A. Perjéssy, E. Kolehmainen, W. Fabian, M. Ludwig, K. Laihia, J. Kulhanek, Z. Šusteková
The infrared absorption bands of the S=O and N-H stretching vibrations as well as the natural abundance 13 C and the 17 O NMR chemical shifts were measured for fifteen substituted benzenesulfonamides in CDCl 3 and acetone-d 6 . For the unsubstituted compound the natural abundance 33 S NMR chemical shift was also measured in acetone-d 6 PM3 charge densities and bond orders were calculated for the completely optimised geometry. Mutual correlations are reported between the wave numbers of the asymmetric SO 2 stretching vibration, the arithmetic means of symmetric and asymmetric NH 2 stretching vibrations, Hammett or + substituent constants, dissociation constants, 1 H, 13 C, 15 N and 17 O NMR chemical shifts as well as the PM3 S=O and N-H bond orders and hydrogen, nitrogen and oxygen atom charge densities. The results of the correlation analysis showed that the factors determining the electronic structure and controlling the dissociation equilibria, the IR and NMR spectral properties of substituted benzenesulfonamides must be the same.
测定了15种取代苯磺酰胺在cdcl3和丙酮- d6中的S=O和N-H伸缩振动的红外吸收带以及13c的自然丰度和17o的核磁共振化学位移。对于未被取代的化合物，在丙酮-d中也测量了天然丰度33 S NMR化学位移6 PM3的电荷密度和键序，计算了完全优化的几何形状。本文报道了不对称so2拉伸振动的波数、对称和不对称nh2拉伸振动的算术平均值、Hammett or +取代基常数、解离常数、1 H、13 C、15 N和17 O核磁共振化学位移以及PM3 S=O和N-H键序与氢原子、氮原子和氧原子电荷密度之间的相互关系。相关分析结果表明，取代苯磺酰胺的电子结构的决定因素和解离平衡的控制因素、红外光谱和核磁共振光谱性质都是相同的。
{"title":"Structure-Reactivity-Spectra Correlations for Substituted Benzenesulfonamides","authors":"A. Perjéssy, E. Kolehmainen, W. Fabian, M. Ludwig, K. Laihia, J. Kulhanek, Z. Šusteková","doi":"10.1080/02786110211430","DOIUrl":"https://doi.org/10.1080/02786110211430","url":null,"abstract":"The infrared absorption bands of the S=O and N-H stretching vibrations as well as the natural abundance 13 C and the 17 O NMR chemical shifts were measured for fifteen substituted benzenesulfonamides in CDCl 3 and acetone-d 6 . For the unsubstituted compound the natural abundance 33 S NMR chemical shift was also measured in acetone-d 6 PM3 charge densities and bond orders were calculated for the completely optimised geometry. Mutual correlations are reported between the wave numbers of the asymmetric SO 2 stretching vibration, the arithmetic means of symmetric and asymmetric NH 2 stretching vibrations, Hammett or + substituent constants, dissociation constants, 1 H, 13 C, 15 N and 17 O NMR chemical shifts as well as the PM3 S=O and N-H bond orders and hydrogen, nitrogen and oxygen atom charge densities. The results of the correlation analysis showed that the factors determining the electronic structure and controlling the dissociation equilibria, the IR and NMR spectral properties of substituted benzenesulfonamides must be the same.","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74662928","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 oxidation reaction of sulfides into sulfoxides with 10% nitric acid can be catalyzed by several transition metal halides. However, the best results are obtained when the metallic center is iron.
几种过渡金属卤化物可以催化硫化物在10%硝酸中氧化生成亚砜。当金属中心为铁时，效果最好。
{"title":"Transition metal halides as catalysts in the oxidation reaction of sulfides into sulfoxides","authors":"L. Rossi, A´ngela Sua´rez","doi":"10.1080/02786110212863","DOIUrl":"https://doi.org/10.1080/02786110212863","url":null,"abstract":"The oxidation reaction of sulfides into sulfoxides with 10% nitric acid can be catalyzed by several transition metal halides. However, the best results are obtained when the metallic center is iron.","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74391856","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}
L. Brandsma, N. Chernysheva, S. V. Zinchenko, B. Trofimov
Lithiated allenes or allenylmagnesium bromides readily react (THF/hexane, m 90 to m 105°C, 10-15 r min) with phenylsulfinylamine to give N -phenyl-2-alkynylsulfinamides. The reaction z of metallated 3-methylbuta-1,2-diene leads to the formation of not only 2-methyl- N -phenylbut-3-yne-2-sulfinamide, but also its allenic isomer, 3-methyl- N -phenylbuta-1,2-diene-1-sulfinamide. Metallated penta-1,2-diene, 1-propa-1,2-dienylcyclohexane and 4,4-dimethylpenta-1,2-diene react with phenylsulfinylamine to form acetylenes 3 , 4 and 6 respectively as a mixture of diastereoisomers.
