The isomerisation of α- and β-benzyl- and substituted-benzyl-naphthalenes catalysed by anhydrous aluminium chloride or toluene-p-sulphonic acid has been studied.Halogen-substituted-benzylnaphthalenes failed to isomerise whilst p-methyl- and p-methoxy-benzylnaphthalenes, isomerise more readily than benzylnaphthalene. The isomerisation is reversible, and aluminium chloride is more effective than toluene-p-sulphonic acid.
{"title":"Reversible isomerisation of alkyl aromatics","authors":"A. Osman, M. Badr, A. Abdel-rahman","doi":"10.1039/J39710002264","DOIUrl":"https://doi.org/10.1039/J39710002264","url":null,"abstract":"The isomerisation of α- and β-benzyl- and substituted-benzyl-naphthalenes catalysed by anhydrous aluminium chloride or toluene-p-sulphonic acid has been studied.Halogen-substituted-benzylnaphthalenes failed to isomerise whilst p-methyl- and p-methoxy-benzylnaphthalenes, isomerise more readily than benzylnaphthalene. The isomerisation is reversible, and aluminium chloride is more effective than toluene-p-sulphonic acid.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"8 1","pages":"2264-2265"},"PeriodicalIF":0.0,"publicationDate":"2007-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87566138","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}
Five compounds have been isolated from the heartwood of Cordyla africana and shown by chemical degradation, synthesis, and spectral considerations to be 2′,4′,5′,6,7-pentamethoxy-, 3′,4′,6,7-tetramethoxy-, 3′,6,7-trimethoxy-4′,5′-methylenedioxy-, and 2′,6,7-trimethoxy-4′,5′-methylenedioxy-isoflavone, together with 6,7-dimethoxy-3′,4′-methylenedioxyisoflavanone. 6,7-Dimethoxy-3′,4′-methylenedioxyisoflavone has been synthesised and reduced to the isoflavanone; the former is considered also to be present in the heartwood. The mass spectra of these and related isoflavones have been analysed and the presence of the 2′-methoxy-group is shown to influence the fragmentation pattern profoundly.
{"title":"Isoflavonoid constituents of the heartwood of Cordyla africana","authors":"R. Campbell, S. H. Harper, A. Kemp","doi":"10.1039/J39690001787","DOIUrl":"https://doi.org/10.1039/J39690001787","url":null,"abstract":"Five compounds have been isolated from the heartwood of Cordyla africana and shown by chemical degradation, synthesis, and spectral considerations to be 2′,4′,5′,6,7-pentamethoxy-, 3′,4′,6,7-tetramethoxy-, 3′,6,7-trimethoxy-4′,5′-methylenedioxy-, and 2′,6,7-trimethoxy-4′,5′-methylenedioxy-isoflavone, together with 6,7-dimethoxy-3′,4′-methylenedioxyisoflavanone. 6,7-Dimethoxy-3′,4′-methylenedioxyisoflavone has been synthesised and reduced to the isoflavanone; the former is considered also to be present in the heartwood. The mass spectra of these and related isoflavones have been analysed and the presence of the 2′-methoxy-group is shown to influence the fragmentation pattern profoundly.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"1 1","pages":"1787-1795"},"PeriodicalIF":0.0,"publicationDate":"1974-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89124518","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}
Citral condenses with olivetol in the presence of pyridine (1 mol) to give citrylidene-cannabis(III)(26%), cannabi-chromen (IV)(15%), its isomer (V)(3%) the bischromen (II)(6%), cannabicyclol (IX)(1%), its isomer (XV)(3%), and the bis-compound (XVI)(1·3%). Cannabichromen when heated with pyridine gives citrylidene-cannabis and cannabicyclol: the latter is also formed from cannabichromen under acid catalysis, and photochemically, in preparatively acceptable yields. Reasons for revising to (IX) the earlier structural proposal (VII) for cannabicyclo, are presented. Cannabichromen and cannabicycol are extractives of Cannabis(hashish).Acid-catalysed reactions of citrylidene-cannabis, cannabichromen, and the citral-olivetol system are discussed. The information accumulated in this, and the preceding paper, is summarised in a scheme for pyridine- and acid-catalysed condensations of citral with resorcinols or phloroglucinols.
