127-06-0 Usage
Description
Acetone oxime, also known as 2-methyl-2-oximinopropane, is an organic compound that exists as white needle-like crystals. It has a melting point of 61°C and a boiling point ranging from 136°C to 134.8°C, depending on the pressure. The relative density of acetone oxime is 0.9113, and it has a refractive index of 1.4156. Acetone oxime is highly soluble in water, ethanol, ether, and acetone, and is also soluble in acid. However, it is easily hydrolyzed in dilute acid and tends to volatilize quickly in the air.
Uses
1. Organic Synthesis and Agriculture:
Acetone oxime is used as an intermediate in organic synthesis and is also utilized in the agricultural industry. Its versatility as a compound allows it to be a valuable component in various chemical reactions and applications.
2. Analytical Reagent for Cobalt Determination:
In the field of analytical chemistry, acetone oxime serves as a reagent for the determination of cobalt. This application highlights its importance in the accurate measurement and analysis of cobalt in different samples.
3. Intermediates in the Production of Caffeine, Theophylline, and SMD:
Acetone oxime is used as an intermediate in the synthesis of various compounds, including caffeine, theophylline, and SMD (S-Methyl-L-Dopa). These substances have wide-ranging applications in the pharmaceutical industry, with caffeine being a popular stimulant and theophylline used as a bronchodilator.
4. Test Reagents for Chromium and Organic Synthesis:
Acetone oxime is also used as test reagents for chromium, in addition to its role in organic synthesis. This demonstrates its utility in detecting and analyzing chromium in various samples.
5. Novel Oxygen Scavenger in Boiler Water:
As a novel oxygen scavenger, acetone oxime is used in boiler water to prevent corrosion and improve the efficiency of the boiler system.
6. Raw Materials for Pharmaceutical, Pesticide, Dyes, and Organic Silane Coupling Agents:
Acetone oxime is employed as a raw material in the production of pharmaceuticals, pesticides, dyes, and organic silane coupling agents. Its diverse applications across these industries underscore its importance in the chemical and manufacturing sectors.
7. Analytical Reagent for Nickel and Cobalt Identification:
In addition to its use in cobalt determination, acetone oxime is also used as an analytical reagent for identifying nickel. This further emphasizes its role in the field of analytical chemistry and the identification of specific metal elements.
Physical and Chemical Properties
Acetone oxime (Abbreviation DMKO for short), also known as dimethyl ketone oxime, is a white flaky crystal at room temperature, relative density: 0.9113, melting point: 60 ℃, flash point: 47.2 ℃, boiling point: 134.8 ℃, toxicity LD50: 5500mg/kg. It is soluble in water and alcohol, ether and other solvents, saturated aqueous solubility is 25% (mass percentage), its aqueous solution is neutral, it hydrolyzes easily in dilute acid, can make potassium permanganate fading at room temperature. Mainly used as chemical oxygen scavenger for industrial boiler feed water, compared with the traditional boiler chemical oxygen scavenger, it has characteristics of less dosage, high oxygen removal efficiency, non-toxic, pollution-free. It is the best drug for the outage protection and passivation treatment of subcritical boiler, also is the ideal products of substituted hydrazine and other traditional chemical oxygen scavengers in medium and high pressure boiler feed water.
Figure 1 the molecular structure of Acetone oxime.
chemical reaction
Acetone oxime has a strong reduction, it is easy to react with oxygen in water to reduce the dissolved oxygen content in water, reaction is as follows:
2C3H7NO + O2 → 2C3H6CO + N2O + H2O and 4 (CH3) 2C = N-OH + O2 → 4 (CH3) 2C = O + 2N2 + H2O
Meanwhile, Acetoxime also reacts with the metal for passivation, reaction is as follows:
2C3H7NO + 6Fe2O3 → 2C3H6CO + N2O + 4Fe3O4 + H2O
Acetoxime can reduce the content of iron in the feed water, to prevent overheating of the metal pipe and corrosion damage of the boiler due to the formation of iron oxide deposits, while with the cleaning effect for copper corrosion products deposited on pipes, economizer, etc. This is the reason that in the early use of acetone oxime, the content of copper in boiler water will be significantly higher.
