67-63-0 Usage
Chemical Description
Different sources of media describe the Chemical Description of 67-63-0 differently. You can refer to the following data:
1. Isopropanol, also known as rubbing alcohol, is a colorless, flammable liquid used as a solvent and disinfectant.
2. Isopropanol is a solvent used in chiral HPLC.
description
Isopropanol is also known as isopropyl alcohol. It is the simplest secondary alcohol and is one of the isomers of n-propanol. It is a kind of flammable liquid which is colorless with strong smell being similar to the smell of the mixture of ethanol and acetone. It is soluble in water, alcohol, ether, benzene, chloroform and most organic solvents and is miscible with water, alcohol, ether and can form azeotrope with water. Density (specific gravity): 0.7863g/cm3, melting point:-88.5 ℃, boiling point: 82.5 ℃, flash point: 11.7 ℃, ignition point: 460 ℃, refractive index: 1.3772. Its vapor can cause slight irritation on the eyes, nose and throat; it can be absorbed through the skin. Its vapor can form explosive mixture with air. Its explosion limit is 2.0% to 12% (by volume). It belongs to a moderate explosive hazardous material and flammable, low toxic substance. The toxicity of its vapors is twice as high as ethanol while oral administration causes the opposite toxicity.
Figure 1 is the structural formula of isopropanol.
In many cases, isopropanol can substitute ethanol as the solvent and is a good solvent and chemical raw materials which can be applied to not only painting, pharmaceuticals, pesticides, cosmetics and other industries, but also the production of acetone, isopropyl ester, isopropylamine (the raw material for production of atrazine), di-isopropyl ether, isopropyl acetate and thymol crystal etc. It was the first product which is made from the petroleum raw material in the history of the development of petrochemicals.
Production Process
In 1855, Frenchman M. Berthelot first reported the production of isopropanol through the hydration reaction between propylene and sulfuric acid, called indirect hydration. In 1919, the Americans C. Ellis had conducted industrial development on this. At the end of 1920, the American Standard Oil Company of New Jersey adopted the approach of Ellis Act and established the production equipment for putting into formal production. In 1951, the British company Imperial Chemical Industries began to produce isopropanol with the direct hydration method from propylene. Since then, many countries have used this method and made related improvements.
Indirect hydration reaction: propylene is first reacted with sulfuric acid to obtain isopropyl hydrogen sulfate, which generates isopropanol after hydrolysis, and the reaction of the formula:
CH3CH = CH2 + H2SO4 → (CH3) 2CHOSO3H
(CH3) 2CHOSO3H + H2O─ → (CH3) 2CHOH + H2SO4
the concentration of the applied sulfuric acid is generally greater than 60% (by mass), and the reaction is conducted at 2~2.8MPa and 60~65 ° C; The hydrolysis reaction happens at slight increased pressure and at below 30 ° C.
Direct hydration: propylene directly has hydration reaction with water in the presence of a catalyst upon heating and increased pressure to generate isopropanol with a selectivity of 96%. Reaction is: CH3CH = CH2 + H2O → (CH3) 2CHOH; the used catalyst includes tungsten compound, phosphate and ion exchange resin; the commonly used catalyst is phosphoric acid catalyst with carrier (see solid acid catalyst) with conditions of 2~6MPa, 240~260 ° C. Compared with the indirect method, this method does not have issue regarding to sulfuric acid corrosion and dilute acid concentration and therefore, it dominant in industrial production.
The above information is edited by the lookchem of Dai Xiongfeng.
Uses
Different sources of media describe the Uses of 67-63-0 differently. You can refer to the following data:
1. Isopropyl alcohol is an important chemical products and raw materials. It is mainly applied to various fields including pharmaceutical, cosmetics, plastics, fragrances, paint as well as being used as the dehydrating agent and cleaning agent in and electronics industry. It can also be used as the reagent for determination of barium, calcium, magnesium, nickel, potassium, sodium and strontium. It can also be used as the reference material of chromatographic analysis.
In the manufacturing industry of circuit board, it is used as a cleaning agent, and the production of PCB holes for conductivity. Many people find that it can not only clean the motherboard with excellent performance, but also get the best results. In addition, it is used for other electronic devices, including cleaning disc cartridge, floppy disk drives, magnetic tape, and the laser tip of the disc driver of CD or DVD player.