{"title":"Synthesis of cannabinoids by pyridine-catalysed citral–olivetol condensation: synthesis and structure of cannabicyclol, cannabichromen, (hashish extractives), citrylidene-cannabis, and related compounds","authors":"L. Crombie, R. Ponsford","doi":"10.1039/J39710000796","DOIUrl":"https://doi.org/10.1039/J39710000796","url":null,"abstract":"Citral condenses with olivetol in the presence of pyridine (1 mol) to give citrylidene-cannabis(III)(26%), cannabi-chromen (IV)(15%), its isomer (V)(3%) the bischromen (II)(6%), cannabicyclol (IX)(1%), its isomer (XV)(3%), and the bis-compound (XVI)(1·3%). Cannabichromen when heated with pyridine gives citrylidene-cannabis and cannabicyclol: the latter is also formed from cannabichromen under acid catalysis, and photochemically, in preparatively acceptable yields. Reasons for revising to (IX) the earlier structural proposal (VII) for cannabicyclo, are presented. Cannabichromen and cannabicycol are extractives of Cannabis(hashish).Acid-catalysed reactions of citrylidene-cannabis, cannabichromen, and the citral-olivetol system are discussed. The information accumulated in this, and the preceding paper, is summarised in a scheme for pyridine- and acid-catalysed condensations of citral with resorcinols or phloroglucinols.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"32 1","pages":"796-804"},"PeriodicalIF":0.0,"publicationDate":"1971-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89791268","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}
Application of the Vilsmeier formylation reaction to 6-methylpurine (I) gave purine-6-malonaldehyde (III), which could be oxidized to purine-6-carboxylic acid (IV), brominated to 6-tribromomethylpurine (V), and hydrolysed to hypoxanthine (VI). Treatment of the reaction mixture of 6-methylpurine (I), dimethylformamide, and phosphoryl chloride with hydrazine, phenylhydrazine, thiosemicarbazide, and hydroxylamine afforded, respectively, 6-(pyrazol-4-yl)-(VII), 6-(1-phenylpyrazol-4-yl)(VIII), 6-(1-thiocarbamolypyrazol-4-yl)(IX), and 6-(isoxazol-4-yl)-purine (X). Similar treatment of compound (I) with the Vilsmeier reagent and aniline produced the monoanil (XIV) of the dialdehyde (III); use of p-bromoaniline yielded a mixture of mono- and bis-p-bromoanils, (XV) and (XVI). Compound (X) gave 8-hydroxypurine-6-carboxylic acid (XI) on oxidation, and purine-6-malonaldehydonitrile (XIII) when heated in dimethyl sulphoxide. The structure of the anil (XV) is discussed in the light of X-ray diffraction studies.
{"title":"Vilsmeier reaction on 6-methylpurine","authors":"D. Brown, A. Giner-Sorolla","doi":"10.1039/J39710000128","DOIUrl":"https://doi.org/10.1039/J39710000128","url":null,"abstract":"Application of the Vilsmeier formylation reaction to 6-methylpurine (I) gave purine-6-malonaldehyde (III), which could be oxidized to purine-6-carboxylic acid (IV), brominated to 6-tribromomethylpurine (V), and hydrolysed to hypoxanthine (VI). Treatment of the reaction mixture of 6-methylpurine (I), dimethylformamide, and phosphoryl chloride with hydrazine, phenylhydrazine, thiosemicarbazide, and hydroxylamine afforded, respectively, 6-(pyrazol-4-yl)-(VII), 6-(1-phenylpyrazol-4-yl)(VIII), 6-(1-thiocarbamolypyrazol-4-yl)(IX), and 6-(isoxazol-4-yl)-purine (X). Similar treatment of compound (I) with the Vilsmeier reagent and aniline produced the monoanil (XIV) of the dialdehyde (III); use of p-bromoaniline yielded a mixture of mono- and bis-p-bromoanils, (XV) and (XVI). Compound (X) gave 8-hydroxypurine-6-carboxylic acid (XI) on oxidation, and purine-6-malonaldehydonitrile (XIII) when heated in dimethyl sulphoxide. The structure of the anil (XV) is discussed in the light of X-ray diffraction studies.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"101 1","pages":"128-132"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73536374","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}
Benzoin reacts with hydrazine hydrochloride in ethanol to give benzil, benzil azine, deoxybenzoin, benzaldehyde, benzonitrile, benzoic acid, ethyl benzoate, desylamine hydrochloride, 3,4,5-triphenylpyrazole, and 3,4,5,6-tetraphenylpyridazine and their hydrochlorides. A mechanism is proposed to account for some of the products, and some reactions of 3,4,5-triphenylpyrazole are described.
