- A study of two geometric isomers of 1,1′-bi-3-cyanocyclohex-2-enylidene
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The preparation, separation, crystal structure and 1H NMR spectra are reported for the two geometrical isomers of 1,1′-bi-3-cyanocyclohex-2-enylidene. The E-isomer crystallized as thin plates in the monoclinic space group P21,/n with a = 5.3980(5), b = 7.0757(7), c = 15.300(2) A, β = 94.571(2)°, and Z = 2. The structure has symmetry C2h. The Z-isomer crystallized as needles in the triclinic space group PT with a = 7.0790(6), b = 11.3155(9), c = 15.386(1) A, α = 104.943° β= 90.164(2)°, γ = 99.494(2)°, and Z = 4. The compound crystallized with two molecules per asymmetric unit. In C6D6,1H NMR signals of the 2-vinyl protons appear almost identical. However, in a mixture of C6D6 and pyridine-d5, the 2-vinyl protons can be distinguished. The structures compare favorably with MM2 calculations.
- Wang, Yonghui,Doering,Staples, Richard J.
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- Preparation of 3-oxocyclohex-1-ene-1-carbonitrile
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Chromium trioxide oxidation of cyclohexenecarbonitrile efficiently provides analytically pure 3-oxocyclohex-1-ene-1-carbonitrile. The procedure is described in detail, providing a very reliable, one-step synthesis of a highly versatile oxonitrile. Georg T
- Fleming, Fraser F.,Zhang, Zhiyu,Wei, Guoqing
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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Paragraph 0143-0145; 0150; 0151; 0162; 0184; 0217; 0228
(2017/10/22)
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- Allylic and benzylic sp3 C-H oxidation in water
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A copper-catalyzed method for the oxidation of allylic and benzylic sp3 C-H by aqueous tert-butyl hydroperoxide (T-Hydro) in water using a recyclable fluorous ligand has been developed. The reaction procedure is tolerant to additional functional groups and the fluorous ligand could be reused with little loss of catalytic activity. This journal is
- Ang, Wei Jie,Lam, Yulin
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p. 1048 - 1052
(2015/03/04)
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- Fluorous bispidine: A bifunctional reagent for copper-catalyzed oxidation and knoevenagel condensation reactions in water
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Fluorous bispidine-type ligands have been developed to facilitate its recovery and reusability and to demonstrate its bifunctional property as a ligand and base in copper-catalyzed aerobic oxidation, the Knoevenagel condensation and tandem oxidation/Knoevenagel condensation in water under mild conditions. Application of the fluorous ligand was also extended to the surfactant-free copper-catalyzed allylic and benzylic sp3 C-H oxidation reaction in water. The fluorous ligands could be recovered using F-SPE with recovery ranging from 91-97% and could be reused five times with little loss of activity.
- Ang, Wei Jie,Chng, Yong Sheng,Lam, Yulin
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p. 81415 - 81428
(2015/10/06)
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- 2-Quinoxalinol diamine Cu(II) complex: Facilitating catalytic oxidation through dual mechanisms
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The Cu(II) complex 1, Cu(II)-6-N-3,5-di-tert-butylsalicylidene-6,7- quinoxalinol-diamine, has been developed to address problems with current methods of catalytic oxidation using tert-butyl hydroperoxide (TBHP). Complex 1 demonstrated an increased capability to utilize TBHP while limiting interference from free radical reactions and was demonstrated to be highly effective in the oxidations of a variety of olefins. the Partner Organisations 2014.
- Li, Yuancheng,Lee, Taebum,Weerasiri, Kushan,Wang, Tanyu,Buss, Emily E.,McKee, Michael L.,Gorden, Anne E. V.
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p. 13578 - 13583
(2014/11/08)
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- Allylic C-H activations using Cu(II) 2-quinoxalinol salen and tert-butyl hydroperoxide
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Using a Cu(II) 2-quinoxalinol salen complex as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant, allylic activations of olefin substrates can be converted to the corresponding enones or 1,4-enediones. Excellent yields can be achieved (up to 99%) within a very short reaction time and with great tolerance for additional functional groups. Possible mechanistic pathways have been characterized using Raman spectroscopy, cyclic voltammetry, and theoretical calculations.