Isopropyl alcohol can also be used as the solvent of oil and gel as well as for the manufacture of fishmeal feed concentrate. Low-quality isopropanol can also be used in automotive fuels. As the raw material of production of acetone, the usage amount of isopropanol is reducing. There are several compounds which are synthesized from isopropanol, such as isopropyl ester, methyl isobutyl ketone, di-isopropylamine, di-isopropyl ether, isopropyl acetate, thymol and many kinds of esters. We can supply isopropanol of different quality depending on the end use it. The conventional quality of anhydrous isopropanol is more than 99%, while the special grade isopropanol content is higher than 99.8% (for flavors and drugs).
2. Isopropyl alcohol is used in the production of acetone, isopropyl halides, glycerin, and aluminum isopropoxide; employed widely as an industrial solvent for paints, polishes, and insecticides; as an antiseptic (rubbing alcohol); and in organic synthesis for introducing the isopropyl or isopropoxy group into the molecule. Being a common laboratory solvent like methanol, the exposure risks are always high; however, its toxicity is comparatively low.
Toxicity
ADI value is not specified (FAO/WHO, 2001).
LD5050: 45rag/kg (rat, oral).
Limited use
FEMA (mg/kg): soft drinks: 25; sweets: 10 to 75; baked good: 75.
Description
Isopropanol is a clear, colorless alcohol that is used in the
production of acetone and as a solvent in the manufacture of
various industrial and commercial products. It is used by the
public for a number of different purposes and is commonly
known as rubbing alcohol. It is flammable and miscible with
both water and many different organic solvents. Isopropanol
can be prepared via three different methods: indirect hydration
of propylene (the ‘strong acid’ method), direct hydration of
propylene, and catalytic hydrogenation of acetone.
Chemical Properties
Isopropyl alcohol is a clear, colorless, mobile, volatile, flammable liquid with a characteristic, spirituous odor resembling that of a mixture of ethanol and acetone; it has a slightly bitter taste.It is miscible with water, ethyl ether, and ethyl alcohol. Isopropyl alcohol is incompatible with strong oxidizers, acetaldehyde, chlorine, ethylene oxide, acids, and isocyanates.
Occurrence
Reported found in apple and cognac aromas (esterified). Also found in apple, banana, grapefruit and lime
juice, melon, papaya, pear, onion, peas, rutabaga, tomato, wheat bread, cheeses, milk, boiled egg, cooked beef, pork and mutton, hop
oil beer, rum, cocoa, coffee, scotch whiskey, grape wines, peanut, pecan, soybean, honey, beans, plum brandy, walnut, crab, clam,
prickly pear and clary sage.
Preparation
Isopropyl alcohol may be prepared from propylene; by the catalytic reduction of acetone, or by fermentation of certain carbohydrates.
Definition
ChEBI: Isopropyl Alcohol is a secondary alcohol that is propane in which one of the hydrogens attached to the central carbon is substituted by a hydroxy group. It is an isomer of propyl alcohol with antibacterial properties.
Application
Isopropyl Alcohol is used in a variety of applications including as a solvent for industrial processes and coating; as a component in cleaning, car care and deicing products; as a wetting agent for printing inks and as a feedstock in the manufacture of ester and Mogas/Luboil additives.isopropyl alcohol is a carrier, anti-bacterial, and solvent for skin care lotions. Isopropyl alcohol is made from propylene, a petroleum derivative.When compared to ethanol, 50% less is required for nucleic acid precipitation, thus minimizing the total volume to be centrifuged for DNA or RNA recovery.Isopropyl alcohol 70% is used as an ingredient in alcohol swabs and alcohol wipes for wound cleaning, it is found in hand sanitizers, and in ear drops to prevent swimmer's ear.
Aroma threshold values
Detection: 40 to 601 ppm
General Description
Volatile, colorless liquid with a sharp musty odor like rubbing alcohol. Flash point of 53°F. Vapors are heavier than air and mildly irritating to the eyes, nose, and throat. Density approximately 6.5 lb / gal. Used in making cosmetics, skin and hair preparations, pharmaceuticals, perfumes, lacquer formulations, dye solutions, antifreezes, soaps, window cleaners. Sold in 70% aqueous solution as rubbing alcohol.
Air & Water Reactions
Highly flammable. Water soluble.
