cas 947-04-6, CYCLODODECANONE ISOOXIME | Articles data

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Dehydrative Beckmann rearrangement and the following cascade reactions
The Beckmann rearrangement has been predominantly studied for the synthesis of amide and lactam. By strategically using the in situ generated Appel's salt or Mitsunobu's zwitterionic adduct as the dehydrating agent, a series of Beckmann rearrangement and following cascade reactions have been developed herein. The protocol allows the conversion of various ketoximes into amide, thioamide, tetrazole and imide products in modular procedures. The generality and tolerance of functionalities of this method have been demonstrated.
Liu, Yinghui,Wei, Yongjiao,Xie, Lan-Gui
supporting information

(2021/11/16)

A process for preparing laurolactam
A novel process for the preparation of laurolactam (laurolactam) is disclosed. More specifically, cyclo dodecanone (C) as a starting material. 12 H22 O Is a process for the preparation of laurolactam with won -pot reactions (one-pot reaction) by adding a hydroxyl ammonium compound and an inorganic acid.
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Paragraph 0034-0042

(2021/10/05)

Efficient nitriding reagent and application thereof
The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
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Paragraph 0420-0423

(2021/03/31)

Synthesis of macrocyclic and medium-sized ring thiolactonesviathe ring expansion of lactams
A side chain insertion method for the ring expansion of lactams into macrocyclic thiolactones is reported, that can also be incorporated into Successive Ring Expansion (SuRE) sequences. The reactions are less thermodynamically favourable than the analogous lactam- and lactone-forming ring expansion processes (with this notion supported by DFT data), but nonetheless, three complementary protecting group strategies have been developed to enable this challenging transformation to be achieved.
Palate, Kleopas Y.,Epton, Ryan G.,Whitwood, Adrian C.,Lynam, Jason M.,Unsworth, William P.
supporting information
p. 1404 - 1411
(2021/02/27)

Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles
Chlorotropylium chloride as a catalyst for the transformations of oximes, ketones, and aldehydes to their corresponding amides and nitriles in excellent yields (up to 99 %) and in short reaction times (mostly 10–15 min). Oximes were electrophilically attacked on the hydroxyl oxygen by chlorotropylium. The produced tropylium oxime ethers were the key intermediates, of which the ketoxime ether led to amide through Beckmann rearrangement, and the aldoxime ether led to nitrile by nitrogen base DBU assisted formal dehydration. This chlorotropylium activation protocol offered general, mild, and efficient avenues bifurcately from oximes to both amides and nitriles by one organocatalyst.
Xu, Jiaxi,Gao, Yu,Li, Zhenjiang,Liu, Jingjing,Guo, Tianfo,Zhang, Lei,Wang, Haixin,Zhang, Zhihao,Guo, Kai
p. 311 - 315
(2020/01/25)

Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
supporting information
p. 281 - 285
(2020/01/28)

METHOD FOR MANUFACTURING CYCLODODECANONE AND APPARATUS FOR MANUFACTURING THE SAME
A method for manufacturing cyclododecanone according to the present invention has an effect of having a significantly high conversion rate of cyclododecene and selectivity of cyclododecanone, can minimize the cost used for equipment and processes, is practical, and has an advantageous effect on industrial mass production compared to the prior art by significantly reducing a reaction residence time and a required reaction volume of a reactor.COPYRIGHT KIPO 2019
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(2020/05/14)

Process for producing laurolactam and its synthesis apparatus
A method for manufacturing laurolactam and a synthesis apparatus thereof according to the present invention have a remarkably high conversion rate of raw materials and selectivity of a target compound, have an effect of synthesizing the target compound with a high yield and high purity, can minimize costs used for equipment and processes, are practical, and have an advantage of being more simplified compared to the prior art.COPYRIGHT KIPO 2019
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(2020/05/14)

Water-dispersible polyamide powder
A powder of polyamide particles, in which: said polyamide includes more than 50 mol % of amine ends among the total number of amine and acid ends of the polyamide; said particles include, on the surface thereof, primary amine groups neutralized by a phosphorous Bronsted acid, such as phosphoric acid; and the D50 of the particles falls within the range of 100 nm to 50 μm, preferably 100 nm to 20 μm. A method for producing such a powder and to the production of aqueous dispersions including same.
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(2019/07/03)

