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Cas Database

74-87-3

74-87-3

Identification

  • Product Name:Methane, chloro-

  • CAS Number: 74-87-3

  • EINECS:200-817-4

  • Molecular Weight:50.4878

  • Molecular Formula: CH3Cl

  • HS Code:2903110000

  • Mol File:74-87-3.mol

Synonyms:chloromethane;

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Safety information and MSDS view more

  • Pictogram(s):HighlyF+,HarmfulXn,ToxicT,FlammableF

  • Hazard Codes:F+,Xn,T,F

  • Signal Word:Danger

  • Hazard Statement:H220 Extremely flammable gasH351 Suspected of causing cancer

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. Artificial respiration may be needed. Refer for medical attention. In case of skin contact ON FROSTBITE: rinse with plenty of water, do NOT remove clothes. Refer for medical attention . In case of eye contact Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician. If swallowed Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician. Inhalation causes nausea, vomiting, weakness, headache, emotional disturbances; high concentrations cause mental confusion, eye disturbances, muscular tremors, cyanosis, convulsions. Contact of liquid with skin may cause frostbite. (USCG, 1999) Flush eyes with water, and hospitalize. Treat with oxygen against shock, and, if indicated administer stimulants. Treat burns of skin in the usual way.

  • Fire-fighting measures: Suitable extinguishing media Suitable extinguishing media: Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide. Special Hazards of Combustion Products: Toxic and irritating gases are generated in fires. Behavior in Fire: Containers may explode (USCG, 1999) Wear self-contained breathing apparatus for firefighting if necessary.

  • Accidental release measures: Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8. Evacuate danger area! Consult an expert! Personal protection: complete protective clothing including self-contained breathing apparatus. Ventilation. NEVER direct water jet on liquid. ACCIDENTAL RELEASE MEASURES: Personal precautions, protective equipment and emergency procedures: Use personal protective equipment. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Remove all sources of ignition. Evacuate personnel to safe areas. Beware of vapors accumulating to form explosive concentrations. Vapors can accumulate in low areas; Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains; Methods and materials for containment and cleaning up: Clean up promptly by sweeping or vacuum.

  • Handling and storage: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2. Fireproof. Ventilation along the floor.Keep container tightly closed in a dry and well-ventilated place. Contents under pressure. Moisture sensitive. Storage class (TRGS 510): Gases

  • Exposure controls/personal protection:Occupational Exposure limit valuesNIOSH considers methyl chloride to be a potential occupational carcinogen.NIOSH usually recommends that occupational exposures to carcinogens be limited to the lowest feasible concentration.Biological limit values Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Eye/face protection Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Respiratory protection Wear dust mask when handling large quantities. Thermal hazards

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Relevant articles and documentsAll total 268 Articles be found

Controlled methyl chloride synthesis at mild conditions using ultrasound irradiation

Iersel, Maikel M. van,Schilt, Marcus A. van,Benes, Nieck E.,Keurentjes, Jos T.F.

, p. 315 - 317 (2010)

A new route for the chlorination of methane is described using ultrasound irradiation, which allows for an intrinsically safe process at ambient pressure and temperature. By tuning the gas feed composition methyl chloride yields of up to 19% have been obtained.

Pressure Dependence of the Rate Constants for the Reactions CH3 + O2 and CH3 + NO from 3 to 10E4 Torr

Kaiser, E. W.

, p. 11681 - 11688 (1993)

