共查询到20条相似文献,搜索用时 10 毫秒
1.
As a part of continuing interest in the zip reaction, we present the results on a carbon ring-enlargement reaction of activated ketones with a CN group as a charge stabilizer. Two series of (1-cyano-2-oxocy-cloalkyl)alkanoates were prepared from 8- and 12-membered cyano-ketones 1 and 2 , respectively, namely the propanoates 3 and 4 , the butanoates 6 , 8 and 9 as well as the pentanoates 12 and 15 . While treatment with t-BuOK of the former two homologous esters resulted in both ring enlargement and competitive transesterification, the pentanoates 12 and 15 afforded mostly the diastereoisomeric mixtures of bicyclic alcohols 20a – c and 31a , b , respectively, which remained intact on further exposure to base. It was shown that – apart from the base used (t-BuOK) vs. Li(i-Pr)2N – the distribution of products was greatly influenced by the ring size of substrates. This is further illustrated by treatment of ketones 34 and 35 with t-BuOK. While the former rearranged smoothly to diketone 36 , no reaction at all took place with the latter. The behavior of the substrates is discussed in terms of steric and energetic reasons. 相似文献
2.
Boris A. Trofimov Alexander M. Vasil’tsov Al’bina I. Mikhaleva Andrey V. Ivanov Elena V. Skital’tseva Elena Yu. Schmidt Elena Yu. Senotrusova Igor A. Ushakov Konstantin B. Petrushenko 《Tetrahedron letters》2009,50(1):97-100
A new highly synthetically potent series of bifunctional pyrroles, 1-vinylpyrrole-2-carbonitriles, were synthesized from readily available 1-vinylpyrrole-2-carbaldehyde oximes by two methods: (1) reaction with acetylene (KOH/DMSO, 70 °C, 10 min, yields 58-67%) and (2) reaction with acetic anhydride (90-100 °C, 5 h, yields 83-93%). Starting from 2-phenyl-1-vinylpyrrole, the one-pot synthesis of the corresponding 1-vinyl-2-carbonitrile was accomplished directly by successive treatment with a DMF/(COCl)2 complex, NH2OH·HCl/NaOAc, and acetic anhydride (yield 58%). 相似文献
3.
A. Ya. Il'chenko V. I. Krokhtyak L. M. Yagupol'skii 《Chemistry of Heterocyclic Compounds》1982,18(10):1095-1097
2-Chlorohexafluorocyclopentene- and 2-chlorooctafluorocyclohexene-1-carbonitriles were synthesized. Products of substitution of the chlorine atoms by a phenylamino group and the fluorine atoms in the position by a phenylimino group were obtained by reaction of the products with aniline. The reactions with amidines of trifluoro- and trichloroacetic acids, as well as with 2-aminopyridine, lead to pyrimidine derivatives with condensed perfluorinated five- and six-membered rings.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1407–1409, October, 1982. 相似文献
4.
M. A. Kuznetsov A. S. Pan’kova A. V. Ushkov S. I. Selivanov 《Russian Journal of Organic Chemistry》2008,44(12):1780-1788
Thermolysis of trans-3-phenyl-1-phthalimidoaziridine-2-carbonitrile and trans-1-phthalimidoaziridine-2,3-dicarbonitrile in the presence of several dipolarophiles involves 1,3-dipolar cycloaddition to intermediate azomethine ylides and leads to 1-phthalimidopyrrolidine derivatives with good yields and high stereoselectivity. Thermally induced opening of the three-membered ring in trans-2,3-disubstituted 1-phthalimidoaziridines occurs in conrotatory mode to produce the corresponding cis-azomethine ylides in keeping with the orbital symmetry conservation rules. The relative configuration of substituents in the dipolarophiles is retained, which implies concerted mechanism of the addition. 相似文献
5.
Sophia S. Michaelidou 《Tetrahedron》2010,66(16):3016-1382
Attempted detosylation of the 3-amino-1-(p-tosylamino)indole-2-carbonitriles 4a-c using either K2CO3 in EtOH or DBU in PhH at reflux gives unexpectedly the 3-(N-p-tosylamino)indole-2-carbonitriles 5a-c, respectively in high yields. Nevertheless, treatment of 1-(p-tosylamino)indoles 4a-c with thiophenol and DBU in PhH at reflux gives the detosylated 3-aminoindole-2-carbonitriles 5a-c. Reaction mechanisms supporting the tosyl migration (4→5) and the reductive detosylation (4→2) are proposed. All new compounds are fully characterised. 相似文献
6.