Process for preparing polymers from monomers comprising laurolactam
Polymers can be prepared from monomers comprising laurolactam, by a process including a. Beckmann rearrangement of cyclododecanone oxime to give laurolactam in the presence of a Beckmann rearrangement catalyst, b. removal of impurities from the laurolactam to obtain purified laurolactam, and c. polymerization of monomers comprising purified laurolactam. For avoidance of discolouration or yellowing under ageing conditions, prior to the polymerization, polycyclic substances containing 24 carbon atoms and at least one heteroatom selected from oxygen and nitrogen and having a molar mass between 300 and 380 g/mol are limited to 500 ppm, based on laurolactam.
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Paragraph 0031-0034

(2019/06/20)

The one-port process for laurolactam from cyclododecanone
The present invention relates to a method for manufacturing laurolactam. More specifically, the present invention relates to a method for manufacturing laurolactam by a one-pot reaction by adding a hydroxyl ammonium compound and a chlorine-based catalyst to a starting cyclododecanone. The method for manufacturing laurolactam according to the present invention does not produce byproducts resulting from the use of an acid catalyst, and does not produce gas by-products that can cause an explosion accident, thereby achieving economic efficiency and stability at the same time.COPYRIGHT KIPO 2019
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Paragraph 0033-0041

(2019/03/12)

Dichloroimidazolidinedione-Activated Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams
A novel protocol for the activation of the Beckmann rearrangement utilizing the readily available and economical geminal dichloroimidazolidinediones (DCIDs) on a substoichiometric scale (10 mol %) has been developed. A unique self-propagating mechanism for the substoichiometric dichloroimidazolidinedione-activated transformation was proposed and validated. The substrate scope of the developed protocol has been demonstrated by 23 examples with good to excellent yields (mostly 90-98%) in a short time (mostly 10-30 min), including a substrate for synthesizing the monomer of nylon-12 and a complicated steroidal substrate on a preparative scale. This research not only unveils for the first time the synthetic potential of substoichiometric amounts of dichloroimidazolidinediones in promoting chemical transformation but also offers yet another important illustration of the self-propagating cycle in the context of the Beckmann rearrangement activated by a structurally novel organic promoter.
Gao, Yu,Liu, Jingjing,Li, Zhenjiang,Guo, Tianfo,Xu, Songquan,Zhu, Hui,Wei, Fulan,Chen, Siming,Gebru, Hailemariam,Guo, Kai
p. 2040 - 2049
(2018/02/23)

Scope and mechanism of a true organocatalytic beckmann rearrangement with a boronic acid/perfluoropinacol system under ambient conditions
Catalytic activation of hydroxyl functionalities is of great interest for the production of pharmaceuticals and commodity chemicals. Here, 2-alkoxycarbonyl- and 2-phenoxycarbonyl-phenylboronic acid were identified as efficient catalysts for the direct and chemoselective activation of oxime N-OH bonds in the Beckmann rearrangement. This classical organic reaction provides a unique approach to prepare functionalized amide products that may be difficult to access using traditional amide coupling between carboxylic acids and amines. Using only 5 mol % of boronic acid catalyst and perfluoropinacol as an additive in a polar solvent mixture, the operationally simple protocol features mild conditions, a broad substrate scope, and a high functional group tolerance. A wide variety of diaryl, aryl-alkyl, heteroaryl-alkyl, and dialkyl oximes react under ambient conditions to afford high yields of amide products. Free alcohols, amides, carboxyesters, and many other functionalities are compatible with the reaction conditions. Investigations of the catalytic cycle revealed a novel boron-induced oxime transesterification providing an acyl oxime intermediate involved in a fully catalytic nonself-propagating Beckmann rearrangement mechanism. The acyl oxime intermediate was prepared independently and was subjected to the reaction conditions. It was found to be self-sufficient; it reacts rapidly, unimolecularly without the need for free oxime. A series of control experiments and 18O labeling studies support a true catalytic pathway involving an ionic transition structure with an active and essential role for the boronyl moiety in both steps of transesterification and rearrangement. According to 11B NMR spectroscopic studies, the additive perfluoropinacol provides a transient, electrophilic boronic ester that is thought to serve as an internal Lewis acid to activate the ortho-carboxyester and accelerate the initial, rate-limiting step of transesterification between the precatalyst and the oxime substrate.
Mo, Xiaobin,Morgan, Timothy D. R.,Ang, Hwee Ting,Hall, Dennis G.
supporting information
p. 5264 - 5271
(2018/04/24)

Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions
The Br?nsted acid-catalyzed synthesis of secondary amides from ketones under mild conditions is described via transoximation and Beckmann rearrangement using O-protected oximes as more stable equivalents of explosive O-protected hydroxylamines. This methodology could be applied to highly rearrangement-selective amide synthesis from α-branched alkyl aryl ketones and performed on a 1-g scale. The presence of water is essential for this reaction, and its role was clarified by isotope-labeling experiments.
Hyodo, Kengo,Hasegawa, Genna,Oishi, Naoki,Kuroda, Kazuma,Uchida, Kingo
p. 13080 - 13087
(2018/11/02)

METHOD FOR PRODUCING AMIDE COMPOUND
PROBLEM TO BE SOLVED: To provide a novel method for producing an amide compound which does not require severe reacting conditions without directly using hydroxylamine and its derivative. SOLUTION: There is provided a method for producing an amide compound which comprises: a step of transferring a ketone compound and an oxime compound to oxime in the presence of an organic solvent and an acid catalyst; and a step of subjecting the oxime to Beckmann rearrangement. The acid catalyst preferably is hydrochloric acid, sulfuric acid, methanesulfonic acid, tosyl acid monohydrate, trifluoromethanesulfonic acid, bistrifluoromethane sulfonimide, a boron trifluoride-diethyl ether complex, scandium trifluoromethanesulfonate (III), iron trifluoromethanesulfonate (III), copper trifluoromethanesulfonate (II), bismuth(III) trifluoromethanesulfonate, titanium tetrachloride or iron trichloride. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0029; 0031

(2018/09/30)

Preparation method of amide
The invention discloses a preparation method of amide, and belongs to the field of organic chemistry. A 1,3-diazacyclothiazolidinedione derivative is used as a novel organic small molecule catalyst to catalyze ketoxime rearrangement reaction, the amide generation speed is high, in most of reactions, within 10-30 minutes, selectivity can reach 98%, and the separating yield can be 95% or above. The preparation method is gentle in reaction conditions, and can be carried out under normal pressure and at the temperature from the room temperature to the temperature of 100 DEG C, instruments and equipment cannot be corroded, environmental pollution cannot be caused, energy is saved, and the industrial application prospect is good. The preparation method of amide is an efficient and environmentally friendly amide preparation method with simple and convenient synthesis steps.
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Paragraph 0071; 0072

(2017/09/01)

Method for efficiently rearranging ketoxime Beckmann by N-methyl pyrrolidone/SOC12 (thionyl chloride)
The invention provides a method for efficiently rearranging ketoxime Beckmann by N-methyl pyrrolidone/SOC12 (thionyl chloride). The method comprises the following steps of at room temperature, reacting the N-methyl pyrrolidone and the SOC12 for 20min, adding ketoxime, continuing to react for 15min, slowly adding water, adding ethyl acetate extraction separating liquid, washing an organic layer by saturated salt water, drying by anhydrous sodium sulfate, evaporating solvent, and separating and purifying by silica-gel column chromatography, so as to obtain amide. The method has the characteristics that the technology process is simple, the reaction time is short, the reaction yield is high, and the like.
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Paragraph 0029-0031

(2017/11/21)

Carbon Tetrabromide/Triphenylphosphine-Activated Beckmann Rearrangement of Ketoximes for Synthesis of Amides
An efficient Beckmann rearrangement of ketoximes was developed using carbon tetrabromide/triphenylphosphine as an organocatalyst without addition of any acids or metals. The reaction showed good functional group tolerance and gave various amides in moderate to good yields.
Gao, Peng,Bai, Zijing
supporting information
p. 1673 - 1677
(2017/10/05)

Amide preparation method
The invention discloses an amide preparation method, and belongs to the field of organic chemistry. The method is characterized in that amid is generated through a catalytic rearrangement reaction of ketoxime in an organic solvent under the action of 1,1-dichlorocycloheptatriene used as a high-efficiency organic catalyst. Compared with present catalysis systems, the method disclosed in the invention has the obvious advantages of low use amount, mildness, high efficiency, wide sources, simplicity in synthesis, multiple kinds, wide range and no metals. The method also has the characteristics of simple steps, few byproducts and high target product yield.
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Paragraph 0036; 0037

(2017/08/28)

A process for preparing laurolactam
The present invention relates to a process for preparing laurolactam, and more specifically, to a process for preparing laurolactam in a one-pot reaction by sequentially adding an azide compound, a reaction solvent, and an acid compound to cyclo dodecanone, which is a starting material.COPYRIGHT KIPO 2018
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Paragraph 0025; 0043-0050

