Alternatively, THEIC can be prepared by reaction of CA and 2-chloroethanol in aqueous caustic (52). THEIC can react further via its hydroxyl fiinctionahty to form esters, ethers, urethanes, phosphites, etc (54). Reaction of CA with epichlorohydrin in alkaline dioxane solution gives... 

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. 

In basic sohition, the alkoxide ions formed by deprotonation are even more effective nucleqrhiles. In ethanol containing sodium ethoxide, 2-chloroethanol reacts about 5000 times faster than ediyl chloridelThe product is ethylene oxide, confirming the involvement of the oxygoi atom as a nucleophile. 

The reagent (1) is easily made from thiol (3) and ethylene oxide or 2-chloroethanol (2). The acid RCOgH is then protected by acid-catalysed ester (4) formation. 

The most commonly employed routes for the preparation of the / -sulfatoethylsulfone group, which is the essential structural feature of vinylsulfone reactive dyes, are illustrated in Scheme 8.5. One method of synthesis involves, initially, the reduction of an aromatic sulfonyl chloride, for example with sodium sulfite, to the corresponding sulfinic acid. Subsequent condensation with either 2-chloroethanol or ethylene oxide gives the / -hydroxyethylsulfone, which is converted into its sulfate ester by treatment with concentrated sulfuric acid at 20 30 °C. An alternative route involves treatment of an aromatic thiol with 2-chloroethanol or ethylene oxide to give the /Miydroxyethylsulfonyl compound which may then be converted by oxidation into the /Miydroxyethylsulfone. 

Hydrolysis of 1,2-dichloroethane under alkaline and neutral conditions yielded vinyl chloride and ethylene glycol, respectively, with 2-chloroethanol, and ethylene oxide forming as the intermediates under neutral conditions (Ellington et al, 1988 Jeffers et al, 1989 Kollig, 1993). The reported hydrolysis half-life in distilled water at 25 °C and pH 7 is 72.0 yr (Jeffers et al, 1989), but in a 0.05 M phosphate buffer solution the hydrolysis half-life is 37 yr (Barbash and Reinhard, 1989). Based on a measured hydrolysis rate constant of 1.8 x 10 at 25 °C and pH 7, the half-life is 71.5 yr (Jeffers and Wolfe, 1996). 

Dunkelberg H Carcinogenic activity of ethylene oxide and its reaction products 2-chloroethanol, 2-bromoethanol, ethylene glycol and diethylene glycol. I. Carcinogenicity of ethylene oxide in comparison with 1,2-propylene oxide after subcutaneous administration in mice. 7M Bakt Hyg I Abt OrigB 174 383-404, 1981... 

Acetylcholine Acetylcholine, 2-acetoxy-A,A,A-trimethylethyl ammonium chloride (13.1.2), is easily synthesized in a number of different ways. For example, 2-chloroethanol is reacted with trimethylamine, and the resulting A,A,A-trimethylethyl-2-ethanolamine hydrochloride (13.1.1), also called choline, is acetylated by acetic acid anhydride or acetylchloride, giving acetylcholine (13.1.2). A second method consists of reacting trimethylamine with ethylene oxide, giving A,A,A-trimethylethyl-2-ethanolamine hydroxide (13.1.3), which upon reaction with hydrogen chloride changes into the hydrochloride (13.1.1), which is further acetylated in the manner described above. Finally, acetylcholine is also formed by reacting 2-chloroethanol acetate with trimethylamine [1-7]. 

Synonyms 2-chloroethanol, 2-chloroethyl alcohol Formula C2H5OCI Stmctme Cl-CH2-CH2-OH MW 80.52 CAS [107-07-3] used as a solvent for cellulose esters and in making ethylene glycol and ethylene oxide colorless liquid with a faint ether odor boils at 129°C freezes at -67°C density 1.197 g/mL at 20°C soluble in water, alcohol, and ether highly toxic. 

An example of mechanism (154) is the reaction of 2-chloroethanol with hydroxide ion to form ethylene oxide. Various lines of evidence, including the actual size of the solvent isotope effect (Ballinger and Long, 1959 Swain et al., 1959), indicate the sequence (159) to (160) as the reaction mechanism... 

Several addition reactions have been or are currently used on a large scale in industrial chemical plants. For example, an older method for the preparation of ethylene oxide employed the addition of chlorine to ethylene in water to form ethylene chlorohydrin or 2-chloroethanol. (In industry, ethene is almost always called ethylene.) Treatment of the chlorohydrin with calcium hydroxide results in the formation of ethylene oxide, which is an important intermediate in the manufacture of ethylene glycol and other products (see the Focus On box on page 375). However, this method is wasteful of... 

