507-20-0Relevant articles and documents
Activation of C-S bond by group 10 metal complexes: Reaction of phosphine ligand tethered with three tert-butylthiophenyl groups with group 10 metal compounds
Takeda, Nobuhiro,Tanaka, Yusuke,Oma, Rin,Sakakibara, Fumiaki,Unno, Masafumi
, p. 922 - 930 (2016)
A new PS3-type tripodal tetradentate ligand, P(2-t-BuSC6H4)3 (1b), was synthesized by reaction of PCl3 with 2-t-BuS(C6H4)Li. Reaction of ligand 1b with NiCl26H2O resulted in the elimination of t-BuCl to afford the corresponding 5-coordinate nickel complex, [NiCl(P(2-SC6H4)(2-t-BuSC6H4)2}] 6. In addition, ligand 1b reacted with [PdCl2(PhCN)2] and [PtCl2(cod)] to give 4-coordinate square planar palladium and platinum complexes, [MCl(P(2-SC6H4)(2-t-BuSC6H4)2}] (7: M = Pd, 8: M = Pt), respectively, via the elimination of t-BuCl. Further elimination of t-BuCl from palladium complex 7 proceeded by heating of 7 in CDCl3 at 100°C for 4h to form dipalladium complex, [Pd2(P(2-SC6H4)2(2-t-BuSC6H4))2] (9). The isopropyl-substituted palladium and platinum complexes, [PdCl{P(2-i-PrSC6H4)3}]Cl (3a) and [PtCl2{P(2-i-PrSC6H4)3}] (5), also underwent the elimination of i-PrCl by the thermolysis in CDCl3 at 60 °C to afford the corresponding complexes, [MCl{P(2-SC6H4)(2-i-PrSC6H4)2}] (11: M = Pd, 12: M = Pt). The structures of these complexes were determined by NMR spectroscopy, elemental analyses, and X-ray crystallography.
Stabilities of Carbonium Ions in Solution. 12. Heats of Formation of Alkyl Chlorides as an Entree to Heats of Solvation of Aliphatic Carbonium Ions
Arnett, Edward M.,Pienta, Norbert J.
, p. 3329 - 3334 (1980)
Heats of formation (ΔHf) of tertiary alkyl chlorides may be calculated from measurements of the heats of hydrochlorination of appropriate olefins at -50 deg C in CH2Cl2.Since many good values for heats of formation of the olefins have been published, the heats of hydrochlorination lead directly to ΔHf for the chlorides, for which few previous values are available.The new data, when combined with previously reported heats of ionization for the chlorides, provide heats of formation for the carbonium ions.Relative values for ΔHf for the carbonium ions are remarkably similar in the gas phase and in SO2ClF, thus supporting the proposal that differential solvation of carbonium ions is small in solvents such as SO2ClF.Because solvation energies are nearly constant for carbonium ions, their relative energies as calculated from quantum theory should apply directly to nonnucleophilic condensed phase values - a situation which is drastically different from that for ammonium or oxonium ions.We have shown previously the close relationship between ionization energies for alkyl chlorides in SO2ClF and their solvolysis rates in ethanol.The present results complete the series of data which are necessary for rigorously relating theoretical calculations of carbonium ion stability to solvolysis reaction rates in solution.Thereby, they help to explain the great success of the carbonium ion theory of organic chemistry.
Matrix Isolation Study of Complexation and Exchange Reactions of Molecular Halogens with tert-Butyl Halides
Bai, Hebi,Ault, Bruce S.
, p. 3080 - 3084 (1991)
The 1/1 molecular complexes of tert-butyl chloride and bromide with ClF, Cl2 and Br2 have been isolated and characterized in argon matrices following twin-jet deposition.Perturbed vibrational modes of the tert-butyl halide, including the carbon-halogen stretching and the CH3 rocking modes, were observed upon complex formation.For the ClF complexes, the red-shifted Cl-F stretching mode was observed as well.The twin-jet codeposition of (CH3)3Br with Cl2 and ClF led to the exchange reaction product (CH3)3CCl, despite the very short mixing time in these experiments.The single-jet codeposition of these pairs of reactants led to further reactions, forming tert-butyl fluoride in the ClF experiments and 1,2-dichloro-2-methylpropane in the reactions of (CH3)3CCl and (CH3)3CBr with Cl2.While the halogen-exchange reactions are very facile, these results support the intermediacy of molecular complexes during the reaction process.
UN NOUVEAU DIPHOSPHENE STABLE : LE BISDIPHOSPHENE
Couret, Claude,Escudie, Jean,Satge, Jacques
, p. 4941 - 4942 (1982)
A new stable diphosphene (Me3Si)3C-P=P-C(SiMe3)3 has been isolated and characterized particularly by its NMR data; the 31P NMR chemical shift appears to be the largest ever observed.
