- Structural, vibrational and DFT studies on 2-chloro-1H-isoindole-1,3(2H)-dione and 2-methyl-1H-isoindole-1,3(2H)-dione
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The Fourier transform infrared (FTIR) and FT-Raman spectra of 2-chloro-1H-isoindole-1,3(2H)-dione and 2-methyl-1H-isoindole-1,3(2H)-dione have been measured in the range of 4000-400 and 4000-100 cm-1, respectively. Complete vibrational assignment and analysis of the fundamental modes of the compounds were performed using the observed FTIR and FT-Raman data. The geometry was optimised without any symmetry constraints using the DFT/B3LYP method with 6-31G(d,p) and 6-311++G(d,p) basis sets. The vibrational frequencies determined experimentally are compared with those obtained theoretically from DFT gradient calculations employing the B3LYP/6-31G(d,p) and B3LYP/6-311++G(d,p) methods for the optimised geometry of the compounds. The structural parameters and normal modes of vibration obtained from DFT method are in good agreement with the experimental data. The force fields obtained from DFT method were utilised and the potential energy distributions of all the fundamental vibrations of the compounds were calculated.
- Arjunan,Saravanan,Ravindran,Mohan
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Read Online
- A convenient method of N-methylphthalimide synthesis
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We suggest a convenient method to obtain N-methylphthalimide with a high yield in the reaction of phthalic anhydride with aqueous methylamine.
- Vasilevskaya,Yakovleva,Kobrin
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Read Online
- Base-controlled product switch in the ruthenium-catalyzed protodecarbonylation of phthalimides: A mechanistic study
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The whole reaction mechanism of the ruthenium-catalyzed protodecarbonylation of N-substituted phthalimides into secondary amides was unravelled by a combined experimental and theoretical study. The chemoselectivity of the reaction, which is catalyzed by para-cymene coordinated Ru(ii) species all over the catalytic cycle, is exclusively controlled by the unique roles of the bases. Meanwhile, in the presence of K2CO3 or KOH at high temperatures, the same product (benzamide) is mainly formed, whereas at low temperatures, KOH led to an unexpected side-product (phthalamic acid) and no reactivity was observed with K2CO3. The non-covalent interactions between the potassium cations and the different carbonyl groups in the molecules are key to providing a thermodynamically favourable pathway with energetically accessible transition states. The unexpected formation of carbon dioxide (CO2) in the course of the reaction originates from the phthalimide substrate and the base K2CO3 in two different elementary steps, respectively.
- D'Alterio, Massimo Christian,Yuan, Yu-Chao,Bruneau, Christian,Talarico, Giovanni,Gramage-Doria, Rafael,Poater, Albert
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Read Online
- Second-generation tags for fluorous chemistry exemplified with a new fluorous Mitsunobu reagent
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(Chemical Equation Presented) A new fluorous DEAD reagent bearing two perfluoro-tert-butyloxy groups with propylene spacers shows excellent promise for use in fluorous Mitsunobu reactions. Pure target products were obtained in good yields after removing fluorous byproducts by FSPE. The new reagent serves as a prototype for a greener second generation of fluorous reagents bearing tags that are not expected to degrade in the environment to compounds that are highly persistent or that bioaccumulate in higher organisms.
- Chu, Qianli,Henry, Christopher,Curran, Dennis P.
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Read Online
- Electroselective and Controlled Reduction of Cyclic Imides to Hydroxylactams and Lactams
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An efficient and practical electrochemical method for selective reduction of cyclic imides has been developed using a simple undivided cell with carbon electrodes at room temperature. The reaction provides a useful strategy for the rapid synthesis of hydroxylactams and lactams in a controllable manner, which is tuned by electric current and reaction time, and exhibits broad substrate scope and high functional group tolerance even to reduction-sensitive moieties. Initial mechanistic studies suggest that the approach heavily relies on the utilization of amines (e.g., i-Pr2NH), which are able to generate α-aminoalkyl radicals. This protocol provides an efficient route for the cleavage of C-O bonds under mild conditions with high chemoselectivity.
- Bai, Ya,Shi, Lingling,Zheng, Lianyou,Ning, Shulin,Che, Xin,Zhang, Zhuoqi,Xiang, Jinbao
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supporting information
p. 2298 - 2302
(2021/04/05)
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- Preparation of alkylated compounds using the trialkylphosphate
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[Problem] trialkylphosphate strong base used reaction agent, a carboxylic acid, a ketone, an aldehyde, amine, amide, thiol, ester or Grignard reagent to a variety of substrates, and/or high efficiency to generate a highly stereoselective alkylation reaction, the alkylated compounds capable of producing new means. [Solution] was used as the alkylating agent in the alkylation of compound trialkylphosphate, strongly basic reaction production use. [Drawing] no
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Paragraph 0184-0185; 0208
(2021/11/02)
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- Preparation method of N-alkyl phthalimide
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The invention discloses a preparation method of N-alkyl phthalimide. The method comprises the steps: taking phthalic anhydride as a raw material, taking an aqueous solution of alkylamine as an imidization reagent ( no other reagents do not need to be added), and directly synthesizing the N-alkyl phthalimide, wherein the yield is high (96% or above), and the purity is high (99% or above). The preparation method is loose in reaction condition, simple in step and easy to implement; no organic solvent is needed, no other substances are discharged except water, and the method is green, free of pollution and suitable for industrial production.