锂化的烯或烯基溴化镁很容易与苯基亚胺反应(THF/己烷，m 90至m 105℃，10-15 r min)得到N -苯基-2-炔基亚胺。金属化3-甲基丁基-1,2-二烯的反应不仅生成了2-甲基- N -苯基-3-炔-2-亚砜酰胺，而且生成了它的异位异构体3-甲基- N -苯基丁基-1,2-二烯-1-亚砜酰胺。金属化的五1,2-二烯，1-丙-1,2-二烯环己烷和4,4-二甲基五1,2-二烯分别与苯基亚胺反应生成乙炔3、4和6作为非对映异构体的混合物。
{"title":"Reaction Of Metallated Allenes With Phenylsulfinylamine","authors":"L. Brandsma, N. Chernysheva, S. V. Zinchenko, B. Trofimov","doi":"10.1080/02786110210635","DOIUrl":"https://doi.org/10.1080/02786110210635","url":null,"abstract":"Lithiated allenes or allenylmagnesium bromides readily react (THF/hexane, m 90 to m 105°C, 10-15 r min) with phenylsulfinylamine to give N -phenyl-2-alkynylsulfinamides. The reaction z of metallated 3-methylbuta-1,2-diene leads to the formation of not only 2-methyl- N -phenylbut-3-yne-2-sulfinamide, but also its allenic isomer, 3-methyl- N -phenylbuta-1,2-diene-1-sulfinamide. Metallated penta-1,2-diene, 1-propa-1,2-dienylcyclohexane and 4,4-dimethylpenta-1,2-diene react with phenylsulfinylamine to form acetylenes 3 , 4 and 6 respectively as a mixture of diastereoisomers.","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77506598","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}
M. T. Omar, A. A. El-Khamry, A. Youssef, S. K. Ramadan
Thionation of 3-substituted-5-(2-aryl-2-oxoethyl)-2-thioxo-4-oxo-1,3-thiazolidines 1a-e either with tetraphosphorous decasulfide or with Lawesson's reagent in xylene affords the respective 3-substituted-5-aryl-2,3-dihydro [2,3-d] 1,3-thiazole-2-thiones 2a-e . However, thionation of 1f affords 3-(3-methylphenyl)-6-(4-ethylphenyl)-2-thio-2,3-dihydrothiazolo[4,5-c]1,2-dithin 3 . The structure of the synthesized compounds were supported by microanalytical and spectral evidence. A rationalization for the route of conversion was also given.
{"title":"Novel synthesis of thieno[2,3-d] and 1,2-dithiino[4,5-c] Thiazoles","authors":"M. T. Omar, A. A. El-Khamry, A. Youssef, S. K. Ramadan","doi":"10.1080/02786110213979","DOIUrl":"https://doi.org/10.1080/02786110213979","url":null,"abstract":"Thionation of 3-substituted-5-(2-aryl-2-oxoethyl)-2-thioxo-4-oxo-1,3-thiazolidines 1a-e either with tetraphosphorous decasulfide or with Lawesson's reagent in xylene affords the respective 3-substituted-5-aryl-2,3-dihydro [2,3-d] 1,3-thiazole-2-thiones 2a-e . However, thionation of 1f affords 3-(3-methylphenyl)-6-(4-ethylphenyl)-2-thio-2,3-dihydrothiazolo[4,5-c]1,2-dithin 3 . The structure of the synthesized compounds were supported by microanalytical and spectral evidence. A rationalization for the route of conversion was also given.","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77771977","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}
F. Baerlocher, M. Baerlocher, R. Langler, S. MacQuarrie, P. E. O'Connor
Previously identified classes of antifungal disulfides are modified by extending alkyl substituents. Although, the principal focus is on f -sulfone disulfides, one nitrophenyl alkyl disulfide and a pair of f -ester disulfides were also prepared and examined. Optimum fungitoxicity is associated with structures which have seven to ten carbon atoms in the form of unbranched chains and/or phenyl rings.
