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Cas Database

110-89-4

110-89-4

Identification

  • Product Name:Piperidine

  • CAS Number: 110-89-4

  • EINECS:203-813-0

  • Molecular Weight:85.149

  • Molecular Formula: C5H11N

  • HS Code:H2(CH2)4NH MOL WT. 85.15

  • Mol File:110-89-4.mol

Synonyms:Azacyclohexane;Cyclopentimine;Cypentil;Hexahydropyridine;Hexazane;Pentamethylenimine;Perhydropyridine;Pyridine, hexahydro-;

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Safety information and MSDS view more

  • Pictogram(s):ToxicT,FlammableF

  • Hazard Codes:T,F

  • Signal Word:Danger

  • Hazard Statement:H225 Highly flammable liquid and vapourH311 Toxic in contact with skin H314 Causes severe skin burns and eye damage H331 Toxic if inhaled

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer for medical attention. In case of skin contact Remove contaminated clothes. Rinse skin with plenty of water or shower. Refer for medical attention . In case of eye contact First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention. If swallowed Rinse mouth. Do NOT induce vomiting. Give one or two glasses of water to drink. Refer for medical attention . Strong local irritant and may cause permanent injury after short exposure to small amounts. Ingestion may involve both irreversible and reversible changes. 30 to 60 mg/kg may cause symptoms in humans. (EPA, 1998) Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mg/kg up to 200 ml of water for dilution if the patent can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . Cover skin burns with dry sterile dressings after decontamination ... . /Organic bases/Amines and related compounds/

  • Fire-fighting measures: Suitable extinguishing media This chemical is a flammable liquid. Small fires: dry chemical, carbon dioxide, water spray, or alcohol foam. Large fires: water spray, fog, or alcohol foam. Move container from fire area if you can do so without risk. Do not get water inside container. Cool containers that are exposed to flames with water from the side until well after fire is out. Withdraw immediately in case of rising sound from venting safety device or any discoloration of tank due to fire. Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Wear self-contained (positive pressure if available) breathing apparatus and full protective clothing. Isolate for ? mile in all directions if tank car or truck is involved in fire. Poisonous gases including nitrogen oxides are produced in fire. Vapors are heavier than air and will collect in low areas. Vapors may travel long distances to ignition sources and flashback. Vapors in confined areas may explode when exposed to fire. Containers may explode in fire. Storage containers and parts of containers may rocket great distances, in many directions. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156 Piperidine evolves explosive concentrations of vapor at normal room temperatures. When heated to decomposition, it emits highly toxic fumes of nitrogen oxides. Dangerous, when exposed to heat, flame, or oxidizers. Avoid 1-Perchlorylpiperidine and oxidizing materials. Piperidine is a reactive compound and forms complexes with the salts of heavy metals. It evolves explosive concentrations of vapor at normal room temperatures. Keep away from igniting sources and heat. (EPA, 1998) Wear self-contained breathing apparatus for firefighting if necessary.

  • Accidental release measures: Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8. Personal protection: self-contained breathing apparatus. Collect leaking and spilled liquid in sealable containers as far as possible. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations. Collect leaking liquid in sealable containers. Absorb remaining liquid in sand or inert absorbent and remove to safe place. (Extra personal protection: self-contained breathing apparatus.)

  • Handling and storage: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2. Fireproof. Separated from strong oxidants, acids and incompatible materials. See Chemical Dangers.Fireproof. Separated from strong oxidants, acids, incompatible materials See Chemical Dangers.

  • Exposure controls/personal protection:Occupational Exposure limit valuesBiological limit values Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Eye/face protection Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Respiratory protection Wear dust mask when handling large quantities. Thermal hazards

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Relevant articles and documentsAll total 347 Articles be found

Role of platinum deposits on titanium(IV) oxide particles: Structural and kinetic analyses of photocatalytic reaction in aqueous alcohol and amino acid solutions

Ohtani, Bunsho,Iwai, Kunihiro,Nishimoto, Sei-Ichi,Sato, Shinri

, p. 3349 - 3359 (1997)