A relative rate technique is used to measure the pressure dependence of the rate constants for reaction 1 (CH3 + O2 + M -> CH3O2 + M) and reaction 3 (CH3 + NO + M -> CH3NO + M) relative to reaction 2 (CH3 + Cl2 -> CH3Cl + Cl).The pressure dependence of the rate constant of reaction 3 at 297 K can be represented in the Troe equation by the parameters (k3)0 = (3.5 +/- 0.4)E-30 cm6 molecule-2 s-1, (k3)infinite = (1.68 +/- 0.1)E-11 cm3 molecule-1 s-1, and Fcent = 0.46.The values of k3 are identical to those observed in recent absolute rate measurements at 296 K and 27-600 Torr, verifying that the rate constant chosen for reaction 2, k2 = 3.95E-12 exp(-530/RT), is both pressure independent and correct at 296 K.This value of k2 was used to determine absolute values of k1 from the k1/k2 in N2 diluent for pressures between 3 and 11000 Torr at 297 K, between 20 and 1500 Torr at 370 K, and between 40 and 1500 Torr at 264 K.All data in N2 can be fitted using the following parameters in the Troe equation: (k1)0 = (7.56 +/- 1.1)E-31 (T/300)-3.64+/-1.0 cm6 molecule-2 s-1; (k1)infinite = (1.31 +/- 0.1)E-12 (T/300)1.2+/-0.8 cm3 molecule-1 s-1; Fcent = 0.48 (264 K), 0.46 (297 K), 0.42 (370 K).Error limits include statistical error and the uncertainty in k2.In He, N2, and SF6 diluents the relative third-body efficiencies are 0.56 : 1.0 : 1.52, respectively, assuming that Fcent is independent of diluent.The high-pressure limit in SF6 is identical to that in N2.Rate constant ratios were also measured at 297 K for CD3 + O2 + M -> CD3O2 + M (1D) between 5 and 6000 Torr.Assuming that k2D = k2, the limiting rate constants using Fcent = 0.46 are (k1D)0 = (11.8 +/- 1.6)E-31 cm6 molecule-2 s-1 and (k1D)infinite = (1.38 +/- 0.08)E-12 cm3 molecule-1 s-1.

Study of the reaction methyl 4-nitrobenzene-sulfonate + Cl- in mixed hexadecyltrimethyl-ammonium chloride-Triton X-100 micellar solutions

Fernandez, Gaspar,Rodriguez, Amalia,Del Mar Graciani, Maria,Munoz, Maria,Moya, Maria Luisa

, p. 45 - 51 (2003)

The reaction methyl 4-nitrobenzenesulfonate + Cl- was studied in hexadecyltrimethylammonium chloride (CTAC) in the absence and presence of 0.1 M NaCl, as well as in mixed CTAC/Triton X-100 (polyoxyethylene(9.5)octylphenyl ether) aqueous micella

Methane to Chloromethane by Mechanochemical Activation: A Selective Radical Pathway

Bilke, Marius,Losch, Pit,Vozniuk, Olena,Bodach, Alexander,Schüth, Ferdi

, p. 11212 - 11218 (2019)

State-of-The-Art processes to directly convert methane into CH3Cl are run under corrosive conditions and typically yield a mixture of chloromethanes requiring subsequent separation. We report a mechanochemical strategy to selectively convert methane to chloromethane under overall benign conditions, employing trichloroisocyanuric acid (TCCA) as a cheap and noncorrosive solid chlorinating agent. TCCA is shown to release active chlorine species upon milling with Lewis acids such as alumina and ceria to functionalize methane at moderate temperatures (4,conv) (g(catalyst) s)-1. Findings were compared to the thermal reaction of methane with TCCA and evidenced that mechanochemical activation permitted significantly lower reaction temperatures (90 vs 200 °C) at a drastically improved CH3Cl selectivity (95% vs 66% at 30% conversion). Considering the characterization of the interaction between TCCA and Lewis acids as well as the in-depth analysis of byproducts, we suggest a plausible reaction mechanism and a possible regeneration of the chlorinating agent.

Vibrational excitation in products of nucleophilic substitution: The dissociation of metastable X-(CH3Y) in the gas phase

Graul, Susan T.,Bowers, Michael T.

