Methyl Trichloroacetate Research Articles

ChemInform Abstract: Molecular Structure of Methyl Trichloroacetate. An IR, Raman and 35Cl NQR Spectroscopic Study.

Chemischer InformationsdienstVolume 17, Issue 37 Physical Organic Chemistry ChemInform Abstract: Molecular Structure of Methyl Trichloroacetate. An IR, Raman and 35Cl NQR Spectroscopic Study. Y. MIDO, Y. MIDOSearch for more papers by this authorK. SUZUKI, K. SUZUKISearch for more papers by this authorN. KOMATSU, N. KOMATSUSearch for more papers by this authorM. HASHIMOTO, M. HASHIMOTOSearch for more papers by this author Y. MIDO, Y. MIDOSearch for more papers by this authorK. SUZUKI, K. SUZUKISearch for more papers by this authorN. KOMATSU, N. KOMATSUSearch for more papers by this authorM. HASHIMOTO, M. HASHIMOTOSearch for more papers by this author First published: September 16, 1986 https://doi.org/10.1002/chin.198637049AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume17, Issue37September 16, 1986 RelatedInformation

Molecular structure of methyl trichloroacetate. An IR, Raman and 35Cl NQR spectroscopic study

The IR and Raman spectra of liquid and crystalline mehtyl trichloroacetate (M-TCA) and its deutrate (M-TCA-d 3) have been recorded. The spectra are analysed on the basis of the spectral comparison with related compounds and also with aid a normal coordinate calculation on M-TCA and M-TCA-d 3. The vibrational and 35Cl NQR spectra indicate that the M-TCA molecule exists in the (itcis) form in relation to the chlorine atom and the carbonyl group. Anomalous temperature dependences of the 35Cl NQR and Raman frequencies observed in crytalline M-TCA are reported and discussed qualitatively.

ChemInform Abstract: THE METHYLATION OF CARBOXYLIC ACIDS USING METHYL TRICHLOROACETATE

AbstractTrich or‐ essigsäureester (II) werden zur Alkylierung bzw. Arylierung der Carbonsäuren (I) zu den Estern (III) benutzt.

ChemInform Abstract: THE SALT‐FREE SYNTHESIS OF ARYL ETHERS USING METHYL TRICHLORACETATE

AbstractDie Phenole (I) werden mit den Halogeniden (II) verethert, wobei Trichloressigsäuremethylester (III) als Halogenwasserstoff‐Fänger eingesetzt wird.

Relative kinetics for the telomerization of propylene by the methyl esters of chloroacetic and trichloroacetic acids and CCl4 induced by Mn2(CO)10 systems

Individual chain transfer constants found for the telomerization of propylene with methyl chloroacetate, methyl trichloroacetate, and CC14 initiated by Mn2(CO)10 are similar to the values obtained in the case of peroxide initiation.

Synthèse de télomères photoréticulables—V. Télomèrisation par catalyse rédox de l'acide acrylique et greffage de groupements photosensibles

Photocrosslinkable telomers containing a cholorinated or a chlorofluorinated sequence have been prepared. They were synthetized in two steps, viz. telomerization by redox catalysis of acrylic acid with carbon tetrachloride methyl trichloroacetate or several chlorofluorinated telogens, followed by grafting photosensitive hydroxylated molecules containing an acrylic or an allylic double bond. Activation of acid functions by reaction with boiling thionyl chloride was necessary before grafting alcohols.

Synthèse de compoisés photoréticulables, 4. Estérification de l'acide acrylique sur les télomères de l'acrylate d'hydroxy‐2 éthyle

AbstractSeveral telomers were prepared by redox catalysis from 2‐hydroxyethyl acrylate (1) and telogens such as carbon tetrachloride, methyl trichloroacetate, 1, 1, 1‐trichlorotrifluoroethane, and 2,4,4,4‐tetrachloro‐2‐methylbutyric acid (2d), as well as block‐cotelomers from 1 and a telomer 4 prepared from chlorotrifluoroethylene and carbon tetrachloride. Polyols (3a–d and 5) with two to twenty primary hydroxyl groups were obtained. They were esterified with acrylic acid, to obtain new photosensitive compositions. (6a–d).

