123-42-2

Basic information

• Product Name: 4-Hydroxy-4-methyl-2-pentanone
• Synonyms: Diacetone Alcohol 〔4-Hydroxy-4-methyl-2-pentanone〕;(CH3)2C(OH)CH2C(O)CH3;2-Hydroxy-2-methyl-4-pentanone;2-Methyl-3-pentanol-4-one;2-Methylpentan-2-ol-4-one;2-Pentanone, 4-hydroxy-4-methyl-;4-hydroxy-4-methyl-2-pentanon;4-hydroxy-4-methyl-2-pentanone(diacetonealcohol)
• CAS NO: 123-42-2
• Molecular Formula: C₆H₁₂O₂
• Molecular Weight: 116.15828
• EINECS: 204-626-7
• Product Categories: Industrial/Fine Chemicals;Building Blocks;C3 to C6;Carbonyl Compounds;Chemical Synthesis;Ketones;Organic Building Blocks;Organic solvents
• Mol File: 123-42-2.mol
• Article Data: 84

Chemical Properties

• Melting Point: -42.8 °C
• Boiling Point: 166 °C(lit.)
• Flash Point: 132 °F
• Appearance: Clear colorless/Liquid
• Density: 0.938 g/mL at 20 °C
• Vapor Density: 4 (vs air)
• Vapor Pressure: <1 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.423(lit.)
• Storage Temp.: Store below +30°C.
• Solubility: Soluble in alcohol, ether (Weast, 1986), and many other solvents, particular ketones such as acetone and 2-butanone.
• PKA: 14.57±0.29(Predicted)
• Explosive Limit: 1.8-6.9%(V)
• Water Solubility: MISCIBLE
• Stability: Stable. Flammable. Incompatible with strong oxidizing agents, amines, ammonia, strong acids, strong bases, alkalies, aluminium.
• Merck: 14,2964
• BRN: 1740440
• CAS DataBase Reference: 4-Hydroxy-4-methyl-2-pentanone(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Hydroxy-4-methyl-2-pentanone(123-42-2)
• EPA Substance Registry System: 4-Hydroxy-4-methyl-2-pentanone(123-42-2)

Safety Data

• Hazard Codes: Xi
• Statements: 36-R36
• Safety Statements: 24/25-S24/25
• RIDADR: UN 1148 3/PG 3
• WGK Germany: 1
• RTECS: SA9100000
• F: 9
• TSCA: Yes
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 123-42-2(Hazardous Substances Data)

Usage

Application

Diacetone alcohol is available in two grades: a commercial grade containing 15% acetone and an acetone-free grade. Both solvent grades of diacetone alcohol may acquire a yellow color on aging; both are good solvents for nitrocellulose, cellulose esters, and several other types of resins. The much slower evaporating diacetone alcohol is similar to acetone in its solvency. It is used in brushing-type cellulose ester lacquers to produce hard and brilliant gloss films. Diacetone alcohol is also used as lacquer thinner and in coating compositions for paper and textiles. Mesityl oxide, the unsaturated medium boiling point ketone that is prepared by the dehydration of diacetone alcohol, will darken and form a solid residue on aging.

Chemical Properties

Different sources of media describe the Chemical Properties of 123-42-2 differently. You can refer to the following data:
1. colourless liquid
2. Diacetone alcohol is a colorless liquid. Mild, mint odor.

Physical properties

Clear, watery, flammable liquid with a mild, pleasant, characteristic odor similar to 2-butanone or the pentanones. Experimentally determined detection and recognition odor threshold concentrations were 1.3 mg/m3 (270 ppbv) and 5.2 mg/m3 (1.1 ppmv), respectively (Hellman and Small, 1974).

Uses

Different sources of media describe the Uses of 123-42-2 differently. You can refer to the following data:
1. Solvent for cellulose acetate, nitrocellulose, celluloid, fats, oils, waxes, resins. As a preservative in pharmaceutical preparations. In some antifreeze solutions and in hydraulic fluids.
2. Solvent for pigments, cellulose, resins, oils, fats, and hydrocarbons; hydraulic brake fluid; antifreeze
3. 4-Hydroxy-4-methyl-2-pentanone is used asa solvent for nitrocellulose, cellulose acetate,resins, fats, oils, and waxes; and in hydraulicfluids and antifreeze solutions..

Production Methods

4-Hydroxy-4-methyl-2-pentanone is manufactured through the action of barium hydroxide, potassium hydroxide, or calcium hydroxide on acetone. Commercial materials may contain up to 15%acetone.

Definition

ChEBI: A beta-hydroxy ketone formed by hydroxylation of 4-methylpentan-2-one at the 4-position. It has been isolated from Achnatherum robustum.

Synthesis Reference(s)

Organic Syntheses, Coll. Vol. 1, p. 199, 1941Tetrahedron Letters, 16, p. 4027, 1975 DOI: 10.1016/S0040-4039(00)91227-9

General Description

A clear colorless liquid with a pleasant odor. Flash point below 141°F. Less dense than water. Vapors heavier than air.

Air & Water Reactions

Highly flammable. Soluble in water.

