Acid-catalyzed Solvolysis Research Articles

Acid-catalyzed solvolysis: unusually rapid solvolysis of 3-fluoronortricyclene in CD3COOD – 0.1 M D2SO4

3-Fluoronortricyclene (1a) undergoes unusually facile solvolysis in CD3COOD – 0.1 M D2SO4 at 67 °C and yields 3-acetoxynortri-cyclene-d3 (1d) which ring-opens to a mixture of deuterated norbornyl diacetates. This result contrasts with the behaviour of 3-chloro- (1b) and 3-bromonortricyclene (1c) that undergo cleavage of the three-membered ring in CD3COOD – 0.1 M D2SO4. The estimated rate acceleration for solvolysis of alkyl fluorides in acid media is 107–108.

ChemInform Abstract: EFFECT OF MEDIUM ON THE ACID‐CATALYZED SOLVOLYSIS OF HYDROXAMIC ACIDS

Chemischer InformationsdienstVolume 9, Issue 38 Preparative Organic Chemistry ChemInform Abstract: EFFECT OF MEDIUM ON THE ACID-CATALYZED SOLVOLYSIS OF HYDROXAMIC ACIDS T. KUCEROVA, T. KUCEROVASearch for more papers by this authorJ. MOLLIN, J. MOLLINSearch for more papers by this author T. KUCEROVA, T. KUCEROVASearch for more papers by this authorJ. MOLLIN, J. MOLLINSearch for more papers by this author First published: September 19, 1978 https://doi.org/10.1002/chin.197838088AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume9, Issue38September 19, 1978 RelatedInformation

Direct C-1 hydroxylation of vitamin D compounds: convenient preparation of 1alpha-hydroxyvitamin D3, 1alpha, 25-dihydroxyvitamin D3, and 1alpha-hydroxyvitamin D2.

An efficient procedure for the direct C-1 hydroxylation of vitamin D compounds has been developed. The method involves conversion of vitamin D3 tosylates to 3,5-cyclovitamin D derivatives, allylic oxidation with selenium dioxide, and acid-catalyzed solvolysis to the 1 alpha-hydroxyvitamin D analogs. When applied to vitamin D3,25-hydroxyvitamin D3, and vitamin D2, this sequence give the corresponding 1alpha-hydroxylated derivatives in 10-15% yield.

Effect of medium on the acid-catalyzed solvolysis of hydroxamic acids

Effect of medium on the acid-catalyzed solvolysis of hydroxamic acids

An unusual arene oxide reaction. Solvent capture during acid-catalyzed solvolysis of 7,12-dimethylbenz(a)anthracene 5,6-oxide.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAn unusual arene oxide reaction. Solvent capture during acid-catalyzed solvolysis of 7,12-dimethylbenz[a]anthracene 5,6-oxideJohn W. Keller, Nitya G. Kundu, and Charles HeidelbergerCite this: J. Org. Chem. 1976, 41, 21, 3487–3489Publication Date (Print):October 1, 1976Publication History Published online1 May 2002Published inissue 1 October 1976https://doi.org/10.1021/jo00883a042RIGHTS & PERMISSIONSArticle Views38Altmetric-Citations6LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (433 KB) Get e-Alerts Get e-Alerts

The Acid-Base Properties, Hydrolytic Mechanism, and Susceptibility to O 2 Oxidation of Fe 4 S 4 (SR) 4 -2 Clusters

The iron-sulfur cluster compounds Fe(4)S(4)(SR)(4) (-2) [where -SR = -SCH(3), -S-C(CH(3))(3), and -S- CH(2)-CH(CH(3))(2)] have been found to represent the base species of weak acids of pK(a) comparable to that of carboxylic acids. The acid species Fe(4)S(4)(SR)(4)H(-) is most subject to reaction with O(2) and to acid-catalyzed solvolysis, while the base species Fe(4)S(4)(SR)(4) (-2) most readily undergoes ligand exchange. The kinetics for hydrolysis of the isobutyl mercaptide cluster salt has been investigated in detail and a mechanism involving the stepwise process [Formula: see text] has been proposed. The importance of the acid-base equilibria in determining the reactivity of the iron-sulfur clusters and its possible importance as a factor in the determination of the potentials of ferredoxins and high potential iron protein are discussed.