The point has been made that the conditions of p-chloroethanol formation are not the same as used for the Wacker oxidation. Cu Pd chlorine-bridged dimers are likely reactants under higher [Cl ] reaction conditions, which may lead to a different reaction mechanism. However, a second stereochemical study also obtained results consistent with trans hydroxypaUadation. When cfr-l,2-dideuteroethene is oxidized in water with PdCl2 under a CO atmosphere, the product is tran5 -2,3-dideutero-jS-propiolactone (Scheme 37). The reaction conditions were, once again, not identical with standard Wacker process conditions, since the solvent was acetonitrile water, the temperature was —25°C, the bis-ethene PdCl2 complex was used, and there was no excess Cl present. Nevertheless, it is clear that, under many reaction conditions, a trans addition of water onto ethene coordinated to Pd is the favored reaction stereochemistry. 

In a stereochemical study f-Cethylenel-da (C2H2D2) [32] was reacted with palladium chloride and cupric chloride under extreme conditions, i. e., extremely high chloride ion concentration as cupric and lithium chlorides. Under such conditions 2-chloroethanol was formed as the main product from ethylene, besides some acetaldehyde [33] (see Section 2.4.1.5.1) this is not the normal product of the Wacker reaction. In the above study the formation of cis-, 2-dideuterioethylene oxide, evidently via 1,2-dideuterio-2-chloroethanoI, suggests trans addition of water (nnh-hydroxypalladation). 

Glycol derivatives, e.g., 2-chloroethanol (eq. (31)) are to a small extent byproducts in the technical olefin oxidation. With a very high concentration (ca. 5 mol/L) of cupric chloride and high pressure, 2-chloroethanol is the main product of ethylene oxidations, besides some acetaldehyde [33]. Cupric chloride is essential. In its absence, in spite of a high chloride ion concentration absolutely no 2-chloroethanol is obtained. It is assumed that analogously to acetaldehyde formation a y9-hydroxyethyl species bonded to a bi- or oligo-Pd-Cu cluster is an intermediate from which 2-chloroethanol is liberated by reductive elimination. 

Storage of vinyl chloride is limited by the rapid metabolism and subsequent excretion. Vinyl chloride is biotransformed by cytochrome P450-mixed function oxidase systems (CYP 2E1), with the two primary metabolites being chloroethylene oxide and chloroacetaldehyde. These materials are further converted to chloroethanol and monochloroacetic acid. Metabolites are primarily excreted in urine. When rats were exposed to vinyl chloride at 100 ppm for 5 h, 70% of the absorbed dose was excreted as urinary metabolites within 24 h. The half-life for urinary excretion in rats was 4h. With an increase in dose via either inhalation or ingestion, the proportion exhaled increased and urinary and fecal elimination decreased. 

The dihydrofurans 60 can be prepared by reaction of malononitrile with either 2-chloroethanols or epoxides (Scheme 11 R1 or R2 = H, Me, Ph). Conversion into the benzamides 61 and oxidation with Ar-brom os ucci n i m ide gives the 2-amidofurans 62 (20-40%) (85CPB937). 

Okahara and coworkers prepared a number of Ai-alkylamino diols that were not symmetric. They first prepared the monochloride derivative of the oligoethylene glycol by reacting ethylene oxide with 2-chloroethanol in an acidic medium (Kuo et al., 1980). The oligomers were separated by distil-... 

CHLOROETHANOL (107-07-3) Forms explosive mixture with air (flash point 140°F/60°C). Violent reaction with strong oxidizers, strong caustics (with fonnation of ethylene oxide), strong acids, aliphatic amines, isocyanates, chlorosulfonic acid, ethylene diamine. Attacks some plastics, rubber, and coatings. Reacts with moisture steam, evolving toxic and corrosive fumes. 

Hydrazinoethanol. 2 -Hydroxyethyl hydrazine /3-hydroxyethylhydrazine Omaflora. CjH8N20, mol wt 76.10. C 31.56%, H 10.60%. N 36.81%, O 21.02%, HOCH2-CH.NHNHj. Prepn from hydrazine monohydrate and 2-chloroethanol Gansser, Rumf, Helv. Chim. Acta 36, 1423 (1953) from hydrazine monohyd/ate and ethylene oxide Gever, O Keefe, (J.S. pat. 2,660,607 (1953 to Eaton Labs.) from hydrazine and ethylene oxide Brit. pat. 776,113 (1957 to Olin Mathieson). 

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