Reactivity Profile

Acetyl bromide reacts violently with alcohols or water, [Merck 11th ed., 1989]. Mixtures of alcohols with concentrated sulfuric acid and strong hydrogen peroxide can cause explosions. Example: An explosion will occur if dimethylbenzylcarbinol is added to 90% hydrogen peroxide then acidified with concentrated sulfuric acid. Mixtures of ethyl alcohol with concentrated hydrogen peroxide form powerful explosives. Mixtures of hydrogen peroxide and 1-phenyl-2-methyl propyl alcohol tend to explode if acidified with 70% sulfuric acid, [Chem. Eng. News 45(43):73(1967); J, Org. Chem. 28:1893(1963)]. Alkyl hypochlorites are violently explosive. They are readily obtained by reacting hypochlorous acid and alcohols either in aqueous solution or mixed aqueous-carbon tetrachloride solutions. Chlorine plus alcohols would similarly yield alkyl hypochlorites. They decompose in the cold and explode on exposure to sunlight or heat. Tertiary hypochlorites are less unstable than secondary or primary hypochlorites, [NFPA 491 M, 1991]. Base-catalysed reactions of isocyanates with alcohols should be carried out in inert solvents. Such reactions in the absence of solvents often occur with explosive violence, [Wischmeyer(1969)].

Health Hazard

Different sources of media describe the Health Hazard of 123-42-2 differently. You can refer to the following data:
1. Vapor is irritating to the mucous membrane of the eye and respiratory tract. Inhalation can cause dizziness, nausea, some anesthesia. Very high concentrations have a narcotic effect. The liquid is not highly irritating to the skin but can cause dermatitis.
2. 4-Hydroxy-4-methyl-2-pentanone is a mildirritant and a strong narcotic. It can causeirritation in the eyes, nose, throat, and skin.The effect on humans, however, is mild at100 ppm concentration.Animal experiments indicated that it couldproduce sleep after a period of restlessnessand excitement. The symptoms of its toxicity are a marked decrease in breathing andblood pressure, and relaxation of the muscles. Ingestion of this compound in highdoses can damage corneal tissue and liver.The oral toxicity in rats was very low, witha LD50 value of 4000 mg/kg..

Fire Hazard

HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water.

Chemical Reactivity

Reactivity with Water : No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.

Safety Profile

Moderately toxic by ingestion and intraperitoneal routes. Mddly toxic by skin contact. Human systemic effects by inhalation: headache, nausea or vomiting, eye and pulmonary changes. A skin, mucous membrane, and severe eye irritant. Can cause anemia and damage to liver and hdneys. Narcotic in high concentration. Flammable liquid when exposed to heat or flame; can react with oxidzing materials. Explosive in the form of vapor when exposed to heat or flame. To fight fire, use alcohol foam, foam, CO2, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes. See also KETONES.

Potential Exposure

It is used as a solvent for pigments, cellulose esters; oils and fats. It is used in hydraulic brake fluids and in antifreeze formulations.

Carcinogenicity

Occupational exposure to 4-hydroxy-4-methyl-2- pentanone is most likely to be by inhalation and skin contact. It presents a low degree of hazard if good work practices are observed. Appropriate protective clothing and eye protection should be made available as prolonged exposure may defat the skin and cause dermatitis. The occurrence of eye, nose, and throat irritation and a recognizable odor at low concentrations should protect against overexposure to 4-hydroxy-4- methyl-2-pentanone.

Environmental fate

Biological. Using the BOD technique to measure biodegradation, the mean 5-d BOD value (mM BOD/mM diacetone alcohol) and ThOD were 3.67 and 45.9%, respectively (Vaishnav et al., 1987). Photolytic. Grosjean (1997) reported a rate constant of 4.0 x 10-12 cm3/molecule?sec at 298 K for the reaction of OH radicals in the atmosphere. Based on a OH concentration of 1.0 x 106 molecule/cm3, the reported half-life of diacetone alcohol is 2.0 d (Grosjean, 1997).

Shipping

UN1148 Diacetone alcohol, Hazard Class: 3; Labels: 3-Flammable liquid.

Purification Methods

The pentanone loses water when heated. It can be dried with CaSO4, then fractionally distilled under reduced pressure. [Beilstein 1 IV 403.]

Incompatibilities

Vapor may form explosive mixture with air. Incompatible with oxidizers (chlorates, nitrates, perox- ides, permanganates, perchlorates, chlorine, bromine, fluo- rine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, and epoxides.

Waste Disposal

Dissolve or mix the material with a combustible solvent and burn in a chemical incinera- tor equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed.

InChI:InChI:1S/C6H12O2/c1-5(7)4-6(2,3)8/h8H,4H2,1-3H3

Synthetic route

acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
at 2 - 100℃; for 168h; Temperature;	99.85%
ruthenium trichloride for 24h; Condensation; Heating;	90%
With 1-bromomagnesio-1-bromo-2,2-diphenylcyclopropane In tetrahydrofuran at -60℃; for 0.5h;	80%

4-(1-Methoxy-2-methylprop-1-enyl)-1,1'-biphenyl (116997-41-2) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + methyl 4-phenylbenzoate (720-75-2) + 1-[(1,1'-biphenyl)-4-yl]-2-hydroxy-2-methylpropan-1-on (7472-38-0) + β,β-Dimethoxy-α,α-dimethyl(1,1'-biphenyl)-4-ethanol

Conditions	Yield
With ozone In trichlorofluoromethane at -70℃; for 0.15h; Further byproducts given;	A n/a B 86% C n/a D n/a

acetone (67-64-1) → 4-methyl-pent-3-en-2-one (141-79-7) + phorone (504-20-1) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
With titanium tetrachloride; NCNMe2 In benzene at 25℃;	A 82% B 2% C 8%
With sodium hydroxide In benzene at 40℃; Mechanism; Kinetics; benzyltriethylammonium chloride presence;
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In benzene at 40℃; reaction order, effect of concentration on the initial rate;
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In benzene at 40℃; Mechanism; effect concentrations, initial rate;
With MgO/ZrO2 mixed oxides at 249.84℃;