, p. 3875 - 3883 (1994)

The relative kinetic energy distributions for the Y- + CH3X nucleophilic substitution products from dissociation of metastable X-(CH3Y) (X = Cl, Br; Y = Br, I) have been analyzed by means of ion kinetic energy spectroscopy, and the results modeled using statistical phase space theory. Comparison of the experimental distributions with the theoretical distributions predicted for statistical partitioning of the available energy reveals that the substitution products are translationally cold. The theoretically calculated distributions can be made to agree with experiment if most of the energy released in the dissociation is assumed to be unavailable for randomization, such that it cannot partition to relative translation. This unavailable energy must correspond to internal energy, most likely vibrational excitation, in the CH3X products. These results are consistent with recent theoretical predictions of non-RRKM dynamics in gas-phase SN2 reactions.

Ponomarev et al.

, (1973)

Rate constants for the gas phase reaction of chloride ion with methyl bromide over the pressure range 300 to 1100 torr

Sahlstrom,Knighton,Grimsrud

, p. 5543 - 5546 (1997)

Rate constants for the reaction of chloride ion with methyl bromide have been determined over a range of buffer gas pressures from 300 to 1100 Torr at 125 °C by ion mobility spectrometry (IMS). The rate constants were found to increase slightly with increased pressure over this range and also increased slightly with a change from nitrogen to methane buffer gas. Parallel measurements for the reaction of chloride ion with n-butyl bromide indicated no dependence of the observed rate constants on changes in the pressure or identity of the buffer gas, as expected. The present measurements indicate that the high-pressure limit (HPL) of kinetic behavior is not achieved for the Cl-/CH3Br reaction system by use of buffer gases in the near-atmospheric pressure range and are consistent with a recent suggestion by Seeley et al. that this reaction should occur with near-collision frequency in its high-pressure limit.

Low-temperature combustion of chlorinated hydrocarbons over CeO 2/H-ZSM5 catalysts

De Rivas, Beatriz,Sampedro, Carmen,López-Fonseca, Rubén,Gutiérrez-Ortiz, Miguel ángel,Gutiérrez-Ortiz, Jose Ignacio

, p. 93 - 101 (2012)

The performance of various CeO2/H-ZSM5 catalysts was evaluated for the oxidation of one of the most common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane. The supported samples with varying CeO2 loading (6-50 wt.%) were prepared by impregnation and subsequently calcined at 550 °C. Structural, morphological and physico-chemical changes caused by the CeO2 addition were analysed by X-ray diffraction, transmission electronic microscopy, N2- physisorption, temperature-programmed desorption of ammonia and temperature-programmed reduction with hydrogen. The enhancement of the catalytic behaviour of the resulting samples with respect to plain H-ZSM5 could be accounted for on the basis of the synergetic role played by oxygen mobility and acid sites. Hence, an optimum cerium loading of 11 wt.% was found with a T 50 value around 210 °C. At 350 °C, where conversion of the chlorinated feed is about 99%, the major oxidation products were carbon oxides and hydrogen chloride with a reduced presence of chlorinated by-products and molecular chlorine. A relatively good catalytic stability was noticed during 80 h time on line.

Kinetics of the liquid-phase hydrochlorination of methanol

Makhin,Zanaveskin,Dmitriev

, p. 163 - 166 (2014)

The kinetics of the liquid-phase hydrochlorination of methanol with hydrogen chloride in the absence of a catalyslt is reported. A kinetic equation is suggested for the reaction. The values of the preexponential factor, activation energy, and empiric coefficients characterizing the influence of the hydration of the chlorine anion on the rate of hydrochlorination have been.

Gorin,Fontana,Kidder

, p. 2128,2135 ()

Boron halide chelate compounds and their activity towards the demethylation of trimethylphosphate

Keizer, Timothy S.,De Pue, Lauren J.,Parkin, Sean,Atwood, David A.

