- Synthesis of 3-(2-Oxo-2,3-dihydrobenzo[b]furan-3-ylidenehydrazono)-2,3- dihydrobenzo[b]furan-2-one
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Reactions of benzophenone and fluoren-9-one hydrazones with (2-hydroxyphenyl)oxoacetic acid gave [carboxy(2-hydroxyphenyl) methylidenehydrazono](2-hydroxyphenyl)acetic acid which underwent intramolecular cyclization with formation of 3-(2-oxo-2,3-dihydrob
- Pulina,Zalesov,Kataev
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Read Online
- Synthesis of symmetrical and asymmetrical azines from hydrazones and/or ferrocenecarboxaldehyde as potential antimicrobial–antitumor agents
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9-Fluorenone azine 2a and benzophenone azine 2b were synthesized, respectively, by treatment of 9-fluorenone hydrazone 1a or benzophenone hydrazone 1b with FeCl3 in chloroform. Ferrocenecarboxaldehyde 3 reacts with 1a or 1b, in ethanol, to furn
- Lasri, Jamal,Aly, Magda M.,Eltayeb, Naser Eltaher,Babgi, Bandar A.
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Read Online
- Cobalt(II) complex of a diazoalkane radical anion
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β-Diketiminate cobalt(I) precursors react with diphenyldiazomethane to give a compound that is shown by computational studies to be a diazoalkane radical anion antiferromagnetically coupled to a high-spin cobalt(II) ion. Thermolysis of this complex result
- Bonyhady, Simon J.,Goldberg, Jonathan M.,Wedgwood, Nicole,Dugan, Thomas R.,Eklund, Andrew G.,Brennessel, William W.,Holland, Patrick L.
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- Iron and Cobalt Diazoalkane Complexes Supported by β-Diketiminate Ligands: A Synthetic, Spectroscopic, and Computational Investigation
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Diazoalkanes are interesting redox-active ligands and also precursors to carbene fragments. We describe a systematic study of the binding and electronic structure of diphenyldiazomethane complexes of β-diketiminate supported iron and cobalt, which span a
- Bonyhady, Simon J.,Derosha, Daniel E.,Vela, Javier,Vinyard, David J.,Cowley, Ryan E.,Mercado, Brandon Q.,Brennessel, William W.,Holland, Patrick L.
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Read Online
- Preparation and application of 5-bromoquinazoline derivative
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The invention discloses a 5-bromoquinazoline derivative shown in the corresponding formula. A synthesis method of the 5-bromoquinazoline derivative compound (I) comprises the following steps: weighing1.18 g of 5-bromoisatin, 2.5503g of ammonium formate an
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Paragraph 0035-0037
(2021/02/16)
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- Preparation and application of chiral quaternary ammonium salt
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The invention provides preparation of chiral quaternary ammonium salt. The structural formula is as follows: a synthesis method of the chiral quaternary ammonium salt compound (I) comprises the following steps: using 10 mol% zinc chloride as a catalyst, firstly adding 22 mmol of anhydrous ZnCl2, 50 mL of absolute methanol, 2.1639 g of sodium hydroxide and 1.5656 g of D-valinol, refluxing the mixture at high temperature for 60 h, stopping the reaction, dissolving the residue with water, extracting with CH2Cl2 (20 mL * 3), drying the organic phase with anhydrous sodium sulfate, rotating to remove the solvent, and recrystallizing the crude product with dichloromethane and absolute ethyl alcohol to obtain a colorless crystal; the application of the chiral quaternary ammonium salt compound (I) is characterized in that the chiral quaternary ammonium salt compound has good catalytic performance in a nitrile silicification reaction of benzaldehyde and a condensation reaction of benzophenone hydrazone, and the conversion rates respectively reach up to 71% and 99%.
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Paragraph 0039-0041
(2021/08/07)
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- Formation of Osmium Alkylidene, Alkylidyne, and Dinitrogen Complexes from Reactions of OsCl2(PPh3)3with Diazoalkanes
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The reactions of OsCl2(PPh3)3 with a series of diazoalkanes were investigated. The reactions with monosubstituted diazoalkanes N2CHR gave the desired osmium alkylidene complexes OsCl2(=CHR)(PPh3)2, the stability of which is dependent on the substituent on the alkylidene carbons. The five-coordinate osmium alkylidene complex OsCl2(=CHCOOMe)(PPh3)2 is thermally stable, whereas the analogous complex OsCl2(=CH-p-tol)(PPh3)2 readily rearranges to its hydrido-alkylidyne form OsHCl2(C-p-tol)(PPh3)2. A substitution reaction of OsCl2(=CHCOOMe)(PPh3)2 with PCy3 produced the hydrido-alkylidyne complex OsHCl2(CCOOMe)(PCy3)2, revealing the effect of the phosphine on the relative stability of OsCl2(=CHCOOMe)(PR3)2 and OsHCl2(CCOOMe)(PR3)2. The reaction of OsCl2(PPh3)3 with the acceptor-acceptor disubstituted diazoalkane dibenzoyl diazomethane, bearing COPh substituents, led to the formation of the metallacyclic complex OsCl2{κ2-N,O-[N2C(COPh)C(Ph)O]}(PPh3)2 due to the chelating effect of dibenzoyl diazomethane. The complex OsCl2(PPh3)3 catalyzed the homocoupling of the diazoalkane N2CPh2 to give the azine Ph2C=N-N=CPh2. The η1-N2 coordinated binuclear complex (Ph3P)2ClOs(μ-Cl)3Os(PPh3)2(N2) was isolated as a minor product, which was considered to be an off-cycle product in the catalytic reaction.