{"title":"3,4,5-Triphenylpyrazoles","authors":"A. Comrie","doi":"10.1039/J39710002807","DOIUrl":"https://doi.org/10.1039/J39710002807","url":null,"abstract":"Benzoin reacts with hydrazine hydrochloride in ethanol to give benzil, benzil azine, deoxybenzoin, benzaldehyde, benzonitrile, benzoic acid, ethyl benzoate, desylamine hydrochloride, 3,4,5-triphenylpyrazole, and 3,4,5,6-tetraphenylpyridazine and their hydrochlorides. A mechanism is proposed to account for some of the products, and some reactions of 3,4,5-triphenylpyrazole are described.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"22 1","pages":"2807-2810"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73646237","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}
The structures and stereochemistry have been elucidated of the products formed in the addition of methanol and of hydrogen to methyl 1,4,5,6,7,7-hexachloronorborna-2,5-diene-2-carboxylate; the epoxidation, the hydroboration–oxidation, and the addition of diazomethane to 1,2,3,4,7,7-hexachloronorborna-2,5-diene; and the lithium aluminium hydride reduction and the reaction of Grignard reagents with 1,4,5,6,7,7-hexachloronorborn-5-en-2-one. The results, when compared with published results of additions to 1,2,3,4,7,7-hexachloronorborna-2,5-diene and to 7,7-dimethylnorborn-2-ene, suggest that steric factors may not be entirely responsible for the direction of reagent attack.
{"title":"Some addition reactions of 1,2,3,4,7,7-hexachloronorborna-2,5-diene, 1,4,5,6,7,7-hexachloronorborn-5-en-2-one, and related compounds","authors":"D. I. Davies, P. Mason, M. J. Parrott","doi":"10.1039/J39710003428","DOIUrl":"https://doi.org/10.1039/J39710003428","url":null,"abstract":"The structures and stereochemistry have been elucidated of the products formed in the addition of methanol and of hydrogen to methyl 1,4,5,6,7,7-hexachloronorborna-2,5-diene-2-carboxylate; the epoxidation, the hydroboration–oxidation, and the addition of diazomethane to 1,2,3,4,7,7-hexachloronorborna-2,5-diene; and the lithium aluminium hydride reduction and the reaction of Grignard reagents with 1,4,5,6,7,7-hexachloronorborn-5-en-2-one. The results, when compared with published results of additions to 1,2,3,4,7,7-hexachloronorborna-2,5-diene and to 7,7-dimethylnorborn-2-ene, suggest that steric factors may not be entirely responsible for the direction of reagent attack.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"99 1","pages":"3428-3437"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73882166","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}
Sulphinic esters of prop-2-ynyl alcohols rearrange thermally to allenyl sulphones. Evidence for a cyclic mechanism for the rearrangement is discussed. (+)-(R)-1-Methylprop-2-ynyl toluene-p-sulphinate rearranges to (–)-buta-1,2-dienyl p-tolyl sulphone, whose absolute configuration, predicted on the basis of a cyclic mechanism for the rearrangement, agrees with that calculated from the polarisability sequence of substituents attached to the chiral system.Sulphenic esters of prop-2-ynyl alcohols rearrange rapidly to allenyl sulphoxides, and the chirality of the allene group derived from an α-substituted prop-2-ynyl alcohol is the same as that generated in the sulphinate → sulphone rearrangement.Sulphinic and sulphenic esters of but-2-yne-1,4-diol rearrange to 2,3-bis-sulphonyl- or sulphinyl-buta-1,3-dienes. Structures of the products obtained have been proven by synthesis.Prototropic equilibration of four-carbon acetylenic–allenic aryl sulphones shows the following decreasing order of stability: ArSO2·CH2·C⋮CMe > ArSO2·CH:C:CHMe > ArSO2·C⋮C·CH2Me.
{"title":"Intramolecular reactions. Part IX. Stereochemistry and mechanism of the rearrangement of acetylenic esters of sulphinic and sulphenic acids to allenes","authors":"Geraldine Smith, C. Stirling","doi":"10.1039/J39710001530","DOIUrl":"https://doi.org/10.1039/J39710001530","url":null,"abstract":"Sulphinic esters of prop-2-ynyl alcohols rearrange thermally to allenyl sulphones. Evidence for a cyclic mechanism for the rearrangement is discussed. (+)-(R)-1-Methylprop-2-ynyl toluene-p-sulphinate rearranges to (–)-buta-1,2-dienyl p-tolyl sulphone, whose absolute configuration, predicted on the basis of a cyclic mechanism for the rearrangement, agrees with that calculated from the polarisability sequence of substituents attached to the chiral system.Sulphenic esters of prop-2-ynyl alcohols rearrange rapidly to allenyl sulphoxides, and the chirality of the allene group derived from an α-substituted prop-2-ynyl alcohol is the same as that generated in the sulphinate → sulphone rearrangement.Sulphinic and sulphenic esters of but-2-yne-1,4-diol rearrange to 2,3-bis-sulphonyl- or sulphinyl-buta-1,3-dienes. Structures of the products obtained have been proven by synthesis.Prototropic equilibration of four-carbon acetylenic–allenic aryl sulphones shows the following decreasing order of stability: ArSO2·CH2·C⋮CMe > ArSO2·CH:C:CHMe > ArSO2·C⋮C·CH2Me.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"15 1","pages":"1530-1535"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73095841","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}
Pentafluorobenzonitrile reacts with ammonia, aniline, and o-phenylenediamine and with chloride, bromide, iodide, methoxide, hydroxide, acetate, benzoate, and azide ions mainly by displacement of the 4-fluorine atom. Reaction with an excess of chloride ion yields pentachlorobenzonitrile. Tetrafluoro-4-iodobenzonitrile undergoes attack at the iodine atom itself in the presence of iodide ion, and 4-benzoyloxytetrafluorobenzonitrile yields tetrafluoro-4-hydroxybenzonitrile when it is treated with dimethylformamide. Pentafluorobenzonitrile may be converted into pentafluorobenzaldehyde by reaction with Raney nickel and into pentafluorobenzophenone by reaction with phenylmagnesium bromide.
