- Mechanochemical Grignard Reactions with Gaseous CO2 and Sodium Methyl Carbonate**
-
A one-pot, three-step protocol for the preparation of Grignard reagents from organobromides in a ball mill and their subsequent reactions with gaseous carbon dioxide (CO2) or sodium methyl carbonate providing aryl and alkyl carboxylic acids in up to 82 % yield is reported. Noteworthy are the short reaction times and the significantly reduced solvent amounts [2.0 equiv. for liquid assisted grinding (LAG) conditions]. Unexpectedly, aryl bromides with methoxy substituents lead to symmetric ketones as major products.
- Pfennig, Victoria S.,Villella, Romina C.,Nikodemus, Julia,Bolm, Carsten
-
supporting information
(2022/01/22)
-
- Cleavage of Carboxylic Esters by Aluminum and Iodine
-
A one-pot procedure for deprotecting carboxylic esters under nonhydrolytic conditions is described. Typical alkyl carboxylates are readily deblocked to the carboxylic acids by the action of aluminum powder and iodine in anhydrous acetonitrile. Cleavage of lactones affords the corresponding ω-iodoalkylcarboxylic acids. Aryl acetylates undergo deacetylation with the participation of the neighboring group. This method enables the selective cleavage of alkyl carboxylic esters in the presence of aryl esters.
- Sang, Dayong,Yue, Huaxin,Fu, Yang,Tian, Juan
-
p. 4254 - 4261
(2021/03/09)
-
- Acetyl nitrate mediated conversion of methyl ketones to diverse carboxylic acid derivatives
-
The development of a novel acetyl nitrate mediated oxidative conversion of methyl ketones to carboxylic acid derivatives is described. By analogy to the haloform reaction and supported by experimental and computational investigation we propose a mechanism for this transformation.
- Bernard, Josephine,Capilato, Joseph N.,Hoy, Erik P.,Mattiucci, Joseph,Pellegrinelli, Peter J.,Perez, Lark J.,Philippi, Shane,Schnorbus, Logan
-
p. 5298 - 5302
(2021/06/30)
-
- Suppressing carboxylate nucleophilicity with inorganic salts enables selective electrocarboxylation without sacrificial anodes
-
Although electrocarboxylation reactions use CO2as a renewable synthon and can incorporate renewable electricity as a driving force, the overall sustainability and practicality of this process is limited by the use of sacrificial anodes such as magnesium and aluminum. Replacing these anodes for the carboxylation of organic halides is not trivial because the cations produced from their oxidation inhibit a variety of undesired nucleophilic reactions that form esters, carbonates, and alcohols. Herein, a strategy to maintain selectivity without a sacrificial anode is developed by adding a salt with an inorganic cation that blocks nucleophilic reactions. Using anhydrous MgBr2as a low-cost, soluble source of Mg2+cations, carboxylation of a variety of aliphatic, benzylic, and aromatic halides was achieved with moderate to good (34-78%) yields without a sacrificial anode. Moreover, the yields from the sacrificial-anode-free process were often comparable or better than those from a traditional sacrificial-anode process. Examining a wide variety of substrates shows a correlation between known nucleophilic susceptibilities of carbon-halide bonds and selectivity loss in the absence of a Mg2+source. The carboxylate anion product was also discovered to mitigate cathodic passivation by insoluble carbonates produced as byproducts from concomitant CO2reduction to CO, although this protection can eventually become insufficient when sacrificial anodes are used. These results are a key step toward sustainable and practical carboxylation by providing an electrolyte design guideline to obviate the need for sacrificial anodes.
- Corbin, Nathan,Lazouski, Nikifar,Manthiram, Karthish,Steinberg, Katherine,Yang, Deng-Tao
-
p. 12365 - 12376
(2021/10/08)
-
- Photochemical Control of the Mechanical and Adhesive Properties of Crystalline Molecular Solids
-
This paper describes a systematic investigation of the mechanical and adhesive properties of four novel photoresponsive crystalline molecular solids. Each molecular solid comprises a benzyl, naphthyl, or adamantyl scaffold modified with a nitrobenzyl photolabile protecting group. Mechanical and adhesive testing, which recorded shear strengths in the range of 50-150 kPa, provide a direct measurement of the strength of the interfacial intermolecular interactions present within these materials. These interactions were visualized and rationalized using X-ray diffraction techniques and light microscopy. Disruption of interfacial interactions is facilitated by light-induced deprotection of the nitrobenzyl group. Depending on the strategic selection of adhesive, UV irradiation may result in up to a 4-fold increase or in a complete elimination in the observed adhesive strength. The change in adhesion exhibited by each material is determined, in part, by the extent of the solid-state photoconversion, which ranges from 5% to 26%, as well as the relative strength of the interfacial interactions present before and after irradiation. This research demonstrates the ability to tailor the emergent macroscopic mechanical properties of crystalline materials through strategic molecular design.
- Blelloch, Nicholas D.,Mitchell, Haydn T.,Greenburg, Louisa C.,Van Citters, Douglas W.,Mirica, Katherine A.
