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Synthesis of 5-Chloro-10,11-Dihydro-5 H -Dibenzo[ a , d ]Cycloheptene-5,10-Sulfide and -5,11-Dichloro-10,11-Dihydro-5 H -Dibenzo[ A , D ]Cycloheptene-5,10-Sulfide and their Oxidation 5-氯-10,11-二氢-5 - H -二苯并[a, d]环庚烯-5,10-硫醚和-5,11-二氯-10,11-二氢-5 - H -二苯并[a, d]环庚烯-5,10-硫醚的合成及其氧化
Pub Date : 2002-01-01 DOI: 10.1080/02786110211428
M. Hegab, A. El-Gazzar, I. Farag, F. A. Gad
The chlorination of 5-thioxo-10,11-dihydro-5 H -dibenzo[ a,d ]cycloheptene 2a gave 5-chloro-10,11-dihydro-5 H -dibenzo[ a,d ]cycloheptene-5,10-sulfide 4 . Chlorination of 5-thioxo-5 H -dibenzo[ a,d ]cycloheptene 2b gave the two isomers cis - and trans -5,11-dichloro-10,11-dihydro-5 H -dibenzo[ a,d ]cycloheptene-5,10-sulfide 7a,b . The two sulfides 4 and 7a,b were oxidized by using mCPBA or H 2 O 2 /AcOH to give the corresponding sulfoxides 5 and 8a,b , respectively. Treatment of the sulfide 7a,b with KI gave the primary ketone 1b together with trans -5-chloro-11-hydroxy-10,11-dihydro-5 H -dibenzo[ a,d ]cycloheptene-5,10-sulfide 9 . The structures of the new compounds were established by different spectroscopic techniques as well as single crystal X-ray diffraction for compounds 4 and 9 .
5-硫氧基-10,11-二氢-5 H -二苯并[a,d]环庚烯2a氯化得到5-氯-10,11-二氢-5 H -二苯并[a,d]环庚烯-5,10-硫4。氯化5-硫氧基-5 H -二苯并[a,d]环庚烯2b得到顺式和反式两种异构体-5,11-二氯-10,11-二氢-5 H -二苯并[a,d]环庚烯-5,10-硫7a,b。两种硫化物4和7a,b分别用mCPBA或h2o2 /AcOH氧化得到相应的亚砜5和8a,b。硫化物7a,b用KI处理得到伯酮1b和反式-5-氯-11-羟基-10,11-二氢-5- H -二苯并[a,d]环庚烯-5,10-硫化物9。通过不同的光谱技术以及化合物4和9的单晶x射线衍射确定了新化合物的结构。
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引用次数: 4
A facile and selective method for oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides with alumina-supported potassium permanganate under solvent-free conditions 在无溶剂条件下,用氧化铝负载的高锰酸钾将硫化物和硫醇氧化成相应的亚砜和二硫化物的一种简便、选择性的方法
Pub Date : 2002-01-01 DOI: 10.1080/02786110213976
A. Hajipour, S. Mallakpour, H. Adibi
This paper describes the facile and selective oxidation of sulfides 1 and thiols 3 to their corresponding sulfoxides 2 and disulfides 4 with potassium permanganate supported on alumina in high yields under solvent-free conditions.
本文介绍了在无溶剂条件下,氧化铝负载高锰酸钾快速、选择性地将硫化物1和硫醇3氧化为相应的亚砜2和二硫化物4。
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引用次数: 18
Synthesis and Reactivity of Unsymmetrical S , S ″ -Dialkyl N -(Arenesulfonyl)Carbondithioimidates 不对称S, S″-二烷基N -(Arenesulfonyl)碳二硫代酰亚胺酯的合成及反应性
Pub Date : 2002-01-01 DOI: 10.1080/02786110210630
W. Rudolf, D. Cleve, A. Riemer
S , S '-Dialkyl N -(arenesulfonyl)carbondithioimidates 3 are prepared either in a one-pot reaction by successive alkylation of disodium salts 2 or by using N -(arenesulfonyl)dithiocarbamates 4 . C,H-Acidic N -(arenesulfonyl)-carbondithioimidates 3a , b , d react with thiacumulenes in the presence of sodium hydride. Subsequent methylation leads to 2,3-dihydrothiazoles 7 and 1,3-dithiols 8 , respectively.