4-chlorobutanal dimethyl acetal (29882-07-3) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 4-iodobutyraldehyde dimethyl acetal (91988-32-8) + 4-iodobutyraldehyde (77406-93-0)

Conditions	Yield
With sodium iodide In acetone at 56℃; for 10h;	A n/a B 80% C n/a

benzyl chloride (100-44-7) + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-Methyl-1-phenyl-2-propanol (100-86-7)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide In N,N-dimethyl-formamide for 5h; electrolysis;	A n/a B 75%

4-(tetrahydropyranyl-2-oxy)-4-methyl-2-pentanone (57283-21-3) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
With poly-p-styryl-acetonyltriphenylphosphonium bromide In methanol at 20℃; for 12h;	74%

acetone (67-64-1) + cis/trans-1,1,2-tribromo-3-phenylcyclopropane → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-(3-phenylcyclopropenyl)-propan-2-ol

Conditions	Yield
Stage #1: cis/trans-1,1,2-tribromo-3-phenylcyclopropane With methyllithium at -80 - 20℃; for 0.5h; Stage #2: acetone	A n/a B 73%
Stage #1: cis/trans-1,1,2-tribromo-3-phenylcyclopropane With methyllithium In diethyl ether at -82 - 20℃; for 0.966667h; Inert atmosphere; Stage #2: acetone In diethyl ether at -60 - 20℃; Inert atmosphere;	A n/a B 106 mg

4-(1-ethoxyethoxy)-4-methyl-2-pentanone → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
With poly-p-styryl-acetonyltriphenylphosphonium bromide In methanol at 20℃; for 10h;	70%

4-(tetrahydrofuranyl-2-oxy)-4-methyl-2-pentanone → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
With poly-p-styryl-acetonyltriphenylphosphonium bromide In methanol at 20℃; for 12h;	70%

5-(trifluoroacetamido)pentyl trifluoroacetate (123934-62-3) + methyl iodide (74-88-4) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + N-methyl-N-(5-hydroxy-1-pentyl)trifluoroacetamide (123934-63-4)

Conditions	Yield
With potassium hydroxide In acetone for 0.0833333h; Heating;	A n/a B 63%

methyl dithioacetate (2168-84-5) + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 3-Hydroxy-3-methyl-butandithiosaeure-methylester (85433-71-2)

Conditions	Yield
With sodium hydride In tetrahydrofuran at -20℃; for 1.58333h;	A n/a B 60%

2-(Trimethylsilyloxy)propene (1833-53-0) + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2,2,3-trimethyl-3-(trimethylsiloxy)oxetane

Conditions	Yield
at 0 - 5℃; for 2h;	A n/a B 55%

acetone (67-64-1) + C14H21ClO2 (770735-80-3) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 1,4,5,6,7,7a-hexahydro-inden-2-one (39163-29-6, 117780-10-6) + 3-(1-hydroxy-1-methyl-ethyl)-5,6,7,7a-tetrahydro-1H,4H-inden-2-one

Conditions	Yield
Stage #1: C14H21ClO2 With N,N-dimethyl-1-naphthalenamine; lithium In tetrahydrofuran at -65℃; for 2h; Stage #2: acetone In tetrahydrofuran at -65 - 20℃; Stage #3: With hydrogenchloride In tetrahydrofuran at 20℃; Further stages.;	A n/a B 35% C 51%

2-methyl-2,4-pentanediol (107-41-5) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + acetone (67-64-1)

Conditions	Yield
With air; hydroxide at 24.85℃; under 760 Torr; Kinetics;	A 49% B 27%

2-methyl-2,4-pentanediol (107-41-5) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
With methyl nitrite; nitrogen(II) oxide at 22.85℃; under 740 Torr; Kinetics; Irradiation;	47%
With ruthenium trichloride; sodium hydroxide; potassium hexacyanoferrate(III) at 30℃; Mechanism; Thermodynamic data; Rate constant; ΔH(excit.), ΔS(excit.); other alcohols; effect of the reagents' concentration on the initial rate, kinetic isotope effect;
With sodium hydroxide; hexacyanoferrate(II); ruthenium(III) In water at 30℃; Kinetics; Further Variations:; Catalysts;

3,3-dimethyldioxirane (74087-85-7) + 4-methyl-2-pentanone (108-10-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 4-(acetyloxy)-4-methyl-2-pentanone (1637-25-8) + 1-(acetyloxy)-4-methyl-2-pentanone (68113-54-2) + 3-(acetyloxy)-4-methyl-2-pentanone (135274-69-0)

Conditions	Yield
In acetone Heating; Yields of byproduct given;	A n/a B 46.5% C n/a D n/a
In acetone Heating; Yield given. Yields of byproduct given;

2,4,6‑trimethyl‑N’‑(1‑phenylethylidene)benzenesulfonohydrazide + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-methyl-3-phenyl-but-3-en-2-ol (25982-72-3) + C12H16O2S

Conditions	Yield
Stage #1: N-(2,4,6-trimethylbenzenesulfonyl)acetophenonehydrazone With n-butyllithium In tetrahydrofuran; hexane at -78 - -65℃; Inert atmosphere; Stage #2: acetone In tetrahydrofuran; hexane	A n/a B 39% C 33%

