123-42-2

Usage

Uses

Used in Chemical Industry:
4-Hydroxy-4-methyl-2-pentanone is used as a solvent for cellulose acetate, nitrocellulose, celluloid, fats, oils, waxes, and resins. It is also used in the production of some antifreeze solutions and hydraulic fluids.
Used in Pharmaceutical Industry:
4-Hydroxy-4-methyl-2-pentanone is used as a preservative in pharmaceutical preparations.
Used in Coating Industry:
4-Hydroxy-4-methyl-2-pentanone is used as a solvent for pigments, cellulose, resins, oils, fats, and hydrocarbons. It is also used in hydraulic brake fluid and antifreeze.
Used in Lacquer Industry:
Diacetone alcohol is available in two grades: a commercial grade containing 15% acetone and an acetone-free grade. Both solvent grades of diacetone alcohol are good solvents for nitrocellulose, cellulose esters, and several other types of resins. The 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.

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.

Synthesis Reference(s)

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

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

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.

Health Hazard

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 4-Hydroxy-4-methyl-2-pentanone 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

• 13635-04-6 3-hydroxy-3-methylbutyronitrile 
• 75-16-1 methylmagnesium bromide 
• 823192-27-4 2,3,5-trimethyl-2,3,5-hexanetriol 
• 75-07-0 acetaldehyde 
• 67-64-1 acetone 
• 60-29-7 diethyl ether 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 917-58-8 potassium ethoxide 
• 1066-26-8 sodium acetylide 
• 625-04-7 4-amino-4-methylpentan-2-one 
• 917-64-6 methyl magnesium iodide 
• 123-54-6 acetylacetone 
• 93-91-4 1-phenylbutan-1,3-dione 
• 4478-63-1 3,4-epoxy-4-methyl-2-pentanone 

Downstream Products

• 91958-63-3 4-methyl-4-(4-nitro-benzoyloxy)-pentan-2-one 
• 108013-89-4 2,4-dimethyl-6-phenyl-5-hexyne-2,4-diol 
• 7177-01-7 2,4-dimethyl-2,4-octanediol 
• 67-63-0 isopropyl alcohol 
• 141-79-7 4-methyl-pent-3-en-2-one 
• 3682-91-5 2,6-dihydroxy-2,6-dimethyl-heptan-4-one 
• 59194-83-1 2,4-Dimethyl-heptan-2,4-diol 
• 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 

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 academic research and scientific papers

Aldol Condensation of Butan-2-one and Pentan-3-one on an Activated Alumina as Monotored via in-situ Carbon-13 Nuclear Magnetic Resonance Spectroscopy

Conventional (13)C nuclear magnetic resonance spectroscopy is used to monitor the reactions of butan-2-one and pentan-3-one adsorbed on alumina.Both reaction sequences proceed via successive aldol condensations.The products observed for butan-2-one (5-methyl-4-hepten-3-one and 4-hydroxy-4-methylpentan-2-one) are those expected for homogeneous base catalysis.A J-modulated spin-echo sequence demonstrates that 5-ethyl-4-methyl-5-hepten-3-one, the β,γ condensation product, is obtained using pentan-3-one.The results demonstrate that conventional (13)C n.m.r. can be effectively used to distinguish reaction pathways and products for surface catalysed reactions.

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

Ozonolysis of enol ethers. Part 8. Ozonation of (1-methoxy-2-methylprop-1-enyl)-1,1′-biphenyl in comparison with related oxygenations

The results of conversions of 4-(1-methoxy-2-methylprop-1-enyl)-1,1′-biphenyl (19) with ozone and with dimethyldioxirane (6b) under 'normal' and 'inverse' conditions are compared with oxygenations by dioxygen under thermal and sensitized photochemical conditions, as well as with the photooxygenation of epoxide 17, formally derived from 19. Ozone consumption varies between 0.7 and 1 mol-equiv. amounts, peroxidic species are not formed. Except for bicyclus 24, ali conversions lead to mixtures of the same [1,1′-biphenyl]-4-yl compounds which only differ by varying percentages. It is concluded that ozonolysis of C=C bonds only represents a special type of electron-transfer oxygenation.

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.

Catalysis by cobalt compounds of aldol and retroaldol reactions

Aldol condensation of acetone, butanone, and 2-pentanone, and retroaldol reaction of neat diacetone alcohol and 3-methyl-3-hydroxyheptan-5-one are catalyzed by (Ph3P)3CoCH3 and (Ph3P)3CoSi(CH3)3.The condensations are reversible and the retroaldol reaction is favoured.Several hindered or cyclic ketones, such as higher homologues, 3-pentanone, methyl isopropyl ketone or cyclohexanone do not condense.By comparison, aliphatic aldehydes react fast and irreversibly to yield products comprised of three aldehyde units. (Ph3P)3CoCH3 also catalyzes protium/deuterium scramblingbetween ketones and acetone-d6.This exchange takes place preferably at the C3 carbon whereas condensation takes place at the C1 carbon.The reactions take place at 20 deg C or below, and of the several organometallic compounds tested only the two mentioned above were found to be active.

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.

Continuous synthesis of triacetonamine over sulfonic acid-functionalized mesoporous silicas

The continuous synthesis of triacetonamine from acetone and ammonia was realized over sulfonic acid-functionalized mesoporous silicas. These catalysts were characterized by TG, XPS, BET, elemental analysis and acid-base titration. The results indicated th

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.