-
p. 6143 - 6154
(2021/11/01)
-
- An Anionic, Chelating C(sp3)/NHC ligand from the Combination of an N-heterobicyclic Carbene and Barbituric Heterocycle
-
The coordination chemistry of the anionic NHC1-based on an imidazo[1,5-a]pyridin-3-ylidene (IPy) platform substituted at the C5 position by an anionic barbituric heterocycle was studied with d6(Ru(II), Mn(I)) and d8(Pd(II), Rh(I), Ir(I), Au(III)) transition-metal centers. While the anionic barbituric heterocycle is planar in the zwitterionic NHC precursor 1·H, NMR spectroscopic analyses supplemented by X-ray diffraction studies evidenced the chelating behavior of ligand 1-through the carbenic and the malonic carbon atoms in all of the complexes, resulting from a deformation of the lateral barbituric heterocycle. The complexes were obtained by reaction of the free carbene with the appropriate metal precursor, except for the Au(III) complex 10, which was obtained by oxidation of the antecedent gold(I) complex [AuCl(1)]?with PhICl2as an external oxidant. During the course of the process, the kinetic gold(I) intermediate 9 resulting from the oxidation of the malonic carbon of the barbituric moiety was isolated upon crystallization from the reaction mixture. The νCOstretching frequencies recorded for complex [Rh(1)(CO)2] (5) demonstrated the strong donating character of the malonate-C(sp3)/NHC ligand 1-. The ruthenium complex [Ru(1)Cl(p-cymene)] (11) was implemented as a precatalyst in the dehydrogenative synthesis of carboxylic acid derivatives from primary alcohols and exhibited high activities at low catalyst loadings (25-250 ppm) and a large tolerance toward functional groups.
- Benaissa, Idir,Gajda, Katarzyna,Vendier, Laure,Lugan, No?l,Kajetanowicz, Anna,Grela, Karol,Michelet, Véronique,César, Vincent,Bastin, Stéphanie
-
supporting information
p. 3223 - 3234
(2021/09/30)
-
- Hydrolysis of amides to carboxylic acids catalyzed by Nb2O5
-
Hydrolysis of amides to carboxylic acids is an industrially important reaction but is challenging due to the difficulty of cleaving the resonance stabilized amidic C-N bond. Twenty-three heterogeneous and homogenous catalysts were examined in the hydrolysis of acetamide. Results showed that Nb2O5was the most effective heterogeneous catalyst with the greatest yield of acetic acid. A series of Nb2O5catalysts calcined at various temperatures were characterized and tested in the hydrolysis of acetamide to determine the effects of crystal phase and surface properties of Nb2O5on catalytic performance. The high catalytic performance observed was attributed mainly to the facile activation of the carbonyl bond by Lewis acid sites that function even in the presence of basic inhibitors (NH3and H2O). The catalytic studies showed the synthetic advantages of the present method, such as simple operation, catalyst recyclability, additive free, solvent free, and wide substrate scope (>40 examples; up to 95% isolated yield).
- Siddiki,Rashed, Md. Nurnobi,Touchy, Abeda Sultana,Jamil, Md. A. R.,Jing, Yuan,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-Ichi
-
p. 1949 - 1960
(2021/03/26)
-
- Oxidation of Primary Alcohols and Aldehydes to Carboxylic Acids via Hydrogen Atom Transfer
-
The oxidation of primary alcohols and aldehydes to the corresponding carboxylic acids is a fundamental reaction in organic synthesis. In this paper, we report a new chemoselective process for the oxidation of primary alcohols and aldehydes. This metal-free reaction features a new oxidant, an easy to handle procedure, high isolated yields, and good to excellent functional group tolerance even in the presence of vulnerable secondary alcohols and tert-butanesulfinamides.
- Tan, Wen-Yun,Lu, Yi,Zhao, Jing-Feng,Chen, Wen,Zhang, Hongbin
-
supporting information
p. 6648 - 6653
(2021/09/08)
-
- ADAMANTANYL-SUBSTITUTED BENZAMIDE COMPOUNDS AND THEIR USE AS P2X7 RECEPTOR ANTAGONISTS
-
The present invention relates to adamantanyl-substituted benzamide compounds and their use as antagonists of the P2X7 purinoreceptor. The invention further relates to methods for the treatment of disease and conditions associated with the P2X7 purinoreceptor.
- -
-
Page/Page column 20-22
(2020/03/15)
-
- A recyclable, metal-free mechanochemical approach for the oxidation of alcohols to carboxylic acids
-
The oxidation of primary alcohols under mechanochemical conditions in a Spex8000M Mixer/Mill was investigated. To facilitate ease of separation and recyclability, a polystyrene-bound version of a TEMPO catalyst was employed. When paired with Oxone in a stainless-steel vial with a stainless-steel ball, several primary alcohols were successfully oxidized to the corresponding carboxylic acids. The product was isolated using gravity filtration, which also allowed for the polystyrene-bound TEMPO catalyst to be recovered and reused in subsequent oxidation reactions. Furthermore, it was demonstrated that the size and steric hindrance of the primary alcohol does not hinder the rate of the reaction. Finally, the aldehyde was selectively obtained from a primary alcohol under ball milling conditions by using a combination of non-supported TEMPO with a copper vial and copper ball.
- Carr, Preston,Denlinger, Kendra Leahy,Mack, James,Waddell, Daniel C.