- Li, Yuancheng,Lee, Tae Bum,Wang, Tanyu,Gamble, Audrey V.,Gorden, Anne E. V.
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experimental part
p. 4628 - 4633
(2012/08/08)
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- Dauben-Michno oxidative transposition of allylic cyanohydrins - Enantiomeric switch of (-)-carvone to (+)-carvone
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Allylic cyanohydrins were subjected to Dauben-Michno oxidation at low temperatures to provide β-cyanoenones in good to excellent yields. The potential of this oxidative transposition as a means of an enantiomeric switch of enones containing a latent plane of symmetry was tested by conversion of (-)-carvone to its enantiomer.
- Hudlicky, Jason R.,Werner, Lukas,Semak, Vladislav,Simionescu, Razvan,Hudlicky, Tomas
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experimental part
p. 535 - 543
(2011/10/03)
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- An unprecedented method for the generation of tert -butylperoxy radical using DIB/TBHP protocol: Solvent effect and application on allylic oxidation
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Figure presented Tert-Butylperoxy radical was generated with PhI(OAc) 2 and tBuOOH. Ester solvent was found to be critical and the protocol was applied in the allylic oxidation of various olefinic substrates, which gave the corresponding α,β-unsaturated enones in good yield and regioselectivity.
- Zhao, Yi,Yeung, Ying-Yeung
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supporting information; experimental part
p. 2128 - 2131
(2010/08/05)
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- Pressure independence of stereomutation and fragmentation in the bis-spirocyclobutanes, anti- and syn-2,9-dicyanodispiro[5.0.5.2]tetradeca-1,8- dienes
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Pressure dependent rate constants and volumes of activation for stereomutational interconversions of the cyclobutanes, anti- and syn-2,9-dicyanodispiro[5.0.5.2]tetradeca-1,8-dienes (anti-G and syn-6), and for their fragmentation to 1-cyano-3-methylenecycl
- Klaerner, Frank-Gerrit,Wurche, Frank,Von Doering, William E.,Yang, Jiade
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p. 18107 - 18113
(2007/10/03)
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- Oxidation of silyl enol ethers by using IBX and IBX·N-oxide complexes: A mild and selective reaction for the synthesis of enones
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α,β-Unsaturated carbonyl compounds can be prepared by the oxidation of trimethylsilyl enol ethers with IBX (1) or IBX·MPO (2). A diverse set of carbonyl compounds can be dehydrogenated with ease by using this method. Trimethylsilyl enol ethers such as 4, which are formed in situ by the addition of an organometallic species to an enone, can be dehydrogenated with 1 or 2 to give a functionalized enone (e. g. 3 → 5). IBX = iodoxybenzoic acid; MPO = 4-methoxypyridine-N-oxide.
- Nicolaou,Gray, David L. F.,Montagnon, Tamsyn,Harrison, Scott T.
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p. 996 - 1000
(2007/10/03)
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- ALLYLIC REARRANGEMENT OF CYANOPHOSPHATE. II. SYNTHESIS OF β-CYANO-α,β-UNSATURATED KETONES
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Boron trifluoride-catalyzed allylic rearrangement of the cyanophosphates of α,β-unsaturated ketones (1a-d, 7 and 14) was found to give the allylic phosphates (3a-d, 9 and 16), which were successfully converted to β-cyano-α,β-unsaturated ketones (6a-d, 13 and 20) by acid hydrolysis (0.5 N HCl) followed by manganese dioxide oxidation of the resulting allylic alcohols(5a-d, 11, 12 and 17).The stereochemical features of the allylic phosphates (9 and 16) are discussed.Keywords-α,β-unsaturated ketone; diethyl phosphorocyanidate; cyanophosphate; allylic rearrangement; boron trifluoride etherate; manganese dioxide; β-cyano-α,β-unsaturated ketone
- Kurihara, Takushi,Miki, Masuo,Yoneda, Ryuji,Harusawa, Shinya
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p. 2747 - 2753
(2007/10/02)
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