Photocatalytic reaction at 298 K by platinum-loaded titanium(IV) oxide (TiO2-Pt) particles suspended in deaerated aqueous solutions of 2-propanol or (S)-lysine (Lys) was investigated. The TiO2 catalysts with various amounts of Pt loadings were prepared by impregnation from aqueous chloroplatinic acid solution onto a commercial TiO2 (Degussa P-25) followed by hydrogen reduction at 753 K. The physical properties of deposited Pt, e.g., particle size, surface area, and electronic state, were studied respectively by transmission electron microscopy, volumetric gas adsorption measurement, and X-ray photoelectron spectroscopy as well as infrared spectroscopy of adsorbed carbon monoxide. The increase in Pt amount mainly resulted in an increase of the number of Pt deposits, not of their size. The catalysts were suspended in the aqueous solutions and photoirradiated at a wavelength >300 nm under an argon (Ar) atmosphere. The overall rate of photocatalytic reactions for both 2-propanol and Lys, corresponding to the rate of consumption of these substrates, was negligible without Pt loading, increased drastically with the loading up to ca. 0.3%, and was almost constant or a little decreased by the further loadings. However, the rate of formation of pipecolinic acid (PCA) from Lys was improved gradually with a increase of Pt loading up to ca. 2 wt %. These dependences were discussed as a function of Pt surface area, which is employed as a measure that includes the properties of both number and size of Pt deposits. For the photocatalytic dehydrogenation of 2-propanol, the rate dependence could be interpreted semiquantitatively with the model that only the TiO2 particles loaded with at least one Pt deposit can photocatalyze, but the reaction rate is independent of the number of Pt deposits. Therefore, the overall rate is proportional to the number of Pt-loaded TiO2 particles. On the other hand, for the interpretation of the rate of PCA and H2 productions, the number of Pt deposits on each TiO2 particle had to be taken into account. The efficient production of PCA at higher Pt loadings was attributed to the reduction of a Schiff base intermediate produced via oxidation of Lys with positive holes and subsequent intramolecular condensation at the Pt deposit that is close to the site for the oxidation. Otherwise, photoexcited electrons are consumed for H2 production and the intermediate remains unreduced or undergoes further oxidation. It was suggested that the intermediate produced at the TiO2 surface sites within a distance of several nanometers from the Pt deposit undergoes efficient reduction to PCA. Thus, the importance of the distribution of Pt deposits for the preparation of highly active and selective TiO2-Pt photocatalyst has been clearly demonstrated.

-

Davies,McGee

, p. 678 (1950)

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Nucleophilic Addition to Olefins. 21. Substituent and Solvent Effects on the Reaction of Benzylidene Meldrum's Acids with Piperidine and Morpholine

Bernasconi, Claude F.,Panda, Markandeswar

, p. 3042 - 3050 (1987)

Rate (k1) and equilibrium constants (K1) for piperidine and morpholine addition to benzylidene Meldrum's acid (BMA) and substituted BMA's (Z=4-NO2, 3-Cl, 4-CN, 4-OMe, 4-NMe2, 4-NEt2) were determined in water and in 50percent, 70percent, and 90percent aqueous Me2SO.The equilibrium for addition is highly favorable, with K1 values (piperidine) as high as 7.8*107M-1, which is the highest value measured in a series of olefins of the type PhCH=CXY.The rates are also quite high (k1 up to 2.1*106M-1s-1), indicating a relatively high intrinsic rate constant (k0=k1 for K1=1) which ranks BMA second among seven PhCH=CXY-type olefins with respect to kinetic reactivity.This ranking is "reasonable" based on a correlation between k0 for nucleophilic addition to PhCH=CXY and k0 for deprotonation of carbon acids of the type CH2XY.βnucn (d log k1/ d log K1, variation of amine) is very amall, particularly in aqueous solution.This result appears to be part of a trend toward lower βnucn values with increasing thermodynamic stability of the adducts of PhCH=CXY. αnucn (d log k1/ d log K1, variation of Z) is significantly larger than βnucn, implying a substantial imbalance in these reactions.However, after correction of αnucn for the effect of the developing positive charge on the amine nitrogen the remaining "true" imbalance is quite small.The small imbalance as well as the high k0 value are consistent with the Meldrum's acid anion deriving most of its exceptional stability from its bislactone structure rather than from resonance.Strong ?-donor substituents (4-NMe2, 4-NEt2) have a strong stabilizing effect on the olefin, leading to a large reduction in K1.Contrary to expectations based on the principle of nonperfect synchronization (PNS), this resonance effect does not lead to a strong reduction of the intrinsic rate constant, probably because the polarization in the olefin (Me2N+=C6H4+CHC(COO)2-C(CH3)2) helps in partially offsetting the PNS effect caused by delayed development of resonance on the carbanionic side of the adduct

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Lijinsky,Epstein

, p. 21,22 (1970)

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An experimental-theoretical study of the factors that affect the switch between ruthenium-catalyzed dehydrogenative amide formation versus amine alkylation

Nova, Ainara,Balcells, David,Schley, Nathan D.,Dobereiner, Graham E.,Crabtree, Robert H.,Eisenstein, Odile

, p. 6548 - 6558 (2010)