-
-
- Preparation method of rimantadine hydrochloride preparation
-
The invention discloses a preparation method of a rimantadine hydrochloride preparation. The preparation method comprises the following steps: preparation of 1-bromoadamantane, preparation of amantadecanoic acid, preparation of adamantanecarbonyl chloride, preparation of adamantyl methy ketone, preparation of 1-amantadine methyl ketone oxime, preparation of rimantadine hydrochloride, and preparation of the rimantadine hydrochloride preparation. The preparation of adamantyl methy ketone comprises the following steps: adding (CH3)3Sb and nickelous formate into a flask; dropwise adding an acetonitrile solution of adamantanecarbonyl chloride, wherein adamantanecarbonyl chloride reacts with (CH3)3Sb to generate adamantyl methy ketone; after reaction, pouring a reaction liquid into ice water; and filtering and drying the mixture to obtain a light yellow precipitate, thereby obtaining the adamantyl methy ketone. The preparation method has the beneficial effects that the preparation method ofrimantadine hydrochloride preparation is good in environmental protection, mild in condition of a synthetic method, simple and feasible in process and high in product yield.
- -
-
-
- Synthesizing method of rimantadine hydrochloride
-
The invention discloses a synthesizing method of rimantadine hydrochloride. The synthesizing method comprises the following steps of preparing of 1-bromoadamantane, preparing of adamantane carboxylicacid, preparing of adamantanecarbonyl chloride, preparing of adamantyl methyl ketone, preparing of 1-amantadine methyl ketone oxime, preparing of rimantadine hydrochloride, and preparing of a rimantadine hydrochloride preparation; in the preparing process of adamantyl methyl ketone: adding trimethylaluminum and cerium formate into a flask, then dripping a benzene solution of adamantanecarbonyl chloride, and enabling the adamantanecarbonyl chloride and the trimethylaluminum to react and generate adamantyl methyl ketone; after reaction is finished, pouring a reaction solution into ice water, filtering and drying, so as to obtain a light yellow precipitate, namely the adamantyl methyl ketone. The synthesizing method has the beneficial effects that the conditions are mild, and the technology is simple and feasible; the usage amount of catalyst is small, the environment-friendly effect is realized, and the yield of product is high.
- -
-
-
- Novel rimantadine analog and synthetic method thereof
-
The invention provides a novel rimantadine analog. The novel rimantadine analog has a structure shown in formula (I). The rimantadine analog has high activity and is more beneficial to clinical use and further development and research of drugs.
- -
-
-
- A kind of anti-influenza virus preparation
-
The present invention discloses an anti-influenza virus preparation, including 1 - bromo adamantane preparation, adamantane formic acid preparation, adamantane chloride preparation, adamantane methyl preparation, 1 - adamantane methyl oxime preparation, hydrochloric acid rimantadine preparation, anti-influenza virus preparation, wherein the adamantane methyl preparation steps are as follows: in the flask to join the three trimethylaluminum, formic acid cerium, then dropwise adamantane formyl chloride [...], the adamantane chloride with three methyl aluminum reaction generating adamantane methyl ketone, after the reaction is completed in the reaction liquid into ice water, then filtering, drying, the resulting pale yellow precipitate adamantane methyl ketone. The beneficial effects: preparation method of this invention mild condition, the process is simple and feasible, high product yield, the system anti- influenza virus preparation can be effective prevention and treatment of type a/b influenza virus infection, also can effectively alleviate the symptoms of the common cold.
- -
-
-
- Preparation method of 1-adamantyl methy ketone
-
The invention belongs to the field of preparation of chemical intermediates, and particularly relates to a preparation method of 1-adamantyl methy ketone. The preparation method comprises the following steps of step 1, enabling adamantane and liquid bromine to react, so as to obtain 1-bromoadamantane; step 2, using concentrated sulfuric acid as a catalyst, adding the 1-bromoadamantane and n-hexane, and dripping formic acid, so as to obtain 1-adamantanecarboxylic acid; step 3, enabling the 1-adamantanecarboxylic acid and thionyl chloride to react, heating and refluxing, extracting by benzene, and directly applying the extracting liquid for the reaction in next step; step 4, dripping a mixed solution of benzene, diethyl malonate and anhydrous ethyl alcohol into a mixed solution of magnesiumpowder, iodine, anhydrous ethyl alcohol and benzene, dripping a benzene solution of 1-adamantanecarbonyl chloride, extracting by benzene, drying and distilling, so as to obtain 2- adamantanecarbonyl diethyl malonate; step 5, adding glacial acetic acid, water and concentrated sulfuric acid into the residue. The preparation method has the advantage that the yield rate is high.
- -
-
-
- Dehydrogenation of Alcohols to Carboxylic Acid Catalyzed by in Situ-Generated Facial Ruthenium- CPP Complex
-
A selective catalytic system for the dehydrogenation of primary alcohols to carboxylic acids using a facial ruthenium complex generated in situ from the [Ru(COD)Cl2]n and a hybrid N-heterocyclic carbene (NHC)-phosphine-phosphine ligand (CPP) has been first reported. The facial coordination model was unveiled by NMR analysis of the reaction mixture. Such a fac-ruthenium catalyst system exhibited high catalytic activity and stability, and a high turnover number of 20 000 could be achieved with catalyst loading as low as 0.002 mol %. The exceedingly high catalyst stability was tentatively attributed to both the anchoring role of NHC and the hemi-lability of phosphines. The catalytic system also features a wide substrate scope. In particular, the facial coordination of CPP ligands was found to be beneficial for sterically hindered alcohols, and ortho-substituted benzylic alcohols and bulky adamantanyl methanol as well as cholesterol were all found to be viable dehydrogenation substrates.