(2018/03/23)

HIERARCHICAL ALUMINOPHOSPHATES AS CATALYSTS FOR THE BECKMANN REARRANGEMENT
Methods for producing lactams from oximes by performing a Beckmann rearrangement using a hierarchical porous aluminophosphate catalyst having interconnected microporous and mesoporous networks are provided. Exemplary catalysts include a plurality of weak Brnsted acid active sites, including silicon-containing aluminophosphates having the IZA framework code AFI, such as SAPO-5, CHA, such as SAPO-34, and FAU, such as SAPO-37.
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Paragraph 00221-00225

(2016/07/05)

RING CLOSING METATHESIS APPROACH TO PRODUCE PRECURSORS OF NYLON 11, 12, AND 13 FROM OLEIC ACID
Provided herein is a method of producing C11, C12, and C13 nylon precursors from oleic acid or esters of oleic acid, the method involving amide formation, ring-closing metathesis, and hydrogenation. Further provided are the products of the method described. Provided herein is a method for producing a lactam, the method comprising the steps of converting oleic acid or an ester of oleic acid into an amide having a general formula of H3C-(CH2)rCH=CH-(CH2)rCONR-(CH2)n-CH=CH2, wherein n is 1, 2, or 3, and R is either hydrogen or benzyl; subjecting the amide to a ring-closing metathesis reaction to produce an intermediate having a general formula of -(CH2)rCONR-(CH2) n-CH=CH2-, wherein n is 1, 2, or 3, R is either hydrogen or benzyl, and both ends are connected to each other; and hydrogenating the intermediate to produce a saturated lactam. In certain embodiments, the saturated lactam has a formula of -NH-(CH2) 10-CO-.
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(2016/01/25)

Iron-Catalyzed C-N Bond Formation via the Beckmann Rearrangement
A simple, iron-based catalytic system allows for facile Beckmann rearrangement of various oximes. The mild conditions avoid the use of harsh or expensive acids, and the reactions do not require an inert atmosphere. Additionally, a range of amides can be accessed through this transformation.
Jefferies, Latisha R.,Weber, Savannah R.,Cook, Silas P.
supporting information
p. 331 - 334
(2015/02/19)

A Deep Cavitand Templates Lactam Formation in Water
Cyclization reactions are common processes in organic chemistry and show familiar patterns of reaction rates vs ring size. While the details vary with the nature of bond being made and the number of unsaturated atoms, small rings typically form quickly despite angle strain, medium size rings form very slowly due to internal strains, and large rings form slowly (when they form at all) because fewer and less probable conformations bring the ends of the substrate together. High dilution is commonly used to slow the competing bi- and higher molecular processes. Here we apply cavitands to the formation of medium size lactams from ω-amino acids in aqueous (D2O) solution. The cavitands bind the amino acids in folded conformations that favor cyclization by bringing the ends closer together. Yields of a 12-membered lactam are improved 4.1-fold and 13-membered lactam 2.8-fold by the cavitand template. The results open possibilities for moving organic reactions into water even when the processes involve dehydration.
Mosca, Simone,Yu, Yang,Gavette, Jesse V.,Zhang, Kang-Da,Rebek, Julius
p. 14582 - 14585
(2015/12/08)

The beckmann rearrangement executed by visible-light-driven generation of vilsmeier-haack reagent
A new and efficient approach for the Beckmann rearrangement is reported. The protocol involves eosin? Y catalyzed, visible-light-mediated in situ formation of the Vilsmeier-Haack reagent from CBr4 and a catalytic amount of DMF for activation of ketoximes at room temperature. The method is operationally simple and avoids the need for any corrosive, water-sensitive reagents and elevated temperatures. Georg Thieme Verlag Stuttgart New York.
Srivastava, Vishnu P.,Yadav, Arvind K.,Yadav, Lal Dhar S.
supporting information
p. 665 - 670
(2014/04/03)

METHOD FOR PRODUCING AMIDE COMPOUND
The present invention relates to a method for producing a high purity, high quality amide compound, particularly, lactam. A first embodiment of the present invention is characterized in that an amount of each of a halide, an aldehyde compound, an alcohol compound and a nitrile compound contained in a solution recycled into an oxime-forming step is controlled to an amount of 0.4 mol % or less based on the ketone as a starting material. A second embodiment of the present invention is characterized in that one or more compounds selected from the group consisting of a ketone, an oxime and an amide compound are purified by hydrogenation and/or crystallization for eliminating impurities containing a double bond. A third embodiment of the present invention is characterized in that a content of impurities having a cyclic bridge structure is controlled by using a cycloalkanone purified by recrystallization.
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Page/Page column 19