A ruthenium(II) diamine complex can catalyze the intramolecular cyclization of amino alcohols H2N(CH2)nOH via two pathways: (i) one yields the cyclic secondary amine by a redox-neutral hydrogen-borrowing route with loss of water; and (ii) the second gives the corresponding cyclic amide by a net oxidation involving loss of H2. The reaction is most efficient in cases where the product has a six-membered ring. The amide and amine pathways are closely related: DFT calculations show that both amine and amide formations start with the oxidation of the amino alcohol, 5-amino-1-pentanol, to the corresponding amino aldehyde, accompanied by reduction of the catalyst. The intramolecular condensation of the amino aldehyde takes place either in the coordination sphere of the metal (path I) or after dissociation from the metal (path II). Path I yields the Ru-bound zwitterionic form of the hemiaminal protonated at nitrogen, which eliminates H2, forming the amide product. In path II, the free hemiaminal dehydrates, giving an imine, which yields the amine product by hydrogenation with the reduced form of the catalyst generated in the initial amino alcohol oxidation. For amide to be formed, the hemiaminal must remain metal-bound in the key intermediate and the elimination of H2 must occur from the same intermediate to provide a vacant site for β-elimination. The elimination of H2 is affected by an intramolecular H-bond in the key intermediate. For amine to be formed, the hemiaminal must be liberated for dehydration to imine and the H2 must be retained on the metal for reduction of the imine intermediate.

Kinetics of Reactions of Cyclic Secondary Amines with 2,4-Dinitro-1-naphthyl Ethyl Ether in Dimethyl Sulfoxide Solution. Spectacular Difference between the Behavior of Pyrrolidine and Piperidine

Bunnett, Joseph F.,Sekiguchi, Shizen,Smith, Lewis A.

, p. 4865 - 4871 (1981)

The reactions named in the title, which form N-(2,4-dinitro-1-naphthyl) derivatives of these heterocyclic amines, occur in two distinct stages.In stage I, the spectrum of a ?-adduct intermediate develops at a rate which is measurable in a stopped flow apparatus; in stage II, it decays at a slower and easily measurable rate.The kinetics of both stage I and stage II have been studied.Pyrrolidine and piperidine are similar in their stage I behavior, but reactivity in stage II is about 11000 times greater in the pyrrolidine system.This huge difference between systems apparently so similar is judged to arise from steric interactions forced by differences in conformation between the amino moieties in the intermediate ? adducts as they release the nucleofuge.It calls into question the rate-limiting proton transfer interpretation of base catalysis in analogous aminodephenoxylation reactions in protic solvents.

SYNTHESIS OF 2-IMIDAZOLINONES

Zav'yalov, S. I.,Dorofeeva, O. V.,Taganova, O. K.

, p. 1534 - 1537 (1985)

-

-

De Mayo,Rigby

, p. 1075 (1950)

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Catalytic Homogeneous Hydrogenation of CO to Methanol via Formamide

Kar, Sayan,Goeppert, Alain,Prakash, G. K. Surya

, p. 12518 - 12521 (2019)

A novel amine-assisted route for low temperature homogeneous hydrogenation of CO to methanol is described. The reaction proceeds through the formation of formamide intermediates. The first amine carbonylation part is catalyzed by K3PO4. Subsequently, the formamides are hydrogenated in situ to methanol in the presence of a commercially available ruthenium pincer complex as a catalyst. Under optimized reaction conditions, CO (up to 10 bar) was directly converted to methanol in high yield and selectivity in the presence of H2 (70 bar) and diethylenetriamine. A maximum TON of 539 was achieved using the catalyst Ru-Macho-BH. The high yield, selectivity, and TONs obtained for methanol production at low reaction temperature (145 °C) could make this process an attractive alternative over the traditional high temperature heterogeneous catalysis.

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Hales,Herington

, p. 616,621 (1957)

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Synthesis of: N -heterocycles from diamines via H2-driven NADPH recycling in the presence of O2

Al-Shameri, Ammar,Borlinghaus, Niels,Weinmann, Leonie,Scheller, Philipp N.,Nestl, Bettina M.,Lauterbach, Lars

, p. 1396 - 1400 (2019)

Herein, we report an enzymatic cascade involving an oxidase, an imine reductase and a hydrogenase for the H2-driven synthesis of N-heterocycles. Variants of putrescine oxidase from Rhodococcus erythropolis with improved activity were identified. Substituted pyrrolidines and piperidines were obtained with up to 97% product formation in a one-pot reaction directly from the corresponding diamine substrates. The formation of up to 93% ee gave insights into the specificity and selectivity of the putrescine oxidase.

-

Zav'yalov,S.I.,Ezhova,G.I.

, (1977)

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The True Fate of Pyridinium in the Reportedly Pyridinium-Catalyzed Carbon Dioxide Electroreduction on Platinum

Olu, Pierre-Yves,Li, Qi,Krischer, Katharina

, p. 14769 - 14772 (2018)

Protonated pyridine (PyH+) has been reported to act as a peculiar and promising catalyst for the direct electroreduction of CO2 to methanol and/or formate. Because of recent strong incentives to turn CO2 into valuable products, this claim triggered great interest, prompting many experiments and DFT simulations. However, when performing the electrolysis in near-neutral pH electrolyte, the local pH around the platinum electrode can easily increase, leading to Py and HCO3? being the predominant species next to the Pt electrode instead of PyH+ and CO2. Using a carefully designed electrolysis setup which overcomes the local pH shift issue, we demonstrate that protonated pyridine undergoes a complete hydrogenation into piperidine upon mild reductive conditions (near 0 V vs. RHE). The reduction of the PyH+ ring occurs with and without the presence of CO2 in the electrolyte, and no sign of CO2 electroreduction products was observed, strongly questioning that PyH+ acts as a catalyst for CO2 electroreduction.