Relative kinetics of Mn2(CO)10-initiated telomerization of ethylene by methyl tri- and monochloroacetates

1. Dimagnesium decacarbonyl [Mn2(CO)10] and systems based on it effectively initiate the telomerization of ethylene with methyl trichloroacetate and methyl monochloroacetate to give the same products as in the case of peroxide initiation. 2. Initiation by the Mn2(CO)10+DMF system of the reaction of ethylene with methyl tri-chloroacetate increases the yield of lower telomers. 3. In the reaction of methyl chloroacetate with ethylene Mn2(CO)10 and its complexes have virtually no effect on chain propagation at the C-H bond of methyl chloroacetate.

Wittig-type Reaction of Dimetallated Carbodianion Species as Produced by Zinc Reduction of gem-Polyhalogen Compounds in the Presence of Lewis Acids

Abstract Treatment of R1COR2 with a suspension prepared from diiodomethane, trimethylaluminum and excess zinc in tetrahydrofuran at room temperature affords olefins R1R2C=CH2 in fair (R1,R2=alkyl) to good (R1=alkyl, R2=H) yields. The ketone methylenation is better carried with another system consisting of CH2Br2–Zn–TiCl4. Ketones and aldehydes are transformed into α-chloro α,β-unsaturated esters or α,β-unsaturated esters in good yields on treatment with methyl trichloroacetate or t-butyl dichloroacetate (ethyl dibromoacetate) in the presence of diethylaluminum chloride and zinc.

Addition of carbon tetrachloride and methyl trichloroacetate to silicon-functional vinylsilanes

Compounds of type XCCl 2CH 2CHClSiY 3 (X = Cl, COOMe; Y = Me, Cl, OEt) were obtained in good yields by the reactions of carbon tetrachloride and methyl trichloroacetate with vinylchlorosilanes or with vinylethoxysilanes in the presence of dichlorotris(triphenylphosphine)ruthenium(II).

Reaction of α-Keto Sulfoxides with Hydrogen Chloride and Trichloroacetic Acid

Abstract α-Keto sulfoxides (1) reacted with hydrogen chloride to afford chloroformates, disulfides, and thiosulfonates. 1 also reacted with trichloroacetic acid to give methyl trichloroacetate, disulfide and thiosulfonate.

Dielectric dispersion and relaxation mechanism in some trichloro esters at microwave frequencies

The permittivity and dielectric loss of three trichloro esters, namely methyl trichloroacetate, ethyl trichloroacetate, and n-propyl trichloroacetate have been measured at frequencies 1 MHz, 9.83, 18.26, 24.50 GHz, and optical frequency at 35 °C. The permittivity and dielectric loss at different frequencies have been plotted against concentration (weight fraction). The slopes of these straight lines have been used for complex plane plots (a″ vs. a′). There are two possible relaxation processes in these molecules, i.e. overall rotation of the molecule and intramolecular group rotation —CCl3 around C—C bond. Whereas the relaxation time for overall rotation is dependent on temperature the relaxation time for group rotation is practically independent of temperature.

Telomerization of propylene with methyl trichloroacetate

1. The telomerization of propylene with methyl trichloroacetate leads to the formation of the telomers where n = 1–3. 2. The partial chain transfer constants in the system propylene-methyl trichloroacetate are one order of magnitude higher than in the reaction of methyl trichloroacetate with ethylene.

Telomerisation par catalyse redox—XII.: Synthese de composes difonctionnels a partir de taxogenes a deux doubles liaisons non conjuguees

2:1 adducts of diethylenic taxogens were obtained by redox catalysis telomerization using methyl trichloroacetate and trichloroacetic acid as telogens. Their chemical transformation has led to new compounds which can be used for block polymerization.

