- Novelties of selective triphasic synthesis of bis-(p-chlorobenzyl) sulfide using hydrogen sulfide and reusable phase transfer catalyst
-
The present investigation is based on the advancement in hydrogen sulfide (H2S) capture and utilization (HSCU). Commercially H2S is absorbed efficiently using alkanolamines such as methyldiethanolamine (MDEA). Aqueous H2S-rich MDEA is proposed to act as a sulfiding agent for aromatic halides such as p-chlorobenzyl chloride (p-CBC) to synthesize value-added thioethers. The objective of the present investigation is to synthesize bis-(p-chlorobenzyl) sulfide (BPCBS), a value-added thioether, selectively using p-CBC and H2S-laden aqueous MDEA. For the immiscible bi-phasic system, reusable solid phase transfer catalyst, polymer-bound tributylmethylammonium chloride (PBTBMAC) was employed under liquid-liquid-solid (L-L-S) mode in the presence of solvent toluene to enhance the reaction rate and product selectivity. Full conversion of p-CBC was obtained with 100% selectivity towards the desired product BPCBS at optimized specific level of process parameters. The catalyst has shown substantial activity even after three times of reuse, which leads to waste minimization and economic benefits. A generalized empirical kinetic model was developed and successfully validated against the experimental results. The triphasic reaction thus leads to process intensification, waste minimization and selectivity enhancement. The process can be utilized as an alternative to many other HSCU processes to utilize the sour gas in synthesizing value-added chemicals.
- Jha, Preeti,Mondal, Ujjal,Gogoi, Devipriya,Singh, Gaurav,Sen, Sujit
-
-
Read Online
- Synthesis method of dibenzyl sulfide
-
As an important organic intermediate and a synthesis reagent, an organic sulfur compound also has unique pharmacological effects of resisting tumors, inflammation, bacteria and oxidation, preventing aging, preventing and treating cardiovascular diseases and the like. The patent develops a method for synthesizing dibenzyl sulfide without metal catalysis. In an acetonitrile solution, benzyl trifluoromethanesulfonic acid quaternary ammonium salt and sodium sulfide nonahydrate are used to synthesize dibenzyl sulfide in a wide substrate range with good to excellent yield through breakage of a carbon-nitrogen bond and generation of a carbon-sulfur bond. The method has the advantages of mild reaction conditions, simple operation, no metal, high yield, wide substrate applicability and the like.
- -
-
Paragraph 0008-0012; 0031-0033
(2021/02/06)
-
- Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
-
Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (H2S) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
- Corma, Avelino,Sorribes, Iván
-
p. 3130 - 3142
(2019/03/13)
-
- Indium-catalyzed direct conversion of dibenzyl ethers to dibenzyl sulfides using elemental sulfur and a hydrosilane and its application to the preparation of benzyl selenides
-
Described herein is a catalytic system composed of an indium(III) compound, a hydrosilane and an easily handled form of elemental sulfur (S8) that effectively and directly catalyzes the sulfidation of dibenzyl ethers to produce dibenzyl sulfides. This system could also be applied to selenium in a straightforward conversion to dibenzyl selenides.
- Sakai, Norio,Takada, Koji,Katayama, Masahiro,Ogiwara, Yohei
-
p. 791 - 793
(2018/06/12)
-
- Phase-vanishing method with gas evolution and its application to organic synthesis
-
Using a phase-vanishing (PV) system, hydrogen, oxygen, and hydrogen sulfide generated in situ from CaH2, KO2, and P2S5, respectively, were directly reacted with substances in the organic phase to afford the desired products. The selective synthesis of sulfides and disulfides was achieved with the evolution of H2S gas via tuning the bases used in the PV method. Using this PV system, reactions with hazardous gaseous reagents can be carried out easily and safely in a common test tube.
- Matake, Ryosuke,Niwa, Yuki,Matsubara, Hiroshi
-
p. 672 - 675
(2016/01/26)
-
- Indium-catalyzed reductive three-component coupling reaction of aliphatic/aromatic carboxylic acids with t-butyl mercaptan leading to unsymmetrical dialkyl sulfides
-
An InI3–TMDS (1,1,3,3-tetramethyldisiloxane) reducing system efficiently catalyzed a sequential three-component coupling of aliphatic carboxylic acids, aromatic carboxylic acids, and t-butyl mercaptan (t-butylthiol), to produce unsymmetrical dialkyl sulfides. With this reducing system, t-butyl mercaptan became a new source of sulfidation via an alkyl t-butyl sulfide that functioned as the reaction intermediate.