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Paragraph 0031-0034
(2021/03/13)
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- Preparation method of N - alkyl -4 -nitrophthalimide
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The invention discloses a preparation method of N - alkyl -4 -nitrophthalimide, which comprises the following steps of 1) mixing phthalic anhydride, alkyl aldehyde and inorganic amine, reacting under the action of hydrogen, cooling and crystallizing, and drying to obtain N -alkyl phthalimide. Step 2) The 1 alkylphthalimide obtained in step N -) is subjected to nitration reaction, and the product is purified and dried to obtain the N -alkyl -4 -nitrophthalimide. The alkyl aldehyde in step 1) is preferably an alkyl aldehyde of carbon 1 - 4. The preparation method has the advantages of wide raw material source, low price, simple process, easiness in large-scale production and the like. Through one-step synthesis, the reaction efficiency is high, the device is simple and easy to operate, and green and environment-friendly.
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Paragraph 0040-0041; 0053-0053; 0055-0056
(2021/10/27)
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- Copper-promoted direct amidation of isoindolinone scaffolds by sodium persulfate
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Isoindolinones are ubiquitous structural motifs in natural products and pharmaceuticals. Establishing an efficient method for structural modification of isoindolinones could significantly facilitate new drug development. Herein, we describe copper-promoted direct amidation of isoindolinone scaffolds mediated by sodium persulfate. The method exhibits mild reaction conditions and high site-selectivity, and enables the structural modification of the drug indobufen ester with various amides with yields of 49 to 98%. It is also gram-scalable. Additionally, the reaction mechanism appears to involve a radical and a carbocationic pathway.
- Lai, Huifang,Lin, Jin,Xu, Jiexin,Zha, Daijun
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supporting information
p. 7621 - 7626
(2021/09/22)
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- Regio- And Stereoselective (S N2) N -, O -, C - And S -Alkylation Using Trialkyl Phosphates
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Bimolecular nucleophilic substitution (S N 2) is one of the most well-known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable, which makes them problematic for laboratory use. In contrast, trialkyl phosphates are inexpensive, readily accessible and stable at room temperature, under air, and are easy to handle, but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various N -, O -, C - and S -nucleophiles using readily available trialkyl phosphates. The reaction proceeds smoothly in excellent yield, and quantitative yield in many cases, and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to 98% ee).
- Banerjee, Amit,Hattori, Tomohiro,Yamamoto, Hisashi
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- Redox-Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C?H Di- and Trifluoromethoxylation
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Applications of TEMPO. catalysis for the development of redox-neutral transformations are rare. Reported here is the first TEMPO.-catalyzed, redox-neutral C?H di- and trifluoromethoxylation of (hetero)arenes. The reaction exhibits a broad substrate scope, has high functional-group tolerance, and can be employed for the late-stage functionalization of complex druglike molecules. Kinetic measurements, isolation and resubjection of catalytic intermediates, UV/Vis studies, and DFT calculations support the proposed oxidative TEMPO./TEMPO+ redox catalytic cycle. Mechanistic studies also suggest that Li2CO3 plays an important role in preventing catalyst deactivation. These findings will provide new insights into the design and development of novel reactions through redox-neutral TEMPO. catalysis.
- Lee, Johnny W.,Lim, Sanghyun,Maienshein, Daniel N.,Liu, Peng,Ngai, Ming-Yu
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supporting information
p. 21475 - 21480
(2020/10/02)
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- [3 + 2] Cycloaddition with photogenerated azomethine ylides in β-cyclodextrin
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Stability constants for the inclusion complexes of cyclohexylphthalimide 2 and adamantylphthalimide 3 with β-cyclodextrin (β-CD) were determined by 1H NMR titration, K = 190 ± 50 M?1, and K = 2600 ± 600 M?1, respectively. Photochemical reactivity of the inclusion complexes 2&at;β-CD and 3&at;β-CD was investigated, and we found out that β-CD does not affect the decarboxylation efficiency, while it affects the subsequent photochemical H-abstraction, resulting in different product distribution upon irradiation in the presence of β-CD. The formation of ternary complexes with acrylonitrile (AN) and 2&at;β-CD or 3&at;β-CD was also essayed by 1H NMR. Although the formation of such complexes was suggested, stability constants could not be determined. Irradiation of 2&at;β-CD in the presence of AN in aqueous solution where cycloadduct 7 was formed highly suggests that decarboxylation and [3 + 2] cycloaddition take place in the ternary complex, whereas such a reactivity from bulky adamantane 3 is less likely. This proof of principle that decarboxylation and cycloaddition can be performed in the β-CD cavity has a significant importance for the design of new supramolecular systems for the control of photoreactivity.
- Basari?, Nikola,Mandi?, Leo,Sohora, Margareta
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p. 1296 - 1304
(2020/07/10)
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- N-methyl-4-nitrophthalimide preparation method
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The invention relates to the technical field of organic synthesis processes, particularly to a N-methyl-4-nitrophthalimide preparation method, which comprises: preparation of a nitrating agent: mixinga nitrate and concentrated sulfuric acid to form a nitrating agent; preparation of N-methylphthalimide: adding methylamine and phthalic anhydride to a solvent, and carrying out heating reflux to obtain N-methylphthalimide; and preparation of N-methyl-4-nitrophthalimide: adding the nitrating agent to the N-methylphthalimide, and carrying out a reaction to form N-methyl-4-nitrophthalimide. According to the present invention, the nitrating agent is prepared at a low temperature by using nitrate and concentrated sulfuric acid so as to avoid the harm of fuming nitric acid to environmental and human body; and after the nitrating reaction is performed with the nitrating agent, the remaining nitrating agent can be recycled by extraction, and can further be added with an auxiliary agent to obtainnitrate or sulfate precipitate as a by-product, wherein ammonium nitrate or ammonium sulfate, and the like can be used as fertilizers so as to achieve environmentally friendly circulation reactions.