S, S '-二烷基N -(芳烃磺酰基)二硫代氨基甲酸酯可以通过二钠盐的连续烷基化在一锅反应中制备,也可以用N -(芳烃磺酰基)二硫代氨基甲酸酯4制备。C, h -酸性N -(arenesulfonyl)-碳二硫代酸盐3a, b, d在氢化钠存在下与噻唑烯反应。随后的甲基化分别生成2,3-二氢噻唑7和1,3-二硫醇8。
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引用次数: 0
Utility of isothiocyanates in heterocyclic synthesis 异硫氰酸酯在杂环合成中的应用
Pub Date : 2002-01-01 DOI: 10.1080/02786110214496
S. El-Desoky, H. Etman, S. Bondock, A. Fadda, M. Metwally
Reaction of substituted pyrazolin-5-one and 3-phenyl-5-isoxazolone 1a-c with phenyl isothiocyanate in basic DMF gave the non-isolable sodium salt of the adduct 2a-c which was treated with HCl to give the corresponding thiocarbamoyl derivatives 3a-c . The latter compounds underwent heterocyclization upon treatment with chloroacetyl chloride and ethyl bromoacetate to give the corresponding thiazolidinone derivatives 6 and 7 . Compound 3a,b was oxidized to yield benzothiazoly pyrazolinone derivatives 8a,b . Also, nucleophilic substitution of 2 and 3 and with different nucleophilic reagents afforded the products 9-14 . Cyclocondensation of the thiocarbamoyl salt with some halogenated esters or acid chloride derivatives such as f -bromopropionate, ethyl chloroformate and f -bromo diethyl malonate afforded cyclized polyfunctionally thiazinone, thiazetidinone and thiazolidinone derivatives respectively 15-17 . The structures of the products were confirmed by spectral and micro analytical data.
取代吡唑啉-5- 1和3-苯基-5-异恶唑酮1a-c与异硫氰酸苯酯在碱性DMF中反应得到加合物2a-c的不可分离钠盐,用HCl处理得到相应的硫氨基基衍生物3a-c。后一种化合物经氯乙酰氯和溴乙酸乙酯处理后杂环化,得到相应的噻唑烷酮衍生物6和7。化合物3a,b被氧化得到苯并噻唑类吡唑啉酮衍生物8a,b。另外,2和3的亲核取代以及与不同的亲核试剂的亲核取代产生产物9-14。硫代氨基甲酸盐与某些卤化酯或酸氯化物衍生物如-溴丙酸酯、氯甲酸乙酯和-溴二乙基丙酸酯进行环缩合反应,分别得到环化的多功能噻嗪酮、噻烷酮和噻唑烷酮衍生物15-17。产物的结构经光谱和微量分析证实。
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引用次数: 29
Polyfunctional 1,3-Dithiolanes from 5,5-Dialkyl-4-Cyanomethylene-1,3-Oxathiolan-2-Ones 由5,5-二烷基-4-氰乙烯-1,3-草硫代烷-2- ones合成的多功能1,3-二硫代烷
Pub Date : 2002-01-01 DOI: 10.1080/02786110210634
I. А. Dorofeev, A. Mal’kina, L. M. Sinegovskaya, B. Trofimov
The interaction of 5,5-dialkyl-4-cyanomethylene-1,3-oxathiolan-2-ones with diethylamine (without catalyst), aliphatic alcohols and ethanethiol (in the presence of triethylamine) occurs under mild conditions (room temperature, 3-12 r h) with ring opening and the subsequent dimerization to give polyfunctional 1,3-dithiolanes.