Telomerisation par catalyse redox—X. Synthese de composes difonctionnels a partir du trichloroacetate de methyle comme agent telogene

Mono-adducts of methyl trichloroacetate with various ethylenic, vinylic, acrylic and allylic taxogens were prepared by redox catalysis. Their chemical transformations have led to difunctional monomers which can be used for polycondensation.

Telomerisation par catalyse redox—II. Telomerisation du styrene, de l'acrylonitrile, et du monochlorotrifluoroethylene par des telogenes chlores

A study has been made, under conditions for telomerization catalysed by a redox system, of the reactivities of styrene, acrylonitrile and monochlorotrifluoroethylene with respect to some telogens viz various chloroethanes, methyl trichloroacetate, CCl 2F.CClF 2 and CClF 2.CClF1. Generally, the selected catalyst system led only to products of monoaddition; these products were isolated and identified.

Organic syntheses by means of metal complexes—XI : Copper complex catalyzed addition reactions of organic polyhalides to acrylic monomers

Telomerization, especially 1:2 adduct formation from organic polyhalides and acrylic monomers catalyzed by a copper complex has been studied. Reaction of carbon tetrachloride with acrylic monomers catalyzed by a copper salt gave a 1:2 adduct. Methyl trichloroacetate afforded a 1:2 adduct with acrylic monomers, addition of LiCl increased the yield. No 1:2 adduct was obtained from CHCl 3 even in the presence of LiCl. The 1:2 adduct formation mechanism is discussed.

Preparation of polyethylene in solution

AbstractPolyethylene was prepared in a homogeneous system at 120°C. Several catalytic systems were employed, all using a soluble vanadium compound. The first consisted of an alkylaluminum compound in conjunction with the vanadium compound and a “promoter.” This promoter, which is believed to act as an oxidizing agent to reactivate dead catalyst sites, was a polyhalo compound with esters of trichloroacetic acid preferred. The promoter was added continuously throughout the polymerization. Polyethylene so produced had a narrow M̄w/M̄n ratio close to the theoretical ratio of 2.0 for a single catalyst site. Up to 266 polymer chains were produced per vanadium atom. In the second system, the cocatalyst was an AlBr3(AlCl3)–(C6H5)4Sn[(C6H5)3Bi] combination. The continuous addition of a promoter such as methyl trichloroacetate was necessary, presumably to reactivate dead catalytic sites. By this procedure, yields up to 6.6 kg of polymer per millimole of vanadium and 30–60 chains per vanadium atom were achieved. The product had a narrow M̄w/M̄n ratio of 2.4 by gel‐permeation chromatography (GPC). A study of the interactions of the catalyst compounds indicated that CCl3COOR does oxidize di‐ and trivalent vanadium.

Organic syntheses by means of metal complexes —VIII : Reactions of methyl trichloroacetate with olefins catalyzed by metal carbonyls

Reactions of methyl trichloroacetate with olefins catalyzed by dicobalt octacarbonyl, cyclopentadienylmolybdenum tricarbonyl dimer and cyclopentadienyliron dicarbonyl dimer have been studied. Products varied depending on catalyst nature. Methyl-4-alkyl-2,2,4-trichlorobutyrate was obtained by the cobalt catalyst. 4-Alkyl-2,2-dichloro-γ-butyrolactone was the main product by the molybdenum and iron catalysts.

Preparation of O-(methoxymethyl)benzophenone oxime and N-(di-phenylmethylene)methoxymethylamine N-oxide and their reactions with trichloroacetic acid

Reactions of the title compounds with trichloroacetic acid have been compared with those of the analogous methylthiomethyl compounds studied earlier. A sequence of reactions produced methoxymethyl trichloroacetate, then methanol, and finally methyl trichloroacetate from both compounds; the N-oxide also isomerised to the oxime O-ether. Added water had little effect on the first stages of the sequence. Reaction schemes are presented that account for the formation and reaction of the identified intermediates.