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Paragraph 0071; 0074; 0077; 0080; 0083; 0086; 0089; 0092
(2019/11/20)
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- Method for selective N-methylation of secondary amide
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The invention relates to a method for selective N-methylation of secondary amide. The method is characterized in that the secondary amide is in an organic solvent N, N-dimethyl formamide or dimethyl sulfoxide, trifluoroacetic acid methyl ester serves as a methylation reagent, and reaction is performed in the presence of sodium hydride, potassium tert-butoxide or sodium methylate, so as to obtain aselective N-methylated product. The method has the characteristics that generally a trifluoroacetylation product is produced when the trifluoroacetic acid methyl ester is reacted with amine compounds, however a N-methylated product can be selectively obtained when the trifluoroacetic acid methyl ester is reacted with secondary amide; the method is simple to operate, low in cost, mild in reactionconditions and high in selectivity, and avoids the use of hypertoxic methylation reagents, such as dimethyl sulfate and methyl iodide.
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Paragraph 0011
(2019/03/08)
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- PPh3/I2/HCOOH: An efficient CO source for the synthesis of phthalimides
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A straightforward and general method has been developed for the synthesis of phthalimide derivatives from 2-iodobenzamides and PPh3/I2/HCOOH in the presence of a catalytic amount of Pd(OAc)2. The reaction results demonstrate that PPh3/I2/HCOOH is a facile, efficient and safe CO source. The whole process is carried out in toluene at 80 °C and furnishes the desired products in good to excellent yields.
- Wang, Yingying,Zhou, Yang,Lei, Min,Hou, Jinjun,Jin, Qinghao,Guo, Dean,Wu, Wanying
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supporting information
p. 1180 - 1185
(2019/01/26)
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- Selective N-Monoalkylation of Amide Derivatives with Trialkyl Phosphates
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A highly selective and easily handled monoalkylation of primary amide derivatives by using trialkyl phosphates as alkylating reagents in cyclopentyl methyl ether (CPME) was developed. Various monoalkylated amide derivatives were efficiently synthesized by changing the alkyl moiety (e.g., methyl, ethyl, butyl, or benzyl) of the trialkyl phosphate. These phosphate reagents are relatively stable and easily available, and CPME is a useful solvent in process chemistry.
- Asai, Shota,Ban, Kazuho,Monguchi, Yasunari,Sajiki, Hironao,Sawama, Yoshinari
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supporting information
p. 322 - 325
(2017/10/31)
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- Electron-Transfer-Induced Intramolecular Heck Carbonylation Reactions Leading to Benzolactones and Benzolactams
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A metal-catalyst-free intramolecular Heck carbonylation reaction of benzyl alcohols and benzyl amines with carbon monoxide under heating at 250 °C affords the corresponding benzolactones and benzolactams in good to excellent yields. A hybrid radical/ionic chain mechanism, involving electron transfer from radical anions generated by nucleophilic attack of alcohols or amines on intermediate acyl radicals, is proposed.
- Fukuyama, Takahide,Bando, Takanobu,Ryu, Ilhyong
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supporting information
p. 3015 - 3021
(2018/06/08)
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- NITROGEN-CONTAINING BIOPOLYMER-BASED CATALYSTS, THEIR PREPARATION AND USES IN HYDROGENATION PROCESSES, REDUCTIVE DEHALOGENATION AND OXIDATION
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The present invention relates to a process for the preparation of a nitrogen containing biopolymer-based catalyst by pyrolysis of a metal complex with a nitrogen-containing biopolymer and to the nitrogen containing biopolymer-based catalysts obtainable by this process. In particular, the invention relates to a nitrogen containing biopolymer-based catalyst comprising metal particles and at least one nitrogen containing carbon layer. The invention also relates to the use of a nitrogen containing biopolymer-based catalyst in a hydrogenation process, preferably in a process for hydrogenation of nitroarenes, nitriles or imines; in a reductive dehalogenation process of C-X bonds, wherein X is CI, Br or I, preferably in a process for dehalogenation of organohalides or in a process for deuterium labelling of arenes via dehalogenation of organohalides; or in an oxidation process. Further, the invention relates to a metal complex with the nitrogen containing biopolymer, wherein the metal is a transition metal selected from the group consisting of manganese, ruthenium, cobalt, rhodium, nickel, palladium and platinum, preferably cobalt or nickel, and wherein the nitrogen containing biopolymer is selected from chitosan, chitin and a polyamino acid, preferably chitosan or chitin.
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Page/Page column 19
(2018/07/29)
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- N - methylation of the sulfoxide of imine derivative (by machine translation)
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A simple, clean and high-effective synthetic method of a novel N-methylated sulfoximine derivative is provided in the invention. The invention relates to the fields of pesticides, organic chemical engineering and fine chemical engineering. The method essentially is an organic synthesis reaction that a methyl free radical, which is generated from peroxides, and a sulfoximine compound are subjected to free radical coupling to form new C-N bonds. The method includes the step of carrying out a reaction to obtain the N-methylated sulfoximine derivative in a common organic solvent under a heating condition from the raw materials including diphenyl sulfoximine and a methylating reagent (peroxides) under the catalysis by copper. The method is 2-20 h in reaction time under a heating and stirring condition. The molar ratio of the raw materials is that the diphenyl sulfoximine to the methylating reagent is 1:0.5-3.0. The raw materials are reacted under the heating condition and then reaction products are subjected to simple after treatments to obtain the N-methylated sulfoximine derivative at a yield being 36-87%. The invention develops a series of N-methylating methods based on a free radical process to prepare a series of N-methylated sulfoximine derivatives. The method is simple in operation and after treatments, and is simple and practical in synthesis of these compounds.