-

Woods,Sanders

, p. 2111 (1946)

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The elimination kinetics and mechanisms of ethyl piperidine-3-carboxylate, ethyl 1-methylpiperidine-3-carboxylate, and ethyl 3-(piperidin-1-yl)propionate in the gas phase

Monsalve, Angiebelk,Rosas, Felix,Tosta, Maria,Herize, Armando,Dominguez, Rosa M.,Brusco, Doris,Chuchani, Gabriel

, p. 106 - 114 (2006)

The gas-phase elimination kinetics of the above-mentioned compounds were determined in a static reaction system over the temperature range of 369-450.3°C and pressure range of 29-103.5 Torr, The reactions are homogeneous, unimolecular, and obey a first-order rate law. The rate coefficients are given by the following Arrhenius expressions: ethyl 3-(piperidin-1-yl) propionate, log κ1(s-1) = (12.79 ± 0.16) - (199.7±2.0) kJ mol-1 (2.303 RT)-1; ethyl 1-methylpiperidine-3-carboxylate, log κ1(s-1) = (13.07 ± 0.12)-(212.8 ± 1.6) kJmol-1 (2,303 RT) -1; ethyl piperidine-3-carboxylate, log κ1(s -1) = (13.12 ± 0.13) - (210.4 ± 1.7) kJ mol -1 (2.303 RT)-1 and 3-piperidine carboxylic acid, log κ1(s-1) = (14.24 ± 0.17) - (234.4 ± 2.2) kJ mol-1 (2.303 RT)-1. The first step of decomposition of these esters is the formation of the corresponding carboxylic acids and ethylene through a concerted six-membered cyclic transition state type of mechanism. The intermediate β-amino acids decarboxylate as the α-amino acids but in terms of a semipolar six-membered cyclic transition state mechanism.

-

Szmaragd,Briner

, p. 553,560 (1949)

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Vapor-phase synthesis of piperidine over SiO2 catalysts

Tsuchiya, Takuma,Kajitani, Yoshihiro,Ohta, Kaishu,Yamada, Yasuhiro,Sato, Satoshi

, p. 42 - 45 (2018)

Vapor phase dehydration of 5-amino-1-pentanol to produce piperidine was investigated over various oxide catalysts such as ZrO2, TiO2, Al2O3 and SiO2. Among the tested catalysts, SiO2 selectively produced piperidine at 300 °C. A high 5-amino-1-pentanol conversion of 99.9% with a piperidine selectivity of 94.8% was achieved over weak acidic SiO2. In an experiment using isotope such as deuterated water, surface hydroxy groups of SiO2 are concluded to be the active centers.

Microwave-assisted synthesis of azoniaspiro compounds using a novel catalyst, 1-azaphenothiazine

Gupta, Archana,Sakhuja, Rajeev,Kushwaha, Khushbu,Jain, Subhash C.

, p. 411 - 416 (2011)

1-Azaphenothiazine catalyses the intramolecular cyclization of N-(bromoalkyl)phthalimides in the presence of anhydrous K2CO 3 to form spiro cyclic quaternary ammonium salts, namely azoniaspiro compounds, under microwave irradiation. A novel and ecofriendly method was developed for the synthesis of azoniaspiro compounds, and the role of azaphenothiazine as a catalyst in such reactions has been established for the first time. In the future, this protocol can be extended to the synthesis of various substituted N-heterocycles by hydrolyzing the resulting azoniaspiro compounds.

Is There a Transition-State Imbalance in Malononitrile Anion Forming Reactions? Kinetics of Piperidine and Morpholine Addition to Substituted Benzylidenemalononitriles in Various Me2SO-Water Mixtures

Bernasconi, Claude F.,Killion, Robert B.