Reactivity Profile
Isopropyl Alcohol can react with AIR and OXYGEN over time to form unstable peroxides that can explode. Contact with 2-butanone increases the rate of peroxide formation. An explosive reaction occurs when Isopropanol is heated with (aluminum isopropoxide + crotonaldehyde). Forms explosive mixtures with trinitromethane and hydrogen peroxide. Reacts with barium perchlorate to form a highly explosive compound. Ignites on contact with dioxygenyl tetrafluoroborate, chromium trioxide and potassium-tert-butoxide. Vigorous reactions occur with (hydrogen + palladium), nitroform, oleum, COCl2, aluminum triisopropoxide and oxidizing agents. Reacts explosively with phosgene in the presence of iron salts. Incompatible with acids, acid anhydrides, halogens and aluminum . Isopropanol can react with PCl3, forming toxic HCl gas. (Logsdon, John E., Richard A. Loke., sopropyl Alcohol. Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. 1996.).
Health Hazard
Exposures to isopropyl alcohol cause irritation to the eyes and mucous membranes. Exposures to isopropyl alcohol for 3–5 min (400 ppm) caused mild irritation of the eyes, nose, and throat, and at 800 ppm these symptoms became severe. Ingestion or an oral dose of 25 mL in 100 mL of water produced hypotension, facial flushing, bradycardia, and dizziness. Ingestion in large quantities caused extensive hemorrhagic tracheobronchitis, bronchopneumonia, and hemorrhagic pulmonary edema. Prolonged skin contact with isopropyl alcohol caused eczema and sensitivity. Delayed dermal absorption is attributed to a number of pediatric poisonings that have occurred following repeated or prolonged sponge bathing with isopropyl alcohol to reduce fever. In several cases, symptoms included respiratory distress, stupor, and coma. Laboratory animals exposed to isopropyl alcohol develop poisoning with symptoms of hind leg paralysis, unsteadiness, lack of muscular coordination, respiratory depression, and stupor. Isopropyl alcohol is a potent CNS depressant, and in large doses causes cardiovascular depression.
Fire Hazard
Isopropyl Alcohol(IPA) is highly flammable in its liquid and vapor forms and flammable atmospheres can be created at temperatures as low as 540°F /120℃ . This means that any environment where IPA is being used needs to be well ventilated. It should be kept away from heat and open flame. As the vapour is heavier than air, it may spread along the ground, so care needs to be taken that the vapour is not ignited by a distant source.
Pharmaceutical Applications
Isopropyl alcohol (propan-2-ol) is used in cosmetics and pharmaceutical
formulations, primarily as a solvent in topical formulations.( It is not recommended for oral use owing to its toxicity.
Although it is used in lotions, the marked degreasing properties
of isopropyl alcohol may limit its usefulness in preparations used
repeatedly. Isopropyl alcohol is also used as a solvent both for tablet
film-coating and for tablet granulation, where the isopropyl
alcohol is subsequently removed by evaporation. It has also been
shown to significantly increase the skin permeability of nimesulide
from carbomer 934.
Isopropyl alcohol has some antimicrobial activity and a 70% v/v aqueous solution is used as a topical disinfectant.
Therapeutically, isopropyl alcohol has been investigated for the
treatment of postoperative nausea or vomiting.
Safety
Isopropyl alcohol is about twice as toxic as ethanol and should therefore not be administered orally; isopropyl alcohol also has an unpleasant taste. Symptoms of isopropyl alcohol toxicity are similar to those for ethanol except that isopropyl alcohol has no initial euphoric action, and gastritis and vomiting are more prominent; see Alcohol. Delta osmolality may be useful as rapid screen test to identify patients at risk of complications from ingestion of isopropyl alcohol. The lethal oral dose is estimated to be about 120–250mL although toxic symptoms may be produced by 20 mL.Adverse effects following parenteral administration of up to 20mL of isopropyl alcohol diluted with water have included only a sensation of heat and a slight lowering of blood pressure. However, isopropyl alcohol is not commonly used in parenteral products.Although inhalation can cause irritation and coma, the inhalation of isopropyl alcohol has been investigated in therapeutic applications.Isopropyl alcohol is most frequently used in topical pharmaceutical formulations where it may act as a local irritant. When applied to the eye it can cause corneal burns and eye damage.LD50 (dog, oral): 4.80 g/kgLD50 (mouse, oral): 3.6 g/kgLD50 (mouse, IP): 4.48 g/kgLD50 (mouse, IV): 1.51 g/kgLD50 (rabbit, oral): 6.41 g/kgLD50 (rabbit, skin): 12.8 g/kgLD50 (rat, IP): 2.74 g/kgLD50 (rat, IV): 1.09 g/kgLD50 (rat, oral): 5.05 g/kg
Synthesis
Synthetically prepared from acetylene or propylene.