- Cui, Mingxu,Jia, Guochen,Sung, Herman H. Y.,Williams, Ian D.
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p. 3833 - 3842
(2021/11/18)
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- Grignard reagent dictated copper(I) phosphines catalyzed reductive coupling of diazo compounds: The chemistry beyond carbene generation
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Copper-dppf catalyzed reductive coupling of diazo compounds through terminal nitrogen is reported. However, copper catalysts are known to produce carbene from diazo compounds; the reaction conditions played an important role in the formation of diazine over carbene generation. Several control experiments have been conducted to understand the reaction mechanism and found that the formation of a copper–Mg heterobimetallic complex would be responsible for the observed reactivity pattern. The reaction produced diazine as a reductive coupling product along with biphenyl as a by-product. All the synthesized diazines have been characterized fully by using analytical and spectroscopic techniques.
- Kuzhalmozhi Madarasi, Packirisamy,Sivasankar, Chinnappan
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- Application of chiral oxazoline-copper complex
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An application of a bis{2-[4(R)-phenyl-4,5-dihydro]-2-oxazoline}phenol-copper complex with a chemical formula shown in the description is characterized in that the complex has a good catalysis performance when used as a catalyst for a reaction of diphenyl
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Page/Page column 8
(2020/01/25)
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- Preparation and application of chiral zinc complex
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The invention discloses a chiral zinc complex, which is prepared from anhydrous zinc chloride and L-phenylglycinol. Compounds are represented by the following Chemical Formula in the specification. The invention discloses a synthetic method of a chiral zi
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Paragraph 0028-0030
(2020/10/14)
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- Palladium-Catalyzed Regioselective Acylation of Diazines with Toluenes: A New Approach to the Synthesis of ortho-Diacylbenzenes
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A highly efficient and practical procedure for chemo- and regioselective synthesis of ortho-diacylbenzenes through Pd-catalyzed oxidative C–H bond activation has been developed. Using this method, a variety of ortho-diacylbenzenes were prepared in moderate to good yields, by direct acylation of diazines with toluene derivatives as acylation source. Ortho-diacylbenzenes may be used as precursors in synthesis of pharmaceuticals and agrochemicals.
- Afaridoun, Hadi,Kianmehr, Ebrahim,Seifinoferest, Behnoush
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supporting information
(2020/08/13)
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- HKUST-1 derived Cu?CuO: X /carbon catalyst for base-free aerobic oxidative coupling of benzophenone imine: High catalytic efficiency and excellent regeneration performance
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The oxidative coupling of imines to ketazine with molecular oxygen is a green process towards the synthesis of hydrazine or hydrazine hydrate, which could efficiently address the economic and environmental issues of the traditional Raschig or peroxide-ketazine process. Herein, we developed an efficient heterogeneous base-free benzophenone imine oxidative coupling route with O2 catalyzed by Cu/CuOx/carbon materials derived from MOFs under mild conditions. Under optimized conditions, the conversion of BI is up to 98.2% and the selectivity of ketamine is 94.9%. This catalyst has excellent structure stability, recycling, and regeneration performance, owing to the carbonization of organic ligands of MOF at high temperature. More importantly, it is confirmed that the metallic Cu core is essential to improve the catalytic performance of the CuO shell in the BI oxidative coupling reaction, due to the promotion of electron transfer in the CuO surface, making dissolved O2 molecules more easily insert oxygen vacancies. This strategy might open an avenue to the sustainable catalytic synthesis of hydrazine or hydrazine hydrate. This journal is
- Bin, Zhu,Changjiu, Xia,Chenhao, Li,Ge, Wang,Hongyi, Gao,Kaimeng, Huang,Min, Lin,Siyuan, Chen,Xingtian, Shu,Xinxin, Peng,Yibin, Luo
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p. 36111 - 36118
(2020/10/27)
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- Access to Cyanoimines Enabled by Dual Photoredox/Copper-Catalyzed Cyanation of O-Acyl Oximes
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An efficient strategy for the synthesis of pharmaceutically important and synthetically useful cyanoimines, as well as cyanamides, has been described. This strategy is enabled by dual photoredox/copper-catalyzed cyanation of O-acyl oximes or O-acyl hydroxamides. This state of the art protocol for cyanoimines and cyanamides features readily available starting materials, mild reaction conditions, good functional group tolerance, and operational simplicity. The resultant cyanoimines can be transformed into structurally diverse and functionally important N-containing heterocycles.
