介绍了Kirk—Othmer Encyclopedia of Chemical Technology（化工技术百科全书）（第五版）电子图书网络版数据库，并对该数据库使用方法和检索途径作出了说明，且结合实例简单地介绍了该数据库的检索方法。

Kirk-Othmer Encyclopedia of Chemical Technology数据库介绍及实例

Boron carbide, which has a high melting point, outstanding hardness, good mechanical properties, low specific weight, great resistance to chemical agents and high neutron absorption cross-section (10BxC, x>4) is currently used in high-technology industries—fast-breeders, lightweight armors and high-temperature thermoelectric conversion.

The contents of this review are: (1) introduction; (2) preparations—industrial preparative routes, powders, sintering (additives, pressureless, hot pressing, HIP); laboratory methods of synthesis (CVD, PVD, plasma, crystal growth); (3) analytical characterization; (4) phase diagram—a peritectic, nearly pure boron, and a wide phase homogeneity range (B4C-B10·5C); (5) rhombohedral crystal structure—a comprehensive model of the whole solid solution is proposed; (6) chemical properties; (7) physical properties—density, mechanical (strength, hardness, toughness) and thermo-electrical properties; (8) main industrial applications; (9) conclusion.

Boron carbide ― a comprehensive review

Bull. Chem. Soc. Jpn. への投稿のすすめ

Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

Electrophilic Perfluoroalkylating Agents.

A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald–Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)+ (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis–decomposition pathway through the intermediate 1-Ad+Cl− ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (kexp) for the solvolysis of 1 were separated into k1-Ad+Cl− and k1-AdSCO+Cl− through a product study and applied to the Grunwald–Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03.

https://www.mdpi.com/1422-0067/22/14/7394/pdf

Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions.

Correlation of the Rates of Solvolysis of the S-Ethyldibenzothiophenium Ion.

When 3-chlorobut-1-ene reacts with an MeCN solution of AgClO4, a silver ion-catalysed allylic rearrangement accompanies the silver ion-assisted reactions which proceed with precipitation of AgCl.

Silver ion‐catalysed rearrangement of an allylic halide

Korrelation der solvolysegeschwindigkeiten von adamantyl-(1)-p-toluolsulfonat

There have been several studies on the solvolysis mechanisms for alkanesulfonyl chlorides (RSO2Cl) and arenesulfonyl chlorides (ArSO2Cl). The earlier of these studies were reviewed a little over thirty years ago by Gordon, Maskill and Ruasse (Chem. Soc. Rev. 1989, 18, 123–151) in a contribution entitled “Sulfonyl Transfer Reactions”. The present review will emphasize more recent contributions and, in particular, the application of the extended Grunwald–Winstein equation and kinetic solvent isotope effects to the solvolysis reactions. There is also an appreciable number of reports concerning the corresponding anhydrides with the chloride leaving group replaced by the appropriate sulfonate leaving group, concerning sulfamoyl chlorides (ZZ'NSO2Cl) with Z and Z' being alkyl or aryl and concerning the solvolysis of chlorosulfate esters (alkoxy- or aryloxysulfonyl chlorides), with the structures ROSO2Cl or ArOSO2Cl. The solvolyses of these additional types of sulfur(VI) substrates will be the topics of a future review.

/pdf/mechanistic-studies-of-the-solvolysis-of-alkanesulfonyl-and-3c3ahmtp.pdf

Dennis N. Kevill

Papers

Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions.

Correlation of the Rates of Solvolysis of the S-Ethyldibenzothiophenium Ion.

Silver ion‐catalysed rearrangement of an allylic halide

Korrelation der solvolysegeschwindigkeiten von adamantyl-(1)-p-toluolsulfonat

Mechanistic studies of the solvolysis of alkanesulfonyl and arenesulfonyl halides