Carcinogenicity
CD-1 mice were exposed by inhalation
to 0, 500, 2500, or 5000 ppm of isopropanol vapor for
6 h/day, 5 days/week for 18 months. An additional group of
mice (all exposure levels) were assigned to a recovery group
that were exposed to isopropanol for 12 months and then
retained until study termination at 18 months. There was
no increased frequency of neoplastic lesions in any of the
isopropanol-exposed animals. Nonneoplastic lesions were
limited to the testes (males) and the kidney. In the testes,
enlargement of the seminal vesicles occurred in the absence
of associated inflammatory or degenerative changes. The
kidney effects included tubular proteinosis and/or tubular
dilatation. The incidence of testicular and kidney effects
was not increased in the isopropanol-exposed recovery
animals.
Environmental Fate
The vast majority of isopropanol in the environment originates
from manufacturing processes. Small amounts are
produced by certain microbes, fungi, and yeast. The high
volatility of isopropanol ensures that when it is released
into the environment in any state, it eventually ends up in
the atmosphere. There, it can be degraded by hydroxyl radicals
or it can return to soil or water through precipitation. Its
half-life in the environment is approximately 3.2 days and is
highly biodegradable; bioaccumulation in plants and animals
does not occur.
storage
Isopropyl alcohol should be stored in a cool, dry, well-ventilated area in tightly sealed containers with a proper label. Outside or detached storage is preferable. Inside storage should be a flammable liquids storage room or cabinet. Workers should not store isopropyl alcohol above 37°C (100°F). Containers of isopropyl alcohol should be protected from physical damage and contact with air, and should be stored separately from strong oxidizers, acetaldehyde, chlorine, ethylene oxide, acids, and isocyanates. Isopropyl alcohol should be transported to the nearest laboratory as quickly as possible in cool containers.
Purification Methods
Isopropyl alcohol is prepared commercially by dissolution of propene in H2SO4, followed by hydrolysis of the sulfate ester. Major impurities are water, lower alcohols and oxidation products such as aldehydes and ketones. Purification of isopropanol follows substantially the same procedure as for n-propyl alcohol. Isopropanol forms a constant-boiling mixture, b 80.3o, with water. Most of the water can be removed from this 91% isopropanol by refluxing with CaO (200g/L) for several hours, then distilling. The distillate can be dried further with CaH2, magnesium ribbon, BaO, CaSO4, calcium, anhydrous CuSO4 or Linde type 5A molecular sieves. Distillation from sulfanilic acid removes ammonia and other basic impurities. Peroxides [indicated by liberation of iodine from weakly acid (HCl) solutions of 2% KI] can be removed by refluxing with solid stannous chloride or with NaBH4 then the alcohol is fractionally distilled. To obtain isopropanol containing only 0.002M of water, sodium (8g/L) is dissolved in material dried by distillation from CaSO4. Isopropyl benzoate (35mL) is then added and, after refluxing for 3hours, the alcohol is distilled through a 50-cm Vigreux column (p 11). [Hine & Tanabe J Am Chem Soc 80 3002 1958.] Other purification steps for isopropanol include refluxing with solid aluminium isopropoxide, refluxing with NaBH4 for 24hours, and removing acetone by treatment with, and distillation from, 2,4-dinitrophenylhydrazine. Peroxides re-form in isopropanol if it is kept for several days in contact with air. [Beilstein 1 IV 1461.]
Toxicity evaluation
Isopropanol is similar to other alcohols in its ability to induce
central nervous system (CNS) depression by enhancing
inhibitory neuronal activity and antagonizing excitatory
neuronal activity. It also can cause localized irritation upon
contact with skin and mucous membranes after dermal exposure
and ingestion, respectively.