2-acetylcyclopentanaone (1670-46-8) → 1,3,5-Trioxan (110-88-3) + 4-butanolide (96-48-0) + glutaric anhydride, (108-55-4) + formic acid (64-18-6) + 1,5-pentanedioic acid (110-94-1) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 4-acetoxybutyric acid (26976-72-7) + 5,6-dioxo-n-heptanoic acid (85951-55-9) + 2-acetyl-2-hydroxycyclopentanone (1262892-77-2) + 2-acetoxycyclopentanone (52789-75-0) + 2-acetyl-2-hydroxymethylcyclopentanone (1167443-17-5) + 1,1'-diacetyl-1,1'-bicyclopentyl-2,2'-dione (1426960-55-5) + 2-acetyl-2,3-epoxycyclopentanone (89540-15-8) + acetic acid (64-19-7)

Conditions	Yield
With oxygen; calcium chloride In acetone at 57℃; for 30h;	A 1% B 2% C 7% D n/a E 7% F 0.014 g G 2% H 13% I 38% J 2% K 5% L 11% M 2% N n/a

...Expand

acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 4-methyl-2-pentanone (108-10-1)

Conditions	Yield
With CaO#dotPd at 120℃; under 21002.1 Torr; for 5h; Reagent/catalyst; Autoclave; Green chemistry;	A n/a B 23.9%
With calcium hydroxide; copper(II) chromite In water at 260℃; for 17h; Direct aqueous phase reforming; Inert atmosphere;

acetone (67-64-1) + (NO)I2> → 4-methyl-pent-3-en-2-one (141-79-7) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 6-hydroxy-2,4-6,8,8-pentamethyl-1,5-diazabicyclo[3.3.0]octa-1,3-dien-1-onium iodide (78570-32-8) + (NO)I(OEt)>, <(NO)I>2(μ-O)>

Conditions	Yield
for 72h; Heating;	A n/a B 5 % Chromat. C 22% D n/a

acetone (67-64-1) → 3,5,5-Trimethylcyclohex-2-en-1-one (78-59-1) + 4-methyl-pent-3-en-2-one (141-79-7) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 1,3,5-trimethyl-benzene (108-67-8)

Conditions	Yield
aluminum oxide at 360℃; Condensation; cyclization;	A 11% B n/a C n/a D n/a
aluminum oxide at 360℃; Product distribution; Further Variations:; Catalysts; Temperatures; Condensation; cyclization;
With MgO/ZrO2 mixed oxides at 249.84℃;

3-hydroxy-3-methylbutyronitrile (13635-04-6) + methylmagnesium bromide (75-16-1) → 4-methyl-pent-3-en-2-one (141-79-7) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
With diethyl ether

3-hydroxy-3-methylbutyronitrile (13635-04-6) + methyl magnesium (1+); bromide → 4-methyl-pent-3-en-2-one (141-79-7) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

2,3,5-trimethyl-2,3,5-hexanetriol (823192-27-4) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
With chromium(VI) oxide; acetic acid

acetaldehyde (75-07-0) + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 4-hydroxypentan-2-one (4161-60-8)

Conditions	Yield
With potassium hydroxide at 5℃;

diethyl ether (60-29-7) + butan-1-ol; magnesium bromide-butylate + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

1-methyl-4-nitrosobenzene (623-11-0) + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
at 23℃; Gleichgewicht;

potassium ethoxide (917-58-8) + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
at 15℃; Gleichgewicht;

sodium acetylide (1066-26-8) + acetone (67-64-1) → 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

acetone (67-64-1) → 4-methyl-pent-3-en-2-one (141-79-7) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2)

Conditions	Yield
at 30 - 75℃; Kinetics; mit sauren Kationen-Austauschern;
at 30 - 75℃; mit sauren Kationen-Austauschern;
With (Ph3P)3CoCH3 at -23 - 25℃; for 24h;

4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 2-methyl-2,4-pentanediol (107-41-5)

Conditions	Yield
With hydrogen In water at 120℃; under 7500.75 Torr; for 3h; Reagent/catalyst; Temperature; Pressure; Solvent;	100%
With sodium tetrahydroborate In methanol at 0 - 20℃; for 1h;	83%
With lithium aluminium tetrahydride In tetrahydrofuran at 20℃; for 3h;	53%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + tryptanthrine (13220-57-0) → 6-hydroxy-6-(2-oxo-4-hydroxy-4-methylpentyl)-indolo[2,1-b]quinazolin-12-one

Conditions	Yield
With potassium carbonate In ethanol; glycerol	100%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 1-bromo-4-hydroxy-4-methylpentan-2-one (5799-84-8)

Conditions	Yield
With bromine In methanol at 0 - 23℃; for 3h;	99%
With bromine In methanol at 0℃; for 3h;	97.9%
With bromine In methanol at 0℃; for 3h;	97.9%
With bromine In diethyl ether

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + acetic anhydride (108-24-7) → 4-(acetyloxy)-4-methyl-2-pentanone (1637-25-8)

Conditions	Yield
With magnesium(II) perchlorate at 20℃; for 6h;	98%
With iodine for 0.5h; Ambient temperature;	95%
With lithium perchlorate at 40℃; for 18h;	90%

3,4-dihydro-2H-pyran (110-87-2) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 4-(tetrahydropyranyl-2-oxy)-4-methyl-2-pentanone (57283-21-3)