5,5-二烷基-4-氰乙基-1,3-氧噻吩-2- 1与二乙胺(无催化剂)、脂肪醇和乙硫醇(在三乙胺存在下)的相互作用在温和条件下(室温,3-12 r h)发生,开环和随后的二聚化得到多官能团1,3-二硫代烷。
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引用次数: 0
Poly(methylene diselenide) and poly(methylene seleno-polysulfido-selenides), -[-CH2Se2-] n -, -[-CH2SeS m Se-] n - 聚(亚甲基二硒化物)和聚(亚甲基硒-聚硫代硒化物),-[- ch2se2 -] n -, -[- ch2ses m Se-] n -
Pub Date : 2002-01-01 DOI: 10.1080/02786110214498
B. Trofimov, E. Deryagina, Emma Sukhomazova, E. Levanova, G. Myachina, S. Korzhova, Yuriy V. Mikhaylik, T. Skotheim
Poly(methylene diselenide), -[-CH2Se2-] n -, when alloyed with sulfur in a 1-4 molar excess of the latter, gives dark orange rubber-like poly(methylene seleno-polysulfido-selenides), -[-CH2SeS m Se-] n -, where m =1-4 representing a new class of S-Se organic polymers having no C-S bonds. At molar ratio sulfur:poly(methylene diselenide) equal to 16 sulfur content does not exceed m =4. The selenium part of the polymer, while alloying with sulfur, is removed from the polymer and forms the compound with sulfur. The polymers demonstrate reversible redox properties and can be employed as active cathode materials in rechargeable lithium cells.
聚(亚甲基二硒化物),-[- ch2se2 -] n -,当与1-4摩尔过量的硫(后者)合金时,得到深橙色的橡胶状聚(亚甲基硒-聚硫-硒化物),-[- ch2ses m Se-] n -,其中m =1-4代表了一类新的没有C-S键的S-Se有机聚合物。在硫与聚亚甲基二烯的摩尔比等于16时,硫含量不超过m =4。聚合物的硒部分在与硫合金化时,从聚合物中除去并与硫形成化合物。该聚合物具有可逆氧化还原特性,可作为可充电锂电池的活性正极材料。
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引用次数: 4
Further Studies and Synthesis of Five-membered Rings via 1,3-Dipolar Cycloaddition of 1-Aza-2-azoniaallene Cations to Isothiocyanates and Nitriles 异硫氰酸酯和腈的1,3-偶极环加成法合成五元环的进一步研究
Pub Date : 2002-01-01 DOI: 10.1080/02786110211429
A. El-Gazzar, M. Hegab, N. A. Hassan
Cycloaddition of 1-aza-2-azoniaallene salts ( 2 , 9 and 17 ) with isothiocyanates gave different types of 1,2,4-triazolium salts ( 5 , 6 and 25-34 ), and 1,3,4-thiadiazolium salts ( 12 , 14 and 19 ). The obtained products depend on: a) the ability of a substituent of the heteroallene salts to undergo a [1,2] shift as a cationic charged migrant or to act as a cationic leaving groups (as a stable carbenium ion), b) Dimroth rearrangement of the initially formed thiadiazolium salts to triazolium salts. Accordingly, 1-aza-2-azoniaallenes ( 22 and 29 ) reacted with nitriles and dinitriles to give 1,2,4-triazolium salts ( 25 , 27 and 32-34 ).
1-氮杂-2-氮杂二烯盐(2,9和17)与异硫氰酸酯环加成得到不同类型的1,2,4-三唑盐(5,6和25-34)和1,3,4-噻二唑盐(12,14和19)。所获得的产物取决于:a)杂二烯盐的取代基作为带阳离子的迁移基团进行[1,2]移位或作为阳离子离开基团(作为稳定的碳离子)的能力,b)最初形成的噻二唑盐到三唑盐的Dimroth重排。因此,1-氮杂-2-氮杂烯(22和29)与腈和二腈反应得到1,2,4-三唑盐(25、27和32-34)。
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引用次数: 4
A convenient synthesis of novel nucleosides of 2-thioxo-5h-3,4-dihydropyrimido[5,4-b]indol-4-one 2-硫氧-5h-3,4-二氢嘧啶[5,4-b]吲哚-4-酮核苷的简便合成
Pub Date : 2002-01-01 DOI: 10.1080/02786110215845
M. Saleh
Reaction of 3-amino-2-ethoxycarbonylindole ( 1 ) with per- O -acetyl-sugar isothiocyanates 2a-c gave the corresponding glycopyranosyl thioureas 3a-c . The N -nucleosides analogues 3-(per- O -acetyl- β -D-glycopyranosyl)-2-thioxo-5H-3, 4-dihydropyrimido [5,4-b] indol- 4 -one 4a-c were obtained by cyclization of 3a-c in the presence of ZnCl2. Deacetylation of 4a-c with sodium methoxide in methanol yielded the free nucleoside derivatives 5a-c . Alkylation of 5a,b with methyl iodide and benzyl bromide gave good yields of the corresponding 2-methylthio 6a,b and the 2-benzylthio 6c,d analogues. The 2-methylsulfonyl compounds 7a,b were obtained from the corresponding 2-methylthio compounds 6a,b by oxidation with m -chloroperoxybenzoic acid.