- Wei, Ziyan,Yu, Shouyun,Zhang, Ai Hua,Zhang, Hao
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p. 7315 - 7320
(2020/10/02)
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- Synthesis method and application of diphenylketone oxime derivative
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The chemical formula of a diphenylketone oxime derivative compound is as shown in the specification. A synthetic method of the diphenylketone oxime derivative compound comprises the following steps: weighing 0.0744 g of zinc chloride, 0.3819 g of diphenyl
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Paragraph 0031-0033
(2019/10/04)
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- Preparation method and application of chiral platinum complex
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The invention relates to a preparation method and application of a chiral platinum complex. The chemical formula of the chiral platinum complex (I) is as shown in the specification. The preparation method includes: weighing 0.0366g of Pt(DMSO)2(NO3)2, dis
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Paragraph 0031-0033
(2019/10/17)
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- Toward a Porphyrin-Style NHC: A 16-Atom Ringed Dianionic Tetra-NHC Macrocycle and Its Fe(II) and Fe(III) Complexes
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N-heterocyclic carbenes (NHCs), and macrocyclic NHCs in particular, have been applied successfully to the stabilization of high oxidation states on transition metal complexes. This access to high oxidation states has enabled their application in oxidative catalysis including aziridination and epoxidation. However, the number of macrocyclic tetra-NHC ligands is still limited, especially those featuring anionic charge, which is beneficial in this regard. In this manuscript, we report a facile and high yielding synthesis for only the second example of such a dianionic, macrocyclic tetra-NHC ligand. This 16-atom macrocycle has the ring size and charge of a porphyrin but with the increased electron donation of NHCs. Its Fe(II) and Fe(III) complexes are reported, and their reactivities for ligand addition and oxidation were tested. Multiple oxidation catalysis reactions were tested with both the Fe(II) and Fe(III) complexes with reagents such as trimethylamine-N-oxide, oxygen (from air), diazodiphenylmethane, and P-tert-butyl-dibenzo-73phosphanorbornadiene (tBuPA) to explore the possibilities for single site oxidation reactions.
- Anneser, Markus R.,Elpitiya, Gaya R.,Powers, Xian B.,Jenkins, David M.
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p. 981 - 987
(2019/02/26)
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- Cp*Co(iii)-catalyzed annulation of azines by C-H/N-N bond activation for the synthesis of isoquinolines
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Herein, an efficient, atom economic and external oxidant free approach has been disclosed for the synthesis of isoquinolines. Azines were employed for annulation reactions with alkynes via sequential C-H/N-N bond activation using an air-stable cobalt catalyst. The method takes advantage of the incorporation of both the nitrogen atoms of azines into the desired isoquinoline products, offering the highest atom economy. In addition, the developed protocol works under external oxidant as well as silver salt free conditions. Furthermore, the established methodology features a relatively broad substrate scope with high product yields and scalability up to the gram level.
- Deshmukh, Dewal S.,Yadav, Prashant A.,Bhanage, Bhalchandra M.
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supporting information
p. 3489 - 3496
(2019/04/14)
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- Rapid and Atom Economic Synthesis of Isoquinolines and Isoquinolinones by C–H/N–N Activation Using a Homogeneous Recyclable Ruthenium Catalyst in PEG Media
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Herein, we report an atom-efficient, rapid, green, and sustainable approach to synthesize isoquinolines and isoquinolinones using a homogeneous recyclable ruthenium catalyst in PEG Media assisted by microwave energy. Dibenzoylhydrazine was used for C–H/N–N activation reactions for the first time in combination with ketazine as oxidizing directing groups for annulation reactions with internal alkynes. The developed protocol is environmentally benign due to significantly shortened times with an easy extraction method, higher atom economy, external oxidant and silver or antimony salt free conditions, applicability to a gram scale synthesis, use of biodegradable solvent and wide substrate scope with higher product yields. Moreover, it is worth noting that the established methodology allowed reuse of the catalytic system for up to five successive runs with minimal loss in activity.
- Deshmukh, Dewal S.,Gangwar, Neha,Bhanage, Bhalchandra M.
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supporting information
p. 2919 - 2927
(2019/05/10)
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- Substituent Effects on Reactions of [RhCl(COD)]2 with Diazoalkanes
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The reactions of [RhCl(COD)]2 with a series of diazoalkanes with different substitutents were investigated. The outcomes of the reactions were found to be substituent-dependent via four different pathways. (1) The reactions with diazoindenes produced ??5-cyclopentadienyl complexes. (2) The reaction with diazofluorene produced a mixture of olefin and azine compounds. (3) The reactions with monosubstituted diazoalkanes RCHN2 (R = Ph, MeO2C) produced olefins RCHa?CHR. (4) The reaction with the disubstituted diazoalkane Ph2CN2 produced the azine Ph2Ca?N-Na?CPh2 only. Computational studies have been carried out to understand the interesting substituent effect by comparing the kinetics and thermodynamics of the reaction pathways. It was found that the reactions with diazocyclopentadiene, diazoindene, and Ph2CN2 are kinetically controlled, while the reactions with RCHN2 and diazofluorene are both thermodynamically and kinetically controlled.