, p. 1463 - 1468 (2002)

Salen(t-Bu)H2 (N,N′-ethylenebis(3,5-di-tert-butyl(2-hydroxy)benzylidenimine) and its derivatives were used to prepare boron compounds having the formula L(BCl2)2 (L = salen(t-Bu) (1), salpen(t-Bu) (2), salben(t-Bu) (3), salpten(t-Bu) (4), salhen(t-Bu) (5)). These are formed from the reaction of the corresponding (L[B(OMe)2]2 with BCl3. In addition to being a new type of boron compound, they are also potential two-point Lewis acids. Indeed, they demonstrate Lewis acidic behavior in the dealkylation of trimethylphosphate. All of the compounds were characterized by mp, elemental analysis, 1H and 11B NMR, IR, MS, and in the case of 2 by X-ray crystallography.

On the mechanism of catalytic oxidation of CH2Cl2 on γ-Al2O3 and its oscillatory behaviour

Haber, Jerzy,Machej, Tadeusz,Derewiński, Miros?aw,Janik, Robert,Kry?ciak, Joanna,Sadowska, Halina

, p. 97 - 112 (1996)

Adsorption of CH2Cl2 and its oxidation with dioxygen have been investigated on pure γ-Al2O3 by means of infrared spectroscopy and gas chromatographic analysis. Infrared spectroscopy showed that CH2Cl2 may be adsorbed on the alumina surface through chlorine ions either on two adjacent exposed Al ions at the (111) plane of Al2O3, or on the isoloated Lewis acid sites. The oxidation of CH2Cl2 at temperatures below 450°C yields an intermediate product CH3Cl with 50% of selectivity whereas the other half of the CH2Cl2 amount is totally oxidized to CO2 and HCl. At temperatures higher than 450°C practically total conversion of CH2Cl2 to CO2 and HCl takes place. Selfsustained oscillations of the CH2Cl2 conversion in a broad range are observed when water vapour is added to the feed. The mechanism explaining the nature of the activity of alumina in the CH2Cl2 oxidation and selectivity to CH3Cl as well as a possible reason of oscillations of the conversion are proposed. by R. Oldenbourg Verlag, 1996.

Looking for a contribution of the non-equilibrium solvent polarization to the activation barrier of the SN2 reaction

Jaworski, Jan S.

, p. 319 - 323 (2002)

The solvent effect on the activation free energy of the Finkelstein reaction between methyl iodide and Cl- ions was analysed in terms of the recent Marcus theory unifying the SN2 and the electron transfer reactions. The homolytic bond dissociation energy and the related resonance energy of interaction of the states seem to be almost solvent independent. The sum of the work term Wr and the solvent reorganization energy λ0/4 depends strongly on the solvent acidity parameter, e.g. ETN, describing the solvation/desolvation of anions. However, after removing the contribution of the specific solvation the linear increase of the remaining part of λ0/4 with the Pekar factor, describing the non-equilibrium solvent polarization, was observed for six aprotic solvents. Copyright

Than,Leitch

, p. 557 (1971)

Highly Selective Catalytic Dechlorination of Dichloromethane to Chloromethane over Al?Ti Mixed Oxide Catalysts

Yoon, Wongeun,Lee, Seungjun,Noh, Yuseong,Park, Seongmin,Kim, Youngmin,Ju Kim, Hyung,Chae, Ho-Jeong,Bae Kim, Won

, p. 5098 - 5108 (2020)

In this paper, a series of Al?Ti mixed oxides with different Al/Ti ratios are prepared by a simple sol-gel method and they are used as active catalysts for selective dechlorination of dichloromethane to chloromethane. The Al?Ti mixed oxide catalyst with the same molar ratio of Al and Ti shows the highest activity in dechlorination of dichloromethane. The strong and abundant Lewis acid sites in the Al?Ti mixed oxides formed along with Al?O?Ti bondings are responsible for the high catalytic activity toward the selective dechlorination reaction in this work. From a kinetic study, the activation energy of this reaction over the optimum Al?Ti mixed oxide catalyst appears to be 59.4 kJ mol?1 based on Langmuir-Hinshelwood model. The improved catalytic performance suggests that the Al?Ti mixed oxide could be used as the effective catalyst for the highly selective dechlorination of dichloromethane to chloromethane.