, p. 2878 - 2885 (1989)

Piperidine and morpholine add to substituted benzylidenemalononitriles (Z-C6H4CH=C(CN)2) to form a zwitterionic adduct, Z-C6H4CH(R2NH+)C(CN)2-(T+/-), which is in rapid acid-base equilibrium with the anionic adduct, Z-C6H4CH(R2N)C(CN)2-(T-).Rate constans for amine addition (k1) were determined by direct rate measurements while equilibrium constans for addition (K1) as well as pKa+/- values of the zwitterions were obtained spectrophotometrically.The bulk of the measurements was carried out in 50percent Me2SO-50percent water with piperidine, while a smaller number of experiments were performed with morpholine, and with both amines in water and in 70percent Me2SO-30percent water.The reactions show the typical bahavior of a carbanion-forming process in which the carbanion derives a good part of its stabilization from polar effects while resonance effects play a more modest role.This behavior includes a high intrinsic rate constant (k0 = k when K = 1), a small transition-state imbalance, and a relatively small solvent effect on the intrinsic rate constant.The observation of an imbalance suggests that the deprotonation of malononitrile derivatives by carboxylate ions should also have an imbalanced transition state.The fact that none has been observed is attributed to a solvation effect of the carboxylic acid, which enhances the Broensted βB value, as recently suggested by Murray and Jencks.The 4-Me2N substituent leads to strong resonance stabilization of the olefin as indicated by a low K1 value.Contrary to expectation of a lowered intrinsic constant, this resonance stabilization has little effect on k0.This suggests theoperation of a compensating factor which increases k0 and which can be understood as an attenuation of the reduction in k0 caused by late development of resonance at the carbanionic center of the adduct.

The Stabilities of Meisenheimer Complexes. Part 32. Rate-limiting Proton Transfer in the Reactions of 1,3,5-Trinitrobenzene with Pyrrolidine and Piperidine

Crampton, Michael R.,Greenhalgh, Colin

, p. 1175 - 1178 (1983)

Rate and equilibrium measurements are reported for the reactions of 1,3,5-trinitrobenzene with pyrrolidine and with piperidine in dimethyl sulphoxide (DMSO) and in a DMSO-water mixture.These reactions lead to the formation of anionic ?-adducts via zwitterionic intermediates and it is shown that proton transfer is rate-limiting or partially rate-limiting.In DMSO the rate of proton transfer is an order of magnitude faster for the reaction with pyrrolidine than for the reaction with piperidine.However, the addition of water reduces this difference.Implications for the mechanism of base catalysis in nucleophilic aromatic substitution reactions are discussed.

Renewable energy storage: Via efficient reversible hydrogenation of piperidine captured CO2

Lu, Mi,Zhang, Jianghao,Yao, Yao,Sun, Junming,Wang, Yong,Lin, Hongfei

, p. 4292 - 4298 (2018)

The storage of renewable energy is the major hurdle during the transition of fossil resources to renewables. A possible solution is to convert renewable electricity to chemical energy carriers such as hydrogen for storage. Herein, a highly efficient formate-piperidine-adduct (FPA) based hydrogen storage system was developed. This system has shown rapid reaction kinetics of both hydrogenation of piperidine-captured CO2 and dehydrogenation of the FPA over a carbon-supported palladium nano-catalyst under mild operating conditions. Moreover, the FPA solution based hydrogen storage system is advantageous owing to the generation of high-purity hydrogen, which is free of carbon monoxide and ammonia. In situ ATR-FTIR characterization was performed in order to provide insight into the reaction mechanisms involved. By integrating this breakthrough hydrogen storage system with renewable hydrogen and polymer electrolyte membrane fuel cells (PEMFC), in-demand cost-effective rechargeable hydrogen batteries could be realized for renewable energy storage.

-

Brown et al.

, p. C1 (1977)

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AN UNUSUAL FRAGMENTATION PROCESS DISCOVERED DURING THE COURSE OF CLEAVAGE OF A CAMPHANIC ACID AMIDE

Kozikowski, Alan P.,Chen, Chinpiao,Ball, Richard G.

, p. 5869 - 5872 (1990)

An unusual fragmentation reaction that affords a carbamoyl anion discovered during the course of the synthesis of rigidified PCP analogues is reported.

-

Jardine,McQuillin

, p. 626 (1970)

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Amines as Leaving Groups in Nucleophilic Aromatic Substitution Reactions

Vargas, Elba B. de,Rossi, Rita H. de,Veglia, Alicia V.

, p. 1976 - 1981 (1986)

The hydrolysis reactions of N-(2,4-dinitrophenyl)piperidine (7) and N-(2,4-dinitrophenyl)morpholine (8) were studied.Both reactions lead quantitatively to the formation of 2,4-dinitrophenol.They are second order toward the HO- concentration and are strongly catalyzed by the amine leaving group.The catalysis is interpreted in terms of the formation of 1,3-? complexes with the amine or the HO-, which then react with another hydroxide ion to give the final product.The reactivity of the 1,3-? complexes toward HO- is higher than that of the substrates themselves.

