排序方式: 共有27条查询结果,搜索用时 31 毫秒
1.
Butylated hydroxytoluene enediyne: access to diradical and electrophilic quinone methide intermediates
下载免费PDF全文
![点击此处可从《Journal of Physical Organic Chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Edyta M. Greer Cesar S. Quezada Christopher V. Cosgriff 《Journal of Physical Organic Chemistry》2015,28(5):365-369
A theoretical study was carried out on the unimolecular reaction of an enediyne with a fused butylated hydroxytoluene to internally scavenge the p‐benzyne diradical sites formed after the Bergman cyclization. The calculations revealed that the conversion of the p‐benzyne diradical (2‐tert‐butyl‐4‐methyl‐5,8‐didehydro‐1‐naphthalenol) to p‐quinone methide is favored over the conversion to a phenoxy/benzene diradical 4 in an approximate 95:5 ratio. Based on this model, the Bergman cyclization leads in a bifunctional manner to intermediates for competing reactivity with intermolecular H‐atom abstraction. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
2.
Sean Stokes & Keith T. Mead 《合成通讯》2013,43(19):2627-2633
A route to aryl-substituted quinolines from N-tosyl 1-azadienes is described. The key steps are a [4 + 2] cycloaddition with benzyne followed by base treatment of the 1,4-dihydroquinoline product. The N-tosyl 1-azadienes were prepared from readily accessible cinnamaldehyde and chalcone substrates by condensation with p-TsNH2. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
3.
Hiroshi Takikawa Arata Nishii Hiromu Takiguchi Hirotoshi Yagishita Masato Tanaka Keiichi Hirano Masanobu Uchiyama Ken Ohmori Keisuke Suzuki 《Angewandte Chemie (International ed. in English)》2020,59(30):12440-12444
An intramolecular benzyne–phenolate [4+2] cycloaddition is reported. Benzyne precursors, having vicinal halogen‐sulfonate functionalities, linked with a phenol(ate) by various tether groups undergo efficient intramolecular [4+2] cycloaddition by treatment with either Ph3MgLi or nBuLi for halogen–metal exchange to form various benzobarrelenes. 相似文献
4.
Sabrina Brait Stefano Deabate Selby A. R. Knox Enrico Sappa 《Journal of Cluster Science》2001,12(1):139-173
A survey of the synthetic pathways and of the reactivity and catalytic activity of transition metal carbonyl clusters substituted with benzyne (and, for comparison, benzene and diene) ligands is given. Cluster-surface analogies are helpful in gaining an understanding of the homogeneous and heterogeneous catalytic behaviour of the clusters. 相似文献
5.
Vagin SI Frickenschmidt A Kammerer B Hanack M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(3):985-991
The zinc dehydrophthalocyanine 2 and zinc dehydrobenzoporhyrazine 8 a were generated from the 1N-aminobenzotriazole-annulated zinc phtalocyanine 1 and zinc benzoporhyrazine 8, respectively, by oxidation with Pb(OAc)(4) in different solvents, for example, diethyl ether, tetrahydrofuran, acetic acid, and benzene. The reactivity of 2 and 8 a was studied in detail. These species not only easily undergo Diels-Alder additions with dienes, but also the used solvents can be added. Among the addition products with solvents ethoxy-, acetoxy-, acetoxybutyloxy-substituted and barrelen-fused phthalocyanines and benzoporpyrazines were isolated. No products resulting from the dimerization of two dehydro species were observed either for 2 or 8 a. Analysis of the reaction products in comparison with those obtained by oxidation of 1-aminobenzotriazole 15 under similar conditions proves a higher reactivity (electrophilicity) of the dehydro-PcZn 2 and dehydro-PzZn 8 a in comparison with unsubstituted benzyne towards the solvents used, such as diethyl ether and benzene. 相似文献
6.