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Paragraph 0047-0048
(2018/04/01)
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- Unmasking Amides: Ruthenium-Catalyzed Protodecarbonylation of N-Substituted Phthalimide Derivatives
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The unprecedented transformation of a wide range of synthetically appealing phthalimides into amides in a single-step operation has been achieved in high yields and short reaction times using a ruthenium catalyst. Mechanistic studies revealed a unique, homogeneous pathway involving five-membered ring opening and CO2 release with water being the source of protons.
- Yuan, Yu-Chao,Kamaraj, Raghu,Bruneau, Christian,Labasque, Thierry,Roisnel, Thierry,Gramage-Doria, Rafael
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supporting information
p. 6404 - 6407
(2017/12/08)
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- NH4I/tert-butyl hydroperoxide-promoted oxidative C–N cleavage of tertiary amines leading to nitroaromatic compounds
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A NH4I/tert-butyl hydroperoxide-promoted oxidation of tertiary N-aryl-N,N-dialkylamines in DMSO has been developed to access nitroaromatic compounds. This methodology involves sequential N-dealkylation reactions in one-pot and a radical pathway is proposed.
- Shao, Ying,Zheng, Hao,Wu, Zhuhong,Huang, Lei,Tong, Jingjing,Wu, Ming,Sun, Xiaoqiang
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p. 504 - 508
(2017/10/03)
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- A Biomass-Derived Non-Noble Cobalt Catalyst for Selective Hydrodehalogenation of Alkyl and (Hetero)Aryl Halides
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Hydrodehalogenation is a straightforward approach for detoxifications of harmful anthropogenic organohalide-based pollutants, as well as removal of halide protecting groups used in multistep syntheses. A novel sustainable catalytic material was prepared from biowaste (chitosan) in combination with an earth-abundant cobalt salt. The heterogeneous catalyst was fully characterized by transmission electron microscope, X-ray diffraction, and X-ray photoelectron spectroscopy measurements, and successfully applied to hydrodehalogenation of alkyl and (hetero)aryl halides with broad scope (>40 examples) and excellent chemoselectivity using molecular hydrogen as a reductant. The general usefulness of this method is demonstrated by successful detoxification of non-degradable pesticides and fire retardants. Moreover, the potential of the catalyst as a deprotection tool is demonstrated in a multistep synthesis of (±)-peronatin B (alkaloid).
- Sahoo, Basudev,Surkus, Annette-Enrica,Pohl, Marga-Martina,Radnik, J?rg,Schneider, Matthias,Bachmann, Stephan,Scalone, Michelangelo,Junge, Kathrin,Beller, Matthias
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supporting information
p. 11242 - 11247
(2017/09/02)
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- Method of synthesizing N-methylphthalimide
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The present invention proposes a method of synthesizing N-methylphthalimide. Phthalimide and formaldehyde are used as main reaction materials subjected to reaction to obtain a production by introducing hydrogen to water. The materials used herein are all bulk basic chemical materials, and the method has the advantages of low equipment investment, low energy consumption and good operation simplicity. Reaction yield is up to 98% and above, conversion rate is greatly increased, and production cost is lower. In addition, water is used as a solvent, and reaction liquid is simply filtered to obtain the product with content of 99% and above. The filtrate needs no any treatment and can be used in next-batch production just after analyzing the formaldehyde content of the filtrate and adjusting PH value, and clean production is truly achieved.
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Paragraph 0036; 0037; 0038; 0039; 0040; 0041-0051
(2017/07/19)
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- A hitherto undescribed addition of the lithium salt of dimethyl methylphosphonate to N-substituted phthalimides
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The hitherto unknown addition of the lithium salt of dimethyl methylphosphonate 6 to the N-substituted phthalimides 7 is described. This reaction allows the synthesis of new systems in which the phosphono group is connected to the heterocyclic skeleton of an isoindolinone at the 3-position by one methylene group.
- Zagórski, Piotr M.,Jó?wiak, Andrzej,P?otka, Mieczys?aw W.,Cal, Dariusz
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supporting information
p. 1835 - 1837
(2016/04/19)
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- Carbonylative synthesis of phthalimides and benzoxazinones by using phenyl formate as a carbon monoxide source
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A simple and efficient palladium-catalyzed carbonylative cyclization of N-substituted 2-iodobenzamides and 2-iodoanilides was investigated for the synthesis of phthalimides and benzoxazinones, respectively, by using phenyl formate as a CO source. The present catalytic protocol circumvents the use of an expensive phosphine ligand as well as solvent in the case of the phthalimide synthesis. Moreover, mild reaction conditions and a tolerance of various functional groups enhance the general applicability of this method.
- Chavan, Sujit P.,Bhanage, Bhalchandra M.
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p. 2405 - 2410
(2015/04/22)
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- Palladium-Catalyzed Aerobic Oxidative Dehydrogenation of Cyclohexenes to Substituted Arene Derivatives
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A palladium(II) catalyst system has been identified for aerobic dehydrogenation of substituted cyclohexenes to the corresponding arene derivatives. Use of sodium anthraquinone-2-sulfonate (AMS) as a cocatalyst enhances the product yields. A wide range of functional groups are tolerated in the reactions, and the scope and limitations of the method are described. The catalytic dehydrogenation of cyclohexenes is showcased in an efficient route to a phthalimide-based TRPA1 activity modulator.
- Iosub, Andrei V.,Stahl, Shannon S.
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supporting information
p. 3454 - 3457
(2015/03/30)
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- Copper-catalyzed N-methylation/ethylation of sulfoximines
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A protocol for the copper-catalyzed N-methylation of sulfoximines with di-tert-butyl peroxide (DTBP) was developed. This protocol has good functional group tolerance leading to N-methylated sulfoximines in moderate to good yields. Besides, N-ethylation of sulfoximines was achieved in the presence of bis(1,1-dimethylpropyl)peroxide as the ethylating agent under a standard procedure.
