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使用邻甲苯基重氮盐与乙醛酸甲酯肟偶联反应高立体选择性合成出 (E)-2-(羟基亚氨基)-2-邻甲基苯乙酸甲酯,经硫酸二甲酯的甲基化反应可得到重要的中间体(E)-2-(甲氧亚氨基)-2-邻甲基苯乙酸甲酯, 再经NBS溴化后与 (E)-芳香醛酮肟进行醚化反应最终得到目标物(αE,E)-α-(甲氧亚氨基)-2-[1-(芳香醛酮肟氧基)甲基]苯乙酸甲酯, 这些化合物多数具有很好的广谱杀菌活性. 相似文献
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以(S)-2-氨基丙醇为手性源与α-溴-3-氯苯丙酮反应, (R)-2-氨基丙醇为手性源与6-甲氧基-2-(2-溴丙酰基)萘反应, 分别合成了手性纯化合物(2R,3R,5S)-3,5-二甲基-2-(3-氯苯基)-2-吗啉醇盐酸盐(4a)和(2S,3S,5R)-3,5-二甲基-2-(6-甲氧基-2-萘基)-2-吗啉醇盐酸盐(4b), 利用X射线单晶衍射仪测定了两化合物的晶体结构和两化合物的空间结构, 并初步分析两化合物空间结构, 化合物4a晶体属正交晶系, 空间群为P21212, 晶胞参数为: a=0.8718(2) nm, b=0.7883(2) nm, c=2.0247(6) nm, Z=4, V=1.3915(7) nm3, Dc=1.328 g/cm3, F(000)=584, R1=0.0399, wR2=0.0797, S=1.042. 化合物4b晶体属正交晶系, 空间群为P212121, 晶胞参数为: a=0.71035 (9) nm, b=0.77703(10) nm, c=2.9820(4) nm, Z=4, V=1.6318(4) nm3, Dc=1.318 g/cm3, F(000)=688, R1=0.0520, wR2=0.1108, S=0.994. 相似文献
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蒽酮(1)与3,5-二甲氧基苯甲醛(2)在吡啶/哌啶中反应生成10-(3,5-二甲氧基苯甲亚基蒽酮(3); 3经Pd/C催化氢化生成10-(3,5-二甲氧基苄基蒽酮(4); 4与3-甲氧基苄基氯(5)进行相转移催化烷基化反应生成10-(3,5-二甲氧基苄基)-10-(3-甲氧基苄基)蒽酮(6); 6经NaBH4还原生成10-(3,5-二甲氧基苄基)-10-(3-甲氧基苄基)-9(10H)-蒽醇(7); 7在酸催化下发生选择性1,7-脱水反应, 生成高三蝶烯(homotriptycene) (8). 其反应机理可能是7在酸存在下生成正碳离子中间体, 然后选择性地亲电进攻富电荷的3,5-二甲氧基苯基, 而不进攻3-甲氧基苯基. 相似文献
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将以烯烃为原料通过Sharpless不对称双羟化等多步反应合成的8种手性β-氨基醇, 作为有机小分子催化剂, 用于催化α,β-不饱和酮的不对称环氧化反应.考察了影响对映选择性的催化剂结构、催化剂用量、氧化剂种类、溶剂、反应温度等因素.结果表明, 当催化剂用量为30 mol%、氧化剂为TBHP(叔丁基过氧化氢)、正己烷溶剂、在室温下、以(1S,2R)-(+)-1,2-二苯基-2-甲氨基乙醇(3)作催化剂时, 所得环氧化物的对映体过量最高为70% ee, 产率最高为84%. 相似文献
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Solvent-controlled chemoselective palladium-catalyzed oligomerization of tert-butyl acetylene is reported in this paper. The reaction was carried out smoothly in benzene/n-BuOH binary solvent system. When unpolar aprotic benzene was the preponderating component in the binary system, a cyclotrimerization
process occurred to produce 1,3,5-tri-tert-butylbenzene via a mechanism of three acetylene molecules, inserted step by step, forming σ-butadienyl-Pd and σ-hexatrienyl-Pd intermediates. While when the polar, protic and strong coordinating component n-BuOH, which aids Cu(II) to cleave the C-Pd σ-bonds and solvate Pd(II), Cu(II) cations, halo anion, σ-butadienyl-Pd intermediate, etc., was increased to a certain extent in the binary solvent system, the reaction proceeded
readily via a n-BuOH-promoted mechanism to give (3Z,5Z)-2,2,7,7-tetramethyl-3,6-dichloro-3,5-octadiene or (3Z,5Z)-2,2,7,7-tetramethyl-3,6-dibromo-3,5-octadiene, respectively. Possible weak hydrogen bonds and n-π weak force between n-BuOH (electron pair donor (EPD)) and tert-butyl acetylene (and σ-butadienyl-Pd intermediate, electron pair acceptor (EPA)) in the latter process were also in favor of the n-BuOH promoted pathway. Meanwhile, the coupling product 2,2,7,7-tetramethyl-3,5-octadiyne was exclusively obtained when the
reaction was conducted in singular polar H2O. Influences of the solvent, catalysts, as well as possible mechanism were discussed in this paper. 相似文献
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Jin-Sheng Cheng Guo-Feng Wei Jin Zhao Shi-Wen Huang Zu-Liang Huang 《Research on Chemical Intermediates》2006,32(9):887-894
Efficient and selective palladium porphyrins-catalyzed olimerization of tert-butyl acetylene to form (3Z,5Z)-2,2,7,7-tetramethyl-3,6-dihalo-3,5-octadiene has been developed in environment-friendly ionic
liquids. The reaction proceeded readily with effective recycling of the ionic liquids and easy isolation of the products. 相似文献