- Liu, Hui-Min,Jian, Lei,Li, Chao,Zhang, Chun-Chun,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua,Li, Rui-Xiang
-
p. 9151 - 9160
(2019/08/12)
-
- Highly active bidentate N-heterocyclic carbene/ruthenium complexes performing dehydrogenative coupling of alcohols and hydroxides in open air
-
Eight bidentate NHC/Ru complexes, namely [Ru]-1-[Ru]-8, were designed and prepared. In particular, [Ru]-2 displayed extraordinary performance even in open air for the dehydrogenative coupling of alcohols and hydroxides. Notably, an unprecedentedly low catalyst loading of 250 ppm and the highest TON of 32 800 and TOF of 3200 until now were obtained.
- Wang, Zhi-Qin,Tang, Xiao-Sheng,Yang, Zhao-Qi,Yu, Bao-Yi,Wang, Hua-Jing,Sang, Wei,Yuan, Ye,Chen, Cheng,Verpoort, Francis
-
supporting information
p. 8591 - 8594
(2019/07/25)
-
- Iridium catalysts for acceptorless dehydrogenation of alcohols to carboxylic acids: Scope and mechanism
-
We introduce iridium-based conditions for the conversion of primary alcohols to potassium carboxylates (or carboxylic acids) in the presence of potassium hydroxide and either [Ir(2-PyCH2(C4H5N2))(COD)]OTf (1) or [Ir(2-PyCH2PBu2t)(COD)]OTf (2). The method provides both aliphatic and benzylic carboxylates in high yield and with outstanding functional group tolerance. We illustrate the application of this method to a diverse variety of primary alcohols, including those involving heterocycles and even free amines. Complex 2 reacts with alcohols to form the crystallographically characterized catalytic intermediates [IrH(η1,η3-C8H12)(2-PyCH2PtBu2)] (2a) and [Ir2H3(CO)(2-PyCH2PtBu2){μ-(C5H3N)CH2PtBu2}] (2c). The unexpected similarities in reactivities of 1 and 2 in this reaction, along with synthetic studies on several of our iridium intermediates, enable us to form a general proposal of the mechanisms of catalyst activation that govern the disparate reactivities of 1 and 2, respectively, in glycerol and formic acid dehydrogenation. Moreover, careful analysis of the organic intermediates in the oxidation sequence enable new insights into the role of Tishchenko and Cannizzaro reactions in the overall oxidation.
- Cherepakhin, Valeriy,Williams, Travis J.
-
p. 3754 - 3763
(2018/05/23)
-
- Zinc Oxide-Catalyzed Dehydrogenation of Primary Alcohols into Carboxylic Acids
-
Zinc oxide has been developed as a catalyst for the dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The reaction is performed in mesitylene solution in the presence of potassium hydroxide, followed by workup with hydrochloric acid. The transformation can be applied to both benzylic and aliphatic primary alcohols and the catalytically active species was shown to be a homogeneous compound by a hot filtration test. Dialkylzinc and strongly basic zinc salts also catalyze the dehydrogenation with similar results. The mechanism is believed to involve the formation of a zinc alkoxide which degrades into the aldehyde and a zinc hydride. The latter reacts with the alcohol to form hydrogen gas and regenerate the zinc alkoxide. The degradation of a zinc alkoxide into the aldehyde upon heating was confirmed experimentally. The aldehyde can then undergo a Cannizzaro reaction or a Tishchenko reaction, which in the presence of hydroxide leads to the carboxylic acid.
- Monda, Fabrizio,Madsen, Robert
-
supporting information
p. 17832 - 17837
(2018/11/23)
-
- Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO2 by Dual Visible-Light–Nickel Catalysis
-
We report the efficient carboxylation of bromides and triflates with K2CO3 as the source of CO2 in the presence of an organic photocatalyst in combination with a nickel complex under visible light irradiation at room temperature. The reaction is compatible with a variety of functional groups and has been successfully applied to the synthesis and derivatization of biologically active molecules. In particular, the carboxylation of unactivated cyclic alkyl bromides proceeded well with our protocol, thus extending the scope of this transformation. Spectroscopic and spectroelectrochemical investigations indicated the generation of a Ni0 species as a catalytic reactive intermediate.
- Meng, Qing-Yuan,Wang, Shun,K?nig, Burkhard
-
supporting information
p. 13426 - 13430
(2017/10/07)
-
- Oxidative cleavage of hydroxamic acid promoted by sodium periodate
-
A series of hydroxamic acids, involving aliphatic, aromatic and cyclic substrates, were transformed to the corresponding carboxylic acids through NaIO4-mediated oxidative cleavage in mild conditions. Esterification of these acids with TMSCHN2 could result in formation of the corresponding methyl ester. This methodology makes good compensation for the existing methods transforming amides to esters. Our results also pave the way to harness hydroxamic acids as useful synthetic building blocks.