Decomposition products of Acetoxime are mainly nitrogen and water, a small amount of formic acid, acetic acid, nitrogen oxides and so on. On the premise of ensuring oxygen removal effect, when the residual amount of DMKO in feed water is controlled to be 5~40μg/L, the formic acid, acetic acid, Cl-, SO42 + was not detected in all tested samples of water vapor, at the same time NO2-and NO3-content of same samples were tested, are also not detected. Therefore, there is no any adverse effects for the use of acetone oxime oxygen in vapor system.
Production method
It is obtained by the reaction of acetone with hydroxylamine hydrochloride. The hydroxylamine hydrochloride solution was slowly added dropwise in acetone, the reaction temperature is controlled at 40-50 ℃. The oximation reaction liquild was neutralized by 40% sodium hydroxide up to basic (pH7-8), cooling and filtration, the crude product was filtered off and add the zeolite, atmospheric distillation, cooling to obtain the finished product crystals.
Passivation agent after Boiler pickling
After the boiler pickling, the metal surface has high activity, it is necessary to use passivating agent to generate dense protective film on metal surfaces to prevent secondary corrosion of metal. Multi-hydrazine, sodium nitrite, sodium tripolyphosphate, etc, is conventionally used as passivating agent. Although the hydrazine and sodium pin Asia have a good passivation effect, but the drug itself has significant side effects to operators and users, it is difficult to handle passivation solution, and it pollutes the environment. Although Passivation method of sodium tripolyphosphate has advantages that its process is simple, liquid waste is easy to handle, but easily lead to the boiler water PH value lower after the unit started, bring some difficulties to control and process the water vapor quality. The experiment proved that replacement of the above passivating agents by acetone oxime (dimethyl ketone oxime) can obtain a satisfactory or better result. And it has the advantages of less dosage, emissions non-toxic pollution-free and so on.
General passivation parameters:
The concentration of Passivating agent: 8000-900mg/l
PH value (ammonia tone) of passivation solution: 9.50-11
The temperature of purified fluid (atmospheric pressure cleaning system): 85-90
Purification Time: 14-18h
Thermal Equipment Disable protection agent
Due to this product has a strong reduction, the solution can form a good magnetic film on the steel surface, thereby effectively delay corrosion during downtime of the thermal equipment. The solution containing acetone oxime (dimethyl ketone oxime) can be implemented in wet protection, can obtain significant inhibition effect.
concentration of Protection liquild: 350-400mg/l (water preparation)
PH:> 10.5 (ammonia adjustment)
During protection, should note:
1. Due to sampling and other reasons that result in loss of protective agents, use dosing devices regularly serviced.
2. The samples tested once a week or a half months, if the concentration of protection liquild is stable, the slow decline for the concentration of iron and oxygen is a normal phenomenon, on the contrary should pinpoint the cause.
Hazards & Safety Information
Category: Oxidant
Toxicity grading: Moderately toxic
Acute toxicity
Oral-rat LD50:> 500 mg/kg, intraperitoneal-Mouse LD50: 4000 mg/kg
Flammability hazard characteristics: In case of fire, it is combustible. Thermal decomposition releases nitrogen oxide gases.
Storage Characteristics: Treasury ventilation, low temperature drying, light loading and unloading, it is stored separately from oxidant and acid.
Extinguishing agent: foam, Carbon dioxide, dry powder, sand
Safety Profile
Moderately toxic by ingestion andintraperitoneal routes. When heated to decomposition itemits toxic fumes of NOx.
Purification Methods
It crystallises from pet ether (b 40-60o) and can be sublimed. [Beilstein 1 H 649, 1 IV 3202.]
