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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2012/12/25 11:11:44」(JST)

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Solvolysis is a special type of nucleophilic substitution (S_N1) or elimination where the nucleophile is a solvent molecule. For certain nucleophiles, there are specific terms for the type of solvolysis reaction. For water, the term is hydrolysis; for alcohols, it is alcoholysis; for ammonia, it is ammonolysis; for glycols, glycolysis; for amines, aminolysis.

Hydrolysis

Main article: hydrolysis

While solvolysis often refers to an organic chemistry context, hydrolysis is very common in inorganic chemistry, where aqua complexes of metal ions react with solvent molecules due to the Lewis acidity of the metal center. For example, aqueous solutions of aluminium chloride are acidic due to the aqua-aluminium complex losing protons to water molecules, giving hydronium ions which lowers the pH.

In organic chemistry, hydrolysis reactions often give two fragments from an initial substrate. For example, the hydrolysis of amides give carboxylic acids and amines; the hydrolysis of esters give alcohols and carboxylic acids.

Alcoholysis

An example of a solvolysis reaction is the reaction of a triglyceride with a simple alcohol such as methanol or ethanol to give the methyl or ethyl esters of the fatty acid, as well as glycerol. This reaction is more commonly known as a transesterification reaction due to the exchange of the alcohol fragments.

Solvolysis of a chiral reactant results in the racemate (as expected in S_N1) but is often accompanied by Walden inversion. This is explained by postulating an intimate ion pair whereby the leaving anion is still in proximity to the carbocation and effectively shielding it from an attack by the nucleophile.

References

Nic, M.; Jirat, J.; Kosata, B., eds. (2006–). "solvolysis". IUPAC Compendium of Chemical Terminology (Online ed.). doi:10.1351/goldbook.S05762. ISBN 0-9678550-9-8. http://goldbook.iupac.org/S05762.html.

English Journal

Studies on synthesis and activation mechanism of mitomycin dimers connected by 1,2-dithiolane and diol linkers.

Kim HR, Kim JJ, Park JJ, Lee SH.SourceCollege of Pharmacy, Duksung Women's University, 419 Ssangmun-dong, Dobong-gu, Seoul 132-714, Republic of Korea.
Bioorganic & medicinal chemistry.Bioorg Med Chem.2012 Oct 1;20(19):5720-9. doi: 10.1016/j.bmc.2012.08.015. Epub 2012 Aug 16.
We report the synthetic and mechanistic studies on a new cyclic disulfide mitomycin dimer, 7-N,7'-N'-(1″,2″-dithiolanyl-3″,5″-dimethylenyl)bismitomycin C (8), and a diol mitomycin dimer, 7-N,7'-N'-(2″,4″-dihydroxy-1″,5″-pentanediyl)bismitomycin C (9). Mitomycin 8 is a dimer connected
PMID 22959767

Chemoassay Screening of DNA-Reactive Mutagenicity with 4-(4-Nitrobenzyl)pyridine - Application to Epoxides, Oxetanes, and Sulfur Heterocycles.

Thaens D, Heinzelmann D, Böhme A, Paschke A, Schüürmann G.SourceUFZ Department of Ecological Chemistry, Helmholtz Centre for Environmental Research , Permoserstraße 15, 04318 Leipzig, Germany.
Chemical research in toxicology.Chem Res Toxicol.2012 Sep 18. [Epub ahead of print]
Organic electrophiles have the potential to covalently attack DNA bases, and thus initiate mutagenic and carcinogenic processes. In this context, aromatic nitrogen sites of the DNA bases are often particularly nucleophilic, with guanine N7 being one of the most favored sites of adduct formation with
PMID 22889134

Japanese Journal

アンモニアボランの研究開発と将来展望(<特集>エネルギーキャリアの研究開発の現状と将来展望)

井上博史
日本エネルギー学会誌 93(5), 407-413, 2014-05-20
… Dehydrogenation of AB was realized by thermolysis and solvolysis (hydrolysis and methanolysis). …
NAID 110009818955

アンモニアボランの研究開発と将来展望 (特集エネルギーキャリアの研究開発の現状と将来展望)

井上博史
Journal of the Japan Institute of Energy = 日本エネルギー学会誌 93(5), 407-413, 2014-05
NAID 40020110495

Liquefaction of Lignocellulosic Biomass in Protonic Solvents

, ,
日本エネルギー学会誌 93(6), 548-554, 2014
… In the solvolysis of cellulose in methanol, methyl-glucopyranosides were the main products formed via the addition of H+ and OCH3– in the presence of a solid catalyst. … This may suggest that the solvents with large self-dissociation constant (K<SUB>SH</SUB>) enhance the solvolysis of cellulose. … In addition, the pore structure and acidity of a solid acid catalyst and type of lignocellulosic biomass also affected the solvolysis. …
NAID 130004741235