- Beckmann-rearrangement of cyclododecanone oxime to ω-laurolactam in the gas phase
-
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.
- Eickelberg,Hoelderich
-
-
Read Online
- One-Pot Preparation of (E)-α,β-Unsaturated Aldehydes by a Julia-Kocienski Reaction of 2,2-Dimethoxyethyl PT Sulfone Followed by Acid Hydrolysis
-
(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.
- Ando, Kaori,Watanabe, Haruka,Zhu, Xiaoxian
-
p. 6969 - 6973
(2021/05/06)
-
- Iron-Catalyzed ?±,?-Dehydrogenation of Carbonyl Compounds
-
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.
- 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)
-
- Selective Reduction of α,β-Unsaturated Weinreb Amides in the Presence of α,β-Unsaturated Esters
-
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.
- Morita, Kenta,Murai, Kenichi,Arisawa, Mitsuhiro,Fujioka, Hiromichi
-
p. 1100 - 1103
(2020/11/25)
-
- A Simple, Mild and General Oxidation of Alcohols to Aldehydes or Ketones by SO2F2/K2CO3 Using DMSO as Solvent and Oxidant
-
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.).
- Zha, Gao-Feng,Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
-
supporting information
p. 2262 - 2267
(2019/04/17)
-
- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
-
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.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
-
supporting information
p. 3190 - 3194
(2019/05/21)
-
- Synthesis of α,β-unsaturated aldehydes as potential substrates for bacterial luciferases
-
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.
- Brodl, Eveline,Ivkovic, Jakov,Tabib, Chaitanya R.,Breinbauer, Rolf,Macheroux, Peter
-
p. 1487 - 1495
(2017/02/18)
-
- Dehydrogenative Synthesis of Linear α,β-Unsaturated Aldehydes with Oxygen at Room Temperature Enabled by tBuONO
-
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.
- Wang, Mei-Mei,Ning, Xiao-Shan,Qu, Jian-Ping,Kang, Yan-Biao
-
p. 4000 - 4003
(2017/06/19)
-
- Oxidative cleavage of allyl ethers by an oxoammonium salt
-
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.
- Kelly, Christopher B.,Ovian, John M.,Cywar, Robin M.,Gosselin, Taylor R.,Wiles, Rebecca J.,Leadbeater, Nicholas E.
-
p. 4255 - 4259
(2015/04/14)
-
- Structure-Activity relationship of aliphatic compounds for nematicidal activity against pine wood nematode (Bursaphelenchus xylophilus)
-
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.
- 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)
-
- Biooxidation of Primary Alcohols to Aldehydes through Hydrogen Transfer Employing Janibacter terrae
-
Chemoselective oxidations still represent a challenge for chemists. Lyophilized cells of Janibacter terrae were employed for the chemoselective oxidation of primary alcohols to the corresponding aldehydes by hydrogen transfer with the use of acetaldehyde as the hydrogen acceptor. Secondary alcohol moieties were transformed at a much slower rate. The substrate spectrum encompasses substituted benzyl alcohols, whereby substrates with a substituent in the meta position were well tolerated, whereas only very small substituants were tolerated in the ortho position. Furthermore, nalkanols and allylic alcohols were transformed with good conversions. The biocatalyst was compatible with DMSO as a water miscible organic solvent up to 30 % v/v.
- Orbegozo, Thomas,De Vries, Johannes G.,Kroutil, Wolfgang
-
experimental part
p. 3445 - 3448
(2010/09/05)
-
- Synthesis, characterization and oxidizing properties of a diorgano tellurone carrying bulky aromatic substituents
-
Bis(2,4,6-triisopropylphenyl) tellurone (Tip2TeO2) was prepared, fully characterized by spectroscopic and X-ray crystallographic analyses, as well as theoretical calculations, and found to be an effective oxidizing agent that was capable of converting alcohols into carbonyl compounds under mild reaction conditions. The Royal Society of Chemistry.
- Oba, Makoto,Okada, Yasunori,Nishiyama, Kozaburo,Shimada, Shigeru,Ando, Wataru
-
supporting information; experimental part
p. 5378 - 5380
(2009/03/11)
-
- Photosensitized oxygenation of diaryl tellurides to telluroxides and their oxidizing properties
-
Photosensitized oxidation of tellurides carrying bulky aromatic substituents afforded the corresponding telluroxides which were found to react with simple alcohols to give the corresponding carbonyl compounds in excellent yields along with the starting tellurides.