- Yuan, Changchun,Du, Biao,Xun, Miao-Miao,Liu, Bo
-
p. 3622 - 3628
(2017/06/13)
-
- A method for synthesizing diamond ethylamine
-
The invention discloses a synthetic method for rimantadine. The synthetic method is characterized by comprising the following steps: firstly, obtaining 1-bromoadamantane by reacting adamantine with liquid bromine; then, acidifying to obtain adamantanecarboxylic acid after reacting 1-bromoadamantane with magnesium and anhydrous ether; obtaining adamantine carbonyl chloride by performing reflux reaction on tehadamantanecarboxylic acid with thionyl chloride; obtaining adamantane methyl ketone by reacting the adamantine carbonyl chloride with (CH3)2CdCu; and finally, obtaining the rimantadine by hydriding and reacting adamantane methyl ketone with hydrochloric acid and ammonia water in the presence of sodium borohydride. The synthetic method disclosed by the invention is gentle in condition, simple in follow-up processing, high in yield, cheap in raw material and low in synthesis cost.
- -
-
Paragraph 0043; 0044
(2017/03/22)
-
- MANUFACTURING METHOD OF HYDROXY ADAMANTANE CARBOXYLIC ACID COMPOUND
-
PROBLEM TO BE SOLVED: To provide a method for easier manufacturing a hydroxy adamantane carboxylic acid at higher yield. SOLUTION: There is provided a manufacturing method of 3-hydroxy adamantane-1-carboxylic acid represented by the formula (2) including Process 1: adamantanol represented by the formula (1) and carbon monoxide or a carbon monoxide source are mixed in a sulphuric acid solution with concentration of 90 mass% or more and Process 2:nitrate is added to the resulting solution. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
- -
-
Paragraph 0043-0044
(2017/03/28)
-
- Ni-Catalyzed Carboxylation of Unactivated Alkyl Chlorides with CO2
-
A catalytic carboxylation of unactivated primary, secondary, and tertiary alkyl chlorides with CO2 at atmospheric pressure is described. This protocol represents the first intermolecular cross-electrophile coupling of unactivated alkyl chlorides, thus leading to new knowledge in the cross-coupling arena.
- B?rjesson, Marino,Moragas, Toni,Martin, Ruben
-
supporting information
p. 7504 - 7507
(2016/07/06)
-
- DMF-mediated deprotection of bulky silyl esters under neutral and fluoride-free conditions
-
Bulky TBDPS and TIPS carboxylic esters were efficiently cleaved by a green and mild protocol using only DMF-H2O (20:1) at 70 °C. The neutral conditions tolerate various common acid- and base-labile functionalities, including alkyl and aryl silyl ethers.
- Chen, Bo,Sun, Hui-Xia,Qin, Jian-Feng,Wang, Bing
-
p. 253 - 255
(2016/01/12)
-
- KetoABNO/NOx Cocatalytic Aerobic Oxidation of Aldehydes to Carboxylic Acids and Access to α-Chiral Carboxylic Acids via Sequential Asymmetric Hydroformylation/Oxidation
-
A method for aerobic oxidation of aldehydes to carboxylic acids has been developed using organic nitroxyl and NOx cocatalysts. KetoABNO (9-azabicyclo[3.3.1]nonan-3-one N-oxyl) and NaNO2 were identified as the optimal nitroxyl and NOx sources, respectively. The mildness of the reaction conditions enables sequential asymmetric hydroformylation of alkenes/aerobic aldehyde oxidation to access α-chiral carboxylic acids without racemization. The scope, utility, and limitations of the oxidation method are further evaluated with a series of achiral aldehydes bearing diverse functional groups.
- Miles, Kelsey C.,Abrams, M. Leigh,Landis, Clark R.,Stahl, Shannon S.
-
supporting information
p. 3590 - 3593
(2016/08/16)
-
- Process for producing hydroxy adamantane carboxylic acid compounds
-
The present invention can provide a process for producing a hydroxy adamantane carboxylic acid compound represented by the above formula (2), which comprises (i) reacting an adamantane compound represented by the above formula (1) with carbon monoxide or with a carbon monoxide source in a proton acid solution prepared at a concentration of 90% by mass or more to thereby cause carboxylation of the OX group(s), and then (ii) adding an oxidizing agent to the reaction mixture to cause oxidation of the bridgehead C—H bond to thereby generate a hydroxyl group.