Conditions	Yield
With N.N'-bis[3,5-bis(trifluoromethyl)phenyl]thiourea at 20℃; for 18h;	98%
With poly-p-styryl-acetonyltriphenylphosphonium bromide In dichloromethane at 20℃; for 15h;	96%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-amino-5-methyl-benzaldehyde (109467-00-7) → 2,6-dimethylquinoline (877-43-0)

Conditions	Yield
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); sodium t-butanolate In toluene at 70℃; Inert atmosphere; Schlenk technique; chemoselective reaction;	98%

3-(trimethylsilyl)-2-oxazolidinone (43112-38-5) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) → (4-Oxo-2-methyl-2-pentoxy)trimethylsilane (55816-61-0)

Conditions	Yield
chloro-trimethyl-silane at 20℃; for 0.166667h;	97%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) → acetone (67-64-1)

Conditions	Yield
With calcium hydroxyapatite at 99.84℃; Flow reactor;	97%
In xylene at 178.1℃; Rate constant; deuterium isotope effects in the thermal decomposition;	95%
aluminum oxide In methanol at 115℃; Mechanism; other temperature, flow velocity;

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + CH3Li*CeCl3 → 2,4-dimethylpentane-2,4-diol (24892-49-7, 139687-48-2)

Conditions	Yield
In tetrahydrofuran at -78℃;	97%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + TaCl3(C4H4BN(CH(CH3)2)2) → TaCl3(C4H4BNH(CH(CH3)2)2)(OC(CH3)2CH2C(CH3)O)

Conditions	Yield
In benzene room temp.; crystn. (conc. pentane soln., -35°C); elem. anal.;	97%

chloro-trimethyl-silane (75-77-4) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) → (4-Oxo-2-methyl-2-pentoxy)trimethylsilane (55816-61-0)

Conditions	Yield
With triethylamine In diethyl ether	95%
With 1H-imidazole In dichloromethane at 0℃; for 6h;

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + C4H9Li*CeCl3 → 2,4-dimethyl-2,4-octanediol (7177-01-7)

Conditions	Yield
In tetrahydrofuran at -78℃;	95%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + C6H5Li*CeCl3 → 2-methyl-4-phenyl-pentane-2,4-diol (21133-79-9)

Conditions	Yield
In tetrahydrofuran at -78℃;	95%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + C8H5Li*CeCl3 → 2,4-dimethyl-6-phenyl-5-hexyne-2,4-diol (108013-89-4)

Conditions	Yield
In tetrahydrofuran at -78℃;	95%

2,3-dihydro-2H-furan (1191-99-7) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 4-(tetrahydrofuranyl-2-oxy)-4-methyl-2-pentanone

Conditions	Yield
With poly-p-styryl-acetonyltriphenylphosphonium bromide In dichloromethane at 20℃; for 15h;	95%

pyrocatechol phosphorochloridite (1641-40-3) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 4-(1,3,2-benzodioxaphosphol-2-yloxy)-4-methylpentan-2-one (1232839-42-7)

Conditions	Yield
With triethylamine In diethyl ether at -15 - 20℃; for 3h; Inert atmosphere;	95%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + phenethylamine (64-04-0) → N-isopropyl-N-(2-phenylethyl)amine (52007-97-3)

Conditions	Yield
With ammonium hexafluorophosphate; trimethylamine-N-oxide; tricarbonyl(η4-1,3-bis(trimethylsilyl)-4,5,6,7-tetrahydro-2H-inden-2-one)iron; hydrogen In methanol at 85℃; under 3750.38 Torr; for 16h; Inert atmosphere;	95%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 4-Hydroxy-heptan-2-on (25290-14-6) → 4-methyl-pent-3-en-2-one (141-79-7) + 3-hepten-2-one (5609-09-6, 69668-88-8, 1119-44-4)

Conditions	Yield
With sulfuric acid In water at 100 - 120℃; for 8h;	A 92.56% B 94.48%

2-methyltetrazole (16681-78-0) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 1-(1,1-dimethyl-3-oxo-butyl)-3-methyl-3H-tetrazol-1-ium; perchlorate

Conditions	Yield
With perchloric acid In water at 20℃; for 48h; Substitution;	94%

1-(4-methoxyphenyl)-1H-tetrazole (21788-28-3) + 4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 2-(1,1-dimethyl-3-oxo-butyl)-4-(4-methoxy-phenyl)-4H-tetrazol-2-ium; perchlorate

Conditions	Yield
With perchloric acid In water at 20℃; for 12h; Substitution;	94%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-amino-5-fluoro benzaldehyde (146829-56-3) → 6-fluoro-2-methyl-quinoline (1128-61-6)

Conditions	Yield
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); sodium t-butanolate In toluene at 70℃; Inert atmosphere; Schlenk technique; chemoselective reaction;	94%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-amino-5-chlorobenzaldehyde (20028-53-9) → 6-chloro-2-methylquinoline (92-46-6)

Conditions	Yield
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); sodium t-butanolate In toluene at 70℃; Inert atmosphere; Schlenk technique; chemoselective reaction;	94%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-amino-6-chlorobenzaldehyde (35490-90-5) → 2-methyl-5-chloroquinoline (4964-69-6)

Conditions	Yield
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); sodium t-butanolate In toluene at 70℃; Inert atmosphere; Schlenk technique; chemoselective reaction;	93%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + methyl iodide (74-88-4) → 2,4-dimethylpentane-2,4-diol (24892-49-7, 139687-48-2)