- Oba, Makoto,Endo, Masaki,Nishiyama, Kozaburo,Ouchi, Akihiko,Ando, Wataru
-
p. 1672 - 1673
(2007/10/03)
-
- Two carbon homologated α,β-unsaturated aldehydes from alcohols using the in situ oxidation-Wittig reaction
-
The in situ oxidation-Wittig reaction, followed by subsequent hydrolysis, has been applied to the conversion of primary alcohols into α,β -unsaturated aldehydes. This conversion, which proceeds via the intermediacy of the homologated unsaturated dioxolanes, gives good to excellent yields with a range of benzylic alcohols and heterocyclic methanols.
- Reid, Mark,Rowe, David J.,Taylor, Richard J. K.
-
p. 2284 - 2285
(2007/10/03)
-
- Asymmetric dihydroxylation and one-pot epoxidation routes to (+)- and (-)-posticlure: A novel trans-epoxide as a sex pheromone component of Orgyia postica (Walker)
-
A highly enantioselective synthesis of (+)- and (-)-posticlure has been achieved. The synthesis features the Sharpless asymmetric dihydroxylation and one-pot epoxidation as the key steps.
- Fernandes, Rodney A,Kumar, Pradeep
-
p. 6685 - 6690
(2007/10/03)
-
- Radical addition to (2,3-epoxy-4-pentenyloxy)trialkylsilanes yielding α,β-unsaturated aldehydes via carbon-carbon bond cleavage
-
Treatment of (2,3-epoxy-4-pentenyloxy)trialkylsilane with radical precursors such as triphenylgermane and α-halo carbonyl compounds in the presence of Et3B yields α,β-unsaturated aldehydes. The reaction involves β-scission of a secondary alkoxy radical that releases a siloxymethyl radical.
- Tanaka, Shinobu,Nakamura, Tomoaki,Yorimitsu, Hideki,Oshima, Koichiro
-
p. 569 - 572
(2007/10/03)
-
- Preparation of Four Geometric Isomers of 4,6-Hexadecadienol, -dienal, and -dienyl Acetate and Their Electro-Antennographic Activity toward Male Eri-Silk Moths
-
Four geometric isomers of 4,6-hexadecadienol and the corresponding -dienal and -dienyl acetate isomers were prepared in order to evaluate their pheromone activity toward male eri-silk moths.We used the electroantennography (EAG)-GLC method to determine EAG activity, with results showing that only 4E,6Z- and 4Z,6E-hexadecadienal were active, while the other compounds were found to be totally inactive.
- Tomida, Ichiro,Iwano, Hidehiko,Ono, Jun,Hirai, Yoshihiko,Fuse, Takao,Hatanaka, Akihiko
-
p. 1158 - 1161
(2007/10/02)
-
- Acid-catalyzed solvolysis of polyenol ethers. III. Effect of the alkoxy moiety
-
The dependence of the solvolysis of polyenol ethers on the nature of the alkoxy moiety has been studied. A new reaction path, leading to the formation of ω-hydroxy (methoxy) substituted aldehydes and -esters, was established. The proposed reaction pathway (scheme 6) is initiated by an electron transfer from the polyenol ether to molecular oxygen, followed by combination of the two radicals to a peroxide zwitterion. Upon protonation, solvent adds to the ω-carbon atom of the polyene to give an intermediate that can either loose water to form an ester, or loose the alkoxy moiety to give an aldehyde. This mechanism is believed to be involved in the strong mutagenic activity displayed by many polyenol ethers, including the natural mutagen fecapentaene-12.
- Nieuwenhuis, Saskia A. M.,Vertegaal, Louis B. J.,De Zoete, Marian C.,Van Der Gen, Arne
-
p. 13207 - 13230
(2007/10/02)
-
- Oxidative deselenylation with sodium perborate and sodium percarbonate
-
In the presence of acetic anhydride, both sodium perborate and sodium percarbonate have been found to be effective reagents for the oxidation of α-phenylselenocarbonyl compounds to α,β-unsaturated carbonyl compounds.
- Kabalka,Reddy,Narayana
-
p. 543 - 548
(2007/10/02)
-
- Acid-catalyzed solvolysis of polyenol ethers. II. Effect of the degree of unsaturation
-
The acid-catalyzed solvolysis of polyenol ethers of glycerol gradually changes with increasing unsaturation from the regular pattern into an anomalous one in which hydroxy- and methoxy-substituted aldehydes are formed.
- Vertegaal,Van Der Gen
-
p. 7301 - 7312
(2007/10/02)
-
- A simple and inexpensive synthesis of 2-alkenals
-
A simple and inexpensive method for the C2 homologation of aldehydes and ketone to 2-alkenals consists of the reaction with allylmagnesium bromide, O-acylation of the resultant 1-alken-4-ol, and ozonolysis.
