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Journal of The Chemical Society B: Physical Organic最新文献

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Reactions between aromatic nitro-compounds and hydroxylamines in alkaline solution. Part I. Kinetic studies 芳香族硝基化合物与羟胺在碱性溶液中的反应。第一部分动力学研究
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710002393
D. J. Cowley, M. H. Millen, W. Waters
{"title":"Reactions between aromatic nitro-compounds and hydroxylamines in alkaline solution. Part I. Kinetic studies","authors":"D. J. Cowley, M. H. Millen, W. Waters","doi":"10.1039/J29710002393","DOIUrl":"https://doi.org/10.1039/J29710002393","url":null,"abstract":"An e.s.r. study shows that the initial reactions in alkali under nitrogen between an aromatic nitro-compound and hydroxylamine or a monosubstituted hydroxylamine are (i)–(iv). K,k1, and k2 have been evaluated by monitoring RNHOH + OH– [graphic omitted] RNHO–+ H2O (i), ArNO2+ RNHO– [graphic omitted] (ArNO2·)–+ RNHO·(ii), 2(ArNO2·) [graphic omitted] Products (iii), 2RNHO· [graphic omitted] Products (iv) the build-up and decay of (ArNO2·)– radical-anions by use of p-nitrobenzoic acid and N-methyl-, N-benzyl-, and N-diphenylmethyl-hydroxylamines.With hydroxylamine the kinetic measurements are much less accurate owing to a pseudo-unimolecular gas evolution which appears to come from reactions (v). Hydroxylamine is also destroyed by reaction (vi), the 2NH2O·→ H4N2O2→ N2+ 2H2O (v), ArNO + 2NH2OH → ArN3+ 3H2O (vi) nitroso-compound being formed by the disproportionation (iii).","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"1 1","pages":"2393-2397"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91343615","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 5
Crystal structure of fusicoccin A p-iodobenzenesulphonate 梭菌素A对碘苯磺酸盐的晶体结构
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710002021
M. Brufani, S. Cerrini, W. Fedeli, A. Vaciago
{"title":"Crystal structure of fusicoccin A p-iodobenzenesulphonate","authors":"M. Brufani, S. Cerrini, W. Fedeli, A. Vaciago","doi":"10.1039/J29710002021","DOIUrl":"https://doi.org/10.1039/J29710002021","url":null,"abstract":"The crystal and molecular structure of the p-iodobenzenesulphonate of fusicoccin A (C42H59IO14S) has been determined by three-dimensional X-ray analysis. The crystals are orthorhombic, space group P212121, with Z= 4 in a unit cell of dimensions: a= 10·32, b= 12·89, c= 35·14 A. The structure was solved by the heavy-atom technique and refined to a final R of 0·116, using 1706 observed reflections.Fusicoccin A, a phytotoxic metabolite of Fusicoccum amygdali, is a glycoside in which the sugar is D-glucose acetylated at C-3′ and etherified by 1,1-dimethylallyl alcohol at C-6′, and the aglycone is a tricyclic system formed by the fusion of one eight and two five membered rings. The absolute configuration is also given.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"49 1","pages":"2021-2026"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90280915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 5
Photochemical reactions of aliphatic aldehydes in solution 脂肪族醛在溶液中的光化学反应
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710002254
J. Coyle
{"title":"Photochemical reactions of aliphatic aldehydes in solution","authors":"J. Coyle","doi":"10.1039/J29710002254","DOIUrl":"https://doi.org/10.1039/J29710002254","url":null,"abstract":"Simple aliphatic aldehydes with a C4 or longer chain undergo ‘type 2’ photoelimination and photocyclisation as major reactions in solution. Both singlet and triplet nπ* states are direct precursors to products in these reactions. Quenching studies show that the triplet lifetime, governed largely by the rate constant for intramolecular hydrogen-abstraction, varies with the substituent at position 4 in the chain.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"51 1","pages":"2254-2256"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75279768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 7
The acid-catalysed hydrolysis and protonation behaviour of hydroxamic acids 羟基肟酸的酸催化水解和质子化行为
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710000123
A. J. Buglass, K. Hudson, J. Tillett
{"title":"The acid-catalysed hydrolysis and protonation behaviour of hydroxamic acids","authors":"A. J. Buglass, K. Hudson, J. Tillett","doi":"10.1039/J29710000123","DOIUrl":"https://doi.org/10.1039/J29710000123","url":null,"abstract":"The acid-catalysed hydrolyses of some para-substituted benzohydroxamic acids have been studied in perchloric, sulphuric, and hydrochloric acids. Plots of the first-order rate-coefficients, k1, against [H+] show maxima which are caused by extensive protonation of the substrate. The mechanism of hydrolysis is found to be similar to that of amides. The protonation behaviour of these compounds correlates better with the amide acidity function HA than with H0.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"10 1","pages":"123-126"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74721769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 15
The infrared and Raman spectra of some thioacetals 某些硫缩醛的红外和拉曼光谱
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710002037
B. Wladislaw, P. Olivato, O. Sala
{"title":"The infrared and Raman spectra of some thioacetals","authors":"B. Wladislaw, P. Olivato, O. Sala","doi":"10.1039/J29710002037","DOIUrl":"https://doi.org/10.1039/J29710002037","url":null,"abstract":"The i.r. and Raman spectra of a number of thioacetals containing aromatic rings have been measured in the range of 1650–1000 cm–1. Assignments for some frequencies are suggested by comparison with reference compounds and with deuteriated products. The influence of one or two sulphur atoms on adjacent group vibrations are demonstrated; methods of differentiation between benzaldehyde and benzophenone thioacetals and of characterization of the phenylthio-group are suggested. Comparison is made between some sulphur compounds and the corresponding oxy- or chloro-analogues.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"50 1","pages":"2037-2040"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74804099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 2