Kinetics of the Reactions of Methyl, Ethyl, Isopropyl, and tert-Butyl Radicals with Molecular Chlorine
Timonen, Raimo S.,Gutman, David
, p. 2987 - 2991 (1986)
The gas-phase kinetics of the reactions of four alkyl radicals (CH3, C2H5, i-C3H7, and t-C4H9) with molecular chlorine have been studied over limited temperature ranges.The reactions were isolated for quantitative study in a tubular reactor coupled to a photoionization mass spectrometer.The radicals were homogeneously generated in the reactor by pulsed photolysis of suitable precursor molecules at 193 nm.The subsequent decays of the radical concentration in the presence of different molecular chlorine concentrations were monitored in real-time experiments.For each reaction studied, rate constants (k) were measured at a minimum of five temperatures.The temperature-dependent expressions for log k derived from these studies for the four R + Cl2 -> RCl + Cl reactions and the temperature ranges covered are as follows: R = CH3 , 296-712 K; R = C2H5 , 295-498 K; R = i-C3H7 , 298-498 K; R = t-C4H9 , 298-498 K.Units are cm3 molecule-1 s-1.The measured rate constants, their closeness to those of corresponding R + O3 rate constants, and the results of a prior study of the dynamics of the CH3 + Cl2 reaction indicate that the reactivity of alkyl radicals with molecular chlorine is determined largely by long-range attractive forces.
Hydrochlorination of Alkenes. 2. Reaction of Gases Hydrogen Chloride and 2-Methylpropene
Costello, Francis,Dalton, David R.,Poole, John A.
, p. 5352 - 5357 (1986)
Mixtures of gaseous hydrogen chloride and gaseous 2-methylpropene at total pressures less than 1 atm yield, exclusively, gaseous 2-chloro-2-methylpropane.Kinetic measurements have been made by proton magnetic resonance and infrared spectroscopy and by observing the pressure change accompanying the reaction.It is concluded that surface catalysis is required for product formation and that the reaction, which occurs at the walls, is most probably between strongly adsorbed hydrogen chloride and weakly adsorbed 2-methylpropene; i.e., a Rideal-Eley mechanism obtains.
Method for synthesizing musk xylene from gamma-lactone byproduct azeotrope
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Paragraph 0044-0049; 0059-0064, (2021/04/17)
The invention discloses a method for synthesizing musk xylene from a gamma-lactone byproduct azeotrope. The method comprises the following steps: 1, carrying out chlorination reaction on tert-butyl alcohol namely a byproduct in the production process of gamma-lactone and hydrochloric acid to obtain chloro-tert-butane; 2, carrying out a condensation reaction on chloro-tert-butane and m-xylene, neutralizing, washing with water, and distilling to recover m-xylene so as to obtain 1,3-dimethyl-5-tert-butyl benzene; and 3, carrying outnitration reaction on 1,3-dimethyl-5-tert-butyl benzene to obtain a musk xylene crude product, carrying out neutralization washing, crystallization, centrifugation and a series of separation and purification to obtain a 99% musk xylene product. An initiator di-tert-butyl peroxide used in the production process of gamma-lactone is hydrolyzed, the high-content musk xylene is prepared from the generated byproduct 80% tert-butyl alcohol and a water azeotrope starting raw material through chlorination, condensation and nitration reactions, the synthesis steps are relatively simple, and the byproduct resources are comprehensively utilized.
Chlorinating preparation method for low-carbon olefins
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Paragraph 0037-0039, (2020/01/12)
The invention discloses a chlorinating preparation method for low-carbon olefins. According to the method, chlorine gas is diluted with inert gas and then reacts with low-carbon olefins, thus, influence caused by microscopic mixing can be obviously reduced, namely, a too high local temperature can be avoided, thus, side reactions including a decarbonization phenomenon caused by the too high localtemperature can be obviously reduced, and a relatively good chloride yield can be obtained.
Method for co-producing methyl chloropropene and 2-chloro-2-methylpropane by chlorination of isobutene
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Paragraph 0022; 0026, (2020/01/12)
The invention discloses a method for co-producing methyl chloropropene and 2-chloro-2-methylpropane by chlorination of isobutene. According to the method, a chlorination reaction is carried out on chlorine or a mixture of chlorine and inert gas and excessive isobutene to obtain products, namely methyl chloropropene and 2-chloro-2-methylpropane. The method can reduce influence of micro-mixing on arapid chlorination reaction of isobutene, decarburization and coking do not occur easily, and 2-chloro-2-methylpropane can be co-produced while the yield of methyl chloropropene is improved.
Aryloxy Triester Phosphoramidates as Phosphoserine Prodrugs: A Proof of Concept Study
Dhiani, Binar A.,James, Edward,Kadri, Hachemi,Lambourne, Olivia A.,Mehellou, Youcef,Miccoli, Ageo,Thornton, Peter J.
supporting information, (2020/03/30)
The specific targeting of protein-protein interactions by phosphoserine-containing small molecules has been scarce due to the dephosphorylation of phosphoserine and its charged nature at physiological pH, which hinder its uptake into cells. To address these issues, we herein report the synthesis of phosphoserine aryloxy triester phosphoramidates as phosphoserine prodrugs that are enzymatically metabolized to release phosphoserine. This phosphoserine-masking approach was applied to a phosphoserine-containing inhibitor of 14-3-3 dimerization, and the generated prodrugs exhibited improved pharmacological activity. Collectively, this provided a proof of concept that the masking of phosphoserine with biocleavable aryloxy triester phosphoramidate masking groups is a viable intracellular delivery system for phosphoserine-containing molecules. Ultimately, this will facilitate the discovery of phosphoserine-containing small-molecule therapeutics.