Asma Hrizi Manon Cailler Moufida Romdhani-Younes Yvan Carcenac Jrme Thibonnet 《Molecules (Basel, Switzerland)》2021,26(17)
An approach for the preparation of polysubstituted indole-2-carbonitriles through a cross-coupling reaction of compounds 1-(but-2-ynyl)-1H-indole-2-carbonitriles and 1-benzyl-3-iodo-1H-indole-2-carbonitriles is described. The reactivity of indole derivatives with iodine at position 3 was studied using cross-coupling reactions. The Sonogashira, Suzuki–Miyaura, Stille and Heck cross-couplings afforded a variety of di-, tri- and tetra-substituted indole-2-carbonitriles. 相似文献
7.
2-烷基环戊-2-烯酮衍生物的合成及抗炎活性研究 总被引:1,自引:0,他引:1
2-烷基环戊-2-烯酮衍生物的合成及抗炎活性研究齐传民计志忠,李玉兰,王彪(北京农业大学应用化学系,北京,100094)(沈阳药科大学)关键词环戊烯酮衍生物,β-氨基甲基酮,Mannich反应,缩合反应,抗炎活性目前,许会抗炎药物是芳香酸类比合物,它... 相似文献
8.
D. V. Osipov V. A. Osyanin Yu. N. Klimochkin 《Russian Journal of Organic Chemistry》2013,49(3):398-402
3-Amino-1H-benzo[f]chromene-2-carbonitriles were synthesized by non-catalytic reaction from Mannich bases of the naphthalene series and malononitrile. Reactive 1-benzylidene(or methylidene)naphthalen-2(1H)-ones were presumed as intermediate products. 相似文献
9.
10.
In Seo Kee 《Tetrahedron letters》2009,50(51):7116-4049
3-Methyl- and 3-ethyl-1-aza-1,3-butadiene-1-carbonitriles were synthesized by reaction of the corresponding 3-alkylacroleins with bis(trimethylsilyl)-carbodiimide using titanium tetrachloride as catalyst. They were highly reactive and difficult to purify rigorously. Attempted anionic polymerizations gave only oligomers of molecular weight ∼500 Da. These 3-alkyl-azadienecarbonitriles cycloadded to the electron-rich olefins iso-butyl vinyl ether and p-methoxystyrene to give [2+4] cycloadducts with moderate yields. 相似文献
11.
利用廉价易得的2-乙烯基苯胺与重氮化合物在三氟乙酸催化下发生[5+1]环化反应, 以中等至良好的产率合成了24种2-芳基喹啉衍生物. 该方法无需金属催化剂, 官能团兼容性好, 反应成本低, 不仅拓展了重氮化合物参与的新型有机反应, 同时也为2-芳基取代喹啉的合成提供了高效、 经济且简洁的新方法. 相似文献
12.
13.
Dirk Schwebel Jeanette Ziegenbalg Jürgen Kopf Paul Margaretha 《Helvetica chimica acta》1999,82(2):177-181
On acetone-sensitized irradiation in the presence of 2,3-dimethylbut-2-ene, α-cyano-α,β-unsaturated δ-lactone 5 is converted both to cyclopentapyrans resulting from stepwise addition of the alkene to the olefinic C(β)- and the nitrile C-atom of triplet excited 5 , and cyclobutapyranes, i.e., [2+2] cycloadducts. Similarly, direct irradiation of 1-benzopyran-3-carbonitrile 6 in the presence of the same alkene affords cyclobutabenzopyran 13 and cyclopentabenzopyran 14 , the latter resulting from an upper excited triplet state of 6 . 相似文献
14.
15.
V. N. Marshalkin A. V. Samet V. V. Semenov 《Chemistry of Heterocyclic Compounds》1998,34(12):1409-1411
Reaction of 2-carbomethoxy-ω-nitroacetophenone with arylmethylenemalononitriles gives the previously unknown 2-amino-4-aryl-5-nitro-6-(2-carbomethoxyphenyl)-4H-pyran-3-carbonitriles.