{"title":"Polyfluoroarenes. Part XVII. Some reactions of pentafluorobenzonitrile","authors":"J. M. Birchall, R. Haszeldine, M. Jones","doi":"10.1039/J39710001343","DOIUrl":"https://doi.org/10.1039/J39710001343","url":null,"abstract":"Pentafluorobenzonitrile reacts with ammonia, aniline, and o-phenylenediamine and with chloride, bromide, iodide, methoxide, hydroxide, acetate, benzoate, and azide ions mainly by displacement of the 4-fluorine atom. Reaction with an excess of chloride ion yields pentachlorobenzonitrile. Tetrafluoro-4-iodobenzonitrile undergoes attack at the iodine atom itself in the presence of iodide ion, and 4-benzoyloxytetrafluorobenzonitrile yields tetrafluoro-4-hydroxybenzonitrile when it is treated with dimethylformamide. Pentafluorobenzonitrile may be converted into pentafluorobenzaldehyde by reaction with Raney nickel and into pentafluorobenzophenone by reaction with phenylmagnesium bromide.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"1 1","pages":"1343-1348"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75496266","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}
The free-radical addition of hydrogen bromide to hexachloromethylenenorbornene affords a 60 : 40 mixture of 1-bromomethyl-2,3,4,5,5,6-endo-hexachloronorborn-2-ene and 5-endo-bromomethyl-1,2,3,4,7,7-hexachloronorborn-2-ene. The aluminium bromide-catalysed ionic addition gives a 68 : 32 mixture of 5-exo-bromo-1,2,3,4,7,7-hexachloro-5-endo-methylnorborn-2-ene and its 5-endo-bromo-epimer.
{"title":"Free-radical reactions of halogenated bridged polycyclic compounds. Part XIII. The addition of hydrogen bromide to hexachloromethylenenorbornene","authors":"R. Alexander, D. I. Davies","doi":"10.1039/J39710000896","DOIUrl":"https://doi.org/10.1039/J39710000896","url":null,"abstract":"The free-radical addition of hydrogen bromide to hexachloromethylenenorbornene affords a 60 : 40 mixture of 1-bromomethyl-2,3,4,5,5,6-endo-hexachloronorborn-2-ene and 5-endo-bromomethyl-1,2,3,4,7,7-hexachloronorborn-2-ene. The aluminium bromide-catalysed ionic addition gives a 68 : 32 mixture of 5-exo-bromo-1,2,3,4,7,7-hexachloro-5-endo-methylnorborn-2-ene and its 5-endo-bromo-epimer.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"4 1","pages":"896-898"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75516427","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}
C. J. Coulson, K. Wooldridge, J. Memel, B. Millard
3-Hydroxy-2,3,4,5-tetrahydro-1,5-benzoxazepine and some related compounds have been synthesised. Attempts to prepare 3-chloro derivatives resulted in ring contraction. Mass spectral studies on these compounds confirmed their structure.
{"title":"The synthesis and mass spectra of 3-hydroxy-2,3,4,5-tetrahydro-1,5-benzoxazepine and related compounds","authors":"C. J. Coulson, K. Wooldridge, J. Memel, B. Millard","doi":"10.1039/J39710001164","DOIUrl":"https://doi.org/10.1039/J39710001164","url":null,"abstract":"3-Hydroxy-2,3,4,5-tetrahydro-1,5-benzoxazepine and some related compounds have been synthesised. Attempts to prepare 3-chloro derivatives resulted in ring contraction. Mass spectral studies on these compounds confirmed their structure.","PeriodicalId":17245,"journal":{"name":"Journal of The Chemical Society C: Organic","volume":"43 1","pages":"1164-1167"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78389228","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：