Detailed kinetic investigation of the C2H5 + Cl2 reaction and analysis of the reaction of CH3 + Cl2 initiated by H-atom contamination at 298 K and at millitorr pressures

Dobis, Otto,Benson, Sidney W.

, p. 283 - 304 (2001)

The bimolecular reaction: C2H5+Cl2 →4 C2H5Cl+Cl is studied in the very low pressure reactor (VLPR) system at 298 K starting with Cl/C2H6/Cl2 mixtures. Mass conservation is found to be 97±3% for the overall chemical change in the system. From the C2H5Cl product formation kinetics, k4 = (1.05±0.05) · 10-12 cm3/(molecule-s) is derived. Two independent estimates of the A factor gives A4 = 1.3 · 10-12 cm3/(molecule-s). These parameters yield a positive activation energy of 0.13 kcal/mol in contrast with recently reported negative activation energy values. Some side reactions of small extent are initiated by H atom contamination in the system. The measurement of CH3Cl product formed from CH3+Cl2 →11 CH3Cl+Cl gives k11 = (3.4±0.3) · 10-12 cm3/(molecule-s) with an estimated A factor of A11 = 5.0 · 10-12 cm3/(molecules). The source of CH3 radicals is the side reaction H+C2H5 → 2CH3. by Oldenbourg Wissenschaftsverlag, Muenchen.

Zeldin, M.

, p. 1179 - 1186 (1971)

Kinetics and thermochemistry of the R + HBr ? RH + Br (R = CH2Cl, CHCl2, CH3CHCl or CH3CCl2) equilibrium

Seetula, Jorma A.

, p. 3069 - 3078 (1996)

The kinetics of the reactions of CH2Cl, CHCl2, CH3CHCl and CH3CCl2 with HBr have been investigated in a heatable tubular reactor coupled to a photoionization mass spectrometer. The radicals, R, were produced homogeneously in the reactor by pulsed 248 nm exciplex laser photolysis. The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature and pressure range. The reactions were studied separately over a wide temperature range and at these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student's t values, units in cm3 molecule-1 s-1): k(CH2Cl) = (6.6 ± 1.7) × 10-13 exp[-(4.1 ± 0.2) kJ mol-1/RT], k(CHCl2) = (4.1 ± 1.0) × 10-13 exp[-(9.8 ± 1.0) kJ mol-1/RT], k(CH3CHCl) = (3.0 ± 0.9) × 10-13 exp[+(3.0 ± 0.2) kJ mol-1/RT] and k(CH3CCl2) = (4.4 ± 0.9) × 10-13 exp[-(5.9 ± 0.7) kJ mol-1/RT]. The kinetic information obtained was combined with the what is known of the recently measured rate constants of the reverse reactions to calculate the entropy and the heat of formation values of the radicals studied. The thermodynamic values were obtained at 298 K using a second law procedure. The results for entropy values are as follows (units in J K-1 mol-1): 271 ± 7 (CH2Cl), 280 ± 7 (CHCl2), 279 ± 6 (CH3CHCl) and 288 ± 5 (CH3CCl2). The results for ΔfH°298 are as follows (units in kJ mol-1): 117.3 ± 3.1 (CH2Cl), 89.0 ± 3.0 (CHCl2), 76.5 ± 1.6 (CH3CHCl) and 42.5 ± 1.7 (CH3CCl2). The C-H bond energy of analogous chlorinated hydrocarbons derived from the enthalpy of reaction values are as follows (units in kJ mol-1): 419.0 ± 2.3 (CH3Cl), 402.5 ± 2.7 (CH2Cl2), 406.6 ± 1.5 (α-C-H bond in CH3CH2Cl) and 390.6 ± 1.5 (α-C-H bond in CH3CHCl2). Improved heats of formation for the CH2ClO2 radical, ΔfH°298(CH2ClO2) = -(4 ± 11) kJ mol-1, and for the CHCl2O2 radical, ΔfH°298(CHCl2O2) = -(17 ± 7) kJ mol-1 are also calculated from the previously measured R′ + O2 ? R′O2 (R′ = CH2Cl or CHCl2) equilibriums.