- Teng, Fan,Cheng, Jiang,Yu, Jin-Tao
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supporting information
p. 9934 - 9937
(2015/10/12)
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- Metal-free C-N cross-coupling of electrophilic compounds and N-haloimides
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When DBU is added, the cross-coupling reaction between alkyl halides (halogen = Cl, Br and I) and N-haloimides (halogen = Cl, Br) occurs, resulting in the formation of aminated products. A halogen bond activated nucleophilic substitution mechanism was proposed. The methodology represents an elegant example of applying the halogen bond activation strategy in an organic transformation.
- Zhang, Luyan,Li, Yanru,Jin, Long-Yi,Liang, Fushun
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p. 65600 - 65603
(2015/08/18)
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- Palladium-catalyzed cycloaminocarbonylation of 2-aminomethyl- and 2-alkylcarbamoylaryl tosylates with CO
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The palladium-catalyzed cycloaminocarbonylation of 2-(aminomethyl)aryl tosylates with CO has been established, by which a variety of salicylaldehyde derived 2-(aminomethyl)aryl tosylates may be cyclocarbonylated in the presence of CO, to afford the corresponding substituted isoindolinones in moderate to excellent yields. Furthermore, the method is also effective for the synthesis of isoindoline-1,3-diones and 2-alkyl-1H-benzo[e]isoindol-3(2H)-ones from 2-(N-alkylcarbamoyl)aryl tosylates and 1-(aminomethyl)naphthalene-2-yl tosylates, respectively.
- Liu, Bin,Wang, Yan,Liao, Benren,Zhang, Chunlei,Zhou, Xigeng
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p. 5776 - 5780
(2015/09/29)
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- Zinc-catalyzed selective reduction of cyclic imides with hydrosilanes: Synthesis of ω-hydroxylactams
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Cyclic imides were selectively reduced to the corresponding ω-hydroxylactams in high yields with (EtO)3SiH (triethoxysilane) or PMHS (polymethylhydrosiloxane) under catalysis of zinc diacetate dehydrate [Zn(OAc)2 2H2O] (10%) and tetramethylethylenediamine (TMEDA) (10%). This catalytic protocol showed good functional group tolerance as well as excellent regioselectivity for unsymmetrical imides bearing coordinating groups adjacent to the carbonyl.
- Ding, Guangni,Lu, Bin,Li, Yuyuan,Wan, Jun,Zhang, Zhaoguo,Xie, Xiaomin
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p. 1013 - 1021
(2015/03/30)
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- Photochemical generation of superbases from carboxylates consisting of phthalimidoacetic acid derivatives and superbases
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We have developed simple and powerful photobase generators capable of highly efficient production of superbases. These photobase generators were prepared by simply mixing phthalimidoacetic acid derivatives with the corresponding superbases. The use of photobase generators enabled anionic UV curing at lower temperatures, in contrast to previous anionic UV curing materials that required heat treatment above 150 °C after UV irradiation. The cured films showed no volume shrinkage.
- Arimitsu, Koji,Fukuda, Ken,Sakai, Nobuhiko
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p. 831 - 833
(2014/06/23)
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- Copper-catalyzed intermolecular amidation and imidation of unactivated alkanes
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We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C-H bonds over tertiary C-H bonds and even occur at primary C-H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO) 2 at 100 C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C-H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C-H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product.
- Tran, Ba L.,Li, Bijie,Driess, Matthias,Hartwig, John F.
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supporting information
p. 2555 - 2563
(2014/03/21)
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- Radical cyclization and 1,5-hydrogen transfer in selected aromatic diazonium salts
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2-(Methyl-(3-methyl-1-phenyl-1H-pyrazol-5-yl)carbamoyl)thiophene- 3-diazonium hydrogen sulfate 20, 2-(methyl-(3-methylisoxazol-5-yl)carbamoyl)- benzenediazonium hydrogen sulfate 21 and 2-(methyl(phenyl)carbamoyl)- benzenediazonium hydrogen sulphate 22 were synthesized and reacted with a CuSO4/NaCl/ascorbic acid combination to give complex mixtures. The structures of the reaction products were elucidated, depending upon the pathways followed. Compound 20 almost exclusively afforded an Ar-5 cyclization product and trace amounts of the product derived from a competing Ar-6 Pschorr closure. In the case of compound 21, the Ar-6 cyclization was not observed, while the Ar-5 cyclization and 1,5-hydrogen radical transfer processes equally occurred. Finally, the Ar-6 cyclization was observed as the main process for compound 22, accompanied by the Ar-5 cyclization and, in a much lesser extent, by an 1,5-hydrogen radical transfer process.
- Maggio, Benedetta,Fontana, Gianfranco,Raffa, Demetrio,Ferrante, Francesco,Daidone, Giuseppe
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- Immobilized palladium metal containing ionic liquid catalyzed one step synthesis of isoindole-1,3-diones by carbonylative cyclization reaction
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Immobilized palladium metal containing ionic liquid (ImmPd-IL) catalyzed carbonylative cyclization reaction of 2-iodobenzoic acid and primary amine provided N-substituted isoindole-1,3-dione derivatives in good to excellent yield. The influence of various reaction parameters including the effect of base, solvent, temperature, time and CO pressure on carbonylative cyclization reaction using ImmPd-IL catalyst was investigated. Using optimized reaction parameters different aromatic, aliphatic and heterocyclic N-substituted isoindole-1,3-dione derivatives were synthesized from corresponding aryl amines. The developed protocol is heterogeneous, phosphine free and requires attainable reaction conditions like atmospheric CO pressure and lesser reaction time. The scope of the developed protocol was also extended for the synthesis of N-substituted isoindole-1,3-diones from methyl-2-iodobenoate and 1,2-diiodo benzene. The ImmPd-IL catalyst was recyclable up to four consecutive cycles and recycled catalyst was characterized by XPS analysis.