(2013/02/28)

GAS AND LIQUID PHASE CATALYTIC BECKMANN REARRANGEMENT OF OXIMES TO PRODUCE LACTAMS
Methods for producing lactams from oximes by performing a Beckmann rearrangement using a silicoaluminophosphate catalyst are provided. These catalysts may be used in gas phase or liquid phase reactions to convert oximes into lactams. High conversion of oxime and high selectivity for the desired lactams are produced using the disclosed methods, including high conversion and selectivity for ε-caprolactam produced from cyclohexanone oxime and high conversion and selectivity for ω-laurolactam produced from cyclododecanone oxime.
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Paragraph 0139-0140

(2013/05/09)

Titanium containing solid core mesoporous silica shell: A novel efficient catalyst for ammoxidation reactions
Novel titanium containing solid core mesoporous shell silica has been synthesized by using octadecyltrichloro silane and triethylamine. The synthesized material was characterized by various physicochemical techniques. The mesoporous character of the material has been revealed from PXRD studies. The presence of octadecyltrichloro silane and triethylamine in the sample has been confirmed from EDAX studies. TG/DTA analysis reveals the thermal characteristics of the synthesized material. The presence of titanium in the frame work and its coordination state has been studies by UV-vis DR studies and XPS analysis. Chemical environment of Si in the framework of the material has been studied by 29SiMASNMR studies. The surface area of the material is found to be around 550 m2g-1 and pore radius is of nano range from BET analysis. The spherical morphology and particle size of the core as well as shell has been found to be 300 nm and 50 nm respectively from TEM analysis. The catalytic application of this material towards the synthesis of caprolactam from cyclohexanone in presence of hydrogen peroxide through ammoxidation reaction has been investigated. The optimum conditions for the reaction have been established. The plausible mechanism for the formation of core silica and conversion of cyclohexanone has been proposed.
Venkatathri,Nookaraju,Rajini,Reddy
p. 143 - 148
(2013/08/24)

Synthesis of lactams using enzyme-catalyzed aminolysis
The formation of caprolactam from 6-aminocaproic acid catalyzed by CALB (N435) is reported. Different lactam ring sizes can be prepared starting from 4-aminobutanoic acid, 5-aminovaleric acid, and 8-aminooctanoic acid. Experiments with mixtures of aminocarboxylic acids have shown that CALB prefers homocyclization of the individual aminocarboxylic acids.
Stavila,Loos
p. 370 - 372
(2013/02/25)

Titanium cation-exchanged montmorillonite as an active heterogeneous catalyst for the Beckmann rearrangement under mild reaction conditions
Titanium cation-exchanged montmorillonite acts as an efficient heterogeneous catalyst for the Beckmann rearrangement of a wide range of ketoximes including aromatic, aliphatic, and alicyclic ketoximes under mild reaction conditions. After the rearrangement reaction, titanium cation-exchanged montmorillonite is easily separated by simple filtration, and can be reused with retention of high efficiency.
Mitsudome, Takato,Matsuno, Tsuyoshi,Sueoka, Shoichiro,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
supporting information
p. 5211 - 5214
(2012/11/07)

Cyanuric chloride catalyzed Beckmann rearrangement of ketoximes in biodegradable ionic liquids
Imidazolium-based ionic liquids (ILs) containing ester moieties in the side chain were successfully used as an alternative to traditional ILs in the Beckmann rearrangement of ketoximes catalyzed by 2,4,6-trichloro[1,3,5]triazine. The procedure is mild and suitable for both aromatic and cycloaliphatic substrates affording the rearrangement products in good to quantitative yields. The process is eco-sustainable since these ILs are biodegradable and in addition they can be recovered and reused.
Maia, Angelamaria,Albanese, Domenico C.M.,Landini, Dario
experimental part
p. 1947 - 1950
(2012/03/22)

Beckmann rearrangement of ketoximes induced by phenyl dichlorophosphate at ambient temperature
Upon treatment with phenyl dichlorophosphate (PhOP=OCl2) in acetonitrile at ambient temperature, a variety of ketoximes underwent a Beckmann rearrangement in an effective manner to afford the corresponding amides in moderate to high yields.
Kuo, Chun-Wei,Hsieh, Min-Tsang,Gao, Shijay,Shao, Yi-Ming,Yao, Ching-Fa,Shia, Kak-Shan
p. 13662 - 13672
(2013/02/23)