Kinetic studies of the formation, acid-catalyzed solvolysis, and cupric ion displacement of a zinc porphyrin in aqueous solutions

The rates of zinc incorporation, zinc demetallation, and cupric ion displacement of zinc in a water-soluble porphyrin were investigated. The tetra-sulfonated tetraphenylporphine TPPS (see Fig. 1) was employed in the studies. The rate of zinc ion incorporation was equal to [ k 1][Zn 2+] [TPPS] where k 1 = 4.76 × 10 −1 M −1 sec −1 at 30°C; the rate of Zn-TPPS demetallation is equal to k d [Zn-TPPS][H +−] c where k d = 10.9 M −2 sec −1 at 30°C; the rate of Cu 2+ replacement in Zn-TPPS is equal to k Cu[Zn-TPPS] [Cu 2+] where k Cu = 5.1 × 10 −3 M −1 sec −1 at 30°C. These rate laws are discussed in terms of the possible mechanisms for the reactions studied.

Isobornyloxycarbonyl Function, a New Convenient Amino-Protecting Group in Peptide Synthesis. I. Synthesis and Properties of Isobornyloxycarbonylamino Acids

Isobornyloxycarbonyl chloride (IBOC-Cl), which is a satisfactorily stable oil, was prepared from isoborneol and phosgene. The chloride, when allowed to react with amino acids, gave the corresponding isobornyloxycarbonyl (IBOC-)-amino acids. In most cases, the IBOC-amino acids could be obtained in crystalline form and in good yields. The IBOC-amino acids are smoothly cleaved by acid-catalyzed solvolysis with trifluoroacetic acid to yield the free amino acids. Since the IBOC-Cl is much easier to prepare than t-butyloxycarbonyl chloride, the new amino-masking method is considered to be of great use in the synthesis of complicated peptides.

Acid-catalyzed solvolysis reactions of zinc porphyrins having various basicities and zinc N-methylporphyrins

Acid-catalyzed solvolysis reactions of zinc porphyrins having various basicities and zinc N-methylporphyrins

Acid-catalyzed solvolysis of benzoin tosylate in aromatic solvents

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAcid-catalyzed solvolysis of benzoin tosylate in aromatic solventsR. Marshall Wilson and John C. SheehanCite this: J. Am. Chem. Soc. 1969, 91, 26, 7378–7380Publication Date (Print):December 1, 1969Publication History Published online1 May 2002Published inissue 1 December 1969https://doi.org/10.1021/ja01054a027RIGHTS & PERMISSIONSArticle Views233Altmetric-Citations3LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (357 KB) Get e-Alerts Get e-Alerts

Organosilicon compounds. LX. Relationship between the acidity of the medium and the rate of acid-catalyzed solvolysis of organosilicon hydrides

Organosilicon compounds. LX. Relationship between the acidity of the medium and the rate of acid-catalyzed solvolysis of organosilicon hydrides

Organosilicon compounds. LXIII. Acid-catalyzed solvolysis of trimethyl-tert-butoxysilane and hexamethyldisiloxane

Organosilicon compounds. LXIII. Acid-catalyzed solvolysis of trimethyl-tert-butoxysilane and hexamethyldisiloxane