Conditions	Yield
With magnesium In diethyl ether Ambient temperature;	92%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + O-(4-methoxybenzyl)-trichloroacetimidate (89238-99-3) → 4-(4-methoxy-benzyloxy)-4-methyl-pentan-2-one

Conditions	Yield
lanthanum(lll) triflate In toluene at 20℃; for 0.0833333h;	92%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-amino-5-bromobenzaldehyde (29124-57-0) → 6-Bromo-2-methyl-quinoline (877-42-9)

Conditions	Yield
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); sodium t-butanolate In toluene at 70℃; Inert atmosphere; Schlenk technique; chemoselective reaction;	92%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) → 4-methyl-pent-3-en-2-one (141-79-7) + diethylamine (109-89-7)

Conditions	Yield
With hexaethylphosphoric triamide at 190℃; further reagent;	A 26.8% B 91.3%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + 2-aminobenzaldehyde (529-23-7) → 2-methylquinoline (91-63-4)

Conditions	Yield
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); sodium t-butanolate In toluene at 70℃; for 8h; Inert atmosphere; Schlenk technique; Sealed tube; stereoselective reaction;	91%
With chloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I); sodium t-butanolate In toluene at 70℃; Inert atmosphere; Schlenk technique; chemoselective reaction;	91%

4-Hydroxy-4-methyl-2-pentanone (123-42-2) + ethyl vinyl ether (109-92-2) → 4-(1-ethoxyethoxy)-4-methyl-2-pentanone

Conditions	Yield
With poly-p-styryl-acetonyltriphenylphosphonium bromide In dichloromethane at 20℃; for 15h;	90%

Upstream product

• 67-64-1 acetone 
• 107-41-5 2-methyl-2,4-pentanediol 
• 4209-91-0 3,5-Dimethyl-3-hexanol 
• 60-29-7 diethyl ether 
• 625-04-7 4-amino-4-methylpentan-2-one 
• 67-66-3 chloroform 
• 124-11-8 non-1-ene 
• 111-66-0 oct-1-ene 
• 100-42-5 styrene 
• 5392-40-5 (E/Z)-3,7-dimethyl-2,6-octadienal 
• 616-38-6 carbonic acid dimethyl ester 
• 1066-26-8 sodium acetylide 
• 917-58-8 potassium ethoxide 
• 623-11-0 1-methyl-4-nitrosobenzene 

Downstream Products

• 91958-63-3 4-methyl-4-(4-nitro-benzoyloxy)-pentan-2-one 
• 7177-01-7 2,4-dimethyl-2,4-octanediol 
• 67-63-0 isopropyl alcohol 
• 59194-83-1 2,4-Dimethyl-heptan-2,4-diol 
• 141-79-7 4-methyl-pent-3-en-2-one 
• 69201-96-3 2,4-dimethyl-2,4-nonanediol 
• 115-19-5 2-methyl-but-3-yn-2-ol 
• 738545-32-9 D,L-4-Hydroxy-2-methylleucin-lacton 
• 21133-79-9 2-methyl-4-phenyl-pentane-2,4-diol 
• 108-75-8 2,4,6-trimethyl-pyridine 
• 89406-85-9 3-isopropyl-2,4,6-trimethylpyridine 
• 107-41-5 2-methyl-2,4-pentanediol 
• 590-36-3 2-methylpentan-2-ol 
• 20342-04-5 2-chloro-3,3,5-trimethyl-2,3-dihydro-1,2λ⁵-oxaphosphole 2-oxide 

Related news

Experimental paperInfluence of temperature on the liquid-to-liquid extraction of 4-Hydroxy-4-methyl-2-pentanone (cas 123-42-2) from aqueous solutions with benzyl alcohol09/25/2019

Solubilities between 323.15 and 413.15 K and equilibrium data between 323.15 and 373.15 K for the water + 4-hydroxy-4-methyl-2-pentanone + benzyl alcohol ternary system are reported in order to obtain the extractive properties of benzyl alcohol for separating 4-hydroxy-4-methyl-2-pentanone from ...detailed

Experimental and theoretical investigations of the kinetics and mechanism of the Cl + 4-Hydroxy-4-methyl-2-pentanone (cas 123-42-2) reaction09/24/2019

The reaction of 4-hydroxy-4-methyl-2-pentanone (4H4M2P) with Cl atoms was studied for the first time experimentally and theoretically. Relative kinetic measurements were carried out at room temperature and 1 bar of synthetic air/N2 in two different environmental chambers: a 300 L Teflon bag and ...detailed

Measurements for the equilibrium conditions of methane hydrate in the presence of cyclopentanone or 4-Hydroxy-4-methyl-2-pentanone (cas 123-42-2) additives09/08/2019

The equilibrium conditions of methane hydrate in the presence of additives of cyclopentanone (C5H8O) or 4-hydroxy-4-methyl-2-pentanone (C6H12O2, also known as diacetone alcohol) in aqueous solutions were experimentally measured in this study. The hydrate-liquid water-vapor (H-Lw-V) three-phase e...detailed

Relevant articles and documents

-

-

Calcium oxide supported on monoclinic zirconia as a highly active solid base catalyst