Photochemistry of adsorbed molecules. XII. Photoinduced ion-molecule reactions at a metal surface for CH3X/RCl/Ag(111) (X = Br, I)

Dixon-Warren, St. J.,Heyd, D. V.,Jensen, E. T.,Polanyi, J. C.

, p. 5954 - 5960 (1993)

A photoinduced ion-molecule reaction is reported between superimposed molecular layers of alkyl halides on a metal substrate CH3X/RCl/Ag(111) (where X = Br or I and R = CCl3, CHCl2, or CH2Cl) to form CH3Cl(ad) (wavelengths 193, 248, and 350 nm).The reaction is mediated by charge-transfer (CT) photodissociation, in which photoelectrons from the metal surface transfer to the lower layer of adsorbate RCl to form RCl-.These negative ions then react with the upper layer CH3X in an ion-molecule reaction to form CH3Cl + X-.The yield of product CH3Cl is found to be enhanced at ca. 1 ML of adsorbed CH3X (upper layer) due to a decrease in the local potential in the region of the adsorbate-adsorbate interface that enhances the probability of CT to the lower layer.In addition to lowering the local potential at the interface, the adsorbed CH3X also lowers the surface work function; as a result changes in the microscopic local potential correlate (via the CT reaction rate) with changes in the observed macroscopic work function.The yield of CH3Cl decreases at still higher CH3X coverage in the upper layer as the work fuction increases.The ion-molecule reaction give evidence of being a concerted process in which the Cl- reacts as it separates from RCl- rather than following separation.The reagent RCl-, as in the surface reaction discussed in the previous paper, is formed by CT from "hot" electrons rather than free photoelectrons.

Stimson,Tilley

, p. 81,82 - 86 (1977)

Temperature dependence of the kinetic isotope effect for a gas-phase SN2 reaction: Cl- + CH3Br

Viggiano,Paschkewitz, John S.,Morris, Robert A.,Paulson, John F.,Gonzalez-Lafont, Angels,Truhlar, Donald G.

, p. 9404 - 9405 (1991)

-

Observation of the XY- abstraction products in the ion-molecule reactions X- + RY → XY- + R: An alternative to the SN2 mechanism at suprathermal collision energies

Cyr, Donna M.,Scarton, M. Georgina,Wiberg, Kenneth B.,Johnson, Mark A.,Nonose, Shinji,Hirokawa, Jun,Tanaka, Hideki,Kondow, Tamotsu,Morris, Robert A.,Viggiano

, p. 1828 - 1832 (1995)

We report the formation of dihalide products from the endothermic gas-phase ion-molecule reaction of Cl- with CH3Br at suprathermal collision energies using both guided ion beam and selected ion flow drift tube (SIFDT) techniques. The cross sections for the Cl- + CH3Br reactions were determined using the guided ion beam apparatus over a center-of-mass collision energy range of 2-15 eV with the ClBr- product displaying a maximum near 7 eV. This result is found to be in good agreement (when convoluted with the appropriate velocity distribution) with the rate constant measured by the SIFDT. ICl- and I2- are also found for the Cl- + CH3I and I- + RI reactions at elevated collision energies (≤1.5 eV) in the SIFDT. The rates for halide displacement are found to be insensitive to collision energy. These results indicate that attack on the C-X bond may not provide an efficient alternative to the SN2 mechanism for halide exchange in the asymmetric X- + CH3Y systems. This conclusion is supported by ab initio calculations (MP2LANL10Z level) which indicate that ClBr- can be formed by collinear attack at the halogen through a Cl?Br?CH3 intermediate.