{"title":"Optimizing disulfide fungitoxicity: Adjustment of hydrocarbon chain length","authors":"F. Baerlocher, M. Baerlocher, R. Langler, S. MacQuarrie, P. E. O'Connor","doi":"10.1080/02786110213980","DOIUrl":"https://doi.org/10.1080/02786110213980","url":null,"abstract":"Previously identified classes of antifungal disulfides are modified by extending alkyl substituents. Although, the principal focus is on f -sulfone disulfides, one nitrophenyl alkyl disulfide and a pair of f -ester disulfides were also prepared and examined. Optimum fungitoxicity is associated with structures which have seven to ten carbon atoms in the form of unbranched chains and/or phenyl rings.","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75644913","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 palladium(0) catalysed allylation reactions of allylic carbonates with chiral sulfinamide anions to give unstable allylic sulfinamide products are described. These products are readily converted to stable, chiral N-benzoyl or N-tosyl allylic amine derivatives with poor to modest enantiomeric purities (ee 23-41%).
{"title":"Synthesis Of Chiral Allylic Amines Via Palladium(0) Catalysed Allylations Of Allylic Carbonates With Chiral Sulfinamide Anions","authors":"Z. Dong, S. Pyne","doi":"10.1080/02786110210632","DOIUrl":"https://doi.org/10.1080/02786110210632","url":null,"abstract":"The palladium(0) catalysed allylation reactions of allylic carbonates with chiral sulfinamide anions to give unstable allylic sulfinamide products are described. These products are readily converted to stable, chiral N-benzoyl or N-tosyl allylic amine derivatives with poor to modest enantiomeric purities (ee 23-41%).","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77068055","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}
A method for synthesis of the (5-methyl-1,3,4-hexatriene-3-yl) phenyl sulfoxide 3 by [2,3]-sigmatropic rearrangement of the (5-methyl-1-hexene-3-yn-5-yl) benzenesulfenate 2 , formed in the reaction of the 5-methyl-1-hexene-3-yn-5-ol 1 with phenylsulfenyl chloride has been created. Five-membered heterocyclizations in electrophile-promoted reactions leading to the synthesis of the 5 H -1,2-oxathiol-2-ium salts and 3-(phenylsulfinyl)-thiophene or -selenophene have been explored. Halogenation of the sulfoxide 3 proceeded with formation of the 4-halo-5 H -1,2-oxathiol-2-ium halides 4 and 5 , while the reactions with phenylsulfenyl and phenylselenenyl chlorides afforded the mixtures of the 2-isopropyl-3-(phenylsulfinyl)-thiophene 6 or -selenophene 8 and 4-phenythio (seleno)-5 H -1,2-oxathiol-2-ium chlorides 7 and 9 .
建立了由5-甲基-1-己烯-3-己烯-5-氨基-5-基苯磺酸盐2与苯基亚砜氯反应生成的(5-甲基-1,3,4-己烯-3-基)苯基亚砜3的[2,3]异位重排合成(5-甲基-1,3,4-己烯-3-基)苯基亚砜3的方法。研究了亲电促进反应中五元杂环化反应，合成了5 H -1,2-草硫醇-2-ium盐和3-(苯基亚砜基)-噻吩或-硒噻吩。亚砜3的卤化反应生成4-卤-5 H -1,2-草硫醇-2-ium halides 4和5，而与苯基亚砜基和苯基亚硒基氯化物的反应生成2-异丙基-3-(苯基亚砜基)-噻吩6或-硒苯8和4-苯基(硒基)-5 H -1,2-草硫醇-2-ium chlorides 7和9的混合物。
{"title":"Alkatrienyl sulfoxides and sulfones. Part II. [1] (5-methyl-1,3,4-hexatriene-3-yl) phenyl sulfoxide-synthesis and electrophile-promoted cyclization reactions","authors":"V. Christov, Ivaylo K. Ivanov","doi":"10.1080/02786110214495","DOIUrl":"https://doi.org/10.1080/02786110214495","url":null,"abstract":"A method for synthesis of the (5-methyl-1,3,4-hexatriene-3-yl) phenyl sulfoxide 3 by [2,3]-sigmatropic rearrangement of the (5-methyl-1-hexene-3-yn-5-yl) benzenesulfenate 2 , formed in the reaction of the 5-methyl-1-hexene-3-yn-5-ol 1 with phenylsulfenyl chloride has been created. Five-membered heterocyclizations in electrophile-promoted reactions leading to the synthesis of the 5 H -1,2-oxathiol-2-ium salts and 3-(phenylsulfinyl)-thiophene or -selenophene have been explored. Halogenation of the sulfoxide 3 proceeded with formation of the 4-halo-5 H -1,2-oxathiol-2-ium halides 4 and 5 , while the reactions with phenylsulfenyl and phenylselenenyl chlorides afforded the mixtures of the 2-isopropyl-3-(phenylsulfinyl)-thiophene 6 or -selenophene 8 and 4-phenythio (seleno)-5 H -1,2-oxathiol-2-ium chlorides 7 and 9 .","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76317882","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}
2-Methylene-4-phenyl-1,3-diselenole was synthesized. It was formylated on the exomethylene carbon in a Vilsmeier-Haack reaction; iodine-morpholine reagent converted it to the E/Z diphenyltetraselenafulvalene derivative.
