20407-84-5Relevant articles and documents
Beckmann-rearrangement of cyclododecanone oxime to ω-laurolactam in the gas phase
Eickelberg,Hoelderich
, p. 42 - 55 (2009)
The classical route for the industrial production of ω-laurolactam is the homogeneously catalyzed Beckmann-rearrangement of cyclododecanone oxime in the liquid state using fuming sulfuric acid catalyst. Contrary to that, a completely different way is shown in the present work. In addition to the use of a solid acid catalyst, the vapor phase was chosen. From a process technical point of view it is a superior route compared with the classical one. Following intensive investigations of the vapor phase behavior of substrate, product and the main by-products, a catalyst screening of the most promising materials was performed. In addition, a modification of the most active catalysts was carried out to get more information about reaction sites and to optimize the catalyst activity. Using an acid treated [Al,B]-BEA zeolite at a temperature of approx. 320 °C and reduced pressures, complete conversion combined with excellent selectivity of 98% were obtained. The accumulation of reactants in the fixed bed was less than 5 wt%. Furthermore, investigations of deactivation and regeneration behavior of the catalyst were done. It could be demonstrated that the catalytic material could be regenerated under oxidative atmosphere as well as under non-oxidative conditions through thermal desorption of the deactivating compounds without any measurable loss of catalytic performance.
Iron-Catalyzed ?±,?-Dehydrogenation of Carbonyl Compounds
Zhang, Xiao-Wei,Jiang, Guo-Qing,Lei, Shu-Hui,Shan, Xiang-Huan,Qu, Jian-Ping,Kang, Yan-Biao
supporting information, p. 1611 - 1615 (2021/03/03)
An iron-catalyzed α,β-dehydrogenation of carbonyl compounds was developed. A broad spectrum of carbonyls or analogues, such as aldehyde, ketone, lactone, lactam, amine, and alcohol, could be converted to their α,β-unsaturated counterparts in a simple one-step reaction with high yields.
One-Pot Preparation of (E)-α,β-Unsaturated Aldehydes by a Julia-Kocienski Reaction of 2,2-Dimethoxyethyl PT Sulfone Followed by Acid Hydrolysis
Ando, Kaori,Watanabe, Haruka,Zhu, Xiaoxian
, p. 6969 - 6973 (2021/05/06)
(E)-α,β-Unsaturated aldehydes were synthesized by the Julia-Kocienski reaction of 2,2-dimethoxyethyl 1-phenyl-1H-tetrazol-5-yl (PT) sulfone 3 with various aldehydes, followed by acid hydrolysis. The reaction could be carried out in one pot, and various (E)-α,β-unsaturated aldehydes were obtained in a short time and with high yields.
Selective Reduction of α,β-Unsaturated Weinreb Amides in the Presence of α,β-Unsaturated Esters
Morita, Kenta,Murai, Kenichi,Arisawa, Mitsuhiro,Fujioka, Hiromichi
, p. 1100 - 1103 (2020/11/25)
α,β-Unsaturated esters were selectively protected in situ in the presence of α,β-unsaturated Weinreb amides using PEt3 and trimethylsilyl trifluoromethanesulfonate (TMSOTf) in toluene under reflux. Diisobutylaluminium hydride (DIBAL-H) reduction of the mixture followed by tetra-n-butylammonium fluoride (TBAF) treatment produced α,β-unsaturated aldehydes in good yields along with the recovered α,β-unsaturated esters.
A Simple, Mild and General Oxidation of Alcohols to Aldehydes or Ketones by SO2F2/K2CO3 Using DMSO as Solvent and Oxidant
Zha, Gao-Feng,Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
supporting information, p. 2262 - 2267 (2019/04/17)
A practical, general and mild oxidation of primary and secondary alcohols to carbonyl compounds proceeds in yields of up to 99% using SO2F2 as electrophile in DMSO as both the oxidant and the solvent at ambient temperature. No moisture- and oxygen-free conditions are required. Stoichiometric amount of inexpensive K2CO3, which generates easy to separate by-products, is used as the base. Thus, 5-gram scale runs proceeded in nearly quantitative yields by a simple filtration as the work-up. The use of a polar solvent such as DMSO, which usually promotes competing Pummerer rearrangement, is also noteworthy. This protocol is compatible with a variety of common N-, O-, and S-functional groups on (hetero)arene, alkene and alkyne substrates (68 examples). The protocol was applied (99% yield) to a formal synthesis of the important cholesterol-lowering drug Rosuvastatin. (Figure presented.).