-

Wilson

, p. 693 (1945)

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A General Catalyst Based on Cobalt Core–Shell Nanoparticles for the Hydrogenation of N-Heteroarenes Including Pyridines

Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Kreyenschulte, Carsten,Murugesan, Kathiravan

, p. 17408 - 17412 (2020)

Herein, we report the synthesis of specific silica-supported Co/Co3O4 core–shell based nanoparticles prepared by template synthesis of cobalt-pyromellitic acid on silica and subsequent pyrolysis. The optimal catalyst material allows for general and selective hydrogenation of pyridines, quinolines, and other heteroarenes including acridine, phenanthroline, naphthyridine, quinoxaline, imidazo[1,2-a]pyridine, and indole under comparably mild reaction conditions. In addition, recycling of these Co nanoparticles and their ability for dehydrogenation catalysis are showcased.

REACTIONS OF ORGANONITROGEN MOLECULES WITH Ni(100).

Schoofs,Benziger

, p. 741 - 750 (1988)

The adsorption and reaction of a variety of organonitrogen compounds on a Ni(100) surface have been examined with temperature-programmed reaction, Auger electron spectroscopy, and infrared spectroscopy. Monomethylamine adsorbs via the nitrogen lone pair of electrons and then undergoes C-N bond scission yielding adsorbed carbon, dihydrogen, and ammonia. Aniline pi -bonds to the surface and polymerizes to form a thermally stable poly(aniline) surface film. Pyridine undergoes a temperature-induced orientational transformation. At low temperatures pyridine adsorbs with its ring parallel to the surface. At higher temperatures it appears to form an alpha -pyridyl species with an activation barrier of 85 kJ/mol. Methyl groups on 2,6-lutidine sterically hinder this reaction.

Cyclization of diols with ammonia over CuO-ZnO-Al2O3 catalyst in the presence of H2

Shuikin, A. N.,Kliger, G. A.,Zaikin, V. G.,Glebov, L. S.

, p. 1966 - 1968 (1995)

Cyclization of diols with ammonia in an H2 atmosphere over an industrial CuO-ZnO-Al2O3 catalyst for the synthesis of methanol (SNM-1) gives nitrogen-containing five-, six-, or seven-membered heterocyclic compounds.The yields of cyclic amines in the 180-230 deg C temperature range are 46 to 97 percent. - Keywords: diols, ammonia, cyclization, heterocyclic amines, copper-containing catalyst

Heat of hydrogenation of a cis imine. An experimental and theoretical study

Wiberg, Kenneth B.,Nakaji, David Y.,Morgan, Kathleen M.

, p. 3527 - 3532 (1993)

The heat of hydrogenation of 1-azacyclopentene was determined via a measurement of the heat of hydrogenation of its trimer, and of the dissociation energy of the trimer. The observed ΔHhydrog was -15.9 ± 0.3 kcal/mol and is considerably smaller than that for cyclopentene (-26.9 ± 0.1 kcal/mol). The data were combined with the results of theoretical calculations (MP3/6-311++G**//RHF/6-31G*) to give information on the heats of formation, heats of hydrogenation, and strain energies of a number of cyclic and acyclic imines. The "resonance energy" of pyridine was estimated based on these data.

Nonlinear organic reaction of 9-fluorenylmethyl carbamates as base amplifiers to proliferate aliphatic amines and their application to a novel photopolymer system

Arimitsu, Koji,Ichimura, Kunihiro

, p. 336 - 343 (2004)

A novel concept of base proliferation for improving the photosensitivity of base-sensitive materials is described by presenting the autocatalytic transformation of 9-fluorenylmethyl carbamates to aliphatic amines. A 9-fluorenylmethyl carbamate, as a base amplifier, was subjected to a base-catalysed fragmentation reaction to liberate the corresponding amine, which can then act as a catalyst for decomposing parent molecules, leading to autocatalytic decomposition. Consequently, the amine is generated from an equimolar amount of the carbamate using a catalytic amount of the same amine. 1-(9-Fluorenylmethoxycarbonyl)piperidine and 1-(9-fluorenylmethoxycarbonyl) cyclohexylamine were suitable as base amplifiers because of their thermal stability under neutral conditions and high base-catalytic reactivity. On the basis of the results, 1,3-bis[1-(9-fluorenylmethoxycarbonyl)-4-piperidyl] propane and 1,6-bis[(9-fluorenylmethoxy)carbonylamino]hexane were designed as base amplifiers which liberate aliphatic diamines to crosslink poly(glycidyl methacrylate) photochemically in the presence of a photobase generator. Addition of the base amplifiers resulted in a marked improvement of the photosensitivity characteristics of the polymer by a factor of 16 and 50, respectively.

