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110-89-4 Usage

Chemical Description

Different sources of media describe the Chemical Description of 110-89-4 differently. You can refer to the following data:
1. Piperidine is a colorless liquid that is used as a solvent and reagent in organic chemistry.
2. Piperidine is a cyclic secondary amine with a five-membered ring.
3. Piperidine is a catalyst used in the reaction.
4. Piperidine is a heterocyclic organic compound that is used as a base in organic synthesis.

Chemical Properties

Different sources of media describe the Chemical Properties of 110-89-4 differently. You can refer to the following data:
1. Clear or slightly yellow liquid
2. Piperidine is a clear, colorless liquid. Pepper, ammonia or amine odor.
3. Piperidine is a strong base (pKb = 2.88) that reacts vigorously with oxidizing materials, is easily ignited, and forms explosive vapor concentrations at room temperature. When heated to decomposition it gives off toxic fumes of NOx (Sax 1984). It behaves like an aliphatic secondary amine and can form complexes with salts of heavy metals (HSDB 1988).
4. Piperidine has a heavy, sweet, floral, animal odor and a burning peppery taste.


Piperidine occurs at low levels in a variety of food products (Neurath et al 1977), including baked ham (0.2 p.p.m.), milk (0.11 p.p.m.) coffee (1 p.p.m. dry) (Singer and Lijinsky 1976) and canned fish (Tanikawa and Motohiro 1960). It is also found in black pepper (Windholz 1983), hemp (Obata and Ishikawa 1960), hemlock (Cromwell 1956) and tobacco (Furia and Bellanca 1975). Piperidine is a natural constituent of skin (Sax and Lewis 1987), human urine (Von Euler 1944), brain (Honegger and Honegger 1960) and cerebrospinal fluid (Perry et al 1964). Humans excrete about 3-20 mg/d in the urine (Reinhardt and Britelli 1981).


Different sources of media describe the Uses of 110-89-4 differently. You can refer to the following data:
1. It is used in organic synthesis, especially inthe preparation of many crystalline derivativesof aromatic nitro compounds.
2. Fits Applied Biosystems 431 and 433A peptide synthesizers.
3. Piperidine is an organic heterocyclic amine widely used as building block and reagent in the synthesis of organic compounds including pharmaceuticals.


Different sources of media describe the Definition of 110-89-4 differently. You can refer to the following data:
1. ChEBI: An azacycloalkane that is cyclohexane in which one of the carbons is replaced by a nitrogen. It is a metabolite of cadaverine, a polyamine found in the human intestine.
2. piperidine: A saturated heterocycliccompound having a nitrogen atom ina six-membered ring, C5H11N; r.d.0.86; m.p. –7°C; b.p. 106°C. The structureis present in many alkaloids

Production Methods

Piperidine is usually prepared by the electrolytic reduction of pyridine. It may also be obtained by heating piperidine with alcoholic KOH or by the cyclization of 1,5-diaminopentane hydrochloride (Windholz 1983). U.S. production in 1983 was approximately 606,000 pounds (HSDB 1988). Commercial piperidine is supplied in two grades, 95 and 98 percent pure (Sax and Lewis 1987).


Usually prepared by electrolytic reduction of pyridine.

Brand name

Cypentil (Abbott).

Aroma threshold values

Detection: 65.8 to 70.6 ppm

General Description

A clear colorless liquid with a pepper-like odor. Less dense than water, but miscible in water. Will float on water. Flash point 37°F. Melting point -15.8°F (-9°C). Boiling point 222.8°F (106°C). May severely irritate skin and eyes. May be toxic by ingestion and inhalation. Vapors heavier than air. Used to make rubber and as a solvent.

Air & Water Reactions

Highly flammable. Miscible in water.

Reactivity Profile

1-Oxa-4-azacyclohexane neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides.

