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.

Kinetics and mechanism of the decomposition of 1-adamantyl chloroformate

Carbamoyl chlorides are important intermediates, both in the research laboratory and in industrial scale syntheses. The most studied and used are the disubstituted derivatives, incorporating either aryl or alkyl groups (Ar2NCOCl or R2NCOCl). Sometimes, the groups are tied back to give a ring and piperidino- and morpholino-derivatives are commonly encountered. Some studies have been made with two different groups attached. Solvolyses tend to occur at the carbonyl carbon, with replacement of the chloride ion. Studies of both rate and products are reviewed and the solvolysis reactions are usually SN1, although addition of an amine leads to a superimposable bimolecular component. Many of the studies under solvolytic conditions include the application of the extended Grunwald–Winstein equation. The monosubstituted derivatives (ArNHCOCl or RNHCOCl) are less studied. They are readily prepared by the addition of HCl to an isocyanate. In acetonitrile, they decompose to set up and reach equilibrium with the isocyanate (ArNCO or RNCO) and HCl. Considering that the structurally related formyl chloride (HOCOCl) is highly unstable (with formation of HCl + CO2), the unsubstituted carbamoyl chloride (H2NCOCl) is remarkably stable. Recommended synthetic procedures require it to survive reaction temperatures in the 300–400 °C range. There has been very little study of its reactions.

https://www.mdpi.com/1422-0067/17/1/111/pdf

Mechanistic Studies of the Solvolyses of Carbamoyl Chlorides and Related Reactions.

Specific rates of solvolysis at 25 o C for p -nitrophenyl chloroformate ( 1 ) are analyzed using the extended (two-term) Grunwald-Winstein equation. For 39 solvents, the sensitivities ( l = 1.68±0.06 and m = 0.46±0.04) towards changes in solvent nucleophilicity ( l ) and solvent ionizing power ( m ) obtained, are similar to those previously observed for phenyl chloroformate ( 2 ) and p -methoxyphenyl chloroformate ( 3 ). The observations incorporating new kinetic data in several fluoroalcohol-containing mixtures, are rationalized in terms of the reaction being sensitive to substituent effects and the mechanism of reaction involving the addition (association) step of an addition-elimination (association-dissociation) pathway being rate-determining. The l / m ratios obtained for 1 , 2 , and 3 , are also compared to the previously published l / m ratios for benzyl chloroformate ( 4 ) and p- nitrobenzyl chloroformate ( 5 ). Keywords: Solvolysis, addition-elimination, association-dissociation,

/pdf/extended-grunwald-winstein-analysis-lfer-used-to-gauge-55oe6xg9w8.pdf

Extended Grunwald-Winstein analysis - LFER used to gauge solvent effects in p-nitrophenyl chloroformate solvolysis.

In almost all cases, Grunwald–Winstein treatments of the specific rates of solvolysis of a series of secondary and tertiary benzylic toluene-p-sulfonates, p-nitrobenzoates, chlorides and bromides exhibit a considerably improved correlation coefficient and a higher F-test value on incorporation of an hI term, where h is the sensitivity towards changes in the recently developed aromatic ring parameter (I). The h values increase on introduction of a second aromatic ring at the α-carbon, on introduction of an electron-withdrawing α-trifluoromethyl group, and on introduction of an electron-supplying aromatic-ring substituent.

Considerably improved Grunwald–Winstein correlatians for solvolyses of several secondary and tertiary benzylic derivatives upon inclusion of a term governed by the aromatic ring parameter (I)

Specific rates of solvolysis in hydroxylic solvents available for the solvolysis of 2-thiophenesulfonyl chloride and phenylmethanesulfonyl chloride are supplemented by determining the values in fluoroalcohol-containing solvents. The data sets are then correlated using the extended Grunwald-Winstein equation. For both substrates, it is found that a single correlation controls the influence of solvent over the full range of solvent composition. The sensitivities to solvent nucleophilicity and solvent ionizing power are compared to values available for other substrates. Three of these previous studies are upgraded by the incorporation of additional specific rate values from the recent literature. With a methyl, isopropyl, benzyl, aromatic or heteroaromatic group as the R group of RSO2Cl, a concerted SN2 mechanism is proposed for the solvolysis.

/pdf/concerted-solvent-processes-for-common-sulfonyl-chloride-5827m99vwe.pdf

Dennis N. Kevill

Papers

Kinetics and mechanism of the decomposition of 1-adamantyl chloroformate

Mechanistic Studies of the Solvolyses of Carbamoyl Chlorides and Related Reactions.

Extended Grunwald-Winstein analysis - LFER used to gauge solvent effects in p-nitrophenyl chloroformate solvolysis.

Considerably improved Grunwald–Winstein correlatians for solvolyses of several secondary and tertiary benzylic derivatives upon inclusion of a term governed by the aromatic ring parameter (I)

Concerted Solvent Processes for Common Sulfonyl Chloride Precursors used in the Synthesis of Sulfonamide-based Drugs