Incompatibilities
Incompatible with oxidizing agents such as hydrogen peroxide and
nitric acid, which cause decomposition. Isopropyl alcohol may be
salted out from aqueous mixtures by the addition of sodium
chloride, sodium sulfate, and other salts, or by the addition of
sodium hydroxide.
Precautions
Workers should wash hands and face thoroughly after handling isopropyl alcohol. Workers should wear gloves, safety glasses and a face shield, boots, apron, and a full impermeable suit is recommended if exposure is possible to a large portion of the body.
Regulatory Status
Included in the FDA Inactive Ingredients Database (oral capsules,
tablets, and topical preparations). Included in nonparenteral
medicines licensed in the UK. Included in the Canadian List of
Acceptable Non-medicinal Ingredients.
Check Digit Verification of cas no
The CAS Registry Mumber 67-63-0 includes 5 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 2 digits, 6 and 7 respectively; the second part has 2 digits, 6 and 3 respectively.
Calculate Digit Verification of CAS Registry Number 67-63:
(4*6)+(3*7)+(2*6)+(1*3)=60
60 % 10 = 0
So 67-63-0 is a valid CAS Registry Number.
InChI:InChI=1/C3H8O/c1-2-3-4/h4H,2-3H2,1H3
67-63-0Relevant articles and documents
HOMOGENEOUS HYDROGENATION OF KETONES TO ALCOHOLS WITH RUTHENIUM COMPLEX CATALYSTS
Sanchez-Delgado, R.A.,Ochoa, O.L. De
, p. 427 - 434 (1980)
A number of ruthenium triphenylphosphine complexes catalyse the reduction of ketones to their corresponding alcohols in the presence of water.The most convenient catalyst precursors are carbonyl containing complexes which do not promote decarbonylation of the substrate.The hydrogenation of acetone with hydridochlorocarbonyltris(triphenylphosphine)ruthenium is first order with respect to the substrate concentration, the catalyst concentration, the hydrogen pressure and the water concentration.Turnover numbers up to 15,000 have been achieved with this catalyst.Other ketones are also reduced by RuHCl(CO)(PPh3)3 and the rate of the reaction is dependent on the nature of the substrate.
Nucleophilic substitution in radicals derived from isopropyl chloride
Kosobutskii
, p. 1050 - 1052 (2003)
-
Kinetics of an Associative Ligand-Exchange Process: Alcohol Exchange with Arsenate(V) Triesters
Baer, Carl D.,Edwards, John O.,Kaus, Malcolm J.,Richmond, Thomas G.,Rieger, Philip H.
, p. 5793 - 5798 (1980)
The rate of alcohol exchange with trialkyl arsenates has been studied by three techniques.Exchange of the straight-chain alcohols (ethyl, n-propyl, n-butyl, and n-pentyl) was studied in acetonitrile solution by using proton NMR line broadening.Activation enthalpies and entropies were found in the ranges 1 to 6kJ mol-1 and -204 and -226 J mol-1 K-1, respectively.The reactions are subject to acid catalysis for which slightly higher ΔH and less negative ΔS values were found.Methyl exchange, studied by the same technique, is about one powere of ten faster.Isopropyl exchange, about three powers of ten slower, was studied in acetonitrile and dichloromethane solutions by deuterium labeling, using proton NMR.The interchange reaction of benzyl alcohol with triisopropyl arsenate in acetonitrile or dichloromethane was followed by spectrophotometry.Hydrogen bonding between alcohol and ester (which complicates order determination) was observed when reactants were at concentrations greater than about 10-2 M.The strongly associative mechanism is discussed.
Hydrodeoxygenation of glycerol into propanols over a Ni/WO3–TiO2 catalyst
Greish, Alexander A.,Finashina, Elena D.,Tkachenko, Olga P.,Nikul'shin, Pavel A.,Ershov, Mikhail A.,Kustov, Leonid M.
, p. 119 - 120 (2020)
Hydrodeoxygenation of glycerol in a flow reactor over a bifunctional Ni/WO3–TiO2 catalyst at 240–255 °C and hydrogen pressure of 3 MPa affords propan-1-ol and propan-2-ol in total yield of 94%.
Electrode Potential of a Dispersed Raney Nickel Electrode during Acetone Hydrogenation: Influence of the Solution and Reaction Kinetics
Pardillos-Guindet, J.,Vidal, S.,Court, J.,Fouilloux, P.