- Chang,Uang,Wu,Yu
-
p. 1033 - 1034
(2007/10/02)
-
- Catalyse par le palladium at la lumiere ultra-violette de l'oxydation d'alcenes par l'oxygene moleculaire
-
The light-promoted oxidation of terminal alkenes by oxygen in the presence of catalytic amounts of palladium(II) complexes led to corresponding α,β-ethylenic carbonyl compounds and methyl ketones; rapid and extensive isomerisation of the starting alkene is observed.The effect of acetone as solvent on the efficiency of these oxidations is discussed.
- Muzart, Jacques,Pale, Patrick,Pete, Jean-Pierre
-
p. 267 - 274
(2007/10/02)
-
- A FACILE AND HIGHLY STEREOSELECTIVE SYNTHESIS OF (2E)-, (2E,4E)-UNSATURATED AMIDES AND RELATED NATURAL PRODUCTS
-
A facile synthesis of (2E)- and (2E, 4E)-unsaturated amides was achieved via arsonium bromides with high stereoselectivity.Its application to the synthesis of related natural products 4 and 5 is also reported.
- Huang, Y. Z.,Shi, Lilan,Yang, Jianhua,Zhang, Jingtao
-
p. 2159 - 2162
(2007/10/02)
-
- Cerium or Ruthenium Catalyzed Oxidation of Alcohols to Carbonyl Compounds by Means of Sodium Bromate
-
Sodium bromate has been found to be effective oxidant for oxidation of alcohols in the presence of cerium or ruthenium compounds in biphase reaction.Selective oxidation of secondary alcohols was performed in the presence of primary ones using cerium(IV) ammonium nitrate (CAN) or cerium(IV) sulfate (CS) as catalyst.For instance, treatment of 1,10-undecanediol with CS/NaBrO3 provided 11-hydroxy-2-undecanone in 82percent yield.Ruthenium catalyzed biphase oxidation of alcohols with sodium bromate provided the corresponding aldehydes or ketones in good to excellent yields.
- Kanemoto, Shigekazu,Tomioka, Hiroki,Oshima, Koichiro,Nozaki, Hitosi
-
p. 105 - 108
(2007/10/02)
-
- ANION OF 1--2-PHENYLSULFONYLCYCLOPROPANE AS A NEW d3-REAGENT: PREPARATION OF β-SUBSTITUTED α,β-UNSATURATED ALDEHYDES
-
Preparation of β-alkylsubstituted α,β-unsaturated aldehydes using a new d3-reagent is described.
- Pohmakotr, Manat,Pisutjaroenpong, Somchai
-
p. 3613 - 3616
(2007/10/02)
-
- THE DIRECT SYNTHESIS OF α,β-UNSATURATED CARBONYL COMPOUNDS BY Pd(II) PROMOTED DEHYDROGENATION OF ALDEHYDES AND KETONES
-
α,β-Unsaturated aldehydes are prepared by the direct dehydrogenation of the corresponding saturated aldehydes by the coupled use of PdCl2(PhCN)2-AgOSO2CF3 in the presence of N-methyl-morpholine in good yields. α,β-Unsaturated ketones are also prepared via the Sn(II) enolate by a one-pot procedure from the corresponding saturated ketones.
- Mukaiyama, Teruaki,Ohshima, Masahiro,Nakatsuka, Takashi
-
p. 1207 - 1210
(2007/10/02)
-
- Cumulated Ylides, XII. A Stereoselective Synthetic Method for (Z)-α,β-Unsaturated Aldehydes
-
(2-Ethoxyvinyl)triphenylphosphonium bromide (5) is converted with sodium amide into the corresponding phosphaallenylide 6 which adds ethanol forming the ylide 7. 7 is also obtained by the reaction of 5 with sodium ethanolate.The Wittig reaction of 7 with aldehydes 2 proceeds with high (Z)-stereoselectivity to give (Z)-α,β-unsaturated acetals 8 which are cleaved under well defined conditions with p-toluenesulfonic acid or with wet silica gel to (Z)-α,β-unsaturated aldehydes 9.
- Bestmann, Hans Juergen,Roth, Kurt,Ettlinger, Manfred
-
p. 161 - 171
(2007/10/02)
-
- PHOTOACTIVATION OF ALKENE OXIDATION BY MOLECULAR OXYGEN IN THE PRESENCE OF PALLADIUM
-
A catalytic cycle which leads to α-β ethylenic ketones and methyl ketones from terminal alkenes in the presence of palladium trifluoroacetate, oxygen and U.V. light is described.
- Muzart, Jacques,Pale, Patrick,Pete, Jean-Pierre
-
p. 3577 - 3578
(2007/10/02)
-