- Sakai, Norio,Yoshimoto, Shunsuke,Miyazaki, Takahiro,Ogiwara, Yohei
-
supporting information
p. 3117 - 3120
(2016/07/06)
-
- Indium-catalyzed direct preparation of dibenzyl sulfides from benzyl alcohols and elemental sulfur with a hydrosilane and its application to the preparation of dibenzyl selenide
-
We describe how a reducing system composed of InI3 and a hydrosilane efficiently and directly introduce elemental sulfur into the structure of dibenzyl sulfides via a nucleophilic substitution of benzyl alcohols. Also, we describe the application of this reducing system in the direct preparation of a dibenzyl selenide derivative with selenium.
- Miyazaki, Takahiro,Katayama, Masahiro,Yoshimoto, Shunsuke,Ogiwara, Yohei,Sakai, Norio
-
supporting information
p. 676 - 679
(2016/01/26)
-
- Indium-catalyzed reductive sulfidation of aromatic carboxylic acids and aldehydes with elemental sulfur to prepare symmetrical benzyl sulfides
-
Described herein is a direct approach to symmetrical thioethers from either aromatic carboxylic acids or aromatic aldehydes with elemental sulfur (S8) by using a reducing system combined with InI3 and 1,1,3,3-tetramethyldisiloxane (TMDS). This sulfidation does not require functionalized sulfur reagents, such as sulfides, disulfides, or metal sulfides, and it simultaneously forms two carbon-sulfur bonds in a single catalytic system. The coupling reaction of either aromatic carboxylic acids or aromatic aldehydes with elemental sulfur in the presence of a catalytic amount of InI3 and TMDS effectively produced the corresponding symmetrical benzyl sulfide derivatives.
- Miyazaki, Takahiro,Nishino, Kota,Yoshimoto, Shunsuke,Ogiwara, Yohei,Sakai, Norio
-
supporting information
p. 1991 - 1994
(2015/03/18)
-
- Indium(III)-catalyzed reductive one-pot synthesis of thioethers from aromatic aldehydes and elemental sulfur
-
Described herein is that a combination of InI3 and 1,1,3,3-tetramethyldisiloxane (TMDS) effectively promotes the reductive thioetherification from aromatic aldehydes with elemental sulfur (S8).
- Miyazaki, Takahiro,Nishino, Kota,Konakahara, Takeo,Sakai, Norio
-
p. 1378 - 1379
(2015/08/18)
-
- Iodine-mediated thioetherification of alcohols with disulfides or NaSh under microwave irradiation
-
An efficient and novel method for the thioetherification of an alcohol with disulfides or NaSH under microwave irradiation is presented. In the presence of iodine, a variety of alcohols were smoothly S-alkylated with disulfides or NaSH to give the corresponding thioethers in moderate to excellent yields. Copyright
- Hu, Bolun,Sun, Leilei,Tang, Riyuan,Hu, Huanan
-
p. 2556 - 2562,7
(2020/09/16)
-
- 2-chloro-1,3-dimethylimidazolinium chloride. 3. Utility for chlorination, oxidation, reduction, and rearrangement reactions
-
2-Chloro-1,3-dimethylimidazolinium chloride (1), which can act as a powerful dehydrating equivalent to DCC (2), is also applicable to chlorination, oxidation, reduction, and rearrangement under nearly neutral conditions. The utility of 1 for these reactions is described.
- Isobe, Toshio,Ishikawa, Tsutomu
-
p. 5832 - 5835
(2007/10/03)
-
- Desulfurization of benzylic mercaptans by triiron dodecacarbonyl under acidic and biphasic conditions
-
The biphasic reaction of benzylic mercaptans with triiron dodecacarbonyl, 48-50% tetrafluoroboric acid, and benzene affords desulfurized products in good to excellent yields. This reaction is superior to that effected in the presence of sodium dodecylbenzenesulfonate, a phase transfer agent for acidic processes.
- Alper, Howard,Sibtain, Fazle
-
p. 225 - 229
(2007/10/02)
-