, p. 12 - 20 (1995)
The hydrogenation of acetone was investigated in basic aquueous solutions with undoped and chromium-doped catalysts.The reaction was carried out under pressure in an autoclave equipped with a reference electrode.The consumption of hydrogen and the electrode potential were measured during the course of the reaction.A mathematical model was applied which fits the experimental kinetic data well.It allows the computation of the rate constant and the absorption equilibrium constants.The kinetics obey a Langmuir-Hinshelwood mechanism with competitive adsorption.The metallic catalyst particles behave like a dispersed electrode and an electrochemical double layers is formed at their surface.In the presence of hydrogen alone, the metal potential obeys the Nernst law for the hydrogen electrode.During acetone hydrogenation, the double layer is modified and the measured potential goes to the positive region for several tens of millivolts, depending on whether the catalyst is doped or not.In all cases an experimental correlation was found between this experimental potential rise and the reaction rate.
CATALYTIC AND STOICHIOMETRIC REDUCTION OF KETONES AND ALDEHYDES BY THE HYDRIDOTETRACARBONYL FERRATE ANION
Marko, Laszlo,Radhi, Mazin A.,Otvos, Irma
, p. 369 - 376 (1981)
Acetone is catalytically reduced to isopropyl alcohol by carbon monoxide and water in the presence of iron carbonyls and triethylamine at 100 deg C and 100 bar.Use of NaOH in place of triethylamine gives a much less efficient catalyst system.The Et3NH*HFe(CO)4 system also catalyses the reduction of n-butyraldehyde to n-butyl alcohol at room temperature in a fast stoichiometric reaction, whereas NaHFe(CO)4 is inactive under the same conditions.The Et3NH+ cation is necessary for the transfer of a proton to the carbonyl group, while the HFe(CO)4- anion carries out nucleophilic attack on carbonyl group and supplies the hydride ion.
Catalytic reduction of acetophenone with transition metal systems containing chiral bis(oxazolines)
Gómez, Montserrat,Jansat, Susanna,Muller, Guillermo,Bonnet, Michel C,Breuzard, Jérémy A.J,Lemaire, Marc
, p. 186 - 195 (2002)
The catalytic behaviour of several Ru, Rh and Ir systems containing bis(oxazoline) ligands (1-6) has been tested in the asymmetric reduction of acetophenone (7) to give 1-phenylethanol (8) by hydrogenation (Ir systems), transfer hydrogenation (Ir and Ru s
-
Osburn,Werkman
, p. 417 (1935)
-
Engineered alkane-hydroxylating cytochrome P450BM3 exhibiting nativelike catalytic properties
Fasan, Rudi,Chen, Mike M.,Crook, Nathan C.,Arnold, Frances H.
, p. 8414 - 8418 (2007)
(Figure Presented) Divide, evolve, and conquer: A domain-based strategy (see scheme) was used to engineer high catalytic and coupling efficiency for propane hydroxylation in a multidomain cytochrome P450 enzyme. The engineered enzymes exhibit high total activities in whole-cell bioconversions of propane to propanol under mild conditions, using air as oxidant.
Synthesis of uniform titanium and 1:1 strontium-titanium carboxyhydrosols by controlled hydrolysis of alkoxymetal carboxylate precursors
Riman,Landham,Bowen
, p. 821 - 826 (1989)
Uniform inorganic carboxhydrosols containing titanium or strontium and titanium cations were precipitated from isopropyl alcohol solutions by the controlled hydrolysis of metal alkoxycarboxylate precursors. The hydrolysis of various triisopropoxytitanium carboxylate compounds yielded the capability to control particle size. Spherical particles of carboxyhydrosols were prepared in mean sizes from 0.4 to 2.9 μm. Controlled hydrolysis of quintaisopropoxystrontium titanium octanoate resulted in slightly agglomerated, uniform 1-μm spheres in a solvent medium in which controlled precipitation of uniform powders was not previously possible. Conversion of the hydrous oxide carboxylate precipitate to the oxide via calcination or hydrothermal treatment was possible.