Enzyme-catalyzed laurolactam synthesis via intramolecular amide bond formation in aqueous solution
Lactam formation from ω-aminocarboxylic acids is thermodynamically unfavored in aqueous solution and therefore hard to achieve. In the present work ω-laurolactam hydrolases from Acidovorax sp. T31 and Cupriavidus sp. U124 were investigated regarding their potential to catalyze lactam formation. Both enzymes are known to hydrolyze laurolactam to 12-aminododecanoic acid. The ω-laurolactam hydrolase genes were expressed in Escherichia coli BL21 (DE3) and the catalytic activity of the respective proteins was investigated. As expected from thermodynamics, only laurolactam hydrolysis but not 12-aminododecanoic acid cyclization was observed in whole-cell biotransformations and cell extract assays. The utilization of 12-aminododecanoic acid methyl ester, as an activated form of 12-aminododecanoic acid, resulted in intramolecular amide bond formation with the product laurolactam. Maximum laurolactam formation rates of 13.5 and 14.3 U g CDW-1 and molar yields of 11.5% and 13.0% were achieved in biotransformations at pH 10 with recombinant E. coli harboring the ω-laurolactam hydrolase from Cupriavidus sp. U124 and Acidovorax sp. T31, respectively. Furthermore, it was shown that under the harsh reaction conditions applied, the utilization of whole-cell biocatalysts enables 17.2-fold higher laurolactam formation activity in comparison to free enzymes in solution. This study shows that hydrolase-catalyzed laurolactam synthesis can be achieved in aqueous solution by selection of an appropriate substrate and reaction pH. Copyright
Ladkau, Nadine,Hermann, Inna,Buehler, Bruno,Schmid, Andreas
scheme or table
p. 2501 - 2510
(2011/11/07)

PROCESS FOR PRODUCTION OF AMIDE OR LACTAM
The present invention relates to a process for producing an amide or lactam, particularly laurolactam, wherein catalytic amounts of an acidic chloride and a Lewis acid are used in Beckmann rearrangement of an oxime compound. In accordance with the process, side reactions during Beckmann rearrangement can be so controlled that selectivity can be improved and strong coloring in the reaction can be prevented, giving a high-quality amide or lactam.
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Page/Page column 5

(2011/02/18)

METHOD FOR PRODUCING AMIDE COMPOUND
This invention relates to a process for producing an amide compound by Beckmann rearrangement of an oxime compound using a compound having at least two electron-withdrawing leaving groups as a rearrangement catalyst, the process comprising a pre-preparation step in which the rearrangement catalyst and at least a part of the oxime compound are mixed and reacted; and a rearrangement reaction step in which the oxime compound is rearranged at a temperature higher than that in the pre-preparation step.
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Page/Page column 15-16

(2012/01/13)

Facile AlCl3-promoted catalytic beckmann rearrangement of ketoximes
Aluminum chloride, an inexpensive and commercially available Lewis acid traditionally employed for Beckmann rearrangement with stoichiometric amounts, has been now found to smoothly promote the Beckmann rearrangement of various ketoximes to the corresponding amides (up to 99% of yield) with 10mol% catalyst loading in anhydrous acetonitrile under reflux temperature.
Liu, Li-Feng,Liu, Hua,Pi, Hong-Jun,Yang, Shuo,Yao, Min,Du, Wenting,Deng, Wei-Ping
experimental part
p. 553 - 560
(2011/04/22)

A mild and highly efficient catalyst for Beckmann rearrangement, BF 3·OEt2
BF3·OEt2 (Boron trifluoride etherate), an inexpensive and commercially easily available Lewis acid stoichiometrically employed for Beckamann rearrangement in general, was now found to efficiently catalyze Beckmann rearrangement of ketoximes into their corresponding amides (up to 99% yield) in anhydrous acetonitrile under reflux temperature.
An, Na,Pi, Hongjun,Liu, Lifeng,Du, Wenting,Deng, Weiping
experimental part
p. 947 - 950
(2012/01/05)

PROCESS FOR PRODUCING LAUROLACTAM
The present invention relates to a process for producing laurolactam from cyclododecanone oxime by liquid-phase rearrangement reaction using trichlorotriazine as a rearrangement catalyst. The present invention can provide a process which can solve the problem of termination of the reaction at a certain conversion, can prevent an inactive precipitate generated from trichlorotriazine from precipitating in the course of the reaction process, and can remove an inactive precipitate, an active intermediate and a residual catalyst.
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Page/Page column 7