Trialkylammonium salt degradation: Implications for methylation and cross-coupling

Assante, Michele,Baillie, Sharon E.,Juba, Vanessa,Leach, Andrew G.,McKinney, David,Reid, Marc,Washington, Jack B.,Yan, Chunhui

, p. 6949 - 6963 (2021/06/02)

Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. 1H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell SN2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse. This journal is

A process of preparing methyl chloride using multistage reaction

-

Paragraph 0092-0100; 0112; 0120, (2020/06/10)

The present invention relates to a method of producing methyl chloride by multistage reactions. The method of the present invention comprises: a) a chlorination step for sufficiently increasing the conversion rate of methane, which is an initial reactant; and b) a subsequent reaction step for actively utilizing hydrogen chloride (HCl), which is a hazardous byproduct of chlorination, efficiently treating harmful hydrogen chloride, and at the same time, improving the overall production of methyl chloride.COPYRIGHT KIPO 2020

Control of methane chlorination with molecular chlorine gas using zeolite catalysts: Effects of Si/Al ratio and framework type

Kwon, Seungdon,Chae, Ho-Jeong,Na, Kyungsu

, p. 111 - 117 (2020/01/31)

CH4 chlorination with Cl2 gas is used for the production of chlorinated products via C–H bond activation in CH4. Due to the high reactivity of Cl2, this reaction can occur spontaneously under UV irradiation or with mild thermal energy even in the absence of a catalyst via a free radical-mediated chain reaction mechanism that undesirably causes excessive chlorination of the CH4 and is thus non-selective. In this work, CH4 chlorination is investigated using HY and MFI zeolites with various Si/Al ratios, by which the reaction is catalytically controlled for selective production of the mono-chlorinated product (CH3Cl). Depending on the framework type, Si/Al ratio of the zeolites, and reaction conditions, different degrees of CH4 conversion, CH3Cl selectivity, and hence CH3Cl yield were achieved, by which systematic relationships between the catalyst properties and performance were discovered. A high aluminum content facilitated the production of CH3Cl with up to ~20 % yield at a high gas hourly space velocity of 2400 cm3gcat?1 h?1 with a CH4/Cl2 ratio of 1 at 350 °C. HY zeolites generally furnished a slightly higher CH3Cl yield than MFI zeolites, which can be attributed to the larger micropores of the HY zeolites that support facile molecular diffusion. With various flow rates and ratios of CH4 and Cl2, the CH4 conversion and CH3Cl selectivity changed simultaneously, with a trade-off relationship. Unfortunately, all zeolite catalysts suffered from framework dealumination due to the HCl produced during the reaction, but it was less pronounced for the zeolites having a low aluminum content. The results shed light on the detailed roles of zeolites as solid-acid catalysts in enhancing CH3Cl production during electrophilic CH4 chlorination.

Process route upstream and downstream products

Process route

1,2-Dichloropropane
26198-63-0,78-87-5

1,2-Dichloropropane

diacetyl peroxide
110-22-5

diacetyl peroxide

methylene chloride
74-87-3

methylene chloride

1,2,2-trichloropropane
3175-23-3

1,2,2-trichloropropane

propenyl chloride
590-21-6

propenyl chloride

Conditions
Conditions Yield
at 80 ℃; weitere Produkte: 1-Chlor-2-methyl-propan, meso-1,2,3,4-Tetrachlor-2,3-dimethyl-butan und racem.-1,2,3,4-Tetrachlor-2,3-dimethyl-butan;
sodium ethanolate
141-52-6

sodium ethanolate

Chloromethyltrimethylsilane
2344-80-1

Chloromethyltrimethylsilane

methylene chloride
74-87-3

methylene chloride

ethyl trimethylsilyl ether
1825-62-3

ethyl trimethylsilyl ether

(trimethylsilyl)methyl ethyl ether
17348-58-2

(trimethylsilyl)methyl ethyl ether

Conditions
Conditions Yield
dichlorotris<(trimethylsiloxy)methyl>phosphorane
74858-10-9