- Cui, Mingxu,Lin, Shujuan,Sung, Herman H. Y.,Williams, Ian D.,Lin, Zhenyang,Jia, Guochen
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p. 905 - 915
(2019/03/04)
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- Transition metal-mediated reductive coupling of diazoesters
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The first transition metal mediated reductive coupling of diazoesters through the terminal nitrogens is reported. The resulting tetrazene-bridged bis(diazenylacetate) serves as a novel dinucleating ligand to iron(III). DFT calculations suggest that the re
- Grass, Amanda,Stoian, Sebastian A.,Lord, Richard L.,Groysman, Stanislav
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supporting information
p. 8458 - 8461
(2019/07/22)
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- Synthesis of Hypervalent Iodine(III) Reagents Containing a Transferable (Diarylmethylene)amino Group and Their Use in the Oxidative Amination of Silyl Ketene Acetals
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The preparation of some hypervalent iodine reagents containing a transferable amino group derived from benzophenone imine derivatives is reported. The reagents can be readily prepared and stored as a bench-stable solid, and were successfully used in the transition-metal-free oxidative amination of silyl ketene acetals to afford the corresponding α-amino esters, the benzophenone imine moieties of which could be easily hydrolyzed, thereby leading to the formation of primary amines.
- Kiyokawa, Kensuke,Okumatsu, Daichi,Minakata, Satoshi
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supporting information
p. 8907 - 8911
(2019/05/28)
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- Synthesis of α-Substituted Primary Benzylamines through Copper-Catalyzed Cross-Dehydrogenative Coupling
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A copper-catalyzed route to α-substituted, primary benzylamines by C-H functionalization of alkylarenes is described. The method directly affords the amine hydrochloride salt. Catalyst loadings down to 0.1 mol % in combination with scalability, insensitivity to air and moisture, and no need for column chromatography makes the procedure highly practical. The facile synthesis of the racemate of a blockbuster drug highlights the relevance for the development of pharmaceuticals. Preliminary mechanistic data are also included.
- Kramer, S?ren
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supporting information
p. 65 - 69
(2019/01/04)
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- Metal-free and fecl3-catalyzed synthesis of azines and 3,5-diphenyl-1H-pyrazole from hydrazones and/or ketones monitored by high resolution ESI+-MS
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9-Fluorenone azine 2a or benzophenone azine 2b have been synthesized, respectively, by treatment of 9-fluorenone hydrazone la or benzophenone hydrazone lb with FeCl3 Lewis acid catalyst in CHCb. Treatment of la and lb with FeCb affords the asymmetrical azine l-(diphenylmethylene)-2-(9H-fluoren-9-ylidene)hydrazine 2c. l,3-Diphenyl-2-propenone 3 reacts with hydrazine to produce l-((E)-l,3-diphenylallylidene)hydrazine 3a. Under prolonged heating, 3a undergoes a cyclization to yield 3,5-diphenyl-lH-pyrazoIe 4. Chalcone 3 reacts with la or lb to produce a mixture of 4 and 2a or 4 and 2b, respectively. The reaction of cyclohexanone 5 with hydrazine leads to the formation of 1,2-dicyclohexylidene hydrazine 6. Ketone 5 reacts with la or lb to give the asymmetrical azine product 6a or 6b, respectively. The progress of the reactions has been monitored by electrospray ionization mass spectrometry (ESI-MS), and the compounds have been characterized by elemental analyses, IR,1H,13C and DEPT-135 NMR spectroscopy and also by high resolution ESI+-MS.
- Lasri, Jamal,Ismail, Ali I.
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p. 362 - 373
(2019/05/21)
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- Synthesis of Benzodihydrofurans by Asymmetric C?H Insertion Reactions of Donor/Donor Rhodium Carbenes
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Metal carbenes appended with two electron-donating groups, known as “donor/donor” carbenes, undergo diastereo- and enantioselective rhodium-catalyzed C?H insertion reactions with ether substrates to form benzodihydrofurans. Unlike the reactions of metal carbenes with electron-withdrawing groups attached, the attenuated electrophilicity enables these reactions to be conducted in Lewis basic solvents (e.g., acetonitrile) and in the presence of water. The diazo precursors for these species are prepared in situ from hydrazone using a mild and chemoselective oxidant (MnO2). Although this sequence often can be performed in one-pot, control experiments have elucidated why a “two-pot” process is often more efficient. A thorough screening of achiral catalysts demonstrated that sterically encumbered catalysts are optimal for diastereoselective reactions. Although efficient insertion into allylic and propargylic C?H bonds is observed, competing dipolar cycloaddition processes are noted for some substrates. The full substrate scope of this useful method of benzodihydrofuran synthesis, mechanisms of side reactions, and computational support for the origins of stereoselectivity are described.
- Lamb, Kellan N.,Squitieri, Richard A.,Chintala, Srinivasa R.,Kwong, Ada J.,Balmond, Edward I.,Soldi, Cristian,Dmitrenko, Olga,Casti?eira Reis, Marta,Chung, Ryan,Addison, J. Bennett,Fettinger, James C.,Hein, Jason E.,Tantillo, Dean J.,Fox, Joseph M.,Shaw, Jared T.
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p. 11843 - 11855
(2017/09/07)
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- A process for preparing 1, 2 - double-(1 - aryl alkyl methylene) method of the hydrazine compound
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The present invention discloses method for preparing a 1,2-bis(1-aralkyl methylene) hydrazine compound. The method comprises the following steps of: dissolving benzene sulfonyl hydrazone into a CH3CN solvent; then adding ammonium persulfate and cesium carbonate to react for 6hours under a condition of 100 DEG C; after the reaction is ended, performing extraction and column chromatographic separation, thereby obtaining the 1,2-bis(1-aralkyl methylene) hydrazine compound. According to the method, ammonium persulfate with a low price is used as a catalyst to catalyze benzene sulfonyl hydrazone to generate degradation reaction; the reaction conditions are mild; the reaction time is short; a post-treatment process is simple; the reaction product is low; and the product yield is high. The 1,2-bis(1-aralkyl methylene) hydrazine compound can be used as a useful synthesis intermediate, and has potential pharmaceutical activity and a wide application.