- Khedkar, Mayur V.,Shinde, Ajinkya R.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
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- Reductive coupling of phthalimides with ketones and aldehydes by low-valent titanium: One-pot synthesis of alkylideneisoindolin-1-ones
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The reductive coupling of phthalimides with ketones and aldehydes by Zn-TiCl4 in THF gave two- and four-electron reduced products, 3-hydroxy-3-(1-hydroxyalkyl)isoindolin-1-ones and alkylideneisoindolin-1-ones, selectively by controlling the rea
- Kise, Naoki,Kawano, Yusuke,Sakurai, Toshihiko
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p. 12453 - 12459
(2014/01/17)
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- Reactivity of ortho-palladated benzamides toward CO, isocyanides, and alkynes. synthesis of functionalized isoindolin-1-ones and 4,5-disubstituted benzo[ c ]azepine-1,3-diones
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Aryl palladium complexes [Pd{C6H4C(O)NRR′-2} I(tmeda)] [NRR′ = NH2 (1a), NHMe (1b), NMe2 (1c); tmeda = N,N,N′,N′-tetramethylethylenediamine] are prepared by oxidative addition of the corresponding 2-iodophenylbenzamides to "Pd(dba)2" ([Pd2(dba)3]·dba; dba = dibenzylideneacetone) in the presence of tmeda. Cationic cyclometalated derivatives [Pd{κ2C,O-C6H4C(O)NRR′- 2}(tmeda)]TfO (2a-c) are obtained by iodide abstraction from the appropriate complex 1 with AgTfO, while the deprotonation of the amide function of 1a or 1b with KOtBu gives the neutral amidate complexes [Pd{κ 2C,N-C6H4C(O)NR-2}(tmeda)] [R = H (3a), Me (3b)]. Complexes 2a,b and 3a,b react with CO under mild conditions to yield phthalimide (4a) or N-methylphthalimide (4b), whereas the reactions of derivatives 1c and 2c with CO are very slow and give N1,N 1,N2,N2-tetramethylphthalamide and phthalic anhydride. The reaction of 1b with 1 equiv of XyNC (Xy = 2,6-dimethylphenyl) or tBuNC affords Pd(0), (tmedaH)I, and 3-(2,6-dimethylphenylimino)-2- methylisoindolin-1-one (5b) or 3-(tert-butylimino)-2-methylisoindolin-1-one (5b′), respectively, while complex 1c reacts with 3 equiv of XyNC to give trans-[Pd{C(i=NXy)C6H4C(O)NMe2-2}I(CNXy) 2] (6). The seven-membered palladacycles [Pd{κ2C,O- C(X)i=C(X′)C6H4C(O)NRR′-2}(tmeda)]TfO [NRR′ = NH2 and X = Ph, X′ = Me (7a); NRR′ = NHMe and X = Ph, X′ = Me (7b), X = X′ = Ph (8b), Et (9b), CO 2Me (10b), X = CO2Me, X′ = Ph (11b), X = CO 2Et, X′ = Ph (12b); NRR′ = NMe2 and X = X′ = Ph (8c), Et (9c)] are obtained from the reactions of 2a-c with alkynes. Treatment of complexes 7a, 7b, 8b, and 9b with CO at room temperature gives the corresponding 2H-benzo[c]azepine-1,3-diones (14), resulting from the insertion of a molecule of CO into the Pd-C bond followed by a C-N reductive coupling. In contrast, the reactions of 11b or 12b with CO in the presence of residual water or 2 equiv of ROH (R = Me, Et) lead to 2-methyl-3- phenylisoindolin-1-one derivatives (15), resulting from a CO insertion followed by an intramolecular aza-Michael addition of the NHMe moiety to the activated vinyl group and subsequent hydrolysis or alcoholysis of the acyl-Pd bond. The neutral complex [Pd(κ2C,O-C14H13O 5)(tmeda)] (18) was synthesized by reacting the cationic derivative 10b with NaOMe in MeOH. Depalladation of 18 gives (E)-4- [methoxy(methoxycarbonyl)methylene]-2-methylisoquinoline-1,3(2H,4H)-dione (19).
- Frutos-Pedreno, Roberto,Gonzalez-Herrero, Pablo,Vicente, Jose,Jones, Peter G.
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p. 4664 - 4676
(2013/09/23)
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- Selective C=O reduction in phthalimide with nickel(0) compounds
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The catalytic reduction of phthalimide was achieved using nickel catalysts. The use of catalytic amounts (20% mol) of [Ni(COD)2] or [(dippe)Ni(μ-H)]2 (1) allowed the monoreduction of phthalimide to yield isoindolinone and benzamide, at 140-180 C and 750 psi of H2. When the N-H moiety of phthalimide was protected with a trimethylsilyl group, both C=O groups were reduced to yield (trimethylsilyl)isoindoline. However, when a methyl moiety was used as the protecting group, the C=O groups and the aromatic ring were reduced, using rather similar reaction conditions, due to the formation of 5 A (average) nickel nanoparticles.
- Arevalo, Alma,Ovando-Segovia, Sebastian,Flores-Alamo, Marcos,Garcia, Juventino J.
