Chlorine acetate

Potassium hydride Air, chlorine, acetic acid, acrolein, acrylonitrile, maleic anhydride, nitroparaf-flns, A-nitrosomethylurea, tetrahydrofuran, water... 

Enols of simple ketones can be generated in high concentration as metastable species by special techniques. Vinyl alcohol, the enol of acetaldehyde, can be generated by very careful hydrolysis of any of several ortho ester derivatives in which the group RC02 is acetate acid or a chlorinated acetate acid. ... 

Rather different experimental results were obtained by de la Mare et a/.208, 209, who studied chlorination by hypochlorous acid in 51, 75 and 98 % aqueous acetic acid. With the latter medium, the chlorination of anisole or m-xylene (at an unspecified temperature) was independent of the concentration of aromatic, and catalysed by perchloric acid to a much greater extent than an equimolar amount of lithium perchlorate the reaction was also catalysed by the base, sodium acetate. The reactive species was postulated as chlorine acetate produced... 

In the absence of added mineral acid, the effective chlorinating species was concluded to be chlorine acetate. Like the catalysed chlorination, the rate of chlorination (of toluene) falls rapidly on changing the solvent from anhydrous to 98 % aqueous acetic acid, passes through a shallow minimum and thence to a maximum in 50 % aqueous acid this was thus attributed to a combination of the decrease in concentration of chlorine acetate as water is added and a solvent effect. By correcting for the change in concentration of chlorine acetate in the different media it was shown that the reaction rate increases as the water content of the media increases. 

Relative rates and partial rate factors have been determined for the chlorination of some aromatics by chlorine acetate in 76 % aqueous acetic acid at 25 °C209 these are given in Table 65. The spread of rates is, therefore, smaller than is found with molecular chlorine and this is entirely consistent with the lower reactivity of the latter reagent. 

The rates of chlorination of benzene, biphenyl, and diphenylmethane by chlorine acetate in 98 % aqueous acetic acid at 25 °C have also been determined and the second-order rate coefficients are 0.00118, 0.0364, and 0.0311, respective-]y209 , 270 jjje varjation in rate with change in water content of the acetic acid was the same as that previously observed209 for toluene, and thus in ca. 75 % aqueous acid the coefficients were 0.00073, 0.027 and 0.0241 however, elsewhere in ref. 209a a 4-fold decrease in rate coefficient for diphenylmethane was claimed to accompany the same increase in water content of the medium. 

Chromic acid and chromium trioxide Chlorine Acetic acid, naphthalene, camphor, glycerol, turpentine, alcohol or other flammable liquids Ammonia, acetylene, butadiene, butane or other petroleum gases, hydrogen, sodium carbide, turpentine, benzene or finely divided metals... 

If nitration under acidic conditions could only be used for the nitration of the weakest of amine bases its use for the synthesis of secondary nitramines would be severely limited. An important discovery by Wright and co-workers " found that the nitrations of the more basic amines are strongly catalyzed by chloride ion. This is explained by the fact that chloride ion, in the form of anhydrous zinc chloride, the hydrochloride salt of the amine, or dissolved gaseous hydrogen chloride, is a source of electropositive chlorine under the oxidizing conditions of nitration and this can react with the free amine to form an intermediate chloramine. The corresponding chloramines are readily nitrated with the loss of electropositive chlorine and the formation of the secondary nitramine in a catalytic cycle (Equations 5.2, 5.3 and 5.4). The mechanism of this reaction is proposed to involve chlorine acetate as the source of electropositive chlorine but other species may play a role. The success of the reaction appears to be due to the chloramines being weaker bases than the parent amines. 

Alkene and alkyne Bromination, acetic acid Chlorination, acetic acid Acid-catalyzed hydration, water... 

Thus hydrocliloric acid reacts in the presence of nitric acid to yield chlorine acetate (a)—a compound with cationic chlorine. The latter in turn forms a chloramine (b) which is nitrated to a nitramine (c). 

Addition of halogens to ketenes 5-27 Addition of HOBr or HOC1 to triple bonds addition of chlorine acetate or other reagents to olefins 5-34 Addition of acyl halides to olefins... 

List of Chlorine Compounds Chlorine Acetate, CH3 COOCl mw 94.49, exists only in soln. This dk-red soln is unstable and frequently explodes when warmed from -70 to -20° it contains both chlorine monoxide (C120) chlorine acetate. It was prepd by MacKenzie et al(Ref 2) according to the method of Schiiczenberger by addg C102 to acetic anhydride. This soln cannot be distilled without expln and is reported likely to explode even without warming it Refs l)Beil 2, 170 318 2)J.C. 