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Paragraph 0043; 0044
(2017/07/21)
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- Cs2CO3-mediated decomposition of N-tosylhydrazones for the synthesis of azines under mild conditions
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Abstract: A facile, environmentally and efficient Cs2CO3-mediated decomposition of N-tosylhydrazones reaction has been developed for the synthesis of functionalized azines under mild conditions. This method offers broad substrate scope, occurs as additive-free, without strong base conditions, utilizes readily available reactants, and forms products in good to high yields. Graphical Abstract: [Figure not available: see fulltext.]
- Luo, Zai-Gang,Liu, Peng,Fang, Yu-Yu,Xu, Xue-Mei,Feng, Cheng-Tao,Li, Zhong,Zhang, Xiao-Mei,He, Jie
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p. 1139 - 1148
(2017/02/10)
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- Hypervalent-iodine(iii) oxidation of hydrazones to diazo compounds and one-pot nickel(ii)-catalyzed cyclopropanation
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A one-pot process for the catalytic cyclopropanation of various alkenes with unsubstituted hydrazones is described. Iodosobenzene (Ph = O) was found to be a competent oxidant of hydrazones to diazo compounds. Ni(OH)2 was chosen as an effective and cheap metal catalyst. The cyclopropane products can be generated efficiently (5 min-4 h) in moderate to good yields (42-91%) under mild (80°C) and neat conditions.
- Liu, Haixuan,Wei, Yunyang,Cai, Chun
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p. 674 - 678
(2016/01/12)
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- Rhodium(III)-catalyzed coupling of aromatic ketazines or oximes with 2-vinyloxirane via C-H activation
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Described herein is a rhodium(III)-catalyzed coupling of aromatic ketazines or oximes with 2-vinyloxirane via directed C-H activation. This reaction proceeds efficiently under mild conditions with a low catalyst loading, especially in conditions with room temperature in the absence of additives for aromatic ketazines. A wide range of substituted substrates is supported and a possible mechanism is proposed according to the experimental results of kinetic isotopic effect, reversibility studies, and catalysis with rhodacycle intermediate c1.
- Wen, Jing,Wu, An,Miao, Yuqin,Zhu, Jin
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supporting information
p. 5512 - 5516
(2015/09/21)
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- Realized C-H functionalization of aryldiazo compounds via rhodium relay catalysis
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An unprecedented C-H functionalization of aryldiazo compounds without a preinstallation of directing group has been realized under mild conditions, which differs from former reports in its use of diazo compounds as coupling partners in directed C-H activations. This novel transformation has been realized by a rhodium self-relay catalysis, a tandem process of the in situ formation of a directing group and sequential C-H bond activation.
- Qiu, Lin,Huang, Daorui,Xu, Guangyang,Dai, Zhenya,Sun, Jiangtao
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supporting information
p. 1810 - 1813
(2015/04/14)
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- Cu(I)-catalyzed coupling of diaryldiazomethanes with terminal alkynes: An efficient synthesis of tri-aryl-substituted allenes
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A highly efficient method for the synthesis of tri-aryl-substituted allenes has been developed through Cu(I)-catalyzed coupling of diaryldiazomethanes with terminal alkynes. The reaction is under mild conditions and uses simple and inexpensive CuI as the catalyst. Mechanistically, the reaction follows a pathway involving Cu(I) carbene migratory insertion.
- Wu, Chenggui,Hu, Fangdong,Liu, Zhenxing,Deng, Guisheng,Ye, Fei,Zhang, Yan,Wang, Jianbo
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p. 9196 - 9201
(2015/11/27)
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- Rh-catalyzed sequential oxidative C-H and N-N bond activation: Conversion of azines into isoquinolines with air at room temperature
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A rhodium-catalyzed sequential oxidative C-H annulation reaction between ketazines and internal alkynes has been developed via C-H and N-N bond activation with air as an external oxidant, which led to an efficient approach toward isoquinolines with high atom efficiency at rt. Utilizing the distinctive reactivity of this catalysis, both N-atoms of the azines could be efficiently incorporated to the desired isoquinolines under very robust and mild reaction conditions.
- Han, Wenjia,Zhang, Guoying,Li, Guangxing,Huang, Hanmin
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supporting information
p. 3532 - 3535
(2014/07/21)
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- Product Selectivity in Solar photocatalytic dehydrazonation of aromatic hydrazones by Tio2-based catalysts
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Product selectivity of ketone and azine in the photocatalytic dehydrazonation of aromatic hydrazones with TiO2-based photocatalysts has been investigated using solar light. Product selectivity is dependent on the nature of the photocatalysts, substituents and the solvents. Loading of metals on TiO2-P25 selectively enhances the formation of azine from benzophenone hydrazone. Solvents such as dichloromethane, chloroform, ethanol, and 2-propanol enhance the formation of azine under solar irradiation. Structures of products have been established by FT-IR, 1H-NMR, 13C-NMR, and GC-MS spectrometry. Supplementary materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file. Copyright Taylor &Francis Group, LLC.