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p. 2939 - 2943
(2013/06/27)
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- Imidazole-promoted synthesis of n-substituted phthalimide from N,N'-disubstituted ureas in solventless conditions
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A series of N-substituted phthalimides was synthesized by a thermal reaction between N,N0-disubstituted ureas and phthalic acid catalyzed by imidazole in solventless conditions. The products have been obtained in moderate to good yields (53-92%). Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications1 to view the free supplemental file. Copyright Taylor & Francis Group, LLC.
- Neves Filho, Ricardo A. W.,Palm-Forster, Mieder A. T.,De Oliveira, Ronaldo N.
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supporting information
p. 1571 - 1576
(2013/05/22)
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- A concise synthesis of 3-(1-alkenyl)isoindolin-1-ones and 5-(1-alkenyl)pyrrol-2-ones by the intermolecular coupling reactions of N-acyliminium ions with unactivated olefins
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A concise synthesis of 3-(1-alkenyl)isoindolin-1-ones and 5-(1-alkenyl)pyrrol-2-ones has been achieved by the coupling reactions of N-acyliminium ions produced from 3-hydroxyisoindol-1-ones or 5-hydroxy-1-pyrrol-2-ones with unactivated olefins in the presence of BF 3·OEt2 at room temperature. For most of the olefins,the reactions afforded the Csp3-Csp2 cross-coupling products,but for the α-methylstyrene and 1-hexene,the Csp3-Csp3 cross-coupling products were obtained.
- Lu, Nianhong,Wang, Lihong,Li, Zhanshan,Zhang, Wei
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supporting information; experimental part
p. 192 - 200
(2012/04/10)
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- Aminomethylation of Michael acceptors: Complementary radical and polar approaches mediated by dialkylzincs
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Phtalimidomethyl iodide and substituted maleimidomethyl iodide were used as radical precursors in dialkylzinc-mediated radical addition to diethyl fumarate. The reactions led stereoselectively to functionalized pyrrolizidines. The radical mechanism was supported by spin-trapping experiments and rationalized by theoretical calculations. Radical additions, on the one hand, and carbozincation followed by transmetalation with copper(I), on the other, were shown to be complementary methods to achieve the formal aminomethylation of activated unsaturated compounds. Copyright
- Maury, Julien,Mouysset, Dominique,Feray, Laurence,Marque, Sylvain R. A.,Siri, Didier,Bertrand, Michele P.
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p. 3241 - 3247
(2012/05/20)
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- N-methylation of NH-containing heterocycles with dimethyl carbonate catalyzed by TMEDA
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A practical method for N-methylation of NH-containing heterocycles using an environmentally safe and less toxic methylating reagent, dimethyl carbonate, has been developed. N,N,N',N'-tetramethylethylenediamine (TMEDA), an extremely active organocatalyst for the methylation of imides, indoles, benzimidazoles, and piperazines in conjunction with dimethyl carbonate, can lead to N-methylation products with high conversion. The reaction sequence consists of competing alkylation and acylation pathways and involves TMEDA as a nucleophilic catalyst. A possible reaction mechanism is discussed based on the reaction results.
- Zhao, Sheng-Yin,Zhang, Hai-Quan,Zhang, Deng-Qing,Shao, Zhi-Yu
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experimental part
p. 128 - 135
(2011/11/01)
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- Microphotochemistry: 4,4′-dimethoxybenzophenone mediated photodecarboxylation reactions involving phthalimides
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A series of 4,4'-dimethoxybenzophenone mediated intra- and intermolecular photodecarboxylation reactions involving phthalimides have been examined under microflow conditions. Conversion rates, isolated yields and chemoselectivities were compared to analogous reactions in a batch photoreactor. In all cases investigated, the microreactions gave superior results thus proving the superiority of microphotochemistry over conventional technologies.
- Shvydkiv, Oksana,Nolan, Kieran,Oelgemoeller, Michael
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supporting information; experimental part
p. 1055 - 1063
(2011/10/04)
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- Rhodium(iii)-catalyzed oxidative carbonylation of benzamides with carbon monoxide
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An efficient strategy for the oxidative carbonylation of aromatic amides via C-H/N-H activation to form phthalimides using an Rh(iii) catalyst has been developed. The reaction shows a preference for C-H bonds of electron-rich aromatic amides and tolerates a variety of functional groups. The Royal Society of Chemistry 2011.
- Du, Ya,Hyster, Todd K.,Rovis, Tomislav
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p. 12074 - 12076
(2011/12/14)
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- Zirconyl chloride: An efficient, water-tolerant, and reusable catalyst for the synthesis of N-methylamides
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ZrOCl28H2O is a highly effective, water-tolerant, and reusable catalyst for the direct condensation of carboxylic acids and N,N-dimethylurea under microwave irradiation to give the corresponding N-methylamides in moderate to excellent yields. Notably, ZrOCl 28H2O is a potentially useful green catalyst due to its low toxicity, easy availability, low cost, ease of handling, easy recovery, good activity, and reusability. Georg Thieme Verlag Stuttgart ? New York.
- Talukdar, Dhrubajyoti,Saikia, Lakhinath,Thakur, Ashim Jyoti
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experimental part
p. 1597 - 1601
(2011/08/06)
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- ANTIBACTERIAL AMINOGLYCOSIDE ANALOGS
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Compounds having antibacterial activity are disclosed. The compounds have the following structure (I): (Formula (I)), including stereoisomers, pharmaceutically acceptable salts and prodrugs thereof, wherein Q1, Q2, R1, R2, R3, Z1 and Z2 are as defined herein. Methods associated with preparation and use of such compounds, as well as pharmaceutical compositions comprising such compounds, are also disclosed.