N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. E-mail: muskat@cacr.ioc.ac.ru.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1661–1663, December, 1998. 相似文献
16.
Matthias Schnitzlein Dr. Chongwei Zhu Dr. Kazutaka Shoyama Prof. Dr. Frank Würthner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(61):e202202053
Palladium-catalyzed [5+2] annulation of 1-boraphenalenes with ortho-dihaloarenes afforded negatively curved π-extended pleiadienes. Two benzo[1,2-i:4,5-i’]dipleiadienes (BDPs) featuring a seven-six-seven-membered ring arrangement were synthesized and investigated. Their crystal structure revealed a unique packing arrangement and theoretical calculations were employed to shed light onto the dynamic behavior of the BDP moiety and its aromaticity. Further, a naphthalene-fused pleiadiene was stitched together by oxidative cyclodehydrogenation to yield an additional five-membered ring. This formal azulene moiety led to distinct changes in optical and redox properties and increased perturbation of the aromatic system. 相似文献
17.
Loza V. V. Gimazetdinov A. M. Miftakhov M. S. 《Russian Journal of Organic Chemistry》2018,54(11):1585-1629
Russian Journal of Organic Chemistry - The review covers the literature on the total synthesis of cross-conjugated cyclopentenone prostaglandins (PGs), published from 2000 until present. In view of... 相似文献
18.
Yoshinori Tominaga Yoshihide Shiroshita Akira Hosomi 《Journal of heterocyclic chemistry》1988,25(6):1745-1749
The reaction of 1-cyanomethylpyridinium chloride or bromide, 1a-i , with 1,1-bis(methylthio)-2-nitroethylene ( 2 ) in the presence of triethylamine as a base in ethanol gave the corresponding 2-methylthioindolizine-3-carbonitrile 3 and 2-methyl-thio-1-nitroindolizine-3-carbonitrile 4 in good yields, respectively. Compounds 3a,f were key intermediates for the synthesis of cycl[3.2.2]azine derivatives. 相似文献
19.
2-Cyano cyanothioformanilide 3a reacts with triphenylphosphine in the presence of water to give 2-(cyanomethyleneamino)benzonitrile 4a, 2-(cyanomethylamino)benzonitrile 5, 3-aminoindole-2-carbonitrile 2a and (2-cyanoindol-3-yl)iminotriphenylphosphorane 6a. In the presence of p-toluenesulfonic acid in MeOH the reaction between 2-cyano cyanothioformanilide 3a and triphenylphosphine (2 equiv) gives 3-aminoindole-2-carbonitrile 2a in 90% yield. Under the same conditions 2-(cyanomethyleneamino)benzonitrile 4a gives anthranilonitrile 8a, 3-aminoindole-2-carbonitrile 2a and N-(2-cyanophenyl)formamide 9. In addition, substituted 2-cyano cyanothioformanilides 3b-f react with triphenylphosphine and p-toluenesulfonic acid in MeOH to give 3-aminoindole-2-carbonitriles 2b-f in 63-75% yields. Under analogous conditions 2-cyano-4,5-dimethoxyphenyl cyanothioformanilide 2g gives only 4,5-dimethoxyanthranilonitrile 8g and 4,6,7-trimethoxyquinazoline-2-carbonitrile 14g, but in refluxing dry PhMe in the absence of p-toluenesulfonic acid 2-cyano-4,5-dimethoxyphenyl cyanothioformanilide 3g, (2-cyano-5,6-dimethoxyindol-3-yl)iminotriphenylphosphorane 6g and 2-(cyanomethyleneamino)-4,5-dimethoxybenzonitrile 4g are obtained. The structure of 2-(cyanomethyleneamino)-4,5-dimethoxybenzonitrile 4g is supported unambiguously via independent synthesis and comparison to the isomeric 6,7-dimethoxyquinazoline-2-carbonitrile 15. All new compounds are fully characterised and a tentative mechanism for the transformation of 2-cyano cyanothioformanilides to indoles is proposed. 相似文献
20.
Russian Journal of Organic Chemistry - A green synthesis of 2-oxo-2H-chromene-3-carbonitriles has been carried out in one step by reacting 2-hydroxybenzaldehydes or 2-hydroxyacetophenones with... 相似文献