Propane reacts with O2 and H2 on gold supported TS-1 to form oxygenates with high selectivity
Bravo-Suarez,Bando,Akita,Fujitani,Fuhrer,Oyama
, p. 3272 - 3274 (2008)
Gold nanoparticles supported on a microporous titanosilicate (TS-1) were found to be highly selective (95%) towards the formation of acetone and isopropanol from propane, O2, and H2 at moderate temperatures (443 K). The Royal Society of Chemistry.
Hydrogenation of acetone on technetium catalysts
Rimar,Pirogova
, p. 398 - 401 (1998)
The catalytic properties of supported mono-and bimetallic catalysts of the Tc/support, M/support, and M-Tc/support types (M = Pt, Pd, Rh, Ru, Ni, Re, Co; supports are γ-Al2O3, MgO, SiO2) were investigated in the acetone hydrogenation. The main products of this reaction are isopropyl alcohol and propane. The catalytic activity in the acetone hydrogenation of the metals studied decreases in the consequence Pt > Tc ≈ Rh > Pd > Ru > Ni ≈ Re > Co (with γ-Al2O3 as the support). The influence of support nature on the catalytic activity was investigated for the Rh-Tc system as an example. A nonadditive increase in the catalytic activity of Rh-Tc/γ-Al203 in comparison with monometallic catalysts was found. The state of the surface of the catalysts was characterized by the UV-VIS diffuse reflectance spectra.
EFFECT OF ISOTOPE SUBSTITUTION ON THE MAGNITUDE OF NONEQUILIBRIUM NUCLEAR POLARIZATION IN PHOTOLYSIS OF ACETONE IN METHANOL
Skakovskii, E. D.,Tychinskaya, L. Yu.,Rykov, S. V.,Yankelevich, A. Z.
, p. 2456 - 2459 (1989)
Polarization of nuclei in both the products of the reactions and in the CHD2OD proton without polarization in the CH3OH protons is observed in irradiation of a solution of acetone in CD3OD in the presence of CHD2OD and CH3OH.Polarization of the protons of the products is strongly dependent on the temperature of the solution and arises in radical pairs; polarization of the proton of partially deuterated methyl alcohol is due to a mechanism of optical nuclear polarization.It was hypothesized that the isotope effect is due to a difference in proton and electron relaxation and to a difference in the rates of cross-relaxation transitions.
Dubey, R. K.,Singh, A.,Mehrotra, R. C.
, p. 169 - 176 (1988)
Ruthenium carbonyl carboxylate complexes with nitrogen-containing ligands III. Catalytic activity in hydrogenation
Frediani, Piero,Bianchi, Mario,Salvini, Antonella,Guarducci, Roberto,Carluccio, Luciano C.,Piacenti, Franco
, p. 187 - 198 (1995)
Several mononuclear and dinuclear ruthenium carbonyl acetate complexes containing bipyridine or phenanthroline have been tested as catalysts in the hydrogenation of alkenes, alkynes and ketones.They are active in polar solvents and in water and the nitrogen-containing ligands are unaltered at the end of the hydrogenation.Keywords: Ruthenium; Carbonyl complexes; N-donors; Hydrogenation; Catalysis; Homogeneous
The role played by acid and basic centers in the activity of biomimetic catalysts of the catalase, peroxidase, and monooxidase reactions
Magerramov,Nagieva
, p. 1895 - 1900 (2010)
The acid-basic centers of heterogeneous carriers of catalase, peroxidase, and monooxigenase biomimetics, in particular, iron protoporphyrin deposited on active or neutral aluminum magnesium silicate, were studied. The catalytic activity of biomimetics was stabilized, which allowed us not only to synthesize fairly effective biomimetics but also to clarify certain details of the mechanism of their action and perform a comparative analysis of the functioning of biomimetics and the corresponding enzymes.
A Cross-Correlation Mechanism for the Formation of Spin Polarization
Tsentalovich, Yu. P.,Frantsev, A. A.,Doktorov, A. B.,Yurkovskaya, A. V.,Sagdeev, R. Z.
, p. 8900 - 8908 (1993)
Photolysis of acetone in the presence of various hydrogen donors and of 3-hydroxy-3-methyl-2-butanone involves the formation of propan-2-olyl radicals which show both electron and nuclear spin polarization.The electron polarization of the radicals leads to additional nuclear polarization of the reaction products.Transfer of electron to nuclear polarization can occur by cross-relaxation and cross-correlation.The latter is descibed in detail.Experimentally, the mechanisms leads to a formation of net nuclear polarization for symmetrical radical pairs as well as an unusual kinetic behavior of multiplet effects.
