Ethyl Trichloroacetate Research Articles

After-effects in polymerizations photo-initiated by manganese carbonyl + halide systems

The presence of certain additives, notably cyclohexanone and acetylacetone, gives rise to relatively high and persistent dark rates of polymerization after irradiation of systems in which polymerization is photosensitized ( λ = 435·8 nm) by manganese carbonyl in association with an organic halide. These large after-effects, which are not specific to a particular monomer, occur only if the additive is present during irradiation; the presence of monomer or halide during illumination is not necessary, and the after-effect develops if these components are added subsequently. It is concluded that the after-effect arises from a species Z, produced by photochemical interaction between manganese carbonyl and the additive, which generates free radicals by reaction with the halide. A kinetic treatment based on these ideas is developed and compared with experimental results obtained on the initiating system manganese carbonyl + ethyl trichloroacetate, with methyl methacrylate as monomer and acetylacetone as additive. Agreement may be obtained on the assumption that photolysis of the carbonyl occurs unsymmetrically, one of the resulting fragments reacting rapidly with halide to generate radicals, the other being trapped by the additive to form Z. At high concentrations of additive and small light doses the concentration of Z after irradiation approaches the total concentration of radicals formed in the light period. The presence of acetylacetone does not affect the rate of radical generation during irradiation; this observation is shown to be incompatible with a simple symmetrical primary photolytic act. The possibilities of a complex primary process are considered. Some experiments on the stability of Z in the absence of halide are discussed.

Solvent-trapping of active species in the photolysis of manganese carbonyl

Photopolymerization of a vinyl monomer initiated by manganese carbonyl in association with ethyl trichloroacetate is followed by a prolonged after-effect if a suitable solvent is present, e.g., acetylacetone or cyclohexanone; the observations are consistent with unsymmetric fission of Mn2(CO)10 on photolysis, and subsequent reaction of one fragment [Mn(CO)6] with solvent to give a species of relatively long life which generates radicals by reaction with the halide.

Synthesis and some reactions of gem-dihalocyclopropyl ethers

1. The best yields of dichlorocarbene adducts of alkyl vinyl ethers are attained by the use of the chloroform method, and the best yields in the case of aryl vinyl ethers are attained by the use of the ethyl trichloroacetate method. 2. The reactions of gem-dichlorocyclopropyl ethers with alkoxides in alcoholic solutions lead to the formation of unsaturated acetals. 3. A study was made of the reduction of aryl 2,2-dichlorocyclopropyi ethers to aryl cyclopropyl ethers under various conditions.

The Reaction of Alkyl Aryl Sulfides with Ethyl Trichloroacetate and Sodium Methoxide1

The Reaction of Alkyl Aryl Sulfides with Ethyl Trichloroacetate and Sodium Methoxide¹

REACTION OF DICHLOROCARBENE WITH FATS AND OILS.

AbstractDichlorocarbene was generated in the presence of lard, olive, safflower, tung and menhaden oil. When solutions of fats or oils in ethyl trichloroacetate were mixed with sodium methoxide inn‐heptane at 2C, unsaturated components were transformed in high conversion to dichlorocyclopropane derivatives; fats were converted to methyl‐and‐ethyl esters (90%) or appeared as glycerides (10%). The proportion of dichlorocyclopropane rings was the same in the glycerides as in the ester products. The reactivity of safflower oil required metered addition of reactants at 25舑55C.Properties were measured on dichlorocyclo‐propanoid fatty esters freed from glycerides but containing saturated esters. Chlorine content ranged from 12舑33%. Compatibility with silicone oils was substantially improved. Viscosities and densities increased with chlorine content. Viscosity indices were 135,150,49,67 and 79 for products from lard, olive, safflower, tung and menhaden oil.Dichlorocarbene could be generated without alcoholysis of glycerides by decomposition of sodium trichloroacetate. This gave dichlorocyclopropanes from safflower oil unsaturates in 50% conversion, but failed with lard.Analyses were performed by TLC, argentation and GLC.

Copper Salts Induced Addition of Ethyl Trichloroacetate to Olefins

Copper Salts Induced Addition of Ethyl Trichloroacetate to Olefins

An Improved Synthesis of Phenyl(trichloro-methyl)mercury from Sodium Methoxide and Ethyl Trichloroacetate

An Improved Synthesis of Phenyl(trichloro-methyl)mercury from Sodium Methoxide and Ethyl Trichloroacetate

Solvent effects on infrared frequencies—III: The carbony bands of ethyl acetate, ethyl trichloroacetate and ethyl trifluoroacetate

The infrared absorption of the carbonyl stretching vibrations of ethyl acetate, ethyl trichloroacetate and ethyl trifluoroacetate has been studied in various solvents. Particular attention has been given to mixed solvents of n-hexane-chloroform and n-hexane-ethanol. All three solutes associate with chloroform; the strength of the interaction decreases progressively in going from ethyl acetate to ethyl trifluoroacetate. Similar effects are observed in mixtures of n-hexane and ethanol with the exception that the solute—solvent interaction is modified considerably by the self-association of the ethanol. The interpretation of the data in terms of classic bulk-dielectric theories is discussed and it is concluded that such theories cannot satisfactorily explain the observed frequency shifts.

An Improved Synthesis of Dichlorocarbene from Ethyl Trichloroacetate1

An Improved Synthesis of Dichlorocarbene from Ethyl Trichloroacetate¹

Nuclear Quadrupole Resonance in Ethyl Chloroformate and Ethyl Trichloroacetate

Nuclear Quadrupole Resonance in Ethyl Chloroformate and Ethyl Trichloroacetate

The Reaction of Ethyl Trichloroacetate with Aromatic Grignard Compounds

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Reaction of Ethyl Trichloroacetate with Aromatic Grignard CompoundsA. Kaluszyner and S. ReuterCite this: J. Am. Chem. Soc. 1953, 75, 20, 5126–5127Publication Date (Print):October 1, 1953Publication History Published online1 May 2002Published inissue 1 October 1953https://doi.org/10.1021/ja01116a513RIGHTS & PERMISSIONSArticle Views77Altmetric-Citations8LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (315 KB) Get e-Alerts Get e-Alerts