- Krishnakumar,Swaminathan
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- Potassium N-iodo p-toluenesulfonamide (TsNIK, iodamine-T): A new reagent for the oxidation of hydrazones to diazo compounds
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A new reagent for the oxidation of hydrazones to diazo compounds is described. N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T) allows the preparation of α-diazoesters, α-diazoamides, α-diazoketones and α-diazophosphonates in good yield and in high purity after a simple extractive work-up. α-Diazoesters were also obtained in high yield from the corresponding ketones through a one-pot process of hydrazone formation/oxidation. Diazo compounds: N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T), readily prepared from p-toluenesulfonamide and iodine in aqueous KOH, is a new reagent for the oxidation of hydrazones to diazo compounds in good yields and high purity (see scheme).
- Nicolle, Simon M.,Moody, Christopher J.
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p. 4420 - 4425
(2014/05/06)
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- Bent CNN bond of diazo compounds, RR′(CN+N-)
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The reaction of ninhydrin with benzophenone hydrazone afforded 2-diazo-3-diphenylmethylenehydrazono-1-indanone 1 and 2-diazo-1,3- bis(diphenylmethylenehydrazono)indan 2. X-ray crystal structure analyses of these products showed that the diazo functional group CN+N - of 1 is bent by 172.9°, while that of 2 has a linear geometry. The crystal structure data of diazo compounds have been retrieved from the Cambridge Structural Database (CSD), which hit 177 entries to indicate that the angle of 172.9° in 1 lies in one of the most bent structures. The CSD search also indicated that diazo compounds consisting of a distorted diazo carbon tend to bend the CN+N- bond. On the basis of DFT calculations (B3LYP/6-311++G(d,p)) of model compounds, it was revealed that the bending of the CNN bond is principally induced by steric factors and that the neighboring carbonyl group also plays a role in bending toward the carbonyl side owing to an electrostatic attractive interaction. The potential surface along the path of CN+N- bending in 2-diazopropane shows a significantly shallow profile with only 4 kcal/mol needed to bend the CN+N - bond from 180° to 160°. Thus, the bending of the diazo group in 1 is reasonable as it is provided with all of the factors for facile bending disclosed in this investigation.
- Akita, Motoko,Takahashi, Mai,Kobayashi, Keiji,Hayashi, Naoto,Tukada, Hideyuki
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p. 346 - 353
(2013/03/28)
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- Arene ci£h amination at nickel in terphenyl-diphosphine complexes with labile metal-arene interactions
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The meta-terphenyl diphosphine, m-P2, 1, was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal-arene interactions on oxidation state and substitution at the metal center. Complex (m-P2)Ni (2) shows strong Ni 0-arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni0 complexes bearing L-type ligands (2-L: L=CH3CN, CO, Ph2CN2), NiIX complexes (3-X: X=Cl, BF4, N3, N3B(C 6F5)3), and [(m-P2)Ni IICl2] (4). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph2Si£CH2), organoazides (RN3: R=para-C6H4OMe, para-C 6H4CF3, 1-adamantyl), and N2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η1-diphenyldiazoalkane adduct (2-Ph2CN2), methylidene insertion into a Nii£P bond followed by rearrangement of a nickel-bound phosphorus ylide (5) to a benzylphosphine (6), Staudinger oxidation of the phosphine arms, and metal-mediated nitrene insertion into an arene Ci£H bond of 1, all derived from the same compound (2). Hydrogen-atom abstraction from a NiI-amide (9) and the resulting nitrene transfer supports the viability of Ni-imide intermediates in the reaction of 1 with 1-azido-arenes. Put a ring on it: The utilization of a meta-terphenyl diphosphine ligand leads to labile metal-arene interactions in Ni complexes in various oxidation states and coordination environments. When these complexes are treated with group-transfer reagents, such as diazoalkanes, sulfur ylides, or azides, various types of ligand-centered reactivity were observed, including methylidene insertion into a Pi£C bond and amination of an arene Ci£H bond. Copyright
- Herbert, David E.,Lara, Nadia C.,Agapie, Theodor
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supporting information
p. 16453 - 16460
(2013/12/04)
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- Diazo compounds as electrophiles to react with 1,4-dilithio-1,3-dienes: Efficient synthesis of 1-imino-pyrrole derivatives
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1-Imino-pyrrole and indole derivatives were synthesized in high yields from the reaction of diaryl diazomethanes with 1,4-dilithio-1,3-dienes. Diaryl diazomethanes reacted as electrophiles in this reaction. An unprecedented Zn-complex was formed via trans
- Zhan, Ming,Zhang, Shaoguang,Zhang, Wen-Xiong,Xi, Zhenfeng
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supporting information
p. 4182 - 4185
(2013/09/12)
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- Chemoselectivity of the 1,3-dipolar cycloaddition of some diazoalkanes with 1,5-benzodiazepine derivatives
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Benzodiazepines are pharmaceutically important synthetic materials. Reaction of the 4-(2-hydroxyphenyl)-1,5-benzodiazepin-2-one with 2-diazopropane (DAP) gave a mixture of the 2-isopropylether of 4-(2-hydroxyphenyl)-3H-1,5- benzodiazepine and 1-isopropyl-4-(2-hydroxyphenyl)-3H-1,5-benzodiazepin-2-one. Whilst diphenyldiazomethane (DPDM) gave 1-benzhydryl-4-(2-hydroxyphenyl)-3H-1,5- benzodiazepin-2-one. Reaction of the corresponding thione with DAP led to the 2-isopropylthioether of 4-(2-hydroxyphenyl)-3H-1,5-benzodiazepine and 1-isopropyl-4-(2-hydroxyphenyl)-1,5-benzodiazepine-2-thione while the reaction with DPDM gave the 2-benzhydrylthioether of 4-(2-hydroxyphenyl)-3H-1,5- benzodiazepine. The characterisation of these prepared-N,-O and-S alkylated benzodiazepines involved 1D and 2D-NMR techniques, mass spectrometry and elemental analysis.