Brunelli, M.,Perego, G.,Lugli, G.,Mazzei, A.
, (1979)
Time-Dependent Self-Assembly of Copper(II) Coordination Polymers and Tetranuclear Rings: Catalysts for Oxidative Functionalization of Saturated Hydrocarbons
Costa, Ines F. M.,Kirillova, Marina V.,André, Vania,Fernandes, Tiago A.,Kirillov, Alexander M.
supporting information, p. 14491 - 14503 (2021/07/19)
This study describes a time-dependent self-assembly generation of new copper(II) coordination compounds from an aqueous-medium reaction mixture composed of copper(II) nitrate, H3bes biobuffer (N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid), ammonium hydroxide, and benzenecarboxylic acid, namely, 4-methoxybenzoic (Hfmba) or 4-chlorobenzoic (Hfcba) acid. Two products were isolated from each reaction, namely, 1D coordination polymers [Cu3(μ3-OH)2(μ-fmba)2(fmba)2(H2O)2]n (1) or [Cu2(μ-OH)2(μ-fcba)2]n (2) and discrete tetracopper(II) rings [Cu4(μ-Hbes)3(μ-H2bes)(μ-fmba)]·2H2O (3) or [Cu4(μ-Hbes)3(μ-H2bes)(μ-fcba)]·4H2O (4), respectively. These four compounds were obtained as microcrystalline air-stable solids and characterized by standard methods, including the single-crystal X-ray diffraction. The structures of 1 and 2 feature distinct types of metal-organic chains driven by the μ3- or μ-OH- ligands along with the μ-benzenecarboxylate linkers. The structures of 3 and 4 disclose the chairlike Cu4 rings assembled from four μ-bridging and chelating aminoalcoholate ligands along with μ-benzenecarboxylate moieties playing a core-stabilizing role. Catalytic activity of 1-4 was investigated in two model reactions, namely, (a) the mild oxidation of saturated hydrocarbons with hydrogen peroxide to form alcohols and ketones and (b) the mild carboxylation of alkanes with carbon monoxide, water, and peroxodisulfate to generate carboxylic acids. Cyclohexane and propane were used as model cyclic and gaseous alkanes, while the substrate scope also included cyclopentane, cycloheptane, and cyclooctane. Different reaction parameters were investigated, including an effect of the acid cocatalyst and various selectivity parameters. The obtained total product yields (up to 34% based on C3H8 or up to 47% based on C6H12) in the carboxylation of propane and cyclohexane are remarkable taking into account an inertness of these saturated hydrocarbons and low reaction temperatures (50-60 °C). Apart from notable catalytic activity, this study showcases a novel time-dependent synthetic strategy for the self-assembly of two different Cu(II) compounds from the same reaction mixture.
Hydrogen-Catalyzed Acid Transformation for the Hydration of Alkenes and Epoxy Alkanes over Co-N Frustrated Lewis Pair Surfaces
Deng, Qiang,Deng, Shuguang,Gao, Ruijie,Li, Xiang,Tsang, Shik Chi Edman,Wang, Jun,Zeng, Zheling,Zou, Ji-Jun
, p. 21294 - 21301 (2021/12/17)
Hydrogen (H2) is widely used as a reductant for many hydrogenation reactions; however, it has not been recognized as a catalyst for the acid transformation of active sites on solid surface. Here, we report the H2-promoted hydration of alkenes (such as styrenes and cyclic alkenes) and epoxy alkanes over single-atom Co-dispersed nitrogen-doped carbon (Co-NC) via a transformation mechanism of acid-base sites. Specifically, the specific catalytic activity and selectivity of Co-NC are superior to those of classical solid acids (acidic zeolites and resins) per micromole of acid, whereas the hydration catalysis does not take place under a nitrogen atmosphere. Detailed investigations indicate that H2 can be heterolyzed on the Co-N bond to form Hδ-Co-N-Hδ+ and then be converted into OHδ-Co-N-Hδ+ accompanied by H2 generation via a H2O-mediated path, which significantly reduces the activation energy for hydration reactions. This work not only provides a novel catalytic method for hydration reactions but also removes the conceptual barriers between hydrogenation and acid catalysis.