Health Hazard

Different sources of media describe the Health Hazard of 110-89-4 differently. You can refer to the following data:
1. 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.
2. Piperidine is a highly toxic compound. Theacute oral toxicity is high in many species oftest animals. The oral LD50 values in miceand rabbits are 30 and 145 mg/kg, respectively(NIOSH 1986). The liquid is moderatelytoxic by skin absorption. Inhalationtoxicity in experimental animals was low,however. A 4-hour exposure to 4000 ppmwas lethal to rats. Piperidine is corrosive toskin. Contact with eyes can produce severeirritation.
3. An irritation threshold of 26 p.p.m. has been reported from studies on human volunteers (Bazarova and Migukina 1975). Levels of 2 to 5 p.p.m. in air have been recorded during the transfer of piperidine from drums in a semi-closed system. At this level, the vapors were intolerable but no irritation was observed (ANON 1982). In an accidental case of skin exposure, third-degree burns developed after only 3 min of skin contact (Linch 1965). Piperidine has a pronounced emetic effect in humans. When administered to schizophrenic patients at doses of 1 to 6 g/d, it was shown to cause nausea and a subjective sense of well being (Giacobini 1976; Tasher et al 1960). The primary, but low-level, means of human exposure, however, is from the natural piperidine content of foods (HSDB 1988).

Fire Hazard

1-Oxa-4-azacyclohexane evolves explosive concentrations of vapor at normal room temperatures. When heated to decomposition, 1-Oxa-4-azacyclohexane emits highly toxic fumes of nitrogen oxides. Dangerous, when exposed to heat, flame, or oxidizers. Avoid 1-Perchloryl1-Oxa-4-azacyclohexane and oxidizing materials. 1-Oxa-4-azacyclohexane is a reactive compound and forms complexes with the salts of heavy metals. 1-Oxa-4-azacyclohexane evolves explosive concentrations of vapor at normal room temperatures. Keep away from igniting sources and heat.

Flammability and Explosibility


Industrial uses

Piperidine is used as a solvent, a curing agent for rubber and epoxy resins, a catalyst in silicone esters, an intermediate in organic synthesis and as a complexing agent (HSDB 1988; Reinhardt and Britelli 1981). It is a trace constituent in oils and fuels (Sax and Lewis 1987). It is used in the manufacture of local anesthetics, analgesics and other pharmaceuticals, and also for wetting agents and germicides (Gehring 1983). It is also used as a flavor additive in soups, meats, condiments, baked goods, candy and non-alcoholic beverages at 0.05-5.0 p.p.m. (Furia and Bellanca 1975).

Safety Profile

Poison by ingestion, skin contact, and intraperitoneal routes. Moderately toxic by subcutaneous route. Mildly toxic by inhalation. An experimental teratogen. Experimental reproductive effects by inhalation. A skin irritant. Mutation data reported. A very dangerous fire hazard when exposed to heat, flame, or oxidizers. Can react vigorously with oxidzing materials. To fight fire, use alcohol foam, CO2, dry chemical. Explodes on contact with 1- perchloryl-piperidme, dqanofurazan, N- nitrosoacetadde. When heated to decomposition it emits highly toxic fumes of NOx. Used in agriculture and pharmaceuticals, and as an intermediate for rubber accelerators. Used in production of drugs of abuse.

Potential Exposure

Piperidine is used in agriculture and pharmaceuticals; intermediate for rubber accelerators; as a solvent; as a curing agent for rubber and epoxy resins; catalyst for condensation reactions; as an ingredient in oils and fuels; complexing agent; manufacture of local anesthetics; in analgesics; pharmaceuticals, wetting agents; and germicides; synthetic flavoring. Not registered as a pesticide in the Unied States.


No tumors were produced in rats given piperidine (0.09%) in drinking water for 1 year. Mice receiving 19 doses of 50 mg/kg by intraperitoneal injection within 61 weeks followed by an 18-week observation period showed no increase in cancer incidences (251). Piperidine and sodium nitrite given together also failed to produce tumors. The failure of this treatment was surprising because nitrosopiperidine induced a high incidence of lung and esophageal tumors. The authors suggest that the relative strong basicity of piperidine reduced the rate of reaction with nitrite to such an extent that an ineffective amount of nitrosopiperidine was formed. In mice that had cholesterol pellets containing piperidine implanted in their bladders and were given sodium nitrite in their drinking water, an increase in bladder cancers was produced. Piperidine given as a series of 24 injections in groups of mice failed to produce lung tumors in the strain A mouse cancer screen. When piperidine and sodium nitrite were incubated in the isolated rat urinary bladder, nitrosopiperidine was detected in the bladder contents. No studies designed to evaluate the carcinogenic potential of piperidine alone following lifetime exposures have been reported.