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Mayumi Chida Satoru Takahashi Ryunosuke Konishi Dr. Takeshi Matsumoto Dr. Akinobu Nakada Dr. Masanori Wakizaka Dr. Wataru Kosaka Prof. Hitoshi Miyasaka Prof. Ho-Chol Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16354-16366
The combination of a cobalt-dioxolene core that exhibits valence tautomerism (VT) with pyridine-3,5-dicarboxylic acid functionalized with chains bearing two, four, or six oxyethylene units led to new complexes ConEGEspy (n = 2, 4, and 6). These complexes commonly form violet crystals of the low-spin (ls)-[CoIII(nEGEspy)2(3,6-DTBSQ)(3,6-DTBCat)] (ls-[CoIII], 3,6-DTBSQ = 3,6-di-tert-butyl semiquinonato, 3,6-DTBCat = 3,6-di-tert-butyl catecholato). Interestingly, violet crystals of Co2EGEspy in the ls-[CoIII] transitioned into a green liquid, accompanied by an almost complete VT shift (94 %) to the high-spin (hs)-[CoII(nEGEspy)2(3,6-DTBSQ)2] (hs-[CoII]) upon melting. In contrast, violet crystals of Co4EGEspy and Co6EGEspy in the ls-[CoIII] exhibited partial VT (33 %) and only a 9.3 % VT shift after melting, respectively. These data demonstrate the tunability of the synchronicity of the molecular VT and macroscopic solid-liquid transitions by optimizing the tethered chains, thus establishing a new strategy for coupling bistable molecules with the macroscopic world. 相似文献
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Yu. A. Sayapin Zyong Ngia Bang V. N. Komissarov I. V. Dorogan V. V. Tkachev G. V. Shilov S. M. Aldoshin V. I. Minkin 《Russian Journal of Organic Chemistry》2009,45(11):1663-1669
Acid-catalyzed reaction of 6,10a-dihydroxy-3,4a,7,9-tetra(tert-butyl)-1,2,4a,10a-tetrahydrodibenzo-[b,e][1,4]dioxine-1,2-dione with 2-methylquinoline derivatives led to the formation of a previously unknown system 6-[(Z)-2-(quinolin-2-yl)-1-hydroxyethen-1-yl]pyran-2-one. The molecular structure of 3,5-di(tert-butyl)-6-[(Z)-2-(7,8-dimethyl-4-chloroquinolin-2-yl)-1-hydroxyvinyl]pyran-2-one was established by XRD method; the energy and structural
characteristics of its isomers in the gas phase and in a polar solvent were calculated by quantumchemical methods (B3LYP/6-31G**). 相似文献
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V. B. Vol’eva T. I. Prokof’eva I. S. Belostotskaya N. L. Komissarova D. B. Gorbunov L. N. Kurkovskaya 《Russian Journal of Organic Chemistry》2011,47(9):1310-1312
Alkylation of pyrocatechol with tert-butyl alcohol in benzene in the presence of sulfuric acid gave 3,5-di-tert-butylbenzene-1,2-diol in a higher yield than in analogous reaction with tert-butyl alcohol. This result was rationalized by reduction of inhibitory effect of liberated water, formation of heterogeneous
system, and occurrence of the alkylation process in nonpolar organic phase. Intermediate products were identified and found
to undergo intra- and intermolecular tert-butyl group transfer with formation of more stable 3,5-di-tertbutylbenzene-1,2-diol. The formation of p-di-tert-butylbenzene indicated participation of benzene in crossalkylation processes. 相似文献
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V. N. Glushakova N. A. Skorodumova V. I. Nevodchikov L. G. Abakumova N. P. Makarenko V. K. Cherkasov N. O. Druzhkov 《Russian Chemical Bulletin》1999,48(5):934-937
Reaction of 3,6-di-tert-butyl-1,2-benzoquinone and 3,6-di-tert-butylcatechol withtert-butyl hydroperoxide in aprotic solvents leads to the generation of semiquinone (SQ.H), alkylperoxy (ROO.), and alkyloxy radicals. The reaction of SQ.H and ROO. produces 2,5-di-tert-butyl-6-hydroxy-1,4-benzoquinone, 3,6-di-tert-butyl-1-oxacyclohepta-3,5-diene-2,7-dione, and 2,5-di-tert-butyl-3,6-dihydroxy-1,4-benzoquinone. The radical generated from solvent attacks SQ.H at position 4 with C−C bond formation. 4-Benzyl-2,5-di-tert-butyl-6-hydroxycyclohexa-2,5-diene-1-dione produced in this way is transformed into 4-benzyl-3,6-di-tert-butyl-1,2-benzoquinone under the reaction conditions.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 943–946, May, 1999. 相似文献
