76-83-5Relevant articles and documents
UNEXPECTED CATALYTIC SULFUR EXTRUSION IN THE REACTION OF TRIPHENYLMETHANESULFENYL CHLORIDE WITH THIOCARBONYLS
Williams, Charles R.,Harpp, David N.
, p. 7633 - 7636 (1991)
When triphenylmethanesulfenyl chloride (1) is treated with thiocarbonyls, an unexpected sulfur extrusion results.The mechanism of the reaction is investigated with the aid of 19F NMR spectroscopy.Indirect evidence for a thiosulfine (10) or dithiirane (11) is presented.
Red and green chemiluminescence of Na, Mg, and lanthanide triphenylmethyl derivatives during oxidation by dioxygen and cerium(IV)
Bulgakov,Kuleshov,Valiullina,Mustafin
, p. 1091 - 1094 (1999)
Chemiluminescence (CL) of triphenylmethyl organometallics (TPM), Ph3CNa, Ph3CMgCl, and Ph3CLnCl2 (Ln = Cd, Eu, and Dy), in THF and toluene during oxidation by O2 and the (NH4)2Ce(NO3)6 complex was found. The first CL is caused by the luminescence of two emitters: (Ph3C.)*, emitting in the green spectral region (λmax = 524, 550 nm), and an unstable product of substitution of the hydrogen atom in the phenyl ring of the Ph3C. radical, emitting in the red region (λmax = 580±20 nm). The emitter of the second CL, Ph3C. *, is generated in the elementary electron transfer from the Ph3C- anion to CeIV, reducing the latter to CeIII.
Process for preparing triphenylchloromethane
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Paragraph 0042-0059, (2021/06/22)
The invention discloses a process for preparing triphenylchloromethane, which comprises the following steps of carrying out Friedel-Crafts reaction on pure benzene and carbon tetrachloride under the catalytic action of anhydrous aluminum trichloride to obtain a product containing Friedel-Crafts reaction liquid, dropwise adding the Friedel-Crafts reaction solution into a pure benzene and hydrochloric acid aqueous solution for quenching reaction, and standing for layering after dropwise adding to obtain an oil phase, introducing dry HCl gas and adding anhydrous calcium chloride into the oil phase, carrying out heat preservation reaction in a temperature environment, and then carrying out filter pressing to obtain an organic phase, carrying out atmospheric distillation on the organic phase, and continuing vacuum drying when no fraction exists to obtain a dry crude product, and adding a xylene solvent into the dried crude product for dissolving, adding anhydrous calcium chloride, introducing dry HCl gas, carrying out a heat preservation reaction in a temperature environment, removing the HCl gas and part of the xylene solvent after the reaction is finished, and carrying out hot filtration, freezing crystallization, filter pressing, washing and drying to obtain the product. The method not only improves the yield and purity of triphenylchloromethane, but also avoids the problem of pollution in the process.
Halogen Transfer to Carbon Radicals by High-Valent Iron Chloride and Iron Fluoride Corroles
Farley, Geoffrey W.,Siegler, Maxime A.,Goldberg, David P.
, p. 17288 - 17302 (2021/11/17)
High-valent iron halide corroles were examined to determine their reactivity with carbon radicals and their ability to undergo radical rebound-like processes. Beginning with Fe(Cl)(ttppc) (1) (ttppc = 5,10,15-tris(2,4,6-triphenylphenyl)corrolato3-), the new iron corroles Fe(OTf)(ttppc) (2), Fe(OTf)(ttppc)(AgOTf) (3), and Fe(F)(ttppc) (4) were synthesized. Complexes 3 and 4 are the first iron triflate and iron fluoride corroles to be structurally characterized by single crystal X-ray diffraction. The structure of 3 reveals an AgI-pyrrole (η2-π) interaction. The Fe(Cl)(ttppc) and Fe(F)(ttppc) complexes undergo halogen transfer to triarylmethyl radicals, and kinetic analysis of the reaction between (p-OMe-C6H4)3C?and 1 gave k = 1.34(3) × 103 M-1 s-1 at 23 °C and 2.2(2) M-1 s-1 at -60 °C, ΔHL = +9.8(3) kcal mol-1, and ΔSL = -14(1) cal mol-1 K-1 through an Eyring analysis. Complex 4 is significantly more reactive, giving k = 1.16(6) × 105 M-1 s-1 at 23 °C. The data point to a concerted mechanism and show the trend X = F- > Cl- > OH- for Fe(X)(ttppc). This study provides mechanistic insights into halogen rebound for an iron porphyrinoid complex.
Synthesis method of triphenylchloromethane
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Paragraph 0018-0024, (2020/05/05)
The invention discloses a synthesis method of triphenylchloromethane, which relates to the technical field of medical intermediates. The synthesis method comprises the following steps of: S1, mixing and stirring benzene and anhydrous ferric trichloride for 10-15 min, and dropwise adding carbon tetrachloride when the liquid temperature is lower than 15 DEG C, S2, after dropwise adding is completed,heating to 150 DEG C while stirring, keeping the kettle pressure at 0.6-0.65 MPa, and carrying out a heat and pressure maintaining reaction for 1 h, and S3, carrying out post-treatment on the reaction solution obtained in the step S2 to obtain triphenylchloromethane. According to the synthesis method of triphenylchloromethane, anhydrous ferric trichloride is used as a catalyst, and the mass ratioof carbon tetrachloride to ferric trichloride is 1: (0.01-0.5), so that side reactions are reduced, reaction post-treatment is simplified, the output of wastewater is reduced, the reaction yield reaches 80-82%, and the purity reaches 99% or above.