- -
-
Page/Page column 7
(2015/06/16)
-
- A manufacturing method of a carboxylic acids and polyadamantane hydroxyacid purification method
-
PROBLEM TO BE SOLVED: To provide an efficient manufacturing method of hydroxy adamantane carboxylic acids that have an adamantane skeleton, and that are the raw materials of a functional resin excellent in an optical characteristic and heat resistance or the like. SOLUTION: The manufacturing method of hydroxy adamantane carboxylic acids comprises as follows. Adamantane diols shown by general formula (1) is made to react with at most two equivalents of a carbon monoxide source based on one equivalent of a hydroxyl group of the adamantane diols in a liquid state protonic acid solvent, and then the crystal of hydroxy adamantane carboxylic acid shown by general formula (2) is filtered to be separated. COPYRIGHT: (C)2013,JPOandINPIT
- -
-
Paragraph 0032; 0033; 0036
(2017/01/02)
-
- Photorelease of incarcerated guests in aqueous solution with phenacyl esters as the trigger
-
We report the clean, efficient photorelease of a series of carboxylic acids embedded in octa acid (OA) host and protected by a p-hydroxyphenacyl cage. A key role is played by the cage by providing hydrophobicity for entry into the OA enclosure and yet readily removable as a photoactivated protecting group for release from the host. The rapid photo-Favorskii rearrangement of the departing chromophore does not react with the host OA but diminishes hydrophobicity of the OA contents, leading to their facile release into the solvent.
- Jagadesan, Pradeepkumar,Da Silva, José P.,Givens, Richard S.,Ramamurthy
-
p. 1276 - 1279
(2015/05/20)
-
- Unexpected dehomologation of primary alcohols to one-carbon shorter carboxylic acids using o-iodoxybenzoic acid (IBX)
-
A novel and efficient transformation of primary alcohols to one-carbon shorter carboxylic acids using IBX is reported. Mechanistic studies revealed that the combination of IBX and molecular iodine produces a different active hypervalent iodine species.
- Xu, Shu,Itto, Kaori,Satoh, Masahide,Arimoto, Hirokazu
-
supporting information
p. 2758 - 2761
(2014/03/21)
-
- 3-(1-Adamantyl)furazans
-
The reactivity of 3-(1-adamantyl)-4-aminofurazan was studied. Upon treatment with oxidizing reagents the amino group is oxidized to azo, azoxy, and nitro groups. The nitration of 3-(1-adamantyl)-4-aminofurazan with nitric acid provided the corresponding n
- Sheremetev,Kozeev,Aleksandrova,Struchkova,Suponitsky
-
p. 1358 - 1369
(2014/01/17)
-
- Release of guests from encapsulated masked hydrophobic precursors by a phototrigger
-
Examples of release of organic acids from encapsulated p-methoxyphenacyl esters provided here demonstrate the value of a phototrigger strategy to release chemicals of interest in water from hydrophobic precursors. In this study, a photochemical β-cleavage process centered on the p-methoxyphenacyl group is exploited to release the acid of interest from a water-soluble capsule made up of octa acid.
- Jayaraj, Nithyanandhan,Jagadesan, Pradeepkumar,Samanta, Shampa R.,Da Silva, Jose P.,Ramamurthy
-
supporting information
p. 4374 - 4377
(2013/09/24)
-
- Phosphorescence of iridium(III) complexes with 2-(2-pyridyl)-1,3,4- oxadiazoles
-
Cationic bis-cyclometalated iridium(III) complexes [(C^N) 2Ir(N^N)](PF6) with 2-(2′-pyridyl)-5-R-1,3,4- oxadiazoles (N^N; R = 1-adamantyl, mesityl, N-diphenylamino) have a redox gap of 2.58-2.68 V and exhibit orange-red phosphorescence in argon-saturated dichloromethane solution with a maximum, quantum yield, and excited-state lifetime of 613-644 nm, 2-6%, and 90-280 ns.
- Shavaleev, Nail M.,Scopelliti, Rosario,Gr?tzel, Michael,Nazeeruddin, Mohammad K.
-
p. 295 - 299
(2013/02/23)
-
- Convenient synthesis of adamantyl-substituted β -lactams via uncatalyzed staudinger reaction
-
A series of C3-position adamantyl-substituted β-lactams were synthesized via uncatalyzed Staudinger reaction between adamantylketene generated by thermal Wolff rearrangement of the corresponding diazo ketone and various imines. The stereochemical outcome of the reaction was mainly the formation of trans-products, a result attributed to a two-step mechanism leading to the most stable products.
- Liu, Mingshun,Chen, Yaqing,Fu, Nanyan
-
p. 1055 - 1062
(2013/02/25)
-
- A new method for the protection of carboxylic acids with a triisopropylsiloxymethyl group
-
An effective method for the protection of carboxylic acids with a triisopropylsiloxymethyl (TIPSOCH2) group is described. The reactions of various carboxylic acids with C12H25SCH 2OTIPS in the presence of CuBrs
- Yoshimura, Hikaru,Eto, Kohei,Takahashi, Keisuke,Ishihara, Jun,Hatakeyama, Susumi
-
p. 1334 - 1339
(2012/11/07)
-
- Koch-Haaf reaction of adamantanols in an acidtolerant hastelloy-made microreactor
-
The Koch-Haaf reaction of adamantanols was successfully carried out in a microflow system at room temperature. By combining an acid-tolerant hastelloy-made micromixer, a PTFE tube, and a hastelloy-made microextraction unit, a packaged reaction-toworkup system was developed. By means of the present system, the multigram scale synthesis of 1-adamantanecarboxylic acid was achieved in ca. one hour operation.