Piperidine is readily absorbed through the gastrointestinal tract, skin and lungs (HSDB 1988). In hens, 35 to 70% of an injected dose is rapidly excreted unchanged in the urine (Williams 1959; Sperber 1949). Rabbits also excrete piperidine unchanged (Hildebrandt 1900). When injected intraventricularly into rats, piperidine disappeared exponentially with a half-life of 20 min (Meek 1973). In a more recent study, Okano et al (1978) found that in rats most of an i.p. dose of [3H]-piperidine was excreted unchanged. Two major metabolites were identified as 3- and 4-hydroxypiperidine. Both compounds were also found in untreated animals and thus are probably metabolites of piperidine of exogenous or endogenous origin. These metabolites represent a detoxification mechanism, since they lack the potent pharmacological activities of the parent compound. Two unidentified metabolites were assumed to be conjugates. In a much earlier study, Novello et al (1926) claimed that piperidine was excreted as the ethereal sulfate. Metabolic studies of analgesics and anesthetics containing the piperidine ring have demonstrated the occurrence of N-hydroxylation, formation of a 6-oxo-derivative, and C-oxidative ring cleavage (Oelschlager and Al Shaik 1985). N-nitrosopiperidine has been synthesized from piperidine and sodium nitrite in the gastric contents,R.L. Reed isolated stomach and isolated small intestine of rats (Alam et al 1971; Epstein 1972).


UN2401 Piperidine, Hazard Class: 8; Labels: 8-Corrosive material, 3-Flammable liquid.

Purification Methods

Dry piperidine with BaO, KOH, CaH2, or sodium, and fractionally distil (optionally from sodium, CaH2, or P2O5). Purify from pyridine by zone melting. [Beilstein 22 H 6, 22


Piperidine is a highly flammable liquid. Vapor may form explosive mixture with air (at room temperature). A medium-strong base. Reacts violently with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Piperidine neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides.

Check Digit Verification of cas no

The CAS Registry Mumber 110-89-4 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,1 and 0 respectively; the second part has 2 digits, 8 and 9 respectively.
Calculate Digit Verification of CAS Registry Number 110-89:
34 % 10 = 4
So 110-89-4 is a valid CAS Registry Number.



According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 12, 2017

Revision Date: Aug 12, 2017


1.1 GHS Product identifier

Product name piperidine

1.2 Other means of identification

Product number -
Other names Azacyclohexane

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only. Food additives -> Flavoring Agents
Uses advised against no data available

1.4 Supplier's details

1.5 Emergency phone number

Emergency phone number -
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

More Details:110-89-4 SDS

110-89-4Related news

Piperidine (cas 110-89-4) alkaloids from Alocasia macrorrhiza08/28/2019

Six previously undescribed piperidine alkaloids were isolated from the rhizomes of Alocasia macrorrhiza (L.) Schott. Their structures were elucidated based on 1D and 2D NMR, IR, HR-ESI-MS spectroscopic analysis and the application of a modified Mosher method. All isolated alkaloids were evaluate...detailed

Short communicationVapor-phase synthesis of Piperidine (cas 110-89-4) over SiO2 catalysts08/25/2019

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 selec...detailed

Mini-reviewRecent advancement of Piperidine (cas 110-89-4) moiety in treatment of cancer- A review08/23/2019

Piperidine is an important pharmacophore, a privileged scaffold and an excellent heterocyclic system in the field of drug discovery which provides numerous opportunities in studying/exploring this moiety as an anticancer agent by acting on various receptors of utmost importance. Cancer is an unc...detailed

Data articleInfluence of Piperidine (cas 110-89-4) ring on stability and reactivity of piperine08/22/2019

The influence of piperidine ring on chemical reactivity and stability of piperine (PPN) was elucidated using quantum chemistry calculations with Density Functional Theory at DFT/B3LYP/6-31G(d,p) level of theory. Conformational analysis and electronic properties for PPN were compared to piperic a...detailed

Piperidine (cas 110-89-4) alkaloids and xanthone from the roots of Caulophyllum robustum Maxim08/21/2019

Two undescribed piperidine racemates, (±)-caulophines A and B (1 and 2), a new N-containing xanthone derivative (3), together with six known piperidines, were isolated from the roots of Caulophyllum robustum Maxim. Their structures were determined by extensive spectroscopic techniques. Compound...detailed

110-89-4Relevant articles and documents

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.

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

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.


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

, p. 1534 - 1537 (1985)


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.

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.

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.

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.

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.

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.

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.


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.

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.

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.

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

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.

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.



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