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.
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.
-
Cook,Parker
, p. 142 (1968)
-
Speer, R. J.
, p. 655 - 659 (1949)
-
Milas,Harris
, p. 2434 (1938)
-
-
Majima,Simanuki
, (1927)
-
Method for synthesizing musk xylene from gamma-lactone byproduct azeotrope
-
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.
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.
Protecting and Leaving Functions of Trimethylsilyl Groups in Trimethylsilylated Silicates for the Synthesis of Alkoxysiloxane Oligomers
Yoshikawa, Masashi,Tamura, Yasuhiro,Wakabayashi, Ryutaro,Tamai, Misa,Shimojima, Atsushi,Kuroda, Kazuyuki
supporting information, p. 13990 - 13994 (2017/10/31)
The concept of protecting groups and leaving groups in organic synthesis was applied to the synthesis of siloxane-based molecules. Alkoxy-functionalized siloxane oligomers composed of SiO4, RSiO3, or R2SiO2 units were chosen as targets (R: functional groups, such as Me and Ph). Herein we describe a novel synthesis of alkoxysiloxane oligomers based on the substitution reaction of trimethylsilyl (TMS) groups with alkoxysilyl groups. Oligosiloxanes possessing TMS groups were reacted with alkoxychlorosilane in the presence of BiCl3 as a catalyst. TMS groups were substituted with alkoxysilyl groups, leading to the synthesis of alkoxysiloxane oligomers. Siloxane oligomers composed of RSiO3 and R2SiO2 units were synthesized more efficiently than those composed of SiO4 units, suggesting that the steric hindrance around the TMS groups of the oligosiloxanes makes a difference in the degree of substitution. This reaction uses TMS groups as both protecting and leaving groups for SiOH/SiO? groups.