Chemoselective and Tandem Reduction of Arenes Using a Metal–Organic Framework-Supported Single-Site Cobalt Catalyst

Akhtar, Naved,Begum, Wahida,Chauhan, Manav,Manna, Kuntal,Newar, Rajashree,Rawat, Manhar Singh

supporting information, (2022/01/19)

The development of heterogeneous, chemoselective, and tandem catalytic systems using abundant metals is vital for the sustainable synthesis of fine and commodity chemicals. We report a robust and recyclable single-site cobalt-hydride catalyst based on a porous aluminum metal–organic framework (DUT-5 MOF) for chemoselective hydrogenation of arenes. The DUT-5 node-supported cobalt(II) hydride (DUT-5-CoH) is a versatile solid catalyst for chemoselective hydrogenation of a range of nonpolar and polar arenes, including heteroarenes such as pyridines, quinolines, isoquinolines, indoles, and furans to afford cycloalkanes and saturated heterocycles in excellent yields. DUT-5-CoH exhibited excellent functional group tolerance and could be reusable at least five times without decreased activity. The same MOF-Co catalyst was also efficient for tandem hydrogenation–hydrodeoxygenation of aryl carbonyl compounds, including biomass-derived platform molecules such as furfural and hydroxymethylfurfural to cycloalkanes. In the case of hydrogenation of cumene, our spectroscopic, kinetic, and density functional theory (DFT) studies suggest the insertion of a trisubstituted alkene intermediate into the Co–H bond occurring in the turnover limiting step. Our work highlights the potential of MOF-supported single-site base–metal catalysts for sustainable and environment-friendly industrial production of chemicals and biofuels.

Metallic Barium: A Versatile and Efficient Hydrogenation Catalyst

Stegner, Philipp,F?rber, Christian,Zenneck, Ulrich,Knüpfer, Christian,Eyselein, Jonathan,Wiesinger, Michael,Harder, Sjoerd

supporting information, p. 4252 - 4258 (2020/12/22)

Ba metal was activated by evaporation and cocondensation with heptane. This black powder is a highly active hydrogenation catalyst for the reduction of a variety of unactivated (non-conjugated) mono-, di- and tri-substituted alkenes, tetraphenylethylene, benzene, a number of polycyclic aromatic hydrocarbons, aldimines, ketimines and various pyridines. The performance of metallic Ba in hydrogenation catalysis tops that of the hitherto most active molecular group 2 metal catalysts. Depending on the substrate, two different catalytic cycles are proposed. A: a classical metal hydride cycle and B: the Ba metal cycle. The latter is proposed for substrates that are easily reduced by Ba0, that is, conjugated alkenes, alkynes, annulated rings, imines and pyridines. In addition, a mechanism in which Ba0 and BaH2 are both essential is discussed. DFT calculations on benzene hydrogenation with a simple model system (Ba/BaH2) confirm that the presence of metallic Ba has an accelerating effect.

Palladium supported on magnesium hydroxyl fluoride: An effective acid catalyst for the hydrogenation of imines and N-heterocycles

Agbossou-Niedercorn, Francine,Corre, Yann,Dongare, Mohan K.,Kemnitz, Erhard,Kokane, Reshma,Michon, Christophe,Umbarkar, Shubhangi B.

supporting information, p. 19572 - 19583 (2021/11/04)

Palladium catalysts supported on acidic fluorinated magnesium hydroxide Pd/MgF2-x(OH)x were prepared through precipitation or impregnation methods. Applications to the hydrogenation of various aldimines and ketimines resulted in good catalytic activities at mild temperatures using one atmosphere of hydrogen. Quinolines, pyridines and other N-heterocycles were successfully hydrogenated at higher temperature and hydrogen pressure using low palladium loadings and without the use of any acid additive. Such reactivity trend confirmed the positive effect of the Br?nsted and Lewis acid sites from the fluorinated magnesium hydroxide support resulting in the effective pre-activation of N-heterocycle substrates and therefore in the good catalytic activity of the palladium nanoparticles during the hydrogenations. As demonstrated in the hydrogenation of imines, the catalyst was recycled up to 10 times without either loss of activity or palladium leaching. This journal is

PRODUCTION METHOD OF CYCLIC COMPOUND

-

Paragraph 0057; 0059; 0062; 0064, (2021/05/05)

PROBLEM TO BE SOLVED: To provide an industrially simple production method of a cyclic compound. SOLUTION: A production method of a cyclic compound includes a step to obtain a reduced form (B) by reducing an unsaturated bond in a ring structure of an aromatic compound (A) by means of catalytic hydrogenation of the aromatic compound (A) or its salt using palladium carbon as a catalyst under a normal pressure, in which the aromatic compound (A) has one or more ring structures selected from a group consisting of a five membered-ring, a six membered-ring, and a condensed ring of the five membered-ring or the six membered-ring with another six membered-ring, a hetero atom can be included in the ring structure, and the aromatic compound (A) can have one or two side chains bonded to the ring structure and does not have any carbon-carbon triple bond in the side chain. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT

Indirect reduction of CO2and recycling of polymers by manganese-catalyzed transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes

Liu, Xin,Werner, Thomas

, p. 10590 - 10597 (2021/08/20)

The reduction of polar bonds, in particular carbonyl groups, is of fundamental importance in organic chemistry and biology. Herein, we report a manganese pincer complex as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and even polyurethanes leading to the corresponding alcohols, amines, and methanol as products. Since these compound classes can be prepared using CO2as a C1 building block the reported reaction represents an approach to the indirect reduction of CO2. Notably, these are the first examples on the reduction of carbamates and urea derivatives as well as on the C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is highlighted by the successful reduction of 12 urea derivatives, 26 carbamates and 11 amides. The corresponding amines, alcohols and methanol were obtained in good to excellent yields up to 97%. Furthermore, polyurethanes were successfully converted which represents a viable strategy towards a circular economy. Based on control experiments and the observed intermediates a feasible mechanism is proposed.