- Fukuyama, Takahide,Mukai, Yu,Ryu, Ilhyong
-
experimental part
p. 1288 - 1293
(2011/10/19)
-
- HISTONE DEACETYLASE INHIBITORS FOR THE TREATMENT OF FUNGAL INFECTIONS
-
Described are bridged compounds of the formula (I), their analogs, tautomeric forms, stereoisomers, geometrical isomers, polymorphs, hydrates, solvates, pharmaceutically acceptable salts, pharmaceutical compositions, metabolites and prodrugs thereof. The invention relates to compositions and methods to treat fungal infection. These compounds are selective HDAC inhibitors that act as inherent antifungal compounds or enhance the activity of other antifungal compounds such as azoles.
- -
-
Page/Page column 21
(2011/06/16)
-
- Metal-free and copper-promoted single-pot hydrocarboxylation of cycloalkanes to carboxylic acids in aqueous medium
-
A simple and effective method for the transformation, under mild conditions and in aqueous medium, of various cycloalkanes (cyclopentane, cyclohexane, methylcyclohexane, cis- and trans-1,2dimethylcyclohexane, cycloheptane, cyclooctane and adamantane) into the corresponding cycloalkanecarboxylic acids bearing one more carbon atom, is achieved. This method is characterized by a singlepot, low-temperature hydrocarboxylation reaction of the cycloalkane with carbon monoxide, water and potassium peroxodisulfate in water/acetonitrile medium, proceeding either in the absence or in the presence of a metal promoter. The influence of various reaction parameters, such as type and amount of metal promoter, solvent composition, temperature, time, carbon monoxide pressure, oxidant and cycloalkane, is investigated, leading to an optimization of the cyclohexane and cyclopentane carboxylations. The highest efficiency is observed in the systems promoted by a tetracopper(II) triethanolaminate-de rived complex, which also shows different bond and stereoselectivity parameters (compared to the metalfree systems) in the carboxylations of methylcyclohexane and stereoisomeric 1,2-dimethylcyclohexanes. A free radical mechanism is proposed for the carboxylation of cyclohexane as a model substrate, involving the formation of an acyl radical, its oxidation and consequent hydroxylation by water. Relevant features of the present hydrocarboxylation method, besides the operation in aqueous medium, include the exceptional metal-free and acid-solvent-free reaction conditions, a rare hydroxylating role of water, substrate versatility, low temperatures (ca. 50°C) and a rather high efficiency (up to 72% carboxylic acid yields based on cycloalkane).
- Kirillova, Marina V.,Kirillov, Alexander M.,Pombeiro, Armando J. L.
-
experimental part
p. 2936 - 2948
(2010/04/03)
-
- TEMPO-mediated environmentally benign oxidation of primary alcohols to carboxylic acids with poly[4-(diacetoxyiodo)styrene]
-
An operationally simple and environmentally benign oxidation of primary alcohols to the corresponding carboxylic acids with a TEMPO-mediated poly[4-(diacetoxyiodo)styrene] system in acetone and water was carried out.
- Tashino, Yousuke,Togo, Hideo
-
p. 2010 - 2012
(2007/10/03)
-
- Adamantane derivatives and process for producing them
-
In the presence of an imide compound (e.g., N-hydroxyphthalimide) shown by the formula (2): wherein R1and R2independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group; or R1and R2may bond together to form a double bond or an aromatic or non-aromatic ring; Y is O or OH and n=1 to 3; or the imide compound and a co-catalyst (e.g., a transition metal compound), an adamantane derivative having a functional group such as a nitro group, an amino group, a hydroxyl group, a carboxyl group, a hydroxymethyl group and an isocyanato group is oxidized with oxygen. According to the above method, an adamantane derivative having a hydroxyl group together with a functional group such as a nitro group, an amino group, a hydroxyl group, a carboxyl group, a hydroxymethyl group and an isocyanato group is efficiently obtained.
- -
-
Page column 49-50
(2010/11/30)
-
- Benzothiadiazine compounds
-
Compound of formula (I): wherein: R1 represents hydroxy, RCO—O— or RCO—NRa—, R2 represents hydrogen, halogen, or hydroxy, R′CO—O or R′CO—NR′a—, R and R′, which may be identical or different, represent linear or branched (C1-C6)alkyl optionally substituted by aryl, linear or branched (C2-C6)alkenyl optionally substituted by aryl, linear or branched (C1-C6)perhaloalkyl, (C3-C7)cycloalkyl, adamantyl, aryl or heteroaryl, Ra and R′a, which may be identical or different, represent hydrogen or linear or branched (C1-C6)alkyl, linear or branched (C1-C6)perhaloalkyl, linear or branched (C1-C6)acyl, aryl or heteroaryl, its isomer and addition salts thereof with a pharmaceutically acceptable acid or base and medicinal products containing the same are useful as AMPA modulators.
- -
-
-
- Catalyst comprising nitrogen-containing heterocyclic compound, and process for producing organic compound using the catalyst
-
A catalyst is for use in a reaction using an oxygen-atom-containing reactant and includes a nitrogen-containing heterocyclic compound of the following formula (1): wherein each of R1and R2is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, and R1and R2may be combined to form a double bond or to form an aromatic or non-aromatic ring with the adjacent two carbon atoms, where one or two of heterocyclic ring containing three nitrogen atoms indicated in the formula may be further formed on the R1or R2, or on the double bond or aromatic or non-aromatic ring formed by R1and R2; X is an oxygen atom or a hydroxyl group; and Y is a single bond, a methylene group, or a carbonyl group. This catalyst can introduce an oxygen-atom-containing group into an organic substrate under mild conditions.