A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
supporting information, p. 3190 - 3194 (2019/05/21)
A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
Dehydrogenative Synthesis of Linear α,β-Unsaturated Aldehydes with Oxygen at Room Temperature Enabled by tBuONO
Wang, Mei-Mei,Ning, Xiao-Shan,Qu, Jian-Ping,Kang, Yan-Biao
, p. 4000 - 4003 (2017/06/19)
Synthesis of linear α,β-unsaturated aldehydes via a room-temperature oxidative dehydrogenation has been realized by the cocatalysis of an organic nitrite and palladium with molecular oxygen as the sole clean oxidant. Linear α,β-unsaturated aldehydes could be efficiently prepared under aerobic catalytic conditions directly from the corresponding saturated linear aldehydes. Besides linear products, the aromatic analogy could also be smoothly achieved by the same standard method. The organic nitrite redox cocatalyst and alcohol solvent play a key role for realizing this method.
Synthesis of α,β-unsaturated aldehydes as potential substrates for bacterial luciferases
Brodl, Eveline,Ivkovic, Jakov,Tabib, Chaitanya R.,Breinbauer, Rolf,Macheroux, Peter
, p. 1487 - 1495 (2017/02/18)
Bacterial luciferase catalyzes the monooxygenation of long-chain aldehydes such as tetradecanal to the corresponding acid accompanied by light emission with a maximum at 490?nm. In this study even numbered aldehydes with eight, ten, twelve and fourteen carbon atoms were compared with analogs having a double bond at the α,β-position. These α,β-unsaturated aldehydes were synthesized in three steps and were examined as potential substrates in vitro. The luciferase of Photobacterium leiognathi was found to convert these analogs and showed a reduced but significant bioluminescence activity compared to tetradecanal. This study showed the trend that aldehydes, both saturated and unsaturated, with longer chain lengths had higher activity in terms of bioluminescence than shorter chain lengths. The maximal light intensity of (E)-tetradec-2-enal was approximately half with luciferase of P. leiognathi, compared to tetradecanal. Luciferases of Vibrio harveyi and Aliivibrio fisheri accepted these newly synthesized substrates but light emission dropped drastically compared to saturated aldehydes. The onset and the decay rate of bioluminescence were much slower, when using unsaturated substrates, indicating a kinetic effect. As a result the duration of the light emission is doubled. These results suggest that the substrate scope of bacterial luciferases is broader than previously reported.
Oxidative cleavage of allyl ethers by an oxoammonium salt
Kelly, Christopher B.,Ovian, John M.,Cywar, Robin M.,Gosselin, Taylor R.,Wiles, Rebecca J.,Leadbeater, Nicholas E.
, p. 4255 - 4259 (2015/04/14)
A method to oxidatively cleave allyl ethers to their corresponding aldehydes mediated by an oxoammonium salt is described. Using a biphasic solvent system and mild heating, cleavage proceeds readily, furnishing a variety of α,β-unsaturated aldehydes and ketones.
Structure-Activity relationship of aliphatic compounds for nematicidal activity against pine wood nematode (Bursaphelenchus xylophilus)
Seo, Seon-M.I.,Junheon, Kim,Eunae, Kim,Park, Hye-M.I.,Kim, Young-Joon,Park, I.L.-Kwon
experimental part, p. 1823 - 1827 (2010/09/09)
Nematicidal activity of aliphatic compounds was tested to determine a structure-activity relationship. There was a significant difference in nematicidal activity among functional groups. In a test with alkanols and 2E-alkenols, compounds with C8-C11 chain length showed 100% nematicidal activity against pine wood nematode, Bursaphelenchus xylophilus, at 0.5 mg/mL concentration. C6-C10 2E-alkenals exhibited >95% nematicidal activity, but the other compounds with C 11-C14 chain length showed weak activity. Nematicidal activity of alkyl acetates with C7-C11 chain length was strong. Compounds belonging to hydrocarbons, alkanals, and alkanoic acetates showed weak activity at 0.5 mg/mL concentration. Nematicidal activity of active compounds was determined at lower concentrations. At 0.25 mg/mL concentration, whole compounds except C8 alkanol, C8 2E-alkenol, and C7 alkanoic acid showed >80% nematicidal activity. C 9-C11 alkanols, C10-C11 2E-alkenols, C8-C9 2E-alkenals, and C9-C10 alkanoic acids showed >80% nematicidal activity at 0.125 mg/mL concentration. Only C11 alkanol exhibited strong nematicidal activity at 0.0625 mg/mL concentration, the lowest concentration that was tested. 2010 American Chemical Society.