{"title":"4-Phenyl-2-methylene-1,3-diselenole: Synthesis and reactions","authors":"Desikan Rajagopal, M. Lakshmikantham, M. Cava","doi":"10.1080/02786110212865","DOIUrl":"https://doi.org/10.1080/02786110212865","url":null,"abstract":"2-Methylene-4-phenyl-1,3-diselenole was synthesized. It was formylated on the exomethylene carbon in a Vilsmeier-Haack reaction; iodine-morpholine reagent converted it to the E/Z diphenyltetraselenafulvalene derivative.","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74605241","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}
Photochemical thioacetylation of (s−)- i -cadinene 1 afforded 5-acetylthio-cadinene 1a which was further reduced into 5-mercapto-cadinene 1b in good yield (80%). Thioepoxydation of trans -1,10-cadinene oxide 1c , prepared from m -CPBA oxidation of 1 , was also investigated. Structural determination of these derivatives was achieved by one- and two dimensional NMR spectroscopy.
(s−)- i -cadinene 1的光化学硫乙酰化得到5-乙酰基硫代cadinene 1a，进一步还原为5-巯基cadinene 1b，收率很高(80%)。研究了以m -CPBA氧化1制备的反式-1,10-二苯二烯氧化物1c的硫代环氧化反应。这些衍生物的结构测定是通过一维和二维核磁共振波谱实现的。
{"title":"Thiol and Thioacetate Derivatives of Δ-Cadinene","authors":"Karine Candela, R. Fellous, D. Joulain, R. Faure","doi":"10.1080/02786110210631","DOIUrl":"https://doi.org/10.1080/02786110210631","url":null,"abstract":"Photochemical thioacetylation of (s−)- i -cadinene 1 afforded 5-acetylthio-cadinene 1a which was further reduced into 5-mercapto-cadinene 1b in good yield (80%). Thioepoxydation of trans -1,10-cadinene oxide 1c , prepared from m -CPBA oxidation of 1 , was also investigated. Structural determination of these derivatives was achieved by one- and two dimensional NMR spectroscopy.","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84261672","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}
Vladimir V. Potapov, S. Amosova, I. V. Doron'kina, A. Starkova, L. Hevesi
The tin tetrachloride-mediated reaction of dialkyl diselenides with phenylacetylene proceeds as syn addition to afford' 2a,b.
四氯化锡介导的二烷基二烯与苯乙炔的反应是通过同步加成得到' 2a,b。
{"title":"Syn addition of dialkyl diselenide to phenylacetylene in the presence of tin tetrachloride","authors":"Vladimir V. Potapov, S. Amosova, I. V. Doron'kina, A. Starkova, L. Hevesi","doi":"10.1080/02786110212866","DOIUrl":"https://doi.org/10.1080/02786110212866","url":null,"abstract":"The tin tetrachloride-mediated reaction of dialkyl diselenides with phenylacetylene proceeds as syn addition to afford' 2a,b.","PeriodicalId":22122,"journal":{"name":"Sulfur Letters","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91431370","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}
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