- Nsira, Asma,Karoui, Ahlem,Gharbi, Rafik,Msaddek, Moncef
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experimental part
p. 152 - 156
(2012/10/07)
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- Carbenoid Etherifications catalyzed by "green" silver nanoparticles and iron-copper nanoparticles
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Etherfication products were obtained from sodium salts of p-toluenesulfonylhydrazones in alcohol solutions at reflux temperature on treatment with catalytic amounts of iron-copper nanoparticles, and silver nanoparticles, which were prepared from Camellia
- Garcia, Marco A.,Garcia-Munoz, Angel,Pena, Josue A.,Trujillo-Reyes, Jessica,Morales-Luckie, Raul A.,Avalos-Borja, Miguel,Vilchis-Nestor, Alfredo R.,Sanchez-Mendieta, Victor,Corona, David,Cuevas-Yanez, Erick
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experimental part
p. 2 - 6
(2012/07/16)
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- Copper-catalyzed oxidative alkynylation of diaryl imines with terminal alkynes: A facile synthesis of ynimines
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An efficient copper-mediated method for the oxidative alkynylation of diaryl imines with terminal alkynes is reported. This reaction provides the first catalytic and general synthesis of ynimines and allows for an easy preparation of these useful building blocks. An improved copper-catalyzed oxidative dimerization of imines to azines and the synthesis of dienes and azadienes from ynimines are also described.
- Laouiti, Anouar,Rammah, Mohamed M.,Rammah, Mohamed B.,Marrot, Jerome,Couty, Francois,Evano, Gwilherm
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supporting information; experimental part
p. 6 - 9
(2012/02/14)
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- Product selectivity in semiconductor-mediated dehydrazonation of benzophenone hydrazone
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Product selectivity in the dehydrazonation of benzophenone hydrazone by photocatalytic oxidation with various semiconductor photocatalysts has been investigated using ultraviolet-A light. TiO2-P25 shows greater product selectivity of benzophenone formation with 93.9% conversion. Doping of metals on TiO2 selectively enhances the formation of azine from hydrazone. Solvents such as dichloromethane, chloroform, and dichloroethane also enhance the formation of azine.
- Krishnakumar,Selvam,Swaminathan
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experimental part
p. 1929 - 1937
(2011/06/26)
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- Facile method for the conversion of semicarbazones/thiosemicarbazones into azines (Under Microwave Irradiation) and oxadiazoles (By Grinding)
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In an effective transformation, semicarbazones/thiosemicarbazones are smoothly converted into azines under microwave irradition. Oxadiazoles are also obtained from semicarbazones by reaction with bromine generated in situ via a grinding reaction in the solid phase. Taylor &Francis Group, LLC.
- Chattopadhyay, Gautam,Ray, Partha Sinha
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p. 2607 - 2614
(2011/08/07)
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- Thermolysis and photolysis of N-benzoylhydrazone derivatives
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Two selected N-benzoylhydrazones were subjected to thermolysis by refluxing at 200 °C. Benzil, benzoic acid, biphenyl, benzanilide together with the corresponding ketones, nitriles, substituted methanes, and imines were isolated. Similar treatment of a third hydrazone at 250 °C afforded, in addition to the previous products, toluene, bibenzyl, stilbene, and 2-phenylindole. Photolysis of the same hydrazones in acetonitrile gave the previously reported products but in different ratios along with azine derivatives and substituted methanes. A free radical mechanism involving homolysis of the N-N and C-N bonds is suggested, substantiated by trapping of the phenyl radical with isoquinoline, to account for the formation of the identified products.
- Gaber, Abd El-Aal M.,Khairou, Khalid S.
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experimental part
p. 1021 - 1027
(2012/07/27)
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- An expeditious and solvent free synthesis of azine derivatives using sulfated anatase-titania as a novel solid acid catalyst
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Solid acid catalyst sulfated anatase-titania (TiO2-SO 42-) has been used for the synthesis of azine derivatives from benzophenone hydrazone and ketones/aldehydes by simple physical grinding. This sulfated titania gives an
- Krishnakumar,Swaminathan
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experimental part
p. 50 - 55
(2012/02/04)
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- Triplet halocarbene chemistry: P-nitrophenylchlorocarbene and p-nitrophenylbromocarbene
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Reactions of p-nitrophenylchlorocarbene with cumene and of p-nitrophenylbromocarbene with toluene afford C-H abstraction-recombination products that suggest the involvement of triplet arylhalocarbenes.