Prof. Takamitsu Fukuda Yuu Kikukawa Shiori Takaishi Prof. Nagao Kobayashi 《化学:亚洲杂志》2012,7(4):751-758
New covalently C60‐conjugated phthalocyanine (Pc) analogues in which the Pc and C60 components are connected by means of a four‐membered ring have been synthesized by taking advantage of a [2+2] cycloaddition reaction of C60 with benzyne units generated from either a phthalocyanine derivative ( 8 ) or its precursor ( 1 ). The reaction of 1 with PhI(OAc)2 and trifluoromethanesulfonic acid (TfOH) followed by the [2+2] cycloaddition of C60 in the presence of tetra‐n‐butylammonium fluoride (TBAF) yielded the C60‐substituted Pc precursor ( 3 ). Mixed condensation of 3 and 4,5‐dibutylsulfonylphthalonitrile ( 4 ) in a thermally promoted template reaction using a nickel salt successfully gave the Pc–C60 conjugate ( 5 ). Results of mass spectrometry and 1H and 13C NMR spectroscopy clearly indicate the formation of the anticipated Pc–C60 conjugate. Direct coupling of C60 with the Pc analogue that contained eight peripheral trimethylsilyl (TMS) groups ( 8 ) also proceeded successfully, such that mono and bis C60‐adducts were detected by their mass, although the isolation of each derivative was difficult. The absorption and magnetic circular dichroism (MCD) spectra of 5 and the reference compound ( 7 ) differ from each other in the Q‐band region, thereby suggesting that the presence of the C60 moiety affects the electronic structure of the conjugate. The reduction and oxidation potentials of 5 and 7 obtained by cyclic voltammetry are comparative, except for the C60‐centered reduction couple at ?1.53 V versus Fc+/Fc in o‐dichlorobenzene (o‐DCB). A one‐electron reduction of 5 and 7 in tetrahydrofuran (THF) by using the sodium mirror technique results in the loss of band intensity in the Q‐band region, whereas the characteristic marker bands for Pc‐ring‐centered reduction appear at around 430, 600, and 900 nm for both compounds. The final spectral shapes of 5 and 7 upon the reduction resemble each other, thus indicating that no significant molecular orbital (MO) interactions between the C60 and Pc units are present for the reduced species of 5 . In contrast, the oxidized species of 5 and 7 generated by the addition of NOBF4 in CH2Cl2 show significantly different absorption spectra from each other. Whereas the broad bands at approximately 400–550 nm of 7 + are indicative of the cationic π‐radical species of metallo‐Pcs and can be assigned to a transition from a low‐lying MO to the half‐filled MO, no corresponding bands were observed for 5 +. These spectral characteristics have been tentatively assigned to the delocalized occupied frontier MOs for 5 +. The experimental results are broadly supported by DFT calculations. 相似文献
7.
Dr. Takayuki Iwata Mizuki Hyodo Takuto Fukami Prof. Dr. Yoshihito Shiota Prof. Dr. Kazunari Yoshizawa Prof. Dr. Mitsuru Shindo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(39):8506-8510
We report herein an efficient method to synthesize triptycenes by the reaction of benzynes and anthranoxides, which are electron-rich and readily prepared from the corresponding anthrones. Using this method, 1,9-syn-substituted triptycenes were regioselectively obtained employing 3-methoxybenzynes. This method was also applied to synthesize pentiptycenes. A DFT study revealed that the cycloaddition of lithium anthranoxide and benzyne proceeds stepwise. 相似文献
8.
Ji-Hong Hu 《合成通讯》2019,49(4):558-562
A facile method to synthesize 2-nitromethyl aromatic ketones was developed. In the method, benzyne was generated in situ for the insertion to α-Nitroketones in one pot to achieve 2-nitromethyl aromatic ketones under mild conditions. Aromatic and aliphatic α-nitroketones were applied in the reaction, and the results show that aliphatic α-nitroketones gave excellent yields (up to 96%), while aromatic α-nitroketones gave moderate yields. The synthesized 2-nitromethyl aromatic ketones could be potential substrates to synthesize isoindoles. 相似文献
9.
Shigetomi T Soejima H Nibu Y Shioji K Okuma K Yokomori Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(29):7742-7748
Treatment of di-tert-butylthioketene S-oxide (5 a) with Lawesson reagent at room temperature resulted in the formation of 3,3-di-tert-butylthiirane-2-thione (4 a) in high yield. The oxidation of 4 a with mCPBA (mCPBA=m-chloroperbenzioc acid) gave 3,3-di-tert-butylthiirane-2-thione S-oxide (6) almost quantitatively. The reactions of 4 a with dimethyl acetylenedicarboxylate (DMAD) and benzyne afforded dimethyl 2-(2,2,4,4-tetramethylpentan-3-ylidene)-1,3-dithiole-4,5-dicarboxylate (13) and 2-(2,2,4,4-tetramethylpentan-3-ylidene)benzo[d][1,3]dithiole (15), respectively, in high yields, suggesting that 4 a is an excellent 1,3-dipole. The reaction of 4 a with ethylenebis(triphenylphosphine)platinum (16) gave dithiolato-platinum complex (22) in high yield. The structure of 22 was determined by X-ray crystallographic analysis. 相似文献
10.
Dr. Hiroshi Takikawa Dr. Arata Nishii Dr. Hiromu Takiguchi Hirotoshi Yagishita Masato Tanaka Dr. Keiichi Hirano Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Ohmori Prof. Dr. Keisuke Suzuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(30):12540-12544
An intramolecular benzyne–phenolate [4+2] cycloaddition is reported. Benzyne precursors, having vicinal halogen-sulfonate functionalities, linked with a phenol(ate) by various tether groups undergo efficient intramolecular [4+2] cycloaddition by treatment with either Ph3MgLi or nBuLi for halogen–metal exchange to form various benzobarrelenes. 相似文献