Calcium oxide supported on ZrO2 is a highly active catalyst for base-catalyzed reactions such as aldol-type reactions and transesterification reactions. The role of key parameters during preparation, that is, impregnation versus precipitation, heat treatment, and metal oxide loading on the basicity and catalytic activity were investigated for CaO supported on ZrO2. An impregnation of 10 wt % CaO on monoclinic zirconia followed by heat treatment at 600°C resulted in high activity for the self-condensation reaction of acetone. An evaluation of a series of CaO/ZrO2 samples with different loadings showed that the activity increased for impregnated amounts per gram catalyst of 0-10 wt % CaO, and at higher loading the activity decreased as a result of a decrease in dispersion. The number of strong base sites (calculated from CO2 desorbed at temperatures higher than 625°C) correlated with the activity. For MgO, CaO, SrO, and BaO on zirconia the catalytic activity increased as the ionic radius of the metal cation increased, suggesting the impact of base strength on catalytic performance. Look at the strong base! If prepared in an optimized way, CaO/ZrO2 is a highly active solid base catalyst. Calcination temperature and the preparation method (impregnation or deposition) have a strong influence on the number of strong base sites, which correlate positively with the activity of the material. Copyright

Analysis of Minor Components by Ultrahigh Resolution NMR. 2. Detection of 0.01percent Diacetone Alcohol in "Pure" Acetone and Direct Measurement of the Rate of the Aldol Condensation of Acetone

Ultrahigh resolution NMR methodology permits the detection of as little as 0.01percent CH3COCH2(OH)C(CH3)2 (2) in a sample of "pure" acetone (1) of natural isotopic composition, with the use of the methyl resonances in the proton-decoupled (13)C NMR spectrum, even though the resonances of 2 are very close to those of 1.Also, all three peaks of the triplet of the (13)CH2D carbon of (13)CH2D-(12)CO-(12)CH3 are fully resolved, even though their intensity is only 0.015percent of that of the main contributor to the spectrum, (13)CH3-(12)CO-(12)CH3, and one of the peaks of the triplet is only 7 Hz away from the main acetone peak.The intensities of the (13)CH2D triplet serve as a calibrator of dynamic range accuracy in (13)C NMR measurements of relative proportions of major and minor components.After addition of aqueous sodium hydroxide to the acetone sample, the growth of the methyl carbon resonances of 2 provides a direct measurement of the rate constant for the aldol dimerization of 1 and also the equilibrium constant for this reaction.This example demonstrates the ability of ultrahigh resolution NMR to study directly the kinetics of reactions that have equilibria highly displaced toward the reagents, instead of the traditional procedure of monitoring only the kinetics of the reverse reaction by starting with pure "products".Artifacts that may interfere with the study of minor components by ultrahigh resolution NMR are discussed.

-

-

Kinetics by Thermometry: An Aldol Condensation Reaction

The princilpes of 'thermokinetic' experiments have been described, whereby the initial rates of chemical reaction in solution are determined by following the temperature rise in an adiabatic system; data are obtained within the first few seconds of mixing, and at rates of the order of one measurement s-1.The procedure has been applied to the base-catalysed condensation reaction of acetone to form diacetone alcohol, an exceptionally difficult reaction to follow because of the small extent to which the reaction proceeds.At 26 deg C, the equilibrium constant for the base-catalysed ionisation of acetone has been established as having a value of 1.2(9) l mol-1 while the rate constant for the ionic dimerisation has the value 2.5(2)E-3 mol l-1 s-1.

-

-

Design and application of the recyclable poly(l-proline-co-piperidine) catalyst for the synthesis of mesityl oxide from acetone

Unexpectedly, l-proline/piperidine was found to be a better recyclable catalyst system than l-proline or piperidine alone in the condensation of acetone to prepare mesityl oxide (MO), an important intermediate in the chemical industry. Binding the catalyst system onto polymer resin enhanced the MO selectivity and reduced the catalyst loss. The mechanism of the bi-component catalyst system was also studied through control reactions, as well as by dynamic calculations. The MO selectivity could reach 74.4% and its isolated yield could reach 73.9%, based on the consumed acetone. Although the result does not immediately meet the requirement of industrial production, this study provides a novel organocatalyst system, which might offer a potential alternative to traditional inorganic catalysts that can be used under mild and neutral conditions.

The mechanism of catalyst deactivation and by-product formation in acetone ammoximation catalyzed by hollow titanium silicalite

The deactivation mechanism of hollow titanium silicalite (HTS) in aqueous ammoximation of acetone was investigated. Amines and polynitro-compounds, formed by alkaline autocatalytic and oxidative coupling reaction respectively, were determined to be the ma

L-Proline and thiourea co-catalyzed condensation of acetone

Amino acid and primary amine/amide co-catalyzed acetone condensation was investigated. It was found that L-proline had overwhelming catalytic activity over other amino acids as well as the analogues with similar structures. Surprisingly, thiourea, a very cheap and stable chemical, was found to be the favorable co-catalyst. Co-catalyzed by the recyclable L-proline and thiourea, condensation of acetone led to the useful products mesityl oxide (MO), diacetone alcohol (DAA) and isophorone (IP) in the excellent 96.3% total selectivity.

Kinetics and products of the reactions of selected diols with the OH radical

Using a relative rate method, rate constants been measured at 296 ± 2 K for the gas-phase reactions of OH radicals with 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, and 2-methyl-2,4-pentanediol, with rate constants (in units of 10-12 cm3 molecule-1 s-1) of 27.0 ± 5.6, 23.6 ± 6.3, 33.2 ± 6.8, and 27.7 ± 6.1, respectively, where the error limits include the estimated overall uncertainty of ±20% in the rate constant for the reference compound. Gas chromatographic analyses showed the formation of 1-hydroxy-2-butanone from 1,2-butanediol, 3-hydroxy-2-butanone from 2,3-butanediol, 1-hydroxy-3-butanone from 1,3-butanediol, and 4-hydroxy-4-methyl-2-pentanone from 2-methyl-2,4-pentanediol, with formation yields of 0.66 ± 0.11, 0.89 ± 0.09, 0.50 ± 0.09, and 0.47 ± 0.09, respectively, where the indicated errors are the estimated overall uncertainties. Pathways for the formation of these products are presented, together with a comparison of the measured and estimated rate constants and product yields.