Check Digit Verification of cas no
The CAS Registry Mumber 127-06-0 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,2 and 7 respectively; the second part has 2 digits, 0 and 6 respectively.
Calculate Digit Verification of CAS Registry Number 127-06:
(5*1)+(4*2)+(3*7)+(2*0)+(1*6)=40
40 % 10 = 0
So 127-06-0 is a valid CAS Registry Number.
InChI:InChI=1/C3H7NO/c1-3(2)4-5/h5H,1-2H3
127-06-0Relevant articles and documents
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Stewart
, p. 410 (1905)
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Rates of Formation of Iminium Ions from Acetone and Monoprotonated 2-pyrrolidine
Hine, Jack,Evangelista, Ramon A.
, p. 3890 - 3892 (1980)
The kinetics of the reaction of 2-pyrrolidine (1) with acetone has been studied by experiments in which the reversibly formed iminium ion is captured irreversibly by hydroxylamine.From experiments over the pH range 8.5-10.6 rate constants for iminium ion formation from 1 and 1-H+ were obtained.These rate constants were smaller than the corresponding rate constant for pyrrolidine, but the value for 1-H+ was large enough to show that the intermediate carbinolamine was undergoing internal acid-catalyzed dehydration to give the iminium ion.
Keana et al.
, p. 119 (1972)
Stereochemical and electronic interaction studies of α-heterosubstituted acetone oximes
Olivato, P. R.,Ribeiro, D. S.,Rittner, R.,Hase, Y.,Pra del, D.,Bombieri, G.
, p. 1479 - 1496 (1995)
The free νC=N bands in the IR spectra of some α-heterosubstituted acetone oximes show the existence of only a monomeric form in chloroform solutions below 1E-2 M, while in carbon tetrachloride self-associated species are also present.The 1H and 13C NMR chemical shift data indicate the predominance of the E over the Z isomer.The ΔνC=N frequency shifts and molecular mechanics strongly suggest that the oximes are in the gauche conformation.X-ray diffraction data have shown that the single dimethylaminoacetone oxime isomer exists in the E configuration and gauche conformation.Non-additivity effects for the α-methylene carbon chemi cal shifts seem to indicate the occurence of a ?C=N/?*C-x interaction besides the ?*C=N/?C-X hyperconjugative interaction.
Chilton,Gowenlock
, (1953)
Kinetics and mechanism of the copper-catalysed oxygenation of 2-nitropropane
Balogh-Hergovich, Eva,Greczi, Zoltan,Kaizer, Jozsef,Speier, Gabor,Reglier, Marius,Giorgi, Michel,Parkanyi, Laszlo
, p. 1687 - 1696 (2002)
Primary and secondary nitro compounds react with dioxygen in the presence of copper metal and N ligands such as N,N,N′,N′-tetramethylethylenediamine (tmeda), 2,2′-bipyridine (bpy), and 1,10-phenantroline (phen) in various solvents to form aldehydes or ketones. More coordinating solvents as well as donor N ligands accelerate the reaction remarkably. The oxygenolysis of 2-nitropropane (NPH) in the presence of copper and tmeda in DMF results in acetone and acetone oxime. The amount of tmeda influences the chemoselectivity, higher tmeda concentrations preferentially lead to the formation of the oxime. The kinetics of the reaction, measured at 90 °C, resulted in a rate equation of first-order dependence on copper and dioxygen and second-order dependence on 2-nitropropane. The rate constant, activation enthalpy, and entropy at 363.16 K are as follows: kcat = (5.37 ± 0.34) × 10-2 Mol-3 dm9 s-1, Ea = 131 ± 4 kJ mol-1, ΔH? = 127 ± 4 kJ mol-1 and ΔS? = 80 ± 13 J mol-1 K-1. The catalytically active intermediates CuII(NP)2(tmeda) and CuII(NO2)2(tmeda) in the catalytic cycle were isolated and their structures determined by X-ray crystallography. The kinetics of the stoichiometric oxygenation of CuII(NP)2(tmeda) to CuII(NO2)2(tmeda) and acetone resulted in the overall second-order rate equation with a rate constant, activation enthalpy, and entropy at 313.16 K of ks = 0.46 ± 0.02 mol-1 dm3 s-1, Ea = 38 ± 1 kJ mol-1, ΔH? = 35 ± 1 kJ mol-1 and ΔS? = -142 ± 13 J mol-1 K-1, respectively. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
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Gowenlock et al.