C(sp3)-H Fluorination with a Copper(II)/(III) Redox Couple
Bower, Jamey K.,Cypcar, Andrew D.,Henriquez, Brenda,Stieber, S. Chantal E.,Zhang, Shiyu
supporting information, p. 8514 - 8521 (2020/05/28)
Despite the growing interest in the synthesis of fluorinated organic compounds, few reactions are able to incorporate fluoride ions directly into alkyl C-H bonds. Here, we report the C(sp3)-H fluorination reactivity of a formally copper(III) fluoride complex. The C-H fluorination intermediate, LCuF, along with its chloride and bromide analogues, LCuCl and LCuBr, were prepared directly from halide sources with a chemical oxidant and fully characterized with single-crystal X-ray diffraction, X-ray absorption spectroscopy, UV-vis spectroscopy, and 1H nuclear magnetic resonance spectroscopy. Quantum chemical calculations reveal significant halide radical character for all complexes, suggesting their ability to initiate and terminate a C(sp3)-H halogenation sequence by sequential hydrogen atom abstraction (HAA) and radical capture. The capability of HAA by the formally copper(III) halide complexes was explored with 9,10-dihydroanthracene, revealing that LCuF exhibits rates 2 orders of magnitude higher than LCuCl and LCuBr. In contrast, all three complexes efficiently capture carbon radicals to afford C(sp3)-halogen bonds. Mechanistic investigation of radical capture with a triphenylmethyl radical revealed that LCuF proceeds through a concerted mechanism, while LCuCl and LCuBr follow a stepwise electron transfer-halide transfer pathway. The capability of LCuF to perform both hydrogen atom abstraction and radical capture was leveraged to enable fluorination of allylic and benzylic C-H bonds and α-C-H bonds of ethers at room temperature.
Straightforward formation of carbocations from tertiary carboxylic acids: Via CO release at room temperature
Bartalucci, Niccolò,Pampaloni, Guido,Marchetti, Fabio,Bortoluzzi, Marco,Zacchini, Stefano
supporting information, p. 1574 - 1577 (2019/04/02)
We report an unprecedented mode of reactivity of carboxylic acids. A series of tertiary carboxylic acids, containing at least one phenyl α-substituent, undergo loss of carbon monoxide at room temperature (295 K), by a one pot reaction with 0.5-1 molar equivalents of WCl6 in dichloromethane. A plausible mechanism for the Ph3CCO2H/WCl6 reaction, leading to [CPh3][WOCl5] and Ph3CCl, is proposed on the basis of DFT calculations. The analogous reactions involving CEt(Ph)2CO2H, CMe(Ph)2CO2H and CMe2(Ph)CO2H selectively afforded stable hydrocarbons (alkene or indene, depending on the case), apparently resulting from the rearrangement of elusive tertiary carbocations.
Recycling and reuse technology for preparing triphenylchloromethane
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Paragraph 0042-0065, (2019/10/01)
The invention provides a recycling and reuse technology for preparing triphenylchloromethane. The technology comprises the following steps that hydrochloric acid or a mixture of the hydrochloric acidand Lewis acid is added into a solvent of triphenylcarbinol, stirring is conducted at a certain temperature, after a reaction is finished, separation is conducted, or after separation, recrystallization is further conducted, and the triphenylchloromethane is obtained after drying, wherein the reaction equation is shown in the description. The reuse technology is a recycling and reuse technology which is wide in raw material source, low in price and simple in production process operation and causes little pollution, and the technology is very suitable for commercialized production.
Organocatalytic Chlorination of Alcohols by P(III)/P(V) Redox Cycling
Longwitz, Lars,Jopp, Stefan,Werner, Thomas
, p. 7863 - 7870 (2019/06/27)
A catalytic system for the chlorination of alcohols under Appel conditions was developed. Benzotrichloride is used as a cheap and readily available chlorinating agent in combination with trioctylphosphane as the catalyst and phenylsilane as the terminal reductant. The reaction has several advantages over other variants of the Appel reaction, e.g., no additional solvent is required and the phosphane reagent is used only in catalytic amounts. In total, 27 different primary, secondary, and tertiary alkyl chlorides were synthesized in yields up to 95%. Under optimized conditions, it was also possible to convert epoxides and an oxetane to the dichlorinated products.
A visible light photoredox catalyzed carbon radical-mediated generation of: Ortho -quinone methides for 2,3-dihydrobenzofuran synthesis
Zhou, Fan,Cheng, Ying,Liu, Xiao-Peng,Chen, Jia-Rong,Xiao, Wen-Jing
supporting information, p. 3117 - 3120 (2019/04/02)
A visible light photoredox-catalyzed carbon radical-mediated strategy for in situ formation of ortho-quinone methides from 2-vinyl phenols is described. This strategy enables a multicomponent cyclization reaction of 2-vinyl phenols, Umemoto's reagent, and