- Moss, Robert A.,Lu, Zhifeng,Sauers, Ronald R.
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body text
p. 5940 - 5942
(2010/11/21)
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- Chemoselectivity of the reactions of diazomethanes with 5-benzylidene-3-phenylrhodanine
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The reactions of 5-benzylidene-3-phenylrhodanine (2; rhodanine = 2-thioxo-1,3-thiazolidin-4-one) with diazomethane (7a) and phenyldiazomethane (7b) occurred chemoselectively at the exocyclic C=C bond to give the spirocyclopropane derivatives 9 and, in the
- Seyfried, Martin S.,Linden, Anthony,Mloston, Grzegorz,Heimgartner, Heinz
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experimental part
p. 1800 - 1816
(2009/12/06)
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- Diazodiphenylmethane and monosubstituted butadienes: Kinetics and a new chapter of vinylcyclopropane chemistry
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Diazodiphenylmethane (DDM) undergoes cycloadditions to 1-substituted buta-1,3-dienes exclusively at the C(3)=C(4) bond. At room temperature, the N2 loss from the initially formed 4,5-dihydro-3H-pyrazoles 2 is faster than the cycloaddition and furnishes the vinylcyclopropane derivatives 7 and 9 with structural retention at the C(1)=C(2) bond. 2-Substituted butadienes react with DDM at the C(3)=C(4) bond to give 12; isoprene, however, affords 3,4/1,2 products in the ratio of 86:14. DDM is a nucleophilic 1,3-dipole: 1-Cyanobutadiene reacts 400 times faster than 1-methoxybuta-1,3-diene (DMF, 40°). The log k2 for the additions to six 1-substituted butadienes show a linear correlation with σp (Hammett) and ρ = +2.9; the log k2 of five 2-substituted butadienes are linearly related to Taft's σI (ρ = +1.7). The structures of the vinylcyclopropanes 7, 9, and 12 are established by NMR spectra and oxidation. A cyclopropyl carbinyl cation is made responsible for the isomerization of 12, R = Ph, Me, by acetic acid to 4-substituted 1,1-diphenylpenta-1,3-dienes 25 and 29; TsOH at 200° converts 25 further to 9,10-dihydro-9-methyl-10-phenyl-9,10-ethanoanthracene (27). Thermal rearrangement of 7, 9, and 12 at 200-300° produces the 3- or 1-substituted 4,4-diphenylcyclopentenes 30 and 31. These give the same mass spectra as the vinylcyclopropanes, and an open-chain distonic radical cation is suggested as common intermediate. Besides spectroscopic evidence for the cyclopentene structures, hydrogenation and epoxidation are described; NMR data support the trans-attack by perbenzoic acid.
- Ohta, Akihiro,Dahl, Klaus,Raab, Rainer,Geittner, Jochen,Huisgen, Rolf
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scheme or table
p. 783 - 804
(2009/03/11)
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- Solvent-free basic or KF/alumina-assisted dehydrogenation of hydrazo compounds
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A reduction of organic solvents in the organic chemical industry is of serious importance for sustainable chemistry. With this viewpoint, we successfully established the useful dehydrogenation of hydrazo compounds using basic alumina or KF/alumina under s
- Mihara, Masatoshi,Nakai, Takeo,Iwai, Toshiyuki,Ito, Takatoshi,Mizuno, Takumi
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p. 2124 - 2126
(2008/02/09)
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- Facile and efficient way to synthesize the radical cyclization precursor methyl 3-(tert-butyl((E)-3-(2,2-diphenylcyclopropyl)-2-propenyl)amino)-3-oxo-2- (phenylseleno)propanoate for kinetic research
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Methyl 3-(tert-butyl((E)-3-(2,2-diphenylcyclopropyl)-2-propenyl)amino)-3- oxo-2-(phenylseleno)propanoate was prepared in 10 steps in good to excellent yield using benzophenone and hydrazine hydrate as the starting materials. Copyright Taylor & Francis Group, LLC.
- Yu, Jindi,Lian, Gaoyan,Zhang, Danwei
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- Thermal and acid-catalyzed transformations of 3H-pyrazoles obtained from diphenyldiazomethane and methyl phenylpropiolate
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Reaction of diphenyldiazomethane with methyl phenylpropiolate in diethyl ether alongside the expected methyl triphenyl-3H-pyrazole-4-and-5-carboxylates (I and II) (38 and 24%) gave rise also to 8% of methyl 3,5-diphenyl-1-(1- ethoxyethyl)-1H-pyrazole-4-ca
- Fedorov,Duisenbaev,Razin,Kuznetsov,Linden
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p. 231 - 240
(2007/10/03)
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- Selective protection of carbonyl compounds as azines and their facile regeneration
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Carbonyl compounds with freshly prepared hydrazinium formate successfully yielded the corresponding azines in excellent yields. In turn, azines were deprotected to the corresponding carbonyls using triethylammonium chlorochromate chemoselectively. Copyright Taylor & Francis Group, LLC.
- Nanjundaswamy,Pasha
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p. 3161 - 3165
(2007/10/03)
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