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Page/Page column 95; 98
(2011/04/26)
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- Novel anilinophthalimide derivatives as potential probes for β-amyloid plaque in the brain
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A group of novel 4,5-dianilinophthalimide derivatives has been synthesized in this study for potential use as β-amyloid (Aβ) plaque probes. Staining of hippocampus tissue sections from Alzheimer's disease (AD) brain with the representative compound 9 indicated selective labeling of it to Aβ plaques. The binding affinity of radioiodinated [125I]9 for AD brain homogenates was 0.21 nM (Kd), and of other derivatives ranged from 0.9 to 19.7 nM, except for N-methyl-4,5-dianilinophthalimide (Ki > 1000 nM). [125I]9 possessed the optimal lipophilicity with Log P value of 2.16, and its in vivo biodistribution in normal mice exhibited excellent initial brain uptake (5.16% ID/g at 2 min after injection) and a fast washout rate (0.56% ID/g at 60 min). The encouraging results suggest that this novel derivative of [123I]9 may have potential as an in vivo SPECT probe for detecting amyloid plaques in the brain.
- Duan, Xin-Hong,Qiao, Jin-Ping,Yang, Yang,Cui, Meng-Chao,Zhou, Jiang-Ning,Liu, Bo-Li
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experimental part
p. 1337 - 1343
(2010/04/26)
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- Desymmetrization of meso-cyclic imides via enantioselective monohydrogenation
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meso-Cyclic imides are monohydrogenated to form the corresponding hydroxy lactams in 88-97% ee using trans-[Ru((R)-BINAP)(H)2((R,R)-dpen)] and related compounds as catalysts with base in THF. The hydrogenation proceeds with high enantiogroup-and chemoselectivity, and it is a desymmetrization reaction, forming up to five stereogenic centers in one reaction. Conversion of a hydroxy lactam into the corresponding iminium ion followed by addition of indene extended the number of stereogenic centers from 5 to 7.
- Takebayashi, Satoshi,John, Jeremy M.,Bergens, Steven H.
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supporting information; experimental part
p. 12832 - 12834
(2010/11/03)
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- Efficient synthesis routes for various phthalimido phosphor esters as antimicrobial agents in terms of structure-activity relationship
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A series of phthalimido phosphor derivatives α-amino-phosphonates, amidophosphonates, phosphonic acid diamides, and oxadiazaphospholes-were prepared by applying different types of phosphorus(III) reagents to 2-methoxy-1H-isoindole-1,3(2H)-dione and 2-anilino-1H-isoindole-1,3(2H)-dione. On the basis of bioassay results, some of the new phosphoryl imides could be considered as lead molecules to be modified in order to improve their antibiotic activity. Springer-Verlag 2010.
- Abdou, Wafaa Mahmoud,Khidre, Rizk E.
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experimental part
p. 219 - 228
(2010/08/05)
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- From conventional to microphotochemistry: Photodecarboxylation reactions involving phthalimides
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A series of acetone-sensitized photodecarboxylation reactions involving phthalimides have been investigated using conventional and microphotochemistry. Both, intra- and intermolecular transformations were compared. In all cases examined, the reactions performed in microreactors were superior in terms of conversions or isolated yields. These findings unambiguously prove the advantage of microphotochemistry over conventional photochemical techniques.
- Shvydkiv, Oksana,Gallagher, Sonia,Nolan, Kieran,Oelgemoeller, Michael
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supporting information; experimental part
p. 5170 - 5173
(2011/02/25)
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- Crucial role of selenium in the virucidal activity of benzisoselenazol- 3(2h)-ones and related diselenides
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Various N-substituted benzisoselenazol-3(2H)-ones and their non-seleniumcontaining analogues have been synthesized and tested against selected viruses (HHV-1, EMCV and VSV) to determine the extent to which selenium plays a role in antiviral activity. The data presented here show that the presence of selenium is crucial for the antiviral properties of benzisoselenazol-3(2H)-ones since their isostructural analogues having different groups but lacking selenium either did not show any antiviral activity or their activity was substantially lower. The open-chain analogues of benzisoselenazol- 3(2H)-ones-diselenides also exhibited high antiviral activity while selenides and disulfides were completely inactive towards model viruses.
- Pietka-Ottlik, Magdalena,Potaczek, Piotr,Piasecki, Egbert,Mlochowski, Jacek
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experimental part
p. 8214 - 8228
(2011/03/19)
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- A convergent, modular access to complex amines
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Various xanthates can be added to N-vinyl phthalimide with little formation of oligomers, if the xanthate is used in excess and the medium slightly diluted. The adduct xanthates thus obtained can in turn undergo radical additions to numerous olefins, providing a convergent and modular access to densely functionalized amines.
- Quiclet-Sire, Béatrice,Revol, Guillaume,Zard, Samir Z.
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experimental part
p. 6656 - 6666
(2010/10/19)
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- Enaminones in heterocyclic synthesis: A novel route to tetrahydropyrimidines, dihydropyridines, triacylbenzenes and naphthofurans under microwave irradiation
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Condensation of phthalimidoacetone (1) with DMFDMA (N,NDimethylformamide dimethyl acetal) has afforded enaminone 2. Refluxing 2 with equimolecular amounts of benzaldehyde and urea in acetic acid afforded a mixture of tetrahydropyrimidine 5 and the dihydropyridine 6. Compound 2 undergoes selfcondensation on heating in acetic acid or under microwave irradiation in presence of acidic zeolite to give 1,3,5-triacylbenzene 9. Reacting enaminone 11a with naphthoquinone 15 afforded the naphthofuran 18. The possible formation of the aldehyde 19 was excluded based on an HMQC experiment, which revealed that the carbonyl carbon is not linked to any hydrogen.
- Al-Mousawi, Saleh Mohammed,El-Apasery, Morsy Ahmed,Elnagdi, Mohamed H.
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experimental part
p. 58 - 67
(2010/05/18)
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