(2011/04/18)

METHOD FOR PREPARING LACTAMES, COMPRISING A PHOTONITROSATION STEP, FOLLOWED BY A BECKMANN TRANSPOSITION STEP
The invention relates to a method for preparing lactames, according to which a photonitrosation of a cycloallcane is carried out using nitrosyl chloride (NOCI). According to the invention, said photonitrosation is carried out by means of LEDs emitting a monochromatic light. The method according to the invention can also include a step comprising Beckmann transposition/dechlorination of the oxime hydrochloride generated during said phonitrosation, preferably carried out in a glass microreactor.
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Page/Page column 4

(2011/06/24)

PRODUCTION METHOD AND BECKMANN REARRANGEMENT CATALYST FOR PRODUCING A CYCLIC LACTAM COMPOUND
Process for producing lactam compounds and Beckmann rearrangement catalysts There is provided a catalyst which is highly active, stable and safe and forms less byproducts for a process for producing a lactam, and a production process. A cycloalkylidene-aminoaxy-1,3,5-triazine compound is provided as a Beckmann rearrangement catalyst and/or a reaction starting material in a reaction process for producing a lactam compound.
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(2010/11/03)

METHOD FOR PRODUCING LACTAM COMPOUND
Disclosed is a method for industrially efficiently producing a lactam compound having 8 to 15 carbon atoms at low cost by allowing a rearrangement reaction of a cyclic oxime compound to proceed without causing large amounts of by-products such as ammonium sulfate. [Solving Means] Disclosed is a method for producing a lactam compound, which includes the step of rearranging a cyclic oxime compound in a nonpolar solvent B in the presence of an aromatic compound A to give the lactam compound, in which the aromatic compound A has a leaving group bonded to a carbon atom constituting its aromatic ring and contains, as an atom constituting the aromatic ring, a heteroatom, or a carbon atom bonded with an electron-withdrawing group, the cyclic oxime compound is represented by following Formula (1): wherein “m” denotes an integer of 7 to 14, and the lactam compound is represented by following Formula (2): wherein “m” is as defined above.
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Page/Page column 7

(2010/03/02)

Cyclopropenium ion catalysed Beckmann rearrangement
1-Chloro-2,3-diphenylcyclopropenium ion was found to be a very efficient organocatalyst (3 mol% loading) for liquid phase Beckmann rearrangement of various ketoximes to the corresponding amides/lactams within 2 h in acetonitrile at reflux temperature. This is the first example of the application of the cyclopropenium ion as a catalyst, which opens up a new aspect of the synthetic utility of aromatic cation based catalysis.
Srivastava, Vishnu P.,Patel, Rajesh,Garima,Yadav, Lal Dhar S.
supporting information; experimental part
p. 5808 - 5810
(2010/10/02)

Bromodimethylsulfonium bromide-ZnCl2: A mild and efficient catalytic system for beckmann rearrangement
Bromodimethylsulfonium bromide, in combination with zinc chloride, has been shown to be an excellent catalytic system for liquid-phase Beckmann rearrangement of various ketoximes into the corresponding amides/lactams in acetonitrile at reflux temperature with good to excellent yields. Georg Thieme Verlag Stuttgart - New York.
Yadav, Lal Dhar S.,Patel, Rajesh,Srivastava, Vishnu P.
experimental part
p. 1771 - 1776
(2010/08/05)

METHOD FOR PRODUCTION OF LAUROLACTAM
PROCESS FOR PRODUCING LAUROLACTAM Provided is a process for efficiently producing laurolactam by simple steps from cyclododecanone and hydroxylamine. This production process comprises the steps of: (a) reacting cyclododecanone with hydroxylamine in an aqueous solution in the presence of an oxime-formation solvent to produce cyclododecanone oxime; (b) separating the reaction mixture obtained after the oxime-forming step into an oil and an aqueous phases and collecting a solution of cyclododecanone oxime of the oil phase; (c) removing a part or all of the oxime-formation solvent and dissolved water from the solution of cyclododecanone oxime which is collected as an oil phase in the oil/aqueous phase separation step, whereby preparing a solution containing a rearrangement solvent to be used in a rearrangement reaction in a later step and the cyclododecanone oxime; (d) producing laurolactam from cyclododecanone oxime by rearrangement reaction using an aromatic-ring containing compound as a rearrangement catalyst; and (e) separating and removing the rearrangement solvent and the rearrangement catalyst from the reaction mixture after the rearrangement step, and purifying the laurolactam. FIG. 1
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(2010/09/17)