The enthalpy of acetone

Measurements of the specific enthalpy increment of acetone are reported; 206 measurements cover the range 373.2 to 623.2 K at pressures from 0.1 to 11.9 MPa.The overall accuracy is 0.6 per cent.The specific enthalpy of the saturated liquid and of the saturated vapour and the enthalpy of vaporization are derived from the measurements.Comparison with cubic equations of state shows that the Patel-Teja equation is the best of those tested.

Kinetics and Equilibrium Data of the Dehydration-Hydration Reaction between Diacetone Alcohol and Mesityl Oxide in Phosphoric Acid

The velocities of dehydration of diacetone alcohol and hydration of mesityl oxide were studied in regions of 8.6-85.2percent phosphoric acid.Because the reactions are acid-catalyzed, the reaction velocities in both directions were increased as the acid concentration increased.The reaction kinetics fit the reversible first-order model with respect to the concentration of reactants, including the activity of water.These results are consisted with the mechanisms proposed by a previous investigator in which the rate-determining step is addition or removal of protons.Equilibrium constants were derived from solution composition and specific rate constants which agreed with each other.The equilibrium constant did not change with with acid concentration in the dilute range, but increased slightly at higher acid concentrations.The reaction velocities and the equilibrium constants increased with increasing temperature, and the activation energies were 18.8 and 12.7 kcal/mol for the dehydration and hydration reactions, respectively.

ALDOL CONDENSATION OF ACETONE IN THE TWO-PHASE SYSTEM SOLID BASE-BENZENE IN THE PRESENCE OF BENZYLTRIETHYLAMMONIUM CHLORIDE

-

Comparative study of the catalytic behaviour of Ru(III) and Ru(VI) on the oxidation of alcohols by hexacyanoferrate(III)

The oxidation reactions of 2-methyl-2,4-pentanediol upon treatment with alkaline hexacyanoferrate(III) using Ru(III) or Ru(VI) as catalysts are governed by two quasi-identical experimental rate equations, which show that both catalysts are equally effective for the oxidation of alcohols by Fe(CN)63-. The reaction mechanism proposed involves the oxidation of 2-methyl-2,4-pentanediol by the catalyst, a process that occurs through the formation of a substrate-catalyst complex. The decomposition of this complex yields Ru(IV) and a protonated ketone (owing to a hydride transfer from the α-C - H bond of the alcohol to the oxoligand of ruthenium) in the case of Ru(VI), but a ketyl radical and Ru(II) (hydrogen transfer) for Ru(III). The role of the co-oxidant, Fe(CN)63-, is to regenerate the catalyst. For both oxidation reactions, the rate constants of complex decomposition and catalyst regeneration have been determined. Copyright

On the Metal Cooperativity in a Dinuclear Copper–Guanidine Complex for Aliphatic C?H Bond Cleavage by Dioxygen

Selective oxidation reactions of organic compounds with dioxygen using molecular copper complexes are of relevance to synthetic chemistry as well as enzymatic reactivity. In the enzyme peptidylglycine α-hydroxylating monooxygenase (PHM), the hydroxylating activity towards aliphatic substrates arises from the cooperative effect between two copper atoms, but the detailed mechanism has yet to be fully clarified. Herein, we report on a model complex showing hydroxylation of an aliphatic ligand initiated by dioxygen. According to DFT calculations, the proton-coupled electron-transfer (PCET) process leading to ligand hydroxylation in this complex benefits from cooperative effects between the two copper atoms. While one copper atom is responsible for dioxygen binding and activation, the other stabilizes the product of intramolecular PCET by copper–ligand charge transfer. The results of this work might pave the way for the directed utilization of cooperative effects in oxidation reactions.

Method for preparing triacetone amine

An improved method is used for preparing triacetone amine while recycling the by-products. This involves treating the crude product from triacetone amine preparation, which leads to an increase in the content of compounds which react readily with ammonia. This method enables efficient recycling of the by-products formed in the synthesis of triacetone amine.

Complete Switch of Reaction Specificity of an Aldolase by Directed Evolution In Vitro: Synthesis of Generic Aliphatic Aldol Products

A structure-guided engineering of fructose-6-phosphate aldolase was performed to expand its substrate promiscuity toward aliphatic nucleophiles, that is, unsubstituted alkanones and alkanals. A “smart” combinatorial library was created targeting residues D6, T26, and N28, which form a binding pocket around the nucleophilic carbon atom. Double-selectivity screening was executed by high-performance TLC that allowed simultaneous determination of total activity as well as a preference for acetone versus propanal as competing nucleophiles. D6 turned out to be the key residue that enabled activity with non-hydroxylated nucleophiles. Altogether 25 single- and double-site variants (D6X and D6X/T26X) were discovered that show useful synthetic activity and a varying preference for ketone or aldehyde as the aldol nucleophiles. Remarkably, all of the novel variants had completely lost their native activity for cleavage of fructose 6-phosphate.