All three chloroacetic acids (chloroacetic acid [MCA], dichloroacetic acid [DCA], and trichloroacetic acid [TCA]) are naturally occurring (7), with TCA being identified in the environment most frequently (reviews (278, 405 108)). However, these chlorinated acetic acids also have anthropogenic sources. The major source of natural TCA appears to be the enzymatic (chloroperoxidase) or abiotic degradation of humic and fulvic acids, which ultimately leads to chloroform and TCA. Early studies (409) and subsequent work confirm both a biogenic and an abiotic pathway. Model experiments with soil humic and fulvic acids, chloroperoxidase, chloride, and hydrogen peroxide show the formation of TCA, chloroform, and other chlorinated compounds (317, 410-412). Other studies reveal an abiotic source of TCA (412, 413). 

Hirvonen, A., Tuhkanen, T., and Kalliokoski, P, Formation of chlorinated acetic during UV/H202 oxidation of ground water contaminated with chlorinated ethylenes, Chemosphere, 32(6), 1091-1102, 1995. 

The reaction can be used for recycling more highly chlorinated acetic acids in the production of monochloroacetic acid. 

Most of the uncertainty in these enthalpies of formation for the chlorinated acetyl chlorides, RCOC1, arise from uncertainties in the corresponding chlorinated acetic acids, RCOOH after all, it is the high-accuracy (basic, aqueous) hydrolysis reaction that interconnects these species that gives us the acyl chloride enthalpies of formation we use. [See G. M. Moselhy and H. O. Pritchard, J. Chem. Thermodyn., 7,977 (1975).] We note that sufficiently few chlorinated acetate esters enjoy sufficiently accurate enthalpies of formation (as determined by combustion measurements) to allow for comparison of RCOC1 and RCOOR for any R. ... 

Chlorinated acetate (see monochloroacetate, dichloroacetate, trichloroacetate, chloral hydrate)... 

Hirvonen a, Tuhkanen T, Kalliokoski P (1996) Formation of Chlorinated Acetic Acids During UV/H202-Oxidation of Ground Water Contaminated with Chlorinated Ethylenes, Chemosphere 32, No. 6 1091-1102. 

Although carboxylic acids generally form 1 1 adducts with alkenes, the resulting esters are easily ionized in the presence of either Lewis or protonic acids. The higher efficiency of chlorinated acetic acids relative to hydrogen halides is ascribed to the ability of their 1 1 adducts to coordinate with excess acid. Alkyl halides are eventually formed when carboxylic acids are used to initiate polymerization in the presence of a Lewis acid due to migration of the carboxylate moiety to the Lewis acid [Eq. (25)]. Similarly, styrene and isobutene polymerizations initiated by preformed alkyl acetate adducts in the presence of BC13 always produce Cl-terminated chains [104,105]. 

SO3 at —78°C converts alkenes to 2-chloro chlorosulfates CICHRCHROSO2CI, which are stable compounds.Chlorine acetate [solutions of which are prepared by treating CI2 with Hg(OAc)2 in an appropriate solvent] adds to alkenes to give acetoxy chlorides.Acetoxy fluorides have been obtained by treatment of alkenes with CH3COOF. ... 

The anhydrides and chloroanhydrides of chlorinated acetic acids and pentafluorobenzoyl chloride are used for the synthesis of chlorinated amides for GC analysis with selective detectors. Diethylpyrocarbon-ate converts primary and secondary amines (including NH3) to N-substituted carbamates ... 

Because methanol is not very polar, the elution of strong organic acids and bases requires a mobile phase with even greater polarity. This has normally been done by adding a very low concentration of acids or bases into methanol, and then the modified methanol is mixed with CO2 for separation. Citric, acetic, and chlorinated acetic acids have been used as acidic secondary modifiers, whereas isopropylamine, triethy-lamine, and tetrabutylammonium hydroxide have been served as basic secondary modifiers. A good example with ternary systems is the separation of benzy-lamines, as shown in Fig. 1. None of the three tested amines were effectively eluted by pure CO2 (Fig. la) however, some of these amines were eluted with very poor peak shapes when methanol was added to the CO2 (Fig. lb). However, the addition of isopropylamine to the methanol-modified mobile phase effectively eluted all of the three benzylamines and dramatically improved the peak shapes, as shown in Fig. Ic. 

Photoreductions of Sorbed Halocarbons. Comparisons of computed rates of halocarbon photoreduction by eaq with observed rates in natural water samples indicate that other reaction pathways are more important. For example, recent results obtained with continuous irradiations indicate that chlorinated acetates produce chloride more efficiently than chloroethanol in solutions of dissolved organic matter that was isolated from the Suwannee River. Observed quantum yields (355 nm) for chloride production at pH 6.2 in aque-... 

Ionic halocarbons, including halogenated carboxylic acids, may form pho-toreactive complexes with transition metals in the aquatic environment. Indeed, complexes of carboxylates with dissolved Fe(III) and iron oxides are very photoreactive under solar radiation (28, 29). Photoreactions of such complexes may help to explain the enhanced photoreactivity of chlorinated acetates in natural water samples. 

Kharasch MS, Urri WH, Jensen EV (1945) Addition of derivatives of chlorinated acetic acids to olefins. J Am Chem Soc 67 1626... 

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