Process route upstream and downstream products

Process route

(E)-1-((4-nitrophenyl)diazenyl)piperidine
52010-83-0

(E)-1-((4-nitrophenyl)diazenyl)piperidine

piperidine
110-89-4

piperidine

4-chlorobenzonitrile
100-00-5

4-chlorobenzonitrile

Conditions
Conditions Yield
piperidinium 4-nitrophenolate
42824-44-2

piperidinium 4-nitrophenolate

piperidine
110-89-4

piperidine

Conditions
Conditions Yield
In acetonitrile; at 24.84 ℃; Equilibrium constant;
In 1,4-dioxane; at 24.84 ℃; Equilibrium constant; Ionic liquid;
piperidinium formate
77984-65-7

piperidinium formate

piperidine
110-89-4

piperidine

hydrogen
1333-74-0

hydrogen

Conditions
Conditions Yield
With 5%-palladium/activated carbon; In ethanol; water; at 40 ℃; under 760.051 Torr; Temperature; Concentration; Inert atmosphere;
N-benzoylpiperidine
776-75-0

N-benzoylpiperidine

piperidine
110-89-4

piperidine

benzyl alcohol
100-51-6,185532-71-2

benzyl alcohol

Conditions
Conditions Yield
With cis-[Ru(CH3CN)2(η3-C3H5)(CO1,5-cyclooctadiene)]BF4; hydrogen; potassium hexamethylsilazane; (2-aminoethyl)diphenylphosphane; In tetrahydrofuran; at 100 ℃; for 24h; under 38002.6 Torr; Autoclave;
N-benzoylpiperidine; With potassium tert-butylate; C16H26BrN3Ru; In isopropyl alcohol; Autoclave; Inert atmosphere; Green chemistry;
With hydrogen; In isopropyl alcohol; at 90 ℃; for 24h; under 19001.3 Torr; Autoclave; Green chemistry;
39 %Spectr.
N-benzyloxypiperidine
46346-67-2

N-benzyloxypiperidine

piperidine
110-89-4

piperidine

N-Formylpiperidine
2591-86-8

N-Formylpiperidine

benzaldehyde
100-52-7

benzaldehyde

N-Benzylpiperidine
2905-56-8

N-Benzylpiperidine

benzyl alcohol
100-51-6,185532-71-2

benzyl alcohol

Conditions
Conditions Yield
With diiron nonacarbonyl; In benzene; at 45 ℃; for 2h; Product distribution; Mechanism; var. reaction partners and times; other N-alkyloxyamines;
piperidin-1-yl benzoate
5542-49-4

piperidin-1-yl benzoate

piperidine
110-89-4

piperidine

2,3,4,5-tetrahydropyridine
505-18-0

2,3,4,5-tetrahydropyridine

cyclohexanol
108-93-0

cyclohexanol

Conditions
Conditions Yield
With potassium phosphate; dichloro(1,5-cyclooctadiene)palladium(II); In 1,4-dioxane; at 110 ℃; for 10h; Inert atmosphere; Schlenk technique;
5-hydroxypentylamine
2508-29-4

5-hydroxypentylamine

piperidine
110-89-4

piperidine

2,3,4,5-tetrahydropyridine
505-18-0

2,3,4,5-tetrahydropyridine

4-pentenyl-1-amine
22537-07-1

4-pentenyl-1-amine

Conditions
Conditions Yield
With Sc1.5Yb0.5O3; at 425 ℃; Inert atmosphere;
piperidine
110-89-4

piperidine

carbamic Acid
463-77-4

carbamic Acid

Conditions
Conditions Yield
5-hydroxypentylamine
2508-29-4

5-hydroxypentylamine

piperidine
110-89-4

piperidine

4-pentenyl-1-amine
22537-07-1

4-pentenyl-1-amine

Conditions
Conditions Yield
With praseodymium oxide; at 425 ℃; Reagent/catalyst; Temperature; Inert atmosphere;
With silica gel; at 300 ℃; for 5h; Temperature; Reagent/catalyst; Flow reactor; Inert atmosphere;
piperidine
110-89-4

piperidine

piperidin-4-ylcarbamic acid benzyl ester
182223-54-7

piperidin-4-ylcarbamic acid benzyl ester

Conditions
Conditions Yield

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