Solvolysis of 3, 4-dialkyl sydnones

The kinetics of solvolysis of various dialkyl sydnones: 3- tert -butyl-4-methyl, 3- n -propyl-4-ethyl, 3-ethyl-4-methyl, 3-isopropyl-4-ethyl, 3- n -propyl-4-methyl, and 3- n -propyl-4- n -butyl sydnone, have been studied spectrophotometrically as a function of HCl and NaOH concentrations, pH, and temperature. The reactivity on acid-catalyzed solvolysis decreased in the order cited with only the first compound exhibiting pH-independent solvolysis and high reactivity, about 600 times that of the others. The reactivities of the remainder were only over a threefold range. The order of reactivity tended to reverse on alkaline solvolysis within a similar range, where 3-ethyl-4-methylsydnone was 1.7 times more reactive than the equally reactive 3- n -propyl-4-ethyl, 3- n -propyl-4-methyl, and 3-isopropyl-4-ethyl sydnones. The 3- n -propyl-4- n -butylsydnone was half as reactive as this group, whereas the 3- tert -butyl-4-methylsydnone was one quarter as reactive. The presence of a-hydrogens on the alkyl substituted sydnones tends to stabilize such structures against hydrogen ion and water attack. This can be explained by postulating extended equilibria among tautomeric structures which decrease the effective concentration of the reactive intermediate. The 3-benzylsydnone demonstrates a reactivity to hydroxyl ion attack equivalent to the more reactive furfuryl sydnone where the electron-attracting powers of the rings are not completely inhibited by the intervening methylene groups. The acid-catalyzed solvolysis of 3-benzylsydnone is of the order of magnitude of other 3-alkyl sydnones with α-hydrogens. The observed second-order dependency of reactivity on hydrogen ion concentration may be assigned to the de-localization of the charge of the singly protonated species, due to the probability of many mesomeric forms with the benzyl substituent.

5-methyl-3 (2H)-furanone from acid-catalyzed solvolysis of 2-deoxy-D-ribose

5-Methyl-3 (2H)-furanone (VIII) is produced from 2-deoxy-D-ribose (I) under defined conditions of acid, temperature, and time, Its production is a direct function of sugar concentration and its ultraviolet absorbance serves as a sensitive assay for the sugar. The compound VIII was identified by spectral data (NMR, U.V., I.R.), thin-layer chromatography R f values in three different solvent systems, and chemical reactivities. The compound VIII obtained from deoxyribose and synthesized by a different route was the same. A mechanism dependent on the direction of water elimination after cyclization, dehydration, and rehydration can explain the formation of VIII and the previously obtained levulinic acid whose production from furfuryl alcohol (III) was explained by a similar mechanism. The spectrally observed kinetic intermediate with a λ max. at 225 mμ is consistent with the proposed mechanism.

Preparation and Acid-Catalyzed Solvolysis of 6-Tosyloxyisophorone

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPreparation and Acid-Catalyzed Solvolysis of 6-TosyloxyisophoroneARTHUR W. FORTCite this: J. Org. Chem. 1961, 26, 2, 332–334Publication Date (Print):February 1, 1961Publication History Published online1 May 2002Published inissue 1 February 1961https://doi.org/10.1021/jo01061a014RIGHTS & PERMISSIONSArticle Views67Altmetric-Citations9LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (350 KB) Get e-Alerts Get e-Alerts

The Acid-catalyzed Solvolysis of Dehydroepiandrosterone Sulfate and Its Significance in the Examination of Urinary 17-Ketosteroids

The Acid-catalyzed Solvolysis of Dehydroepiandrosterone Sulfate and Its Significance in the Examination of Urinary 17-Ketosteroids

The Acid-Catalyzed Solvolysis of Alkoxymethyl Esters. Part III. Reaction Rates and Products in the Solvolysis of Ethoxymethyl Acetate in Ethanol-Water Mixtures.

The Acid-Catalyzed Solvolysis of Alkoxymethyl Esters. Part III. Reaction Rates and Products in the Solvolysis of Ethoxymethyl Acetate in Ethanol-Water Mixtures.

The Acid-Catalyzed Solvolysis of Alkoxymethyl Esters. Part II. Reaction Rates and Products in the Solvolysis of Methoxymethyl Esters in Methanol-Water Mixtures.

The Acid-Catalyzed Solvolysis of Alkoxymethyl Esters. Part II. Reaction Rates and Products in the Solvolysis of Methoxymethyl Esters in Methanol-Water Mixtures.