- -
-
-
- Koch carbonylation using silver trifluoromethanesulfonate
-
Koch carbonylation was carried out using silver trifluoromethanesulfonate (AgOTf). Tertiary alcohols were transformed into the corresponding carboxylic acids in good yield under carbon monoxide atmosphere (5 MPa: initial pressure) at 150°C. It can be assumed that under these reaction conditions, a strong acid, in which a silver(I) cation participates, would be generated from AgOTf.
- Mori, Hajime,Mori, Aya,Xu, Qiang,Souma, Yoshie
-
p. 7871 - 7874
(2007/10/03)
-
- Novel application of a solid super acid, sulfated zirconia, as a catalyst for Koch carbonylation reaction
-
A solid superacid, sulfated zirconia, worked well in the Koch reaction. Under optimized conditions, tertiary alcohols were selectively transformed to the corresponding carboxylic acids (34-72%), while primary alcohols were transformed to the corresponding ethers (58-72%).
- Mori, Hajime,Wada, Aya,Xu, Qiang,Souma, Yoshie
-
p. 136 - 137
(2007/10/03)
-
- NITRATION OR CARBOXYLATION CATALYSTS
-
In the presence of an imide compound (e.g., N-hydroxyphthalimide) shown by the following formula (1): ???wherein R1and R2represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group and a cycloalkyl group, and R1and R2may bond together to form a double bond, or an aromatic or non-aromatic ring, and Y is an O or OH, and n denotes 1 to 3;, a substrate is allowed to contact with at least one reactant selected from (i) a nitrogen oxide and (ii) a mixture of carbon monoxide and oxygen to be introduced with at least one functional group selected from a nitro group and a carboxyl group. The nitrogen oxide includes, for example, a compound represented by the formula NxOy(e.g., N2O3, NO2). The substrate includes, for example, a compound having a methine carbon atom (e.g., adamantane), a compound having a methyl group or a methylene group at an adjacent moiety of an aromatic ring. According to such reaction, the substrate can be efficiently nitrated or carboxylated even in a mild or moderate condition.
- -
-
-
- Oxoammonium salts. 6. 4-Acetylamino-2,2,6,6-tetramethylpiperidine-1- oxoammonium perchlorate: A stable and convenient reagent for the oxidation of alcohols. Silica gel catalysis
-
4-Acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium perchlorate, 1, is a stable, nonhygroscopic oxoammonium salt that is easily prepared and can be used for the oxidation of alcohols to ketones or aldehydes in near quantitative yields. The reaction is colorimetric, does not require anhydrous conditions, does not involve heavy metals, and can be carried out conveniently. Furthermore, the oxidant can be easily regenerated. The oxidation is somewhat specific in that the relative reactivities of an allyl alcohol (geraniol), benzaldehyde, and 1-decanol are about 100:1:0.1. The reaction is catalyzed by silica gel.
- Bobbitt, James M.
-
p. 9367 - 9374
(2007/10/03)
-
- Fluorescent Sensors for Molecules Guest-Responsive Monomer and Excimer Fluorescence of 6A,6B-; 6A,6C-; 6A,6D-; and 6A,6E-Bis(2-naphthylsulfonyl)-γ-cyclodextrins
-
Flexible hosts, 6A,6B-; 6A,6C-; 6A,6D-; and 6A,6E-bis(2-naphthylsulfonyl)-γ-cyclodextrins (γ-1, γ-2, γ-3, and γ-4, respectively) were used as fluorescent sensors with which a variety of organic compounds were detected by naphthalene excimer and monomer emissions. In a 10 vol% ethylene glycol aqueous solution, γ-1 exhibits almost pure monomer fluorescence while γ-2, γ-3, and γ-4 exhibit both monomer and excimer emissions. The intensities of the emissions changed upon addition of guest species, particularly in the case of γ-2 and γ-3, and the guest-induced intensity variations were used as sensitivity factors of the sensors. When (-)-borneol (5), cyclohexanol (6), cyclododecanol (7), and 1-adamantanecarboxylic acid (8) were added to each host solution, γ-2, γ-3, and γ-4 increased the excimer emission intensity but decreased the monomer one, the absolute intensity variations being 6 5≈8 1. When geraniol (9), nerol (10), and (-)-menthol (11) were added, the hosts decreased intensities in both monomer and excimer emissions for 9 and 10 while their emission variations for 11 were similar to those of 5. For steroids such as cholic acid (12), deoxycholic acid (13), chenodeoxycholic acid (14), and ursodeoxycholic acid (15), γ-4 showed depression in the excimer emission and enhancement in the monomer one while γ-2 and γ-3 showed complicated features in which the excimer emission was enhanced with the order of 15 14 13≈12 but the monomer one was depressed or enhanced depending on the hosts. All these data demonstrate that the hosts can be used as sensors for molecular recognition.
- Hamada, Fumio,Minato, Shingo,Osa, Tetsuo,Ueno, Akihiko
-
p. 1339 - 1346
(2007/10/03)
-