, p. 3587,3588 (1973)
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Cyclization of N-allylthiourea derivatives by the action of α-chloronitrosoalkanes
Tkachenko,Pushin,Sokolov,Fedoseev,Martynov
, p. 347 - 350 (1998)
A convenient method is proposed for obtaining difficultly available derivatives of 2-amino-5-chloromethyl-2-thiazoline by the cyclization of N-allylthioureas under the action of α-chloronitrosoalkanes. It is assumed that the reaction proceeds as a halogenophilic process leading to the intermediate formamidinesulfenyl chloride which is rapidly and selectively cyclized with the formation of 2-amino-2-thiazoline derivatives. 1998 Plenum Publishing Corporation.
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Prati
, p. 310 (1894)
-
-
Menard,Aston
, p. 1601 (1934)
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Nickel-Catalyzed NO Group Transfer Coupled with NOxConversion
Padmanaban, Sudakar,Choi, Jonghoon,Vazquez-Lima, Hugo,Ko, Donghwi,Yoo, Dagyum,Gwak, Jinseong,Cho, Kyung-Bin,Lee, Yunho
supporting information, p. 4585 - 4593 (2022/03/02)
Nitrogen oxide (NOx) conversion is an important process for balancing the global nitrogen cycle. Distinct from the biological NOx transformation, we have devised a synthetic approach to this issue by utilizing a bifunctional metal catalyst for producing value-added products from NOx. Here, we present a novel catalysis based on a Ni pincer system, effectively converting Ni-NOx to Ni-NO via deoxygenation with CO(g). This is followed by transfer of the in situ generated nitroso group to organic substrates, which favorably occurs at the flattened Ni(I)-NO site via its nucleophilic reaction. Successful catalytic production of oximes from benzyl halides using NaNO2 is presented with a turnover number of >200 under mild conditions. In a key step of the catalysis, a nickel(I)-?NO species effectively activates alkyl halides, which is carefully evaluated by both experimental and theoretical methods. Our nickel catalyst effectively fulfills a dual purpose, namely, deoxygenating NOx anions and catalyzing C-N coupling.
Visible-Light-Mediated Strategies for the Preparation of Oxime Ethers Derived from O-H Insertions of Oximes into Aryldiazoacetates
Duarte, Marcelo,Jurberg, Igor D.,Le?o, Luiz Paulo M. O.,Saito, Felipe A.,Stivanin, Mateus L.
supporting information, p. 17528 - 17532 (2021/12/02)
Two visible-light-mediated O-H insertion protocols involving oximes and aryldiazoacetates leading to different products depending on the solvent employed are reported. In DCM, direct O-H insertion takes place. In THF, there is the additional incorporation of the ring-opened form of this solvent into the structure of the product. These metal-free protocols are mild and tolerant to air and moisture. The preparation of an acaricide has been developed as an example of synthetic application.
Arylboronic Acid-Catalyzed C-Allylation of Unprotected Oximes: Total Synthesis of N-Me-Euphococcine
Kürti, László,Kattamuri, Padmanabha V.,Siitonen, Juha H.,Yousufuddin, Muhammed
supporting information, (2020/03/24)
O-Unprotected keto-and aldoximes are readily C-allylated with allyl diisopropyl boronate in the presence of arylboronic acid catalysts to yield highly substituted N-α-secondary and tertiary homoallylic hydroxylamines. The method was used in the total synthesis of the trace alkaloid N-Me-Euphococcine.