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L. P. Stepovik M. V. Gulenova A. S. Shavyrin G. K. Fukin 《Russian Journal of General Chemistry》2006,76(8):1275-1281
Systems consisting of metal (Al, Ti, Zr) tert-butylate and tert-butyl hydroperoxide oxidize 3,6-di-tert-butyl-o-benzoquinone under mild conditions (room temperature, benzene). With (t-BuO)3Al and (t-BuO)4Zr, the major reaction products are 5-hydroxy-3,6-di-tert-butyl-2,3-epoxy-p-benzoquinone, and with (t-BuO)4Ti, 2-hydroxy-3,6-di-tert-butyl-p-benzoquinone. Under the conditions of this reaction, 3,6-di-tert-butylpyrocatechol initially transforms into 3,6-di-tert-butyl-o-benzoquinone. The reactions involve metalcontaining peroxides. 相似文献
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V. V. Tkachev G. V. Shilov S. M. Aldoshin E. A. Gusakov Yu. A. Sayapin A. A. Bumber V. N. Komissarov V. I. Minkin 《Russian Journal of Organic Chemistry》2012,48(2):151-157
By the XRD analysis the structure was established of 1-(7,8-dimethyl-4-chloroquinolin-2-yl)-2-[3,5-di(tert-butyl)-6-oxo-6H-pyran-2-yl]ethane-1,2-dione formed as a result of the oxidation of 3,5-di(tert-butyl)-6-[(Z)-2-(quinolin-2-yl)-1-hydroxyethen-1-yl]pyran-2-ones. By the cyclic voltammetry the oxidation of 1-(quinolin-2-yl)-2-(pyran-2-yl)ethane-1,2-dione
derivatives was shown to proceed in two stages. 相似文献
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The title dicarboxylic acid 1d has been prepared in 24% overall yield via, 1,4-diazabicyclo[2.2.2]octane (DABCO)-catalyzed coupling of ethanal and tert-butyl propenoate ( 3 ) to 4 , SN2′-reaction to tert-butyl (Z)-2-romomethyl-2-butenoate ( 5a ), dehydrobrominatin to tert-butyl 2-methylidene-3-butenoate ( 2c ), dimerizatoin to di-tert-butyl 4-vinyl-1-cyclohexene-1,4-dicarboxylate ( 1c ) and acidic ester cleavage. Acidic cleavage of easily obtainable 5a affords (Z)-2-bromomethyl-2-butenoic acid ( 5a ) in 68% yield with respect to ethanal. 相似文献
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M. Vorona I. Potorochina G. Veinberg S. Belyakov I. Shestakova I. Kanepe E. Lukevics 《Chemistry of Heterocyclic Compounds》2009,45(12):1532-1538
The sulfoxide of 6Z-[2-(methoxyimino)propylidene]penicillanic acid tert-butyl ester and the sulfones of 6Z-[2-(hydroxyimino-, methoxyimino-, benzyloxyimino-, 2-bromo- and 4-bromobenzyloxyimino)-propylidene]penicillanic acid in the
syn and anti forms have been synthesized by the condensation of the sulfoxide and sulfone of 6Z-acetylmethylenepenicillanic acid tert-butyl ester with hydroxylamine, methoxyamine, benzyloxyamine, 2-bromo- and 4-bromobenzyloxyamines. The syn and anti isomers
of 3Z-(2-methoxyiminopropylidene)-4R-(benzothiazolyl-2-dithio)-2-oxoazetidinyl-1R-(2-propenyl)acetic acid tert-butyl ester were obtained by opening of the thiazolidine ring in 6Z-[2-(methoxy-imino)propylidene]-1-oxopenicillanic acid tert-butyl ester with 2-mercaptobenzothiazole. The 3Z-(2-methoxyiminopropylidene)-4R-(methylsulfonyl)-2-oxoazetidinyl-1-(2-propylidene)acetic acid tert-butyl ester was synthesized by the interaction of 1,8-diazobicyclo[5.4.0]undec-7-ene and methyl iodide with 6Z-[2-(methoxyimino)propylidene]-1,1-dioxopenicillanic acid tert-butyl ester. A dependence of the cytotoxic effect in relation to cancer and normal cells in vitro on the structure of the
substituent in position 6 and the syn and anti isomerism of the oxyimino group was established for the synthesized compounds. 相似文献