Field and charge-transfer theory for the quantitative correlation of substituent effects in aromatic molecules. Part III. Thermal heterolytic addition and elimination reactions of substituted benzenes 芳香分子中取代基效应定量关联的场和电荷转移理论。第三部分。取代苯的热杂解加成和消去反应
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710001540
M. Godfrey
{"title":"Field and charge-transfer theory for the quantitative correlation of substituent effects in aromatic molecules. Part III. Thermal heterolytic addition and elimination reactions of substituted benzenes","authors":"M. Godfrey","doi":"10.1039/J29710001540","DOIUrl":"https://doi.org/10.1039/J29710001540","url":null,"abstract":"Expressions, based on simple reaction models, for the effects of substituents on the equilibrium constants and rate constants of the reactions mentioned in the title are derived. Conditions under which ρσ relationships should be valid are established. Various theoretical σ and ρ scales are evaluated and are shown to be in good agreement with empirical scales when they ought to be. The calculations of all of the theoretical scales involve only one measured value of a substituent effect on a reaction.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"32 1","pages":"1540-1544"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72908924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 2
Kinetics and mechanism of electrophilic substitution of heteroaromatic compounds. Part XXIII. Acid-catalysed hydrogen exchange of quinoline, isoquinoline, and their N-oxides 杂芳烃化合物的亲电取代动力学及机理。二十三。喹啉、异喹啉及其n -氧化物的酸催化氢交换
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710000004
U. Bressel, A. Katritzky, J. Lea
{"title":"Kinetics and mechanism of electrophilic substitution of heteroaromatic compounds. Part XXIII. Acid-catalysed hydrogen exchange of quinoline, isoquinoline, and their N-oxides","authors":"U. Bressel, A. Katritzky, J. Lea","doi":"10.1039/J29710000004","DOIUrl":"https://doi.org/10.1039/J29710000004","url":null,"abstract":"Rate profiles are reported for the title reactions. Exchanges are shown to proceed on the conjugate acid species at various positions in the carbocyclic rings. Exchange in the heterocyclic rings occurs by deprotonation α to nitrogen, and probably via covalent hydrated species β to nitrogen.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"89 S1","pages":"4-10"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72560144","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 10
Acid-catalysed formation of monoacetals from n-butyraldehyde and certain D-glucitol derivatives 正丁醛和某些d-葡萄糖醇衍生物在酸催化下形成单缩醛
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710000957
T. G. Bonner, E. J. Bourne, P. J. V. Cleare, R. Cole, D. Lewis
{"title":"Acid-catalysed formation of monoacetals from n-butyraldehyde and certain D-glucitol derivatives","authors":"T. G. Bonner, E. J. Bourne, P. J. V. Cleare, R. Cole, D. Lewis","doi":"10.1039/J29710000957","DOIUrl":"https://doi.org/10.1039/J29710000957","url":null,"abstract":"Acid-catalysed condensation of n-butyraldehyde with (a) 1-deoxy-D-glucitol yields a 2,3-acetal as a kinetically controlled product and the 2,4-acetal as the thermodynamically controlled product, (b) 2-deoxy-D-glucitol yields the 1,3-acetal as the kinetically controlled product and the 3,4-acetal(s) as the thermodynamically controlled product, and (c) 3-O-methyl-D-glucitol yields the 2,4-acetal as the predominant product throughout the reaction.In aqueous acid there is no evidence that 1,3-O-butylidene-2-deoxy-D-glucitol undergoes intramolecular conversion; instead substantial hydrolysis to the polyol and aldehyde occurs before the synthesis of the 3,4-acetal(s).","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"09 1","pages":"957-962"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84255822","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 4
The effect of pH on the racemisation rate of 4,4′-biquinolyl pH值对4,4′-双喹啉消旋速率的影响
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710001907
M. Crawford, R. Ingle
{"title":"The effect of pH on the racemisation rate of 4,4′-biquinolyl","authors":"M. Crawford, R. Ingle","doi":"10.1039/J29710001907","DOIUrl":"https://doi.org/10.1039/J29710001907","url":null,"abstract":"The rate of racemisation of optically active 4,4′-biquinolyl varies only slightly from one solvent to another but drops about tenfold in strong acid. The effect is attributed mainly to alteration of the molecular dimensions on protonation.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"72 1","pages":"1907-1912"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84343632","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 1
The conformational analysis of saturated heterocycles. Part XXX. 3-Alkyl tetrahydro-1,3-oxazines 饱和杂环的构象分析。XXX一部分。3-Alkyl tetrahydro-1, 3-oxazines
Journal of The Chemical Society B: Physical Organic Pub Date : 1971-01-01 DOI: 10.1039/J29710001300
Richard A. Jones, A. Katritzky, D. L. Trepanier
{"title":"The conformational analysis of saturated heterocycles. Part XXX. 3-Alkyl tetrahydro-1,3-oxazines","authors":"Richard A. Jones, A. Katritzky, D. L. Trepanier","doi":"10.1039/J29710001300","DOIUrl":"https://doi.org/10.1039/J29710001300","url":null,"abstract":"Tetrahydro-1,3-oxazine and its N-methyl, ethyl, isopropyl, and t-butyl derivatives have been prepared, and the dipole moments of the four last compounds measured. Provisional conclusions regarding the conformations of these compounds are presented.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"46 1","pages":"1300-1302"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84576002","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 6
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