3-氨基-2-乙氧基羰基吲哚(1)与每- O -乙酰基糖异硫氰酸酯2a-c反应得到相应的甘氨酰硫脲3a-c。在ZnCl2的存在下,将3a-c环化,得到了N -核苷类似物3-(per- O -乙酰基- β -d -glycopyranosyl)-2-硫氧基- 5h - 3,4 -二氢嘧啶[5,4-b]吲哚- 4- 1 4a-c。4a-c与甲氧基钠在甲醇中脱乙酰化,得到游离核苷衍生物5a-c。5a,b与碘化甲酯和苄基溴的烷基化反应得到了相应的2-甲基硫代6a,b和2-甲基硫代6c,d类似物的良好产率。由相应的2-甲基硫代化合物6a、b与间氯过氧苯甲酸氧化得到2-甲基磺酰基化合物7a、b。
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引用次数: 3
In pursuit of the elusive trithia[1.1.1]propellane: Synthesis of potential 1,3-dithietane precursors 寻找难以捉摸的三硫醚[1.1.1]推进剂:潜在的1,3-二己烷前体的合成
Pub Date : 2002-01-01 DOI: 10.1080/02786110212860
U. Zoller, Fayun Chen
High-level ab initio calculations predicted the strained three-membered trithia[1.1.1]propellane 1a (X=Y=Z=S) to be a tightly-bound molecule which should be experimentally accessible. In analogy to the successful synthesis of'the [1.1.1] propellane, our synthesis strategy focused on the attempted preparation of 1,3-dihalo-trithia-bicyclo[1.1.1] pentanes 2 , to serve as a precursor for the target molecule. However, 1a proved to be unattainable via the planned strategy beyond the stage of the readily synthesized, substituted 1,3-dithietanes 3 , due to the inaccessibility of 2 from the latter. The successfully synthesized 1,3-dithietanes 5c,d are expected to provide 2 , the key precursor of 1 via 1,3-dihalogenation-dehalogenation.
高水平从头计算预测应变三元trithia[1.1.1]推进剂1a (X=Y=Z=S)是一个紧密结合的分子,应该可以在实验上得到。与成功合成[1.1.1]推进剂类似,我们的合成策略集中在尝试制备1,3-二卤-三硫-双环[1.1.1]戊烷2,作为目标分子的前体。然而,在易于合成取代的1,3-二硫烷3的阶段之外,1a被证明是无法通过计划的策略获得的,因为后者无法获得2。成功合成的1,3-二硫烷5c,d有望通过1,3-二卤化-脱卤化反应提供1的关键前体2。
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引用次数: 2
Novel synthesis of phthalazine derivatives as antimicrobial agents 新型酞嗪类抗菌药物的合成
Pub Date : 2002-01-01 DOI: 10.1080/02786110213977
Y. Issac, Eman El-Karim, S. Donia, Mohamed Behalow
Reaction of 4-(phenoxathiin-2-yl)-1-oxy or mercaptophthalazines 2a,c with phthalyl or tosylamino acids 3 and 4 has been found to yield 5,6a-j . Hydrazinolysis of 5,6a-e furnished amino derivatives 5,6k-o . Some of the newly synthesized products were tested for their antimicrobial activities.
4-(2-基苯氧嘧啶)-1-氧或巯基酞嗪2a,c与邻苯二甲酸或苯三胺酸3和4反应得到5,6a-j。含5,6a-e的氨基衍生物5,6k-o的肼解。对部分新合成产物进行了抗菌活性测试。
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引用次数: 19
期刊
Sulfur Letters
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