dichlorotris<(trimethylsiloxy)methyl>phosphorane

methylene chloride
74-87-3

methylene chloride

Trimethylmethoxysilane
1825-61-2

Trimethylmethoxysilane

tri(hydroxymethyl)phosphine oxide
1067-12-5

tri(hydroxymethyl)phosphine oxide

Conditions
Conditions Yield
With methanol; In dichloromethane; at -70 ℃; Yield given;
hydrogenchloride
7647-01-0,15364-23-5

hydrogenchloride

2-methyl-5-phenyl-2H-tetrazole
20743-49-1

2-methyl-5-phenyl-2H-tetrazole

5-Phenyl-1H-tetrazole
18039-42-4,3999-10-8

5-Phenyl-1H-tetrazole

methylene chloride
74-87-3

methylene chloride

ammonia
7664-41-7

ammonia

methylamine
74-89-5

methylamine

Conditions
Conditions Yield
at 150 ℃; und andere Zersetzungsprodukte;
hydrogenchloride
7647-01-0,15364-23-5

hydrogenchloride

methyl bromide
74-83-9

methyl bromide

methylene chloride
74-87-3

methylene chloride

hydrogen bromide
10035-10-6,12258-64-9

hydrogen bromide

Conditions
Conditions Yield
at 333 ℃; Kinetics;
hydrogenchloride
7647-01-0,15364-23-5

hydrogenchloride

methyl bromide
74-83-9

methyl bromide

methylene chloride
74-87-3

methylene chloride

hydrogen bromide
10035-10-6,12258-64-9

hydrogen bromide

Conditions
Conditions Yield
at 170 ℃; Kinetics;
at 84 ℃; Kinetics;
trichloro-chloromethoxy-silane
18157-08-9

trichloro-chloromethoxy-silane

hydrogenchloride
7647-01-0,15364-23-5

hydrogenchloride

tetrachlorosilane
10026-04-7,53609-55-5

tetrachlorosilane

methylene chloride
74-87-3

methylene chloride

dichloromethane
75-09-2

dichloromethane

Conditions
Conditions Yield
at 200 ℃;
(Oph-2-Ome)SiCl<sub>3</sub>
18141-30-5

(Oph-2-Ome)SiCl3

tetrachlorosilane
10026-04-7,53609-55-5

tetrachlorosilane

methylene chloride
74-87-3

methylene chloride

Conditions
Conditions Yield
under 30 Torr;
methyl iodide
74-88-4

methyl iodide

methylene chloride
74-87-3

methylene chloride

hydrogen iodide
10034-85-2

hydrogen iodide

Conditions
Conditions Yield
With hydrogenchloride; Irradiation (UV/VIS); photochemical reaction;;
With HCl; Irradiation (UV/VIS); photochemical reaction;;
methanol
67-56-1

methanol

sulfur dichloride
10545-99-0

sulfur dichloride

hydrogenchloride
7647-01-0,15364-23-5

hydrogenchloride

disulfur dichloride
10025-67-9

disulfur dichloride

thionyl chloride
7719-09-7

thionyl chloride

methylene chloride
74-87-3

methylene chloride

Conditions
Conditions Yield
In neat (no solvent); vigorous reaction in coldness;;

Global suppliers and manufacturers

Global( 44) Suppliers
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  • Amadis Chemical Co., Ltd.
  • Business Type:Lab/Research institutions
  • Contact Tel:86-571-89925085
  • Emails:sales@amadischem.com
  • Main Products:29
  • Country:China (Mainland)
  • Chemwill Asia Co., Ltd.
  • Business Type:Manufacturers
  • Contact Tel:021-51086038
  • Emails:sales@chemwill.com
  • Main Products:56
  • Country:China (Mainland)
  • Kono Chem Co.,Ltd
  • Business Type:Other
  • Contact Tel:86-29-86107037-8015
  • Emails:info@konochemical.com
  • Main Products:82
  • Country:China (Mainland)
  • Antimex Chemical Limied
  • Business Type:Lab/Research institutions
  • Contact Tel:0086-21-50563169
  • Emails:anthony@antimex.com
  • Main Products:163
  • Country:China (Mainland)
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