In situ multinuclear solid-state NMR spectroscopy study of Beckmann rearrangement of cyclododecanone oxime in ionic liquids: The nature of catalytic sites
The Beckmann rearrangement of cyclododecanone oxime into ω-laurolactam has been investigated in four ionic liquids: 1-butyl-3-methylimidazolium hexafluorophosphate and tetrafluoroborate ([C4mim], [C4mim]), and 1-butyl-2,3-dimethylimidazolium and 1-butyl-4-methylpyridinium hexafluorophosphates ([C4mpyr], [C4m2im]), in a batch reactor as well as by 'in situ' multinuclear solid-state NMR spectroscopy. The Beckmann rearrangement reaction of cyclododecanone oxime takes place in [C4mim] and [C4mpyr] with excellent activity and selectivity, while practically null activity is observed in [C4m2im] and [C4mim]. The results obtained indicate that a very low level of hydrolysis of the PF6- anion in [C4mim] and [C4mpyr] occurs under reaction conditions (130 °C), and the HF formed at the level of ppm acts as catalyst in the Beckmann rearrangement with excellent conversion and selectivity.
Blasco,Corma,Iborra,Lezcano-Gonzalez,Monton
experimental part
p. 78 - 83
(2011/02/21)

Catalytic Beckmann rearrangement of cyclododecanone oxime
The catalytic Beckmann rearrangement of cyclododecanone oxime (CDOX) was investigated in silane-nitrile-solvent systems. We have found that chlorosilanes, such as trimethylchlorosilane and tetrachlorosilane, are effective catalysts to produce ω- laurolactam (LRL) at 100 °C. Tetrachlorosilane is the most active catalyst, and hydrocarbon solvents such as cyclohexane, hexane, and decane are suitable for the system. Nitriles such as acetonitrile and benzonitrile would play an important role as a remover of silane species from the produced LRL-silane salt.
Sato, Satoshi,Hoshino, Hideaki,Sugimoto, Tsunemi,Kashiwagi, Kohichi
supporting information; experimental part
p. 1319 - 1320
(2011/02/17)

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
experimental part
p. 42 - 55
(2009/06/17)

PURIFICATION OF A CRUDE LACTAM MIXTURE BY MEANS OF MELT CRYSTALLIZATION
The present invention provides a method for purifying laurolactam from a crude lactam mixture. In the method of the present invention, laurolactam is selectively crystallized by melt crystallization with controlled cooling of the crude lactam mixture.
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(2009/04/24)

METHOD FOR PRODUCTION OF LAUROLACTAM
Disclosed is a method for producing laurolactam from cyclododecanone and hydroxylamine in a simple process and with high efficiency. The method comprises the following steps (a) to (e): (a) reacting cyclododecanone with hydroxylamine in an aqueous solution in the presence of an excess amount of cyclododecanone or a solvent to produce cyclododecanone oxime; (b) separating the reaction mixture obtained after the oxime-forming step into an oil and an aqueous phases and collecting a solution of cyclododecanone oxime of the oil phase as; (c) removing dissolved water from the solution of cyclododecanone oxime which is collected as an oily phase in the oil/aqueous phase separation step; (d) producing laurolactam from cyclododecanone oxime by rearrangement reaction using an aromatic-ring containing compound as a rearrangement catalyst; and (e) separating the produced laurolactam from the reaction mixture after the rearrangement step and purifying the laurolactam.
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(2009/12/07)

Unexpected results from the re-investigation of the Beckmann rearrangement of ketoximes into amides by using TsCl
TsCl (p-toluenesulfonyl chloride), a commercially available organosulfonyl chloride, has been widely used as a stoichiometric dehydrogenation reagent in the transformation of ketoximes into corresponding amides via the Beckmann rearrangement. It has been now found to catalyze the Beckmann rearrangement with high catalytic efficiency, converting a wide range of ketoximes into their corresponding amides under mild condition with good to excellent yields (up to 99% of yield with 1-5 mol % of catalyst loading).
Pi, Hong-Jun,Dong, Jin-Dong,An, Na,Du, Wenting,Deng, Wei-Ping
